Coulson & Richardson’s
CHEMICAL ENGINEERING
VOLUME 6
Coulson & Richardson’s Chemical Engineering
Chemical Engineering, Volume 1, Sixth edition
Fluid Flow, Heat Transfer and Mass Transfer
J. M. Coulson and J. F. Richardson
with J. R. Backhurst and J. H. Harker
Chemical Engineering, Volume 2, Fifth edition
Particle Technology and Separation Processes
J. F. Richardson and J. H. Harker
with J. R. Backhurst
Chemical Engineering, Volume 3, Third edition
Chemical & Biochemical Reactors & Process Control
Edited by J. F. Richardson and D. G. Peacock
Chemical Engineering, Second edition
Solutions to the Problems in Volume 1
J. R. Backhurst and J. H. Harker with J. F. Richardson
Chemical Engineering, Solutions to the Problems
in Volumes 2 and 3
J. R. Backhurst and J. H. Harker with J. F. Richardson
Chemical Engineering, Volume 6, Fourth edition
Chemical Engineering Design
R. K. Sinnott
Elsevier Butterworth-Heinemann
Linacre House, Jordan Hill, Oxford OX2 8DP
30 Corporate Drive, MA 01803
First published 1983
Second edition 1993
Reprinted with corrections 1994
Reprinted with revisions 1996
Third edition 1999
Reprinted 2001, 2003
Fourth edition 2005
Copyright 1993, 1996, 1999, 2005 R. K. Sinnott. All rights reserved
The right of R. K. Sinnott to be identified as the author of this work
has been asserted in accordance with the Copyright, Designs and
Patents Act 1988
No part of this publication may be reproduced in any material form (including
photocopying or storing in any medium by electronic means and whether
or not transiently or incidentally to some other use of this publication) without
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Typeset by Laserwords Private Limited, Chennai, India
Contents
PREFACE TO FOURTH EDITION
xvii
PREFACE TO THIRD EDITION
xx
PREFACE TO SECOND EDITION
xxi
PREFACE TO FIRST EDITION
xxiii
SERIES EDITOR’S PREFACE
xxiv
ACKNOWLEDGEMENT
xxv
1
Introduction to Design
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
2
1
Introduction
Nature of design
1.2.1
The design objective (the need)
1.2.2
Data collection
1.2.3
Generation of possible design solutions
1.2.4
Selection
The anatomy of a chemical manufacturing process
1.3.1
Continuous and batch processes
The organisation of a chemical engineering project
Project documentation
Codes and standards
Factors of safety (design factors)
Systems of units
Degrees of freedom and design variables. The mathematical representation
of the design problem
1.9.1
Information flow and design variables
1.9.2
Selection of design variables
1.9.3
Information flow and the structure of design problems
Optimisation
1.10.1
General procedure
1.10.2
Simple models
1.10.3
Multiple variable problems
1.10.4
Linear programming
1.10.5
Dynamic programming
1.10.6
Optimisation of batch and semicontinuous processes
References
Nomenclature
Problems
1
1
3
3
3
4
5
7
7
10
12
13
14
15
15
19
20
24
25
25
27
29
29
29
30
31
32
Fundamentals of Material Balances
34
2.1
2.2
2.3
2.4
2.5
34
34
34
35
36
Introduction
The equivalence of mass and energy
Conservation of mass
Units used to express compositions
Stoichiometry
v
vi
CONTENTS
2.6
2.7
2.8
2.9
2.10
2.11
2.12
2.13
2.14
2.15
2.16
2.17
2.18
2.19
2.20
2.21
3
Choice of system boundary
Choice of basis for calculations
Number of independent components
Constraints on flows and compositions
General algebraic method
Tie components
Excess reagent
Conversion and yield
Recycle processes
Purge
By-pass
Unsteady-state calculations
General procedure for material-balance problems
References (Further Reading)
Nomenclature
Problems
37
40
40
41
42
44
46
47
50
52
53
54
56
57
57
57
Fundamentals of Energy Balances (and Energy Utilisation)
60
3.1
3.2
3.3
60
60
61
61
61
61
61
62
62
62
67
68
70
71
72
73
75
77
79
80
81
82
84
90
93
93
99
101
101
101
102
103
105
107
110
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111
115
117
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123
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.16
3.17
Introduction
Conservation of energy
Forms of energy (per unit mass of material)
3.3.1
Potential energy
3.3.2
Kinetic energy
3.3.3
Internal energy
3.3.4
Work
3.3.5
Heat
3.3.6
Electrical energy
The energy balance
Calculation of specific enthalpy
Mean heat capacities
The effect of pressure on heat capacity
Enthalpy of mixtures
3.8.1
Integral heats of solution
Enthalpy-concentration diagrams
Heats of reaction
3.10.1
Effect of pressure on heats of reaction
Standard heats of formation
Heats of combustion
Compression and expansion of gases
3.13.1
Mollier diagrams
3.13.2
Polytropic compression and expansion
3.13.3
Multistage compressors
3.13.4
Electrical drives
Energy balance calculations
Unsteady state energy balances
Energy recovery
3.16.1
Heat exchange
3.16.2
Heat-exchanger networks
3.16.3
Waste-heat boilers
3.16.4
High-temperature reactors
3.16.5
Low-grade fuels
3.16.6
High-pressure process streams
3.16.7
Heat pumps
Process integration and pinch technology
3.17.1
Pinch technology
3.17.2
The problem table method
3.17.3
The heat exchanger network
3.17.4
Minimum number of exchangers
3.17.5
Threshold problems
CONTENTS
3.18
3.19
3.20
4
Flow-sheeting
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
5
3.17.6
Multiple pinches and multiple utilities
3.17.7
Process integration: integration of other process operations
References
Nomenclature
Problems
Introduction
Flow-sheet presentation
4.2.1
Block diagrams
4.2.2
Pictorial representation
4.2.3
Presentation of stream flow-rates
4.2.4
Information to be included
4.2.5
Layout
4.2.6
Precision of data
4.2.7
Basis of the calculation
4.2.8
Batch processes
4.2.9
Services (utilities)
4.2.10
Equipment identification
4.2.11
Computer aided drafting
Manual flow-sheet calculations
4.3.1
Basis for the flow-sheet calculations
4.3.2
Flow-sheet calculations on individual units
Computer-aided flow-sheeting
Full steady-state simulation programs
4.5.1
Information flow diagrams
Manual calculations with recycle streams
4.6.1
The split-fraction concept
4.6.2
Illustration of the method
4.6.3
Guide rules for estimating split-fraction coefficients
References
Nomenclature
Problems
Piping and Instrumentation
5.1
5.2
5.3
5.4
5.5
5.6
5.7
Introduction
The P and I diagram
5.2.1
Symbols and layout
5.2.2
Basic symbols
Valve selection
Pumps
5.4.1
Pump selection
5.4.2
Pressure drop in pipelines
5.4.3
Power requirements for pumping liquids
5.4.4
Characteristic curves for centrifugal pumps
5.4.5
System curve (operating line)
5.4.6
Net positive suction head (NPSH)
5.4.7
Pump and other shaft seals
Mechanical design of piping systems
5.5.1
Wall thickness: pipe schedule
5.5.2
Pipe supports
5.5.3
Pipe fittings
5.5.4
Pipe stressing
5.5.5
Layout and design
Pipe size selection
Control and instrumentation
5.7.1
Instruments
5.7.2
Instrumentation and control objectives
5.7.3
Automatic-control schemes
vii
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124
127
128
130
133
133
133
134
134
134
135
139
139
140
140
140
140
140
141
142
143
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168
171
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172
176
185
187
188
188
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194
194
195
195
197
199
199
201
206
208
210
212
213
216
216
217
217
217
218
218
227
227
227
228
viii
CONTENTS
5.8
Typical control systems
5.8.1
Level control
5.8.2
Pressure control
5.8.3
Flow control
5.8.4
Heat exchangers
5.8.5
Cascade control
5.8.6
Ratio control
5.8.7
Distillation column control
5.8.8
Reactor control
5.9
Alarms and safety trips, and interlocks
5.10 Computers and microprocessors in process control
5.11 References
5.12 Nomenclature
5.13 Problems
6
Costing and Project Evaluation
6.1
6.2
6.3
6.4
6.5
Introduction
Accuracy and purpose of capital cost estimates
Fixed and working capital
Cost escalation (inflation)
Rapid capital cost estimating methods
6.5.1
Historical costs
6.5.2
Step counting methods
6.6
The factorial method of cost estimation
6.6.1
Lang factors
6.6.2
Detailed factorial estimates
6.7
Estimation of purchased equipment costs
6.8 Summary of the factorial method
6.9 Operating costs
6.9.1
Estimation of operating costs
6.10 Economic evaluation of projects
6.10.1
Cash flow and cash-flow diagrams
6.10.2
Tax and depreciation
6.10.3
Discounted cash flow (time value of money)
6.10.4
Rate of return calculations
6.10.5
Discounted cash-flow rate of return (DCFRR)
6.10.6
Pay-back time
6.10.7
Allowing for inflation
6.10.8
Sensitivity analysis
6.10.9
Summary
6.11 Computer methods for costing and project evaluation
6.12 References
6.13 Nomenclature
6.14 Problems
7
Materials of Construction
7.1
7.2
7.3
7.4
Introduction
Material properties
Mechanical properties
7.3.1
Tensile strength
7.3.2
Stiffness
7.3.3
Toughness
7.3.4
Hardness
7.3.5
Fatigue
7.3.6
Creep
7.3.7
Effect of temperature on the mechanical properties
Corrosion resistance
7.4.1
Uniform corrosion
7.4.2
Galvanic corrosion
229
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230
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231
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233
235
236
238
239
240
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244
245
247
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253
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260
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274
274
275
278
279
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280
284
284
284
285
285
285
286
286
286
287
287
287
288
289
CONTENTS
7.5
7.6
7.7
7.8
7.9
7.10
7.11
7.12
7.13
7.14
7.15
7.16
8
7.4.3
Pitting
7.4.4
Intergranular corrosion
7.4.5
Effect of stress
7.4.6
Erosion-corrosion
7.4.7
High-temperature oxidation
7.4.8
Hydrogen embrittlement
Selection for corrosion resistance
Material costs
Contamination
7.7.1
Surface finish
Commonly used materials of construction
7.8.1
Iron and steel
7.8.2
Stainless steel
7.8.3
Nickel
7.8.4
Monel
7.8.5
Inconel
7.8.6
The Hastelloys
7.8.7
Copper and copper alloys
7.8.8
Aluminium and its alloys
7.8.9
Lead
7.8.10
Titanium
7.8.11
Tantalum
7.8.12
Zirconium
7.8.13
Silver
7.8.14
Gold
7.8.15
Platinum
Plastics as materials of construction for chemical plant
7.9.1
Poly-vinyl chloride (PVC)
7.9.2
Polyolefines
7.9.3
Polytetrafluroethylene (PTFE)
7.9.4
Polyvinylidene fluoride (PVDF)
7.9.5
Glass-fibre reinforced plastics (GRP)
7.9.6
Rubber
Ceramic materials (silicate materials)
7.10.1
Glass
7.10.2
Stoneware
7.10.3
Acid-resistant bricks and tiles
7.10.4
Refractory materials (refractories)
Carbon
Protective coatings
Design for corrosion resistance
References
Nomenclature
Problems
Design Information and Data
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
Introduction
Sources of information on manufacturing processes
General sources of physical properties
Accuracy required of engineering data
Prediction of physical properties
Density
8.6.1
Liquids
8.6.2
Gas and vapour density (specific volume)
Viscosity
8.7.1
Liquids
8.7.2
Gases
Thermal conductivity
8.8.1
Solids
8.8.2
Liquids
ix
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293
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298
299
299
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300
300
300
300
301
301
301
301
302
302
302
302
302
303
303
304
304
304
304
305
305
305
305
307
307
309
309
309
311
312
313
314
314
315
316
316
320
320
320
321
x
CONTENTS
8.8.3
Gases
8.8.4
Mixtures
8.9
Specific heat capacity
8.9.1
Solids and liquids
8.9.2
Gases
8.10 Enthalpy of vaporisation (latent heat)
8.10.1
Mixtures
8.11 Vapour pressure
8.12 Diffusion coefficients (diffusivities)
8.12.1
Gases
8.12.2
Liquids
8.13 Surface tension
8.13.1
Mixtures
8.14 Critical constants
8.15 Enthalpy of reaction and enthalpy of formation
8.16 Phase equilibrium data
8.16.1
Experimental data
8.16.2
Phase equilibria
8.16.3
Equations of state
8.16.4
Correlations for liquid phase activity coefficients
8.16.5
Prediction of vapour-liquid equilibria
8.16.6
K -values for hydrocarbons
8.16.7
Sour-water systems (Sour)
8.16.8
Vapour-liquid equilibria at high pressures
8.16.9
Liquid-liquid equilibria
8.16.10 Choice of phase equilibria for design calculations
8.16.11 Gas solubilities
8.16.12 Use of equations of state to estimate specific enthalpy and density
8.17 References
8.18 Nomenclature
8.19 Problems
9
Safety and Loss Prevention
9.1
9.2
9.3
9.4
9.5
9.6
9.7
9.8
9.9
Introduction
Intrinsic and extrinsic safety
The hazards
9.3.1
Toxicity
9.3.2
Flammability
9.3.3
Explosions
9.3.4
Sources of ignition
9.3.5
Ionising radiation
9.3.6
Pressure
9.3.7
Temperature deviations
9.3.8
Noise
Dow fire and explosion index
9.4.1
Calculation of the Dow F & EI
9.4.2
Potential loss
9.4.3
Basic preventative and protective measures
9.4.4
Mond fire, explosion, and toxicity index
9.4.5
Summary
Hazard and operability studies
9.5.1
Basic principles
9.5.2
Explanation of guide words
9.5.3
Procedure
Hazard analysis
Acceptable risk and safety priorities
Safety check lists
Major hazards
9.9.1
Computer software for quantitative risk analysis
321
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329
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333
335
335
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339
339
339
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341
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348
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350
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353
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358
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361
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363
365
366
368
368
369
370
371
371
375
377
378
379
381
382
383
384
389
390
392
394
395
CONTENTS
9.10
9.11
10
References
Problems
Equipment Selection, Specification and Design
10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8
10.9
10.10
10.11
10.12
10.13
10.14
10.15
10.16
Introduction
Separation processes
Solid-solid separations
10.3.1
Screening (sieving)
10.3.2
Liquid-solid cyclones
10.3.3
Hydroseparators and sizers (classifiers)
10.3.4
Hydraulic jigs
10.3.5
Tables
10.3.6
Classifying centrifuges
10.3.7
Dense-medium separators (sink and float processes)
10.3.8
Flotation separators (froth-flotation)
10.3.9
Magnetic separators
10.3.10 Electrostatic separators
Liquid-solid (solid-liquid) separators
10.4.1
Thickeners and clarifiers
10.4.2
Filtration
10.4.3
Centrifuges
10.4.4
Hydrocyclones (liquid-cyclones)
10.4.5
Pressing (expression)
10.4.6
Solids drying
Separation of dissolved solids
10.5.1
Evaporators
10.5.2
Crystallisation
Liquid-liquid separation
10.6.1
Decanters (settlers)
10.6.2
Plate separators
10.6.3
Coalescers
10.6.4
Centrifugal separators
Separation of dissolved liquids
10.7.1
Solvent extraction and leaching
Gas-solids separations (gas cleaning)
10.8.1
Gravity settlers (settling chambers)
10.8.2
Impingement separators
10.8.3
Centrifugal separators (cyclones)
10.8.4
Filters
10.8.5
Wet scrubbers (washing)
10.8.6
Electrostatic precipitators
Gas liquid separators
10.9.1
Settling velocity
10.9.2
Vertical separators
10.9.3
Horizontal separators
Crushing and grinding (comminution) equipment
Mixing equipment
10.11.1 Gas mixing
10.11.2 Liquid mixing
10.11.3 Solids and pastes
Transport and storage of materials
10.12.1 Gases
10.12.2 Liquids
10.12.3 Solids
Reactors
10.13.1 Principal types of reactor
10.13.2 Design procedure
References
Nomenclature
Problems
xi
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398
400
400
401
401
401
404
405
405
405
406
406
407
407
408
408
408
409
415
422
426
426
434
434
437
440
440
445
445
446
446
447
448
448
448
450
458
459
459
460
461
461
463
465
468
468
468
476
476
477
479
481
482
483
486
486
490
491
xii
11
CONTENTS
Separation Columns (Distillation, Absorption and Extraction)
11.1
11.2
11.3
11.4
11.5
11.6
11.7
11.8
11.9
11.10
11.11
11.12
11.13
11.14
Introduction
Continuous distillation: process description
11.2.1
Reflux considerations
11.2.2
Feed-point location
11.2.3
Selection of column pressure
Continuous distillation: basic principles
11.3.1
Stage equations
11.3.2
Dew points and bubble points
11.3.3
Equilibrium flash calculations
Design variables in distillation
Design methods for binary systems
11.5.1
Basic equations
11.5.2
McCabe-Thiele method
11.5.3
Low product concentrations
11.5.4
The Smoker equations
Multicomponent distillation: general considerations
11.6.1
Key components
11.6.2
Number and sequencing of columns
Multicomponent distillation: short-cut methods for stage and reflux requirements
11.7.1
Pseudo-binary systems
11.7.2
Smith-Brinkley method
11.7.3
Empirical correlations
11.7.4
Distribution of non-key components (graphical method)
Multicomponent systems: rigorous solution procedures (computer methods)
11.8.1
Lewis-Matheson method
11.8.2
Thiele-Geddes method
11.8.3
Relaxation methods
11.8.4
Linear algebra methods
Other distillation systems
11.9.1
Batch distillation
11.9.2
Steam distillation
11.9.3
Reactive distillation
Plate efficiency
11.10.1 Prediction of plate efficiency
11.10.2 O’Connell’s correlation
11.10.3 Van Winkle’s correlation
11.10.4 AIChE method
11.10.5 Entrainment
Approximate column sizing
Plate contactors
11.12.1 Selection of plate type
11.12.2 Plate construction
Plate hydraulic design
11.13.1 Plate-design procedure
11.13.2 Plate areas
11.13.3 Diameter
11.13.4 Liquid-flow arrangement
11.13.5 Entrainment
11.13.6 Weep point
11.13.7 Weir liquid crest
11.13.8 Weir dimensions
11.13.9 Perforated area
11.13.10 Hole size
11.13.11 Hole pitch
11.13.12 Hydraulic gradient
11.13.13 Liquid throw
11.13.14 Plate pressure drop
11.13.15 Downcomer design [back-up]
Packed columns
11.14.1 Types of packing
493
493
494
495
496
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497
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498
499
501
503
503
505
507
512
515
516
517
517
518
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523
526
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543
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545
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552
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557
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561
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567
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570
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572
572
572
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574
574
575
575
577
587
589
CONTENTS
11.15
11.16
11.17
11.18
11.19
12
11.14.2 Packed-bed height
11.14.3 Prediction of the height of a transfer unit (HTU)
11.14.4 Column diameter (capacity)
11.14.5 Column internals
11.14.6 Wetting rates
Column auxiliaries
Solvent extraction (liquid liquid extraction)
11.16.1 Extraction equipment
11.16.2 Extractor design
11.16.3 Extraction columns
11.16.4 Supercritical fluid extraction
References
Nomenclature
Problems
Heat-transfer Equipment
12.1
12.2
Introduction
Basic design procedure and theory
12.2.1
Heat exchanger analysis: the effectiveness NTU method
12.3 Overall heat-transfer coefficient
12.4 Fouling factors (dirt factors)
12.5 Shell and tube exchangers: construction details
12.5.1
Heat-exchanger standards and codes
12.5.2
Tubes
12.5.3
Shells
12.5.4
Tube-sheet layout (tube count)
12.5.5
Shell types (passes)
12.5.6
Shell and tube designation
12.5.7
Baffles
12.5.8
Support plates and tie rods
12.5.9
Tube sheets (plates)
12.5.10 Shell and header nozzles (branches)
12.5.11 Flow-induced tube vibrations
12.6 Mean temperature difference (temperature driving force)
12.7 Shell and tube exchangers: general design considerations
12.7.1
Fluid allocation: shell or tubes
12.7.2
Shell and tube fluid velocities
12.7.3
Stream temperatures
12.7.4
Pressure drop
12.7.5
Fluid physical properties
12.8 Tube-side heat-transfer coefficient and pressure drop (single phase)
12.8.1
Heat transfer
12.8.2
Tube-side pressure drop
12.9 Shell-side heat-transfer and pressure drop (single phase)
12.9.1
Flow pattern
12.9.2
Design methods
12.9.3
Kern’s method
12.9.4
Bell’s method
12.9.5
Shell and bundle geometry
12.9.6
Effect of fouling on pressure drop
12.9.7
Pressure-drop limitations
12.10 Condensers
12.10.1 Heat-transfer fundamentals
12.10.2 Condensation outside horizontal tubes
12.10.3 Condensation inside and outside vertical tubes
12.10.4 Condensation inside horizontal tubes
12.10.5 Condensation of steam
12.10.6 Mean temperature difference
12.10.7 Desuperheating and sub-cooling
xiii
593
597
602
609
616
616
617
617
618
623
624
624
627
630
634
634
635
636
636
638
640
644
645
647
647
649
649
650
652
652
653
653
655
660
660
660
661
661
661
662
662
666
669
669
670
671
693
702
705
705
709
710
710
711
716
717
717
717
xiv
CONTENTS
12.11
12.12
12.13
12.14
12.15
12.16
12.17
12.18
12.19
12.20
12.21
13
12.10.8 Condensation of mixtures
12.10.9 Pressure drop in condensers
Reboilers and vaporisers
12.11.1 Boiling heat-transfer fundamentals
12.11.2 Pool boiling
12.11.3 Convective boiling
12.11.4 Design of forced-circulation reboilers
12.11.5 Design of thermosyphon reboilers
12.11.6 Design of kettle reboilers
Plate heat exchangers
12.12.1 Gasketed plate heat exchangers
12.12.2 Welded plate
12.12.3 Plate-fin
12.12.4 Spiral heat exchangers
Direct-contact heat exchangers
Finned tubes
Double-pipe heat exchangers
Air-cooled exchangers
Fired heaters (furnaces and boilers)
12.17.1 Basic construction
12.17.2 Design
12.17.3 Heat transfer
12.17.4 Pressure drop
12.17.5 Process-side heat transfer and pressure drop
12.17.6 Stack design
12.17.7 Thermal efficiency
Heat transfer to vessels
12.18.1 Jacketed vessels
12.18.2 Internal coils
12.18.3 Agitated vessels
References
Nomenclature
Problems
Mechanical Design of Process Equipment
13.1
Introduction
13.1.1
Classification of pressure vessels
13.2 Pressure vessel codes and standards
13.3 Fundamental principles and equations
13.3.1
Principal stresses
13.3.2
Theories of failure
13.3.3
Elastic stability
13.3.4
Membrane stresses in shells of revolution
13.3.5
Flat plates
13.3.6
Dilation of vessels
13.3.7
Secondary stresses
13.4 General design considerations: pressure vessels
13.4.1
Design pressure
13.4.2
Design temperature
13.4.3
Materials
13.4.4
Design stress (nominal design strength)
13.4.5
Welded joint efficiency, and construction categories
13.4.6
Corrosion allowance
13.4.7
Design loads
13.4.8
Minimum practical wall thickness
13.5 The design of thin-walled vessels under internal pressure
13.5.1
Cylinders and spherical shells
13.5.2
Heads and closures
13.5.3
Design of flat ends
13.5.4
Design of domed ends
13.5.5
Conical sections and end closures
719
723
728
731
732
735
740
741
750
756
756
764
764
765
766
767
768
769
769
770
771
772
774
774
774
775
775
775
777
778
782
786
790
794
794
795
795
796
796
797
798
798
805
809
809
810
810
810
811
811
812
813
814
814
815
815
815
817
818
819
CONTENTS
13.6
13.7
13.8
13.9
13.10
13.11
13.12
13.13
13.14
13.15
13.16
13.17
13.18
13.19
13.20
14
Compensation for openings and branches
Design of vessels subject to external pressure
13.7.1
Cylindrical shells
13.7.2
Design of stiffness rings
13.7.3
Vessel heads
Design of vessels subject to combined loading
13.8.1
Weight loads
13.8.2
Wind loads (tall vessels)
13.8.3
Earthquake loading
13.8.4
Eccentric loads (tall vessels)
13.8.5
Torque
Vessel supports
13.9.1
Saddle supports
13.9.2
Skirt supports
13.9.3
Bracket supports
Bolted flanged joints
13.10.1 Types of flange, and selection
13.10.2 Gaskets
13.10.3 Flange faces
13.10.4 Flange design
13.10.5 Standard flanges
Heat-exchanger tube-plates
Welded joint design
Fatigue assessment of vessels
Pressure tests
High-pressure vessels
13.15.1 Fundamental equations
13.15.2 Compound vessels
13.15.3 Autofrettage
Liquid storage tanks
Mechanical design of centrifuges
13.17.1 Centrifugal pressure
13.17.2 Bowl and spindle motion: critical speed
References
Nomenclature
Problems
General Site Considerations
14.1
14.2
14.3
14.4
14.5
14.6
14.7
Introduction
Plant location and site selection
Site layout
Plant layout
14.4.1
Techniques used in site and plant layout
Utilities
Environmental considerations
14.6.1
Waste management
14.6.2
Noise
14.6.3
Visual impact
14.6.4
Legislation
14.6.5
Environmental auditing
References
xv
822
825
825
828
829
831
835
837
839
840
841
844
844
848
856
858
858
859
861
862
865
867
869
872
872
873
873
877
878
879
879
879
881
883
885
889
892
892
892
894
896
897
900
902
902
905
905
905
906
906
APPENDIX A: GRAPHICAL SYMBOLS FOR PIPING SYSTEMS AND PLANT
908
APPENDIX B: CORROSION CHART
917
APPENDIX C: PHYSICAL PROPERTY DATA BANK
937
APPENDIX D: CONVERSION FACTORS FOR SOME COMMON SI UNITS
958
xvi
CONTENTS
APPENDIX E: STANDARD FLANGES
960
APPENDIX F: DESIGN PROJECTS
965
APPENDIX G: EQUIPMENT SPECIFICATION (DATA) SHEETS
990
APPENDIX H: TYPICAL SHELL AND TUBE HEAT EXCHANGER TUBE-SHEET LAYOUTS
1002
AUTHOR INDEX
1007
SUBJECT INDEX
1017
CHAPTER 1
Introduction to Design
1.1. INTRODUCTION
This chapter is an introduction to the nature and methodology of the design process, and
its application to the design of chemical manufacturing processes.
1.2. NATURE OF DESIGN
This section is a general, somewhat philosophical, discussion of the design process; how a
designer works. The subject of this book is chemical engineering design, but the methodology of design described in this section applies equally to other branches of engineering
design.
Design is a creative activity, and as such can be one of the most rewarding and satisfying
activities undertaken by an engineer. It is the synthesis, the putting together, of ideas to
achieve a desired purpose. The design does not exist at the commencement of the project.
The designer starts with a specific objective in mind, a need, and by developing and
evaluating possible designs, arrives at what he considers the best way of achieving that
objective; be it a better chair, a new bridge, or for the chemical engineer, a new chemical
product or a stage in the design of a production process.
When considering possible ways of achieving the objective the designer will be
constrained by many factors, which will narrow down the number of possible designs;
but, there will rarely be just one possible solution to the problem, just one design. Several
alternative ways of meeting the objective will normally be possible, even several best
designs, depending on the nature of the constraints.
These constraints on the possible solutions to a problem in design arise in many ways.
Some constraints will be fixed, invariable, such as those that arise from physical laws,
government regulations, and standards. Others will be less rigid, and will be capable of
relaxation by the designer as part of his general strategy in seeking the best design. The
constraints that are outside the designer’s influence can be termed the external constraints.
These set the outer boundary of possible designs; as shown in Figure 1.1. Within this
boundary there will be a number of plausible designs bounded by the other constraints,
the internal constraints, over which the designer has some control; such as, choice of
process, choice of process conditions, materials, equipment.
Economic considerations are obviously a major constraint on any engineering design:
plants must make a profit.
Time will also be a constraint. The time available for completion of a design will
usually limit the number of alternative designs that can be considered.
1
2
CHEMICAL ENGINEERING
Region of all designs
Resourc
es
ns
la
da
rds
son
ds
Metho
ts
e
Tim
n
nel
Eco
Sta
n
od
es
Possible designs
an
dc
train
cons
omic
s
Materials
Plausible
designs
Per
f
Sa
Pr
con ocess
diti
ons
l law
f
gu ice o
o
s
Ch oces
pr
re
sica
y
et
P hy
tio
ols
Government contr
“External” constraints
“Internal” constraints
Figure 1.1.
Design constraints
Objective
(design
specification)
Collection of data,
physical
properties design
methods
Generation of
possible designs
Selection and
evaluation
(optimisation)
Final
design
Figure 1.2.
The design process
The stages in the development of a design, from the initial identification of the objective
to the final design, are shown diagrammatically in Figure 1.2. Each stage is discussed in
the following sections.
Figure 1.2 shows design as an iterative procedure; as the design develops the designer
will be aware of more possibilities and more constraints, and will be constantly seeking
new data and ideas, and evaluating possible design solutions.
INTRODUCTION TO DESIGN
3
1.2.1. The design objective (the need)
Chaddock (1975) defined design as, the conversion of an ill-defined requirement into a
satisfied customer.
The designer is creating a design for an article, or a manufacturing process, to fulfil a
particular need. In the design of a chemical process, the need is the public need for the
product, the commercial opportunity, as foreseen by the sales and marketing organisation.
Within this overall objective the designer will recognise sub-objectives; the requirements
of the various units that make up the overall process.
Before starting work the designer should obtain as complete, and as unambiguous, a
statement of the requirements as possible. If the requirement (need) arises from outside the
design group, from a client or from another department, then he will have to elucidate the
real requirements through discussion. It is important to distinguish between the real needs
and the wants. The wants are those parts of the initial specification that may be thought
desirable, but which can be relaxed if required as the design develops. For example, a
particular product specification may be considered desirable by the sales department, but
may be difficult and costly to obtain, and some relaxation of the specification may be
possible, producing a saleable but cheaper product. Whenever he is in a position to do so,
the designer should always question the design requirements (the project and equipment
specifications) and keep them under review as the design progresses.
Where he writes specifications for others, such as for the mechanical design or purchase
of a piece of equipment, he should be aware of the restrictions (constraints) he is placing
on other designers. A tight, well-thought-out, comprehensive, specification of the requirements defines the external constraints within which the other designers must work.
1.2.2. Data collection
To proceed with a design, the designer must first assemble all the relevant facts and
data required. For process design this will include information on possible processes,
equipment performance, and physical property data. This stage can be one of the most
time consuming, and frustrating, aspects of design. Sources of process information and
physical properties are reviewed in Chapter 8.
Many design organisations will prepare a basic data manual, containing all the process
“know-how” on which the design is to be based. Most organisations will have design
manuals covering preferred methods and data for the more frequently used, routine, design
procedures.
The national standards are also sources of design methods and data; they are also design
constraints.
The constraints, particularly the external constraints, should be identified early in the
design process.
1.2.3. Generation of possible design solutions
The creative part of the design process is the generation of possible solutions to the
problem (ways of meeting the objective) for analysis, evaluation and selection. In this
activity the designer will largely rely on previous experience, his own and that of others.
4
CHEMICAL ENGINEERING
It is doubtful if any design is entirely novel. The antecedence of most designs can usually
be easily traced. The first motor cars were clearly horse-drawn carriages without the
horse; and the development of the design of the modern car can be traced step by step
from these early prototypes. In the chemical industry, modern distillation processes have
developed from the ancient stills used for rectification of spirits; and the packed columns
used for gas absorption have developed from primitive, brushwood-packed towers. So,
it is not often that a process designer is faced with the task of producing a design for a
completely novel process or piece of equipment.
The experienced engineer will wisely prefer the tried and tested methods, rather than
possibly more exciting but untried novel designs. The work required to develop new
processes, and the cost, is usually underestimated. Progress is made more surely in small
steps. However, whenever innovation is wanted, previous experience, through prejudice,
can inhibit the generation and acceptance of new ideas; the “not invented here” syndrome.
The amount of work, and the way it is tackled, will depend on the degree of novelty
in a design project.
Chemical engineering projects can be divided into three types, depending on the novelty
involved:
1. Modifications, and additions, to existing plant; usually carried out by the plant design
group.
2. New production capacity to meet growing sales demand, and the sale of established
processes by contractors. Repetition of existing designs, with only minor design
changes.
3. New processes, developed from laboratory research, through pilot plant, to a
commercial process. Even here, most of the unit operations and process equipment
will use established designs.
The first step in devising a new process design will be to sketch out a rough block
diagram showing the main stages in the process; and to list the primary function (objective)
and the major constraints for each stage. Experience should then indicate what types of
unit operations and equipment should be considered.
Jones (1970) discusses the methodology of design, and reviews some of the special
techniques, such as brainstorming sessions and synectics, that have been developed to
help generate ideas for solving intractable problems. A good general reference on the art
of problem solving is the classical work by Polya (1957); see also Chittenden (1987).
Some techniques for problem solving in the Chemical Industry are covered in a short text
by Casey and Frazer (1984).
The generation of ideas for possible solutions to a design problem cannot be separated
from the selection stage of the design process; some ideas will be rejected as impractical
as soon as they are conceived.
1.2.4. Selection
The designer starts with the set of all possible solutions bounded by the external
constraints, and by a process of progressive evaluation and selection, narrows down the
range of candidates to find the “best” design for the purpose.
5
INTRODUCTION TO DESIGN
The selection process can be considered to go through the following stages:
Possible designs (credible) within the external constraints.
Plausible designs (feasible) within the internal constraints.
Probable designs likely candidates.
Best design (optimum) judged the best solution to the problem.
The selection process will become more detailed and more refined as the design progresses
from the area of possible to the area of probable solutions. In the early stages a coarse
screening based on common sense, engineering judgement, and rough costings will usually
suffice. For example, it would not take many minutes to narrow down the choice of raw
materials for the manufacture of ammonia from the possible candidates of, say, wood,
peat, coal, natural gas, and oil, to a choice of between gas and oil, but a more detailed
study would be needed to choose between oil and gas. To select the best design from the
probable designs, detailed design work and costing will usually be necessary. However,
where the performance of candidate designs is likely to be close the cost of this further
refinement, in time and money, may not be worthwhile, particularly as there will usually
be some uncertainty in the accuracy of the estimates.
The mathematical techniques that have been developed to assist in the optimisation of
designs, and plant performance, are discussed briefly in Section 1.10.
Rudd and Watson (1968) and Wells (1973) describe formal techniques for the preliminary screening of alternative designs.
1.3. THE ANATOMY OF A CHEMICAL MANUFACTURING
PROCESS
The basic components of a typical chemical process are shown in Figure 1.3, in which
each block represents a stage in the overall process for producing a product from the raw
materials. Figure 1.3 represents a generalised process; not all the stages will be needed for
any particular process, and the complexity of each stage will depend on the nature of the
process. Chemical engineering design is concerned with the selection and arrangement
of the stages, and the selection, specification and design of the equipment required to
perform the stage functions.
Recycle of unreacted
material
By-products
Wastes
Raw
material
storage
Feed
preparation
Reaction
Product
separation
Stage 1
Stage 2
Stage 3
Stage 4
Figure 1.3.
Product
purification
Stage 5
Product
storage
Sales
Stage 6
Anatomy of a chemical process
Stage 1. Raw material storage
Unless the raw materials (also called essential materials, or feed stocks) are supplied
as intermediate products (intermediates) from a neighbouring plant, some provision will
6
CHEMICAL ENGINEERING
have to be made to hold several days, or weeks, storage to smooth out fluctuations and
interruptions in supply. Even when the materials come from an adjacent plant some
provision is usually made to hold a few hours, or even days, supply to decouple the
processes. The storage required will depend on the nature of the raw materials, the method
of delivery, and what assurance can be placed on the continuity of supply. If materials are
delivered by ship (tanker or bulk carrier) several weeks stocks may be necessary; whereas
if they are received by road or rail, in smaller lots, less storage will be needed.
Stage 2. Feed preparation
Some purification, and preparation, of the raw materials will usually be necessary before
they are sufficiently pure, or in the right form, to be fed to the reaction stage. For example,
acetylene generated by the carbide process contains arsenical and sulphur compounds, and
other impurities, which must be removed by scrubbing with concentrated sulphuric acid
(or other processes) before it is sufficiently pure for reaction with hydrochloric acid to
produce dichloroethane. Liquid feeds will need to be vaporised before being fed to gasphase reactors, and solids may need crushing, grinding and screening.
Stage 3. Reactor
The reaction stage is the heart of a chemical manufacturing process. In the reactor the
raw materials are brought together under conditions that promote the production of the
desired product; invariably, by-products and unwanted compounds (impurities) will also
be formed.
Stage 4. Product separation
In this first stage after the reactor the products and by-products are separated from any
unreacted material. If in sufficient quantity, the unreacted material will be recycled to
the reactor. They may be returned directly to the reactor, or to the feed purification and
preparation stage. The by-products may also be separated from the products at this stage.
Stage 5. Purification
Before sale, the main product will usually need purification to meet the product specification. If produced in economic quantities, the by-products may also be purified for sale.
Stage 6. Product storage
Some inventory of finished product must be held to match production with sales. Provision
for product packaging and transport will also be needed, depending on the nature of the
product. Liquids will normally be dispatched in drums and in bulk tankers (road, rail and
sea), solids in sacks, cartons or bales.
The stock held will depend on the nature of the product and the market.
Ancillary processes
In addition to the main process stages shown in Figure 1.3, provision will have to be
made for the supply of the services (utilities) needed; such as, process water, cooling
INTRODUCTION TO DESIGN
7
water, compressed air, steam. Facilities will also be needed for maintenance, firefighting,
offices and other accommodation, and laboratories; see Chapter 14.
1.3.1. Continuous and batch processes
Continuous processes are designed to operate 24 hours a day, 7 days a week, throughout
the year. Some down time will be allowed for maintenance and, for some processes,
catalyst regeneration. The plant attainment; that is, the percentage of the available hours
in a year that the plant operates, will usually be 90 to 95%.
hours operated
ð 100
8760
Batch processes are designed to operate intermittently. Some, or all, the process units
being frequently shut down and started up.
Continuous processes will usually be more economical for large scale production. Batch
processes are used where some flexibility is wanted in production rate or product specification.
Attainment % D
Choice of continuous versus batch production
The choice between batch or continuous operation will not be clear cut, but the following
rules can be used as a guide.
Continuous
1.
2.
3.
4.
5.
6.
Production rate greater than 5 ð 106 kg/h
Single product
No severe fouling
Good catalyst life
Proven processes design
Established market
Batch
1.
2.
3.
4.
5.
6.
Production rate less than 5 ð 106 kg/h
A range of products or product specifications
Severe fouling
Short catalyst life
New product
Uncertain design
1.4. THE ORGANISATION OF A CHEMICAL ENGINEERING
PROJECT
The design work required in the engineering of a chemical manufacturing process can be
divided into two broad phases.
Phase 1. Process design, which covers the steps from the initial selection of the process
to be used, through to the issuing of the process flow-sheets; and includes the selection,
8
CHEMICAL ENGINEERING
Project specification
Initial evaluation.
Process selection.
Preliminary flow diagrams.
Material and energy balances.
Preliminary equipment selection
and design.
Process flow-sheeting.
Preliminary cost estimation.
Authorisation of funds.
Detailed process design.
Flow-sheets.
Chemical engineering equipment
design and specifications.
Reactors, Unit operations, Heat exchangers,
Miscellaneous equipment.
Materials selection.
Process manuals
Piping and instrument design
Instrument selection
and specification
Electrical,
Motors, switch gear,
substations, etc.
Pumps and compressors.
Selection and specification
Piping design
Vessel design
Structural design
Heat exchanger design
Plant layout
Utilities and other services.
Design and specification
General civil work.
Foundations, drains,
roads, etc.
Buildings.
Offices, laboratories,
control rooms, etc.
Project cost estimation.
Capital authorisation
Purchasing/procurement
Raw material specification.
(contracts)
Construction
Start-up
Operating manuals
Operation
Sales
Figure 1.4.
The structure of a chemical engineering project
INTRODUCTION TO DESIGN
9
specification and chemical engineering design of equipment. In a typical organisation,
this phase is the responsibility of the Process Design Group, and the work will be mainly
done by chemical engineers. The process design group may also be responsible for the
preparation of the piping and instrumentation diagrams.
Phase 2. The detailed mechanical design of equipment; the structural, civil and electrical
design; and the specification and design of the ancillary services. These activities will be
the responsibility of specialist design groups, having expertise in the whole range of
engineering disciplines.
Other specialist groups will be responsible for cost estimation, and the purchase and
procurement of equipment and materials.
The sequence of steps in the design, construction and start-up of a typical chemical
process plant is shown diagrammatically in Figure 1.4 and the organisation of a typical
project group in Figure 1.5. Each step in the design process will not be as neatly separated
from the others as is indicated in Figure 1.4; nor will the sequence of events be as clearly
defined. There will be a constant interchange of information between the various design
sections as the design develops, but it is clear that some steps in a design must be largely
completed before others can be started.
A project manager, often a chemical engineer by training, is usually responsible for the
co-ordination of the project, as shown in Figure 1.5.
Process section
Process evaluation
Flow-sheeting
Equipment specifications
Construction section
Construction
Start-up
Procurement
section
Estimating
Inspection
Scheduling
Project
manager
Specialist design sections
Vessels
Layout
Control
and instruments
Compressors
and turbines
pumps
Civil work
structures
buildings
Piping
valves
Heat exchangers
fired heaters
Electrical
Utilities
Figure 1.5.
Project organisation
As was stated in Section 1.2.1, the project design should start with a clear specification
defining the product, capacity, raw materials, process and site location. If the project is
based on an established process and product, a full specification can be drawn up at
the start of the project. For a new product, the specification will be developed from an
economic evaluation of possible processes, based on laboratory research, pilot plant tests
and product market research.
10
CHEMICAL ENGINEERING
The organisation of chemical process design is discussed in more detail by Rase and
Barrow (1964) and Baasel (1974).
Some of the larger chemical manufacturing companies have their own project design
organisations and carry out the whole project design and engineering, and possibly
construction, within their own organisation. More usually the design and construction, and
possibly assistance with start-up, is entrusted to one of the international contracting firms.
The operating company will often provide the “know-how” for the process, and will
work closely with the contractor throughout all stages of the project.
1.5. PROJECT DOCUMENTATION
As shown in Figure 1.5 and described in Section 1.4, the design and engineering of
a chemical process requires the co-operation of many specialist groups. Effective cooperation depends on effective communications, and all design organisations have formal
procedures for handling project information and documentation. The project documentation will include:
1. General correspondence within the design group and with:
government departments
equipment vendors
site personnel
the client
2. Calculation sheets
design calculations
costing
computer print-out
3. Drawings
flow-sheets
piping and instrumentation diagrams
layout diagrams
plot/site plans
equipment details
piping diagrams
architectural drawings
design sketches
4. Specification sheets
for equipment, such as:
heat exchangers
pumps
5. Purchase orders
quotations
invoices
All documents should be assigned a code number for easy cross referencing, filing and
retrieval.
Calculation sheets
The design engineer should develop the habit of setting out calculations so that they can
be easily understood and checked by others. It is good practice to include on calculation
INTRODUCTION TO DESIGN
11
sheets the basis of the calculations, and any assumptions and approximations made, in
sufficient detail for the methods, as well as the arithmetic, to be checked. Design calculations are normally set out on standard sheets. The heading at the top of each sheet should
include: the project title and identification number and, most importantly, the signature
(or initials) of the person who checked the calculation.
Drawings
All project drawings are normally drawn on specially printed sheets, with the company
name; project title and number; drawing title and identification number; draughtsman’s
name and person checking the drawing; clearly set out in a box in the bottom right-hand
corner. Provision should also be made for noting on the drawing all modifications to the
initial issue.
Drawings should conform to accepted drawing conventions, preferably those laid down
by the national standards. The symbols used for flow-sheets and piping and instrument
diagrams are discussed in Chapter 4. Drawings and sketches are normally made on
detail paper (semi-transparent) in pencil, so modifications can be easily made, and prints
taken.
In most design offices Computer Aided Design (CAD) methods are now used to produce
the drawings required for all the aspects of a project: flow-sheets, piping and instrumentation, mechanical and civil work.
Specification sheets
Standard specification sheets are normally used to transmit the information required for
the detailed design, or purchase, of equipment items; such as, heat exchangers, pumps,
columns.
As well as ensuring that the information is clearly and unambiguously presented,
standard specification sheets serve as check lists to ensure that all the information required
is included.
Examples of equipment specification sheets are given in Appendix G.
Process manuals
Process manuals are often prepared by the process design group to describe the process and
the basis of the design. Together with the flow-sheets, they provide a complete technical
description of the process.
Operating manuals
Operating manuals give the detailed, step by step, instructions for operation of the process
and equipment. They would normally be prepared by the operating company personnel,
but may also be issued by a contractor as part of the contract package for a less experienced
client. The operating manuals would be used for operator instruction and training, and
for the preparation of the formal plant operating instructions.
12
CHEMICAL ENGINEERING
1.6. CODES AND STANDARDS
The need for standardisation arose early in the evolution of the modern engineering
industry; Whitworth introduced the first standard screw thread to give a measure of
interchangeability between different manufacturers in 1841. Modern engineering standards
cover a much wider function than the interchange of parts. In engineering practice
they cover:
1.
2.
3.
4.
5.
Materials, properties and compositions.
Testing procedures for performance, compositions, quality.
Preferred sizes; for example, tubes, plates, sections.
Design methods, inspection, fabrication.
Codes of practice, for plant operation and safety.
The terms STANDARD and CODE are used interchangeably, though CODE should
really be reserved for a code of practice covering say, a recommended design or operating
procedure; and STANDARD for preferred sizes, compositions, etc.
All of the developed countries, and many of the developing countries, have national
standards organisations, responsible for the issue and maintenance of standards for the
manufacturing industries, and for the protection of consumers. In the United Kingdom
preparation and promulgation of national standards are the responsibility of the British
Standards Institution (BSI). The Institution has a secretariat and a number of technical
personnel, but the preparation of the standards is largely the responsibility of committees
of persons from the appropriate industry, the professional engineering institutions and
other interested organisations.
In the United States the government organisation responsible for coordinating information on standards is the National Bureau of Standards; standards are issued by Federal,
State and various commercial organisations. The principal ones of interest to chemical
engineers are those issued by the American National Standards Institute (ANSI), the
American Petroleum Institute (API), the American Society for Testing Materials (ASTM),
and the American Society of Mechanical Engineers (ASME) (pressure vessels). Burklin
(1979) gives a comprehensive list of the American codes and standards.
The International Organization for Standardization (ISO) coordinates the publication of
international standards.
All the published British standards are listed, and their scope and application described,
in the British Standards Institute Catalogue; which the designer should consult. The
catalogue is available online, go to the BSI group home page, www.bsi-global.com.
As well as the various national standards and codes, the larger design organisations
will have their own (in-house) standards. Much of the detail in engineering design work
is routine and repetitious, and it saves time and money, and ensures a conformity between
projects, if standard designs are used whenever practicable.
Equipment manufacturers also work to standards to produce standardised designs and
size ranges for commonly used items; such as electric motors, pumps, pipes and pipe
fittings. They will conform to national standards, where they exist, or to those issued by
trade associations. It is clearly more economic to produce a limited range of standard
sizes than to have to treat each order as a special job.
INTRODUCTION TO DESIGN
13
For the designer, the use of a standardised component size allows for the easy integration
of a piece of equipment into the rest of the plant. For example, if a standard range of
centrifugal pumps is specified the pump dimensions will be known, and this facilitates the
design of the foundations plates, pipe connections and the selection of the drive motors:
standard electric motors would be used.
For an operating company, the standardisation of equipment designs and sizes increases
interchangeability and reduces the stock of spares that have to be held in maintenance
stores.
Though there are clearly considerable advantages to be gained from the use of standards
in design, there are also some disadvantages. Standards impose constraints on the designer.
The nearest standard size will normally be selected on completing a design calculation
(rounding-up) but this will not necessarily be the optimum size; though as the standard
size will be cheaper than a special size, it will usually be the best choice from the point of
view of initial capital cost. Standard design methods must, of their nature, be historical,
and do not necessarily incorporate the latest techniques.
The use of standards in design is illustrated in the discussion of the pressure vessel
design standards (codes) in Chapter 13.
1.7. FACTORS OF SAFETY (DESIGN FACTORS)
Design is an inexact art; errors and uncertainties will arise from uncertainties in the design
data available and in the approximations necessary in design calculations. To ensure that
the design specification is met, factors are included to give a margin of safety in the
design; safety in the sense that the equipment will not fail to perform satisfactorily, and
that it will operate safely: will not cause a hazard. “Design factor” is a better term to use,
as it does not confuse safety and performance factors.
In mechanical and structural design, the magnitude of the design factors used to allow
for uncertainties in material properties, design methods, fabrication and operating loads
are well established. For example, a factor of around 4 on the tensile strength, or about
2.5 on the 0.1 per cent proof stress, is normally used in general structural design. The
selection of design factors in mechanical engineering design is illustrated in the discussion
of pressure vessel design in Chapter 13.
Design factors are also applied in process design to give some tolerance in the design.
For example, the process stream average flows calculated from material balances are
usually increased by a factor, typically 10 per cent, to give some flexibility in process
operation. This factor will set the maximum flows for equipment, instrumentation, and
piping design. Where design factors are introduced to give some contingency in a process
design, they should be agreed within the project organisation, and clearly stated in the
project documents (drawings, calculation sheets and manuals). If this is not done, there
is a danger that each of the specialist design groups will add its own “factor of safety”;
resulting in gross, and unnecessary, over-design.
When selecting the design factor to use a balance has to be made between the desire
to make sure the design is adequate and the need to design to tight margins to remain
competitive. The greater the uncertainty in the design methods and data, the bigger the
design factor that must be used.
14
CHEMICAL ENGINEERING
1.8. SYSTEMS OF UNITS
To be consistent with the other volumes in this series, SI units have been used in this
book. However, in practice the design methods, data and standards which the designer will
use are often only available in the traditional scientific and engineering units. Chemical
engineering has always used a diversity of units; embracing the scientific CGS and MKS
systems, and both the American and British engineering systems. Those engineers in the
older industries will also have had to deal with some bizarre traditional units; such as
degrees Twaddle (density) and barrels for quantity. Desirable as it may be for industry
world-wide to adopt one consistent set of units, such as SI, this is unlikely to come about
for many years, and the designer must contend with whatever system, or combination of
systems, his organisation uses. For those in the contracting industry this will also mean
working with whatever system of units the client requires.
It is usually the best practice to work through design calculations in the units in which
the result is to be presented; but, if working in SI units is preferred, data can be converted
to SI units, the calculation made, and the result converted to whatever units are required.
Conversion factors to the SI system from most of the scientific and engineering units used
in chemical engineering design are given in Appendix D.
Some license has been taken in the use of the SI system in this volume. Temperatures are
given in degrees Celsius (Ž C); degrees Kelvin are only used when absolute temperature
is required in the calculation. Pressures are often given in bar (or atmospheres) rather
than in the Pascals (N/m2 ), as this gives a better feel for the magnitude of the pressures.
In technical calculations the bar can be taken as equivalent to an atmosphere, whatever
definition is used for atmosphere. The abbreviations bara and barg are often used to denote
bar absolute and bar gauge; analogous to psia and psig when the pressure is expressed
in pound force per square inch. When bar is used on its own, without qualification, it is
normally taken as absolute.
For stress, N/mm2 have been used, as these units are now generally accepted by
engineers, and the use of a small unit of area helps to indicate that stress is the intensity of
force at a point (as is also pressure). For quantity, kmol are generally used in preference
to mol, and for flow, kmol/h instead of mol/s, as this gives more sensibly sized figures,
which are also closer to the more familiar lb/h.
For volume and volumetric flow, m3 and m3 /h are used in preference to m3 /s, which
gives ridiculously small values in engineering calculations. Litres per second are used for
small flow-rates, as this is the preferred unit for pump specifications.
Where, for convenience, other than SI units have been used on figures or diagrams, the
scales are also given in SI units, or the appropriate conversion factors are given in the
text. The answers to some examples are given in British engineering units as well as SI,
to help illustrate the significance of the values.
Some approximate conversion factors to SI units are given in Table 1.1. These are
worth committing to memory, to give some feel for the units for those more familiar with
the traditional engineering units. The exact conversion factors are also shown in the table.
A more comprehensive table of conversion factors is given in Appendix D.
Engineers need to be aware of the difference between US gallons and imperial gallons
(UK) when using American literature and equipment catalogues. Equipment quoted in an
15
INTRODUCTION TO DESIGN
Table 1.1.
Quantity
Approximate conversion units
British
Eng. unit
SI unit
approx.
exact
Energy
Specific enthalpy
Specific heat capacity
1 Btu
1 Btu/lb
1 Btu/lb° F
(CHU/lb° C)
1 kJ
2 kJ/kg
4 kJ/kg° C
1.05506
2.326
4.1868
Heat transfer coeff.
1 Btu/ft2 h° F
(CHU/ft2 h° C)
6 W/m2 ° C
5.678
Viscosity
1 centipoise
1 lbf /ft h
1 dyne/cm
1 mNs/m2
0.4 mNs/m2
1 mN/m
1.000
0.4134
1.000
Pressure
1 lbf /in2
1 atm
7 kN/m2
1 bar
105 N/m2
6.894
1.01325
Density
1 lb/ft3
1 g/cm3
16 kg/m3
1 kg/m3
16.0190
Volume
1 imp gal.
Flow-rate
1 imp gal/m
4.5 ð 103 m3
4.5461 ð 103
Surface tension
16 m3 /h
16.366
Note:
1 US gallon D 0.84 imperial gallons (UK)
1 barrel (oil) D 50 US gall ³ 0.19 m3 (exact 0.1893)
1 kWh D 3.6 MJ
American catalogue in US gallons or gpm (gallons per minute) will have only 80 per cent
of the rated capacity when measured in imperial gallons.
The electrical supply frequency in these two countries is also different: 60 Hz in the US
and 50 Hz in the UK. So a pump specified as 50 gpm (US gallons), running at 1750 rpm
(revolutions per second) in the US would only deliver 35 imp gpm if operated in the UK;
where the motor speed would be reduced to 1460 rpm: so beware.
1.9. DEGREES OF FREEDOM AND DESIGN VARIABLES.
THE MATHEMATICAL REPRESENTATION OF
THE DESIGN PROBLEM
In Section 1.2 it was shown that the designer in seeking a solution to a design problem
works within the constraints inherent in the particular problem.
In this section the structure of design problems is examined by representing the general
design problem in a mathematical form.
1.9.1. Information flow and design variables
A process unit in a chemical process plant performs some operation on the inlet material
streams to produce the desired outlet streams. In the design of such a unit the design
calculations model the operation of the unit. A process unit and the design equations
16
CHEMICAL ENGINEERING
Input
streams
Input
information
Unit
Calculation
method
Figure 1.6.
Output
streams
Output
information
The “design unit”
representing the unit are shown diagrammatically in Figure 1.6. In the “design unit” the
flow of material is replaced by a flow of information into the unit and a flow of derived
information from the unit.
The information flows are the values of the variables which are involved in the design;
such as, stream compositions, temperatures, pressure, stream flow-rates, and stream
enthalpies. Composition, temperature and pressure are intensive variables: independent of
the quantity of material (flow-rate). The constraints on the design will place restrictions on
the possible values that these variables can take. The values of some of the variables will
be fixed directly by process specifications. The values of other variables will be determined
by “design relationships” arising from constraints. Some of the design relationships will
be in the form of explicit mathematical equations (design equations); such as those
arising from material and energy balances, thermodynamic relationships, and equipment
performance parameters. Other relationships will be less precise; such as those arising
from the use of standards and preferred sizes, and safety considerations.
The difference between the number of variables involved in a design and the number
of design relationships has been called the number of “degrees of freedom”; similar to the
use of the term in the phase rule. The number of variables in the system is analogous to the
number of variables in a set of simultaneous equations, and the number of relationships
analogous to the number of equations. The difference between the number of variables
and equations is called the variance of the set of equations.
If Nv is the number of possible variables in a design problem and Nr the number of
design relationships, then the “degrees of freedom” Nd is given by:
Nd D Nv Nr
⊲1.1⊳
Nd represents the freedom that the designer has to manipulate the variables to find the
best design.
If Nv D Nr , Nd D 0 and there is only one, unique, solution to the problem. The problem
is not a true design problem, no optimisation is possible.
If Nv < Nr , Nd < 0, and the problem is over defined; only a trivial solution is possible.
If Nv > Nr , Nd > 0, and there is an infinite number of possible solutions. However,
for a practical problem there will be only a limited number of feasible solutions. The
value of Nd is the number of variables which the designer must assign values to solve
the problem.
How the number of process variables, design relationships, and design variables defines
a system can be best illustrated by considering the simplest system; a single-phase, process
stream.
17
INTRODUCTION TO DESIGN
Process stream
Consider a single-phase stream, containing C components.
Variable
Number
Stream flow-rate
Composition (component concentrations)
Temperature
Pressure
Stream enthalpy
1
C
1
1
1
Total, Nv D C C 4
Relationships between variables
Number
Composition⊲1⊳
Enthalpy⊲2⊳
1
1
Total, Nr D 2
Degrees of freedom Nd D Nv Nr D ⊲C C 4⊳ 2 D C C 2
(1) The sum of the mass or mol, fractions, must equal one.
(2) The enthalpy is a function of stream composition, temperature and pressure.
Specifying (C C 2) variables completely defines the stream.
Flash distillation
The idea of degrees of freedom in the design process can be further illustrated by considering a simple process unit, a flash distillation. (For a description of flash distillation see
Volume 2, Chapter 11).
F2, P2, T2, (xi)2
F1, P1, T1, (xi)1
q
Figure 1.7.
F3, P3, T3, (xi)3
Flash distillation
The unit is shown in Figure 1.7, where:
F D stream flow rate,
P D pressure,
T D temperature,
xi D concentration, component i,
q D heat input.
Suffixes, 1 D inlet, 2 D outlet vapour, 3 D outlet liquid.
18
CHEMICAL ENGINEERING
Variable
Number
3⊲C C 2⊳1
Streams (free variables)⊲1⊳
Still
pressure
temperature
heat input
1
1
1
Nr D 3C C 9
Relationship
Number
Material balances (each component)
Heat balance, overall
v l e relationships⊲2⊳
Equilibrium still restriction⊲3⊳
C
1
C
4
2C C 5
Degrees of freedom Nd D ⊲3C C 9⊳ ⊲2C C 5⊳ D C C 4
(1) The degrees of freedom for each stream. The total variables in each stream could have been used, and
the stream relationships included in the count of relationships.
This shows how the degrees of freedom for a complex unit can be built up from the degrees of freedom of
its components. For more complex examples see Kwauk (1956).
(2) Given the temperature and pressure, the concentration of any component in the vapour phase can be
obtained from the concentration in the liquid phase, from the vapour liquid equilibrium data for the system.
(3) The concept (definition) of an equilibrium separation implies that the outlet streams and the still are at
the same temperature and pressure. This gives four equations:
P2 D P3 D P
T2 D T3 D T
Though the total degrees of freedom is seen to be (C C 4) some of the variables will
normally be fixed by general process considerations, and will not be free for the designer
to select as “design variables”. The flash distillation unit will normally be one unit in a
process system and the feed composition and feed conditions will be fixed by the upstream
processes; the feed will arise as an outlet stream from some other unit. Defining the feed
fixes (C C 2) variables, so the designer is left with:
⊲C C 4⊳ ⊲C C 2⊳ D 2
as design variables.
Summary
The purpose of this discussion was to show that in a design there will be a certain
number of variables that the designer must specify to define the problem, and which he
can manipulate to seek the best design. In manual calculations the designer will rarely
INTRODUCTION TO DESIGN
19
need to calculate the degrees of freedom in a formal way. He will usually have intuitive
feel for the problem, and can change the calculation procedure, and select the design
variables, as he works through the design. He will know by experience if the problem is
correctly specified. A computer, however, has no intuition, and for computer-aided design
calculations it is essential to ensure that the necessary number of variables is specified to
define the problem correctly. For complex processes the number of variables and relating
equations will be very large, and the calculation of the degrees of freedom very involved.
Kwauk (1956) has shown how the degrees of freedom can be calculated for separation
processes by building up the complex unit from simpler units. Smith (1963) uses Kwauk’s
method, and illustrates how the idea of “degrees of freedom” can be used in the design
of separation processes.
1.9.2. Selection of design variables
In setting out to solve a design problem the designer has to decide which variables are to
be chosen as “design variables”; the ones he will manipulate to produce the best design.
The choice of design variables is important; careful selection can simplify the design
calculations. This can be illustrated by considering the choice of design variables for a
simple binary flash distillation.
For a flash distillation the total degrees of freedom was shown to be (C C 4), so for
two components Nd D 6. If the feed stream flow, composition, temperature and pressure
are fixed by upstream conditions, then the number of design variables will be:
N0d D 6 ⊲C C 2⊳ D 6 4 D 2
So the designer is free to select two variables from the remaining variables in order to
proceed with the calculation of the outlet stream compositions and flows.
If he selects the still pressure (which for a binary system will determine the vapour
liquid equilibrium relationship) and one outlet stream flow-rate, then the outlet compositions can be calculated by simultaneous solution of the mass balance and equilibrium
relationships (equations). A graphical method for the simultaneous solution is given in
Volume 2, Chapter 11.
However, if he selects an outlet stream composition (say the liquid stream) instead of
a flow-rate, then the simultaneous solution of the mass balance and v l e relationships
would not be necessary. The stream compositions could be calculated by the following
step-by-step (sequential) procedure:
1. Specifying P determines the v l e relationship (equilibrium) curve from experimental data.
2. Knowing the outlet liquid composition, the outlet vapour composition can be calculated from the v l e relationship.
3. Knowing the feed and outlet compositions, and the feed flow-rate, the outlet stream
flows can be calculated from a material balance.
4. An enthalpy balance then gives the heat input required.
The need for simultaneous solution of the design equations implies that there is a
recycle of information. Choice of an outlet stream composition as a design variable in
20
CHEMICAL ENGINEERING
x2 (or x3)
Feed
Select
F1
x1
P1
T1
P
F2 (or F3)
F3 (or F2)
x2
x3
T
Direction of calculation
(a)
x2 (or x3)
x3
F2
F3
T
F1
x1
P1
T1
Feed
P
x2 (or x3)
Select
Direction of calculation
(b)
Figure 1.8.
Information flow, binary flash distillation calculation (a) Information recycle (b) Information flow
reversal
effect reverses the flow of information through the problem and removes the recycle; this
is shown diagrammatically in Figure 1.8.
1.9.3. Information flow and the structure of design problems
It was shown in Section 1.9.2. by studying a relatively simple problem, that the way
in which the designer selects his design variables can determine whether the design
calculations will prove to be easy or difficult. Selection of one particular set of variables
can lead to a straightforward, step-by-step, procedure, whereas selection of another set
can force the need for simultaneous solution of some of the relationships; which often
requires an iterative procedure (cut-and-try method). How the choice of design variables,
inputs to the calculation procedure, affects the ease of solution for the general design
problem can be illustrated by studying the flow of information, using simple information
flow diagrams. The method used will be that given by Lee et al. (1966) who used a form
of directed graph; a biparte graph, see Berge (1962).
The general design problem can be represented in mathematical symbolism as a series
of equations:
fi ⊲vj ⊳ D 0
where j D 1, 2, 3, . . . , Nv ,
i D 1, 2, 3, . . . , Nr
Consider the following set of such equations:
f1 ⊲v1 , v2 ⊳ D 0
f2 ⊲v1 , v2 , v3 , v5 ⊳ D 0
21
INTRODUCTION TO DESIGN
f3 ⊲v1 , v3 , v4 ⊳ D 0
f4 ⊲v2 , v4 , v5 , v6 ⊳ D 0
f5 ⊲v5 , v6 , v7 ⊳ D 0
There are seven variables, Nv D 7, and five equations (relationships) Nr D 5, so the
number of degrees of freedom is:
Nd D Nv Nr D 7 5 D 2
The task is to select two variables from the total of seven in such a way as to give the
simplest, most efficient, method of solution to the seven equations. There are twenty-one
ways of selecting two items from seven.
In Lee’s method the equations and variables are represented by nodes on the biparte
graph (circles), connected by edges (lines), as shown in Figure 1.9.
f node
f1
v1
Figure 1.9.
v1
v node
Nodes and edges on a biparte graph
Figure 1.9 shows that equation f1 contains (is connected to) variables v1 and v2 . The
complete graph for the set of equations is shown in Figure 1.10.
f1
v1
Figure 1.10.
f2
v2
f3
v3
v4
f4
v5
f5
v6
v7
Biparte graph for the complete set of equations
The number of edges connected to a node defines the local degree of the node p.
For example, the local degree of the f1 node is 2, p⊲f1 ⊳ D 2, and at the v5 node it is 3,
p⊲v5 ⊳ D 3. Assigning directions to the edges of Figure 1.10 (by putting arrows on the
lines) identifies one possible order of solution for the equations. If a variable vj is defined
as an output variable from an equation fi , then the direction of information flow is from
the node fi to the node vj and all other edges will be oriented into fi . What this means,
mathematically, is that assigning vj as an output from fi rearranges that equation so that:
fi ⊲v1 , v2 , . . . , vn ⊳ D vj
vj is calculated from equation fi .
22
CHEMICAL ENGINEERING
The variables selected as design variables (fixed by the designer) cannot therefore be
assigned as output variables from an f node. They are inputs to the system and their edges
must be oriented into the system of equations.
If, for instance, variables v3 and v4 are selected as design variables, then Figure 1.11
shows one possible order of solution of the set of equations. Different types of arrows
are used to distinguish between input and output variables, and the variables selected as
design variables are enclosed in a double circle.
v3
v4
f1
f2
f3
v1
v2
v5
f4
f5
v6
v7
Design variables (inputs)
Inputs
Outputs
Figure 1.11.
An order of solution
Tracing the order of the solution of the equations as shown in Figure 1.11 shows how
the information flows through the system of equations:
1. Fixing v3 and v4 enables f3 to be solved, giving v1 as the output. v1 is an input to
f1 and f2 .
2. With v1 as an input, f1 can be solved giving v2 ; v2 is an input to f2 and f4 .
3. Knowing v3 , v1 and v2 , f2 can be solved to give v5 ; v5 is an input to f4 and f5 .
4. Knowing v4 , v2 and v5 , f4 can be solved to give v6 ; v6 is an input to f5 .
5. Knowing v6 and v5 , f5 can be solved to give v7 ; which completes the solution.
This order of calculation can be shown more clearly by redrawing Figure 1.11 as shown
in Figure 1.12.
v5
v3
v3
f3
v1
f1
v2
f2
v5
f4
v6
f5
v2
v4
v4
Figure 1.12.
Figure 1.11 redrawn to show order of solution
v7
23
INTRODUCTION TO DESIGN
With this order, the equations can be solved sequentially, with no need for the simultaneous solution of any of the equations. The fortuitous selection of v3 and v4 as design
variables has given an efficient order of solution of the equations.
If for a set of equations an order of solution exists such that there is no need for the
simultaneous solution of any of the equations, the system is said to be “acyclic”, no
recycle of information.
If another pair of variables had been selected, for instance v5 and v7 , an acyclic order
of solution for the set of equations would not necessarily have been obtained.
For many design calculations it will not be possible to select the design variables so as
to eliminate the recycle of information and obviate the need for iterative solution of the
design relationships.
For example, the set of equations given below will be cyclic for all choices of the two
possible design variables.
f1 ⊲x1 , x2 ⊳ D 0
f2 ⊲x1 , x3 , x4 ⊳ D 0
f3 ⊲x2 , x3 , x4 , x5 , x6 ⊳ D 0
f4 ⊲x4 , x5 , x6 ⊳ D 0
Nd D 6 4 D 2
The biparte graph for this example, with x3 and x5 selected as the design variables
(inputs), is shown in Figure 1.13.
x3
x5
f1
f2
f3
f4
x1
x2
x4
x6
Figure 1.13.
One strategy for the solution of this cyclic set of equations would be to guess (assign
a value to) x6 . The equations could then be solved sequentially, as shown in Figure 1.14,
to produce a calculated value for x6 , which could be compared with the assumed value
and the procedure repeated until a satisfactory convergence of the assumed and calculated
value had been obtained. Assigning a value to x6 is equivalent to “tearing” the recycle
loop at x6 (Figure 1.15). Iterative methods for the solution of equations are discussed by
Henley and Rosen (1969).
When a design problem cannot be reduced to an acyclic form by judicious selection of
the design variables, the design variables should be chosen so as to reduce the recycle of
24
CHEMICAL ENGINEERING
x3
f1
f2
x5
f3
f4
x6
x1
x2
x4
x6
Assumed
value
Calculated
value
Figure 1.14.
x3
x5
f4
x4
x1
f2
f1
x2
x4
x6
x6
f3
x3
x5
Figure 1.15.
information to a minimum. Lee and Rudd (1966) and Rudd and Watson (1968) give an
algorithm that can be used to help in the selection of the best design variables in manual
calculations.
The recycle of information, often associated with the actual recycle of process material,
will usually occur in any design problem involving large sets of equations; such as in the
computer simulation of chemical processes. Efficient methods for the solution of sets of
equations are required in computer-aided design procedures to reduce the computer time
needed. Several workers have published algorithms for the efficient ordering of recycle
loops for iterative solution procedures, and some references to this work are given in the
chapter on flow-sheeting, Chapter 4.
1.10. OPTIMISATION
Design is optimisation: the designer seeks the best, the optimum, solution to a problem.
Much of the selection and choice in the design process will depend on the intuitive
judgement of the designer; who must decide when more formal optimisation techniques
can be used to advantage.
The task of formally optimising the design of a complex processing plant involving
several hundred variables, with complex interactions, is formidable, if not impossible.
The task can be reduced by dividing the process into more manageable units, identifying
the key variables and concentrating work where the effort involved will give the greatest
INTRODUCTION TO DESIGN
25
benefit. Sub-division, and optimisation of the sub-units rather than the whole, will not
necessarily give the optimum design for the whole process. The optimisation of one unit
may be at the expense of another. For example, it will usually be satisfactory to optimise
the reflux ratio for a fractionating column independently of the rest of the plant; but if the
column is part of a separation stage following a reactor, in which the product is separated
from the unreacted materials, then the design of the column will interact with, and may
well determine, the optimisation of the reactor design.
In this book the discussion of optimisation methods will, of necessity, be limited to a
brief review of the main techniques used in process and equipment design. The extensive
literature on the subject should be consulted for full details of the methods available, and
their application and limitations; see Beightler and Wilde (1967), Beveridge and Schechter
(1970), Stoecker (1989), Rudd and Watson (1968), Edgar and Himmelblau (2001). The
books by Rudd and Watson (1968) and Edgar and Himmelblau (2001) are particularly
recommended to students.
1.10.1. General procedure
When setting out to optimise any system, the first step is clearly to identify the objective:
the criterion to be used to judge the system performance. In engineering design the
objective will invariably be an economic one. For a chemical process, the overall objective
for the operating company will be to maximise profits. This will give rise to sub-objectives,
which the designer will work to achieve. The main sub-objective will usually be to
minimise operating costs. Other sub-objectives may be to reduce investment, maximise
yield, reduce labour requirements, reduce maintenance, operate safely.
When choosing his objectives the designer must keep in mind the overall objective.
Minimising cost per unit of production will not necessarily maximise profits per unit time;
market factors, such as quality and delivery, may determine the best overall strategy.
The second step is to determine the objective function: the system of equations, and
other relationships, which relate the objective with the variables to be manipulated to
optimise the function. If the objective is economic, it will be necessary to express the
objective function in economic terms (costs).
Difficulties will arise in expressing functions that depend on value judgements; for
example, the social benefits and the social costs that arise from pollution.
The third step is to find the values of the variables that give the optimum value of the
objective function (maximum or minimum). The best techniques to be used for this step
will depend on the complexity of the system and on the particular mathematical model
used to represent the system.
A mathematical model represents the design as a set of equations (relationships) and, as
was shown in Section 1.9.1, it will only be possible to optimise the design if the number
of variables exceeds the number of relationships; there is some degree of freedom in the
system.
1.10.2. Simple models
If the objective function can be expressed as a function of one variable (single degree of
freedom) the function can be differentiated, or plotted, to find the maximum or minimum.
26
CHEMICAL ENGINEERING
This will be possible for only a few practical design problems. The technique is illustrated in Example 1.1, and in the derivation of the formula for optimum pipe diameter in
Chapter 5. The determination of the economic reflux ratio for a distillation column, which
is discussed in Volume 2, Chapter 11, is an example of the use of a graphical procedure
to find the optimum value.
Example 1.1
The optimum proportions for a cylindrical container. A classical example of the optimisation of a simple function.
The surface area, A, of a closed cylinder is:
A D ð D ð L C 2 D2
4
where D D vessel diameter
L D vessel length (or height)
This will be the objective function which is to be minimised; simplified:
D2
2
For a given volume, V, the diameter and length are related by:
V D D2 ð L
4
and
4V
LD
D2
and the objective function becomes
f⊲D ð L⊳ D D ð L C
⊲equation A⊳
⊲equation B⊳
D2
4V
C
D
2
Setting the differential of this function zero will give the optimum value for D
f⊲D⊳ D
4V
CDD0
D2
3 4V
DD
From equation B, the corresponding length will be:
3 4V
LD
So for a cylindrical container the minimum surface area to enclose a given volume is
obtained when the length is made equal to the diameter.
In practice, when cost is taken as the objective function, the optimum will be nearer
L D 2D; the proportions of the ubiquitous tin can, and oil drum. This is because the cost
INTRODUCTION TO DESIGN
27
will include that of forming the vessel and making the joints, in addition to cost of the
material (the surface area); see Wells (1973).
If the vessel is a pressure vessel the optimum length to diameter ratio will be even
greater, as the thickness of plate required is a direct function of the diameter; see
Chapter 13. Urbaniec (1986) gives procedures for the optimisation of tanks and vessel,
and other process equipment.
1.10.3. Multiple variable problems
The general optimisation problem can be represented mathematically as:
f D f⊲v1 , v2 , v3 , . . . , vn ⊳
⊲1.2⊳
where f is the objective function and v1 , v2 , v3 , . . . , vn are the variables.
In a design situation there will be constraints on the possible values of the objective
function, arising from constraints on the variables; such as, minimum flow-rates, maximum
allowable concentrations, and preferred sizes and standards.
Some may be equality constraints, expressed by equations of the form:
m D m ⊲v1 , v2 , v3 , . . . , vn ⊳ D 0
⊲1.3⊳
Others as inequality constraints:
p D p ⊲v1 , v2 , v3 , . . . , vn ⊳ Pp
⊲1.4⊳
The problem is to find values for the variables v1 to vn that optimise the objective function:
that give the maximum or minimum value, within the constraints.
Analytical methods
If the objective function can be expressed as a mathematical function the classical methods
of calculus can be used to find the maximum or minimum. Setting the partial derivatives
to zero will produce a set of simultaneous equations that can be solved to find the optimum
values. For the general, unconstrained, objective function, the derivatives will give the
critical points; which may be maximum or minimum, or ridges or valleys. As with single
variable functions, the nature of the first derivative can be found by taking the second
derivative. For most practical design problems the range of values that the variables
can take will be subject to constraints (equations 1.3 and 1.4), and the optimum of the
constrained objective function will not necessarily occur where the partial derivatives
of the objective function are zero. This situation is illustrated in Figure 1.16 for a twodimensional problem. For this problem, the optimum will lie on the boundary defined by
the constraint y D a.
The method of Lagrange’s undetermined multipliers is a useful analytical technique for
dealing with problems that have equality constraints (fixed design values). Examples of
the use of this technique for simple design problems are given by Stoecker (1989), Peters
and Timmerhaus (1991) and Boas (1963a).
28
CHEMICAL ENGINEERING
f(v)
Feasible region
y=a
Minimum of
function
v
Figure 1.16.
Effect of constraints on optimum of a function
Search methods
The nature of the relationships and constraints in most design problems is such that
the use of analytical methods is not feasible. In these circumstances search methods,
that require only that the objective function can be computed from arbitrary values of
the independent variables, are used. For single variable problems, where the objective
function is unimodal, the simplest approach is to calculate the value of the objective
function at uniformly spaced values of the variable until a maximum (or minimum) value
is obtained. Though this method is not the most efficient, it will not require excessive
computing time for simple problems. Several more efficient search techniques have been
developed, such as the method of the golden section; see Boas (1963b) and Edgar and
Himmelblau (2001).
Efficient search methods will be needed for multi-dimensional problems, as the number
of calculations required and the computer time necessary will be greatly increased,
compared with single variable problems; see Himmelblau (1963), Stoecker (1971),
Beveridge and Schechter (1970), and Baasel (1974).
Two variable problems can be plotted as shown in Figure 1.17. The values of the
objective function are shown as contour lines, as on a map, which are slices through the
three-dimensional model of the function. Seeking the optimum of such a function can be
75%
Yield contours
80%
Pressure
85%
90%
Temperature
Figure 1.17.
Yield as a function of reactor temperature and pressure
INTRODUCTION TO DESIGN
29
likened to seeking the top of a hill (or bottom of a valley), and a useful technique for
this type of problem is the gradient method (method of steepest ascent, or descent), see
Edgar and Himmelblau (2001).
1.10.4. Linear programming
Linear programming is an optimisation technique that can be used when the objective
function and constraints can be expressed as a linear function of the variables; see Driebeek
(1969), Williams (1967) and Dano (1965).
The technique is useful where the problem is to decide the optimum utilisation of
resources. Many oil companies use linear programming to determine the optimum schedule
of products to be produced from the crude oils available. Algorithms have been developed
for the efficient solution of linear programming problems and the SIMPLEX algorithm,
Dantzig (1963), is the most commonly used.
Examples of the application of linear programming in chemical process plant design
and operation are given by Allen (1971), Rudd and Watson (1968), Stoecker (1991), and
Urbaniec (1986).
1.10.5. Dynamic programming
Dynamic programming is a technique developed for the optimisation of large systems;
see Nemhauser (1966), Bellman (1957) and Aris (1963).
The basic approach used is to divide the system into convenient sub-systems and
optimise each sub-system separately, while taking into account the interactions between
the sub-systems. The decisions made at each stage contribute to the overall systems
objective function, and to optimise the overall objective function an appropriate combination of the individual stages has to be found. In a typical process plant system the
possible number of combinations of the stage decisions will be very large. The dynamic
programming approach uses Bellman’s “Principle of Optimality”,† which enables the
optimum policy to be found systematically and efficiently by calculating only a fraction
of the possible combinations of stage decisions. The method converts the problem from
the need to deal with “N” optimisation decisions simultaneously to a sequential set of “N”
problems. The application of dynamic programming to design problems is well illustrated
in Rudd and Watson’s book; see also Wells (1973) and Edgar and Himmelblau (2001).
1.10.6. Optimisation of batch and semicontinuous processes
In batch operation there will be periods when product is being produced, followed by nonproductive periods when the product is discharged and the equipment prepared for the
next batch. The rate of production will be determined by the total batch time, productive
† Bellman’s (1957) principle of optimality: “An optimal policy has the property that, whatever the initial state
and the initial decision are, the remaining decisions must constitute an optimal policy with regard to the state
resulting from the first decision.”
30
CHEMICAL ENGINEERING
plus non-productive periods.
Batches per year D
8760 ð plant attainment
batch cycle time
⊲1.5⊳
where the “plant attainment” is the fraction of the total hours in a year (8760) that the
plant is in operation.
Annual production D quantity produced per batch ð batches per year.
Cost per unit of production D
annual cost of production
annual production rate
⊲1.6⊳
With many batch processes, the production rate will decrease during the production
period; for example, batch reactors and plate and frame filter presses, and there will
be an optimum batch size, or optimum cycle time, that will give the minimum cost per
unit of production.
For some processes, though they would not be classified as batch processes, the period
of continuous production will be limited by gradual changes in process conditions; such
as, the deactivation of catalysts or the fouling of heat-exchange surfaces. Production will
be lost during the periods when the plant is shut down for catalyst renewal or equipment
clean-up, and, as with batch process, there will be an optimum cycle time to give the
minimum production cost.
The optimum time between shut-downs can be found by determining the relationship
between cycle time and cost per unit of production (the objective function) and using one
of the optimisation techniques outlined in this section to find the minimum.
With discontinuous processes, the period between shut-downs will usually be a function
of equipment size. Increasing the size of critical equipment will extend the production
period, but at the expense of increased capital cost. The designer must strike a balance
between the savings gained by reducing the non-productive period and the increased
investment required.
1.11. REFERENCES
ALLEN, D. H. (1971) Brit. Chem. Eng. 16, 685. Linear programming models.
ARIS, R. (1963) Discrete Dynamic Programming (Blaisdell).
BAASEL, W. D. (1965) Chem. Eng., NY 72 (Oct. 25th) 147. Exploring response surfaces to establish optimum
conditions.
BAASEL, W. D. (1974) Preliminary Chemical Engineering Plant Design (Elsevier).
BEIGHTLER, C. S. and WILDE, D. J. (1967) Foundations of Optimisation (Prentice-Hall).
BELLMAN, R. (1957) Dynamic Programming (Princeton University, New York).
BERGE, C. (1962) Theory of Graphs and its Applications (Wiley).
BEVERIDGE, G. S. G. and SCHECHTER, R. S. (1970) Optimisation: Theory and Practice (McGraw-Hill).
BOAS, A. H. (1963a) Chem. Eng., NY 70 (Jan. 7th) 95. How to use Lagrange multipliers.
BOAS, A. H. (1963b) Chem. Eng., NY 70 (Feb. 4th) 105. How search methods locate optimum in univariate
problems.
BURKLIN, C. R. (1979) The Process Plant Designers Pocket Handbook of Codes and Standards (Gulf).
CASEY, R. J. and FRAZER, M. J. (1984) Problem Solving in the Chemical Industry (Pitman).
CHADDOCK, D. H. (1975) Paper read to S. Wales Branch, Institution of Mechanical Engineers (Feb. 27th).
Thought structure, or what makes a designer tick.
31
INTRODUCTION TO DESIGN
CHITTENDEN, D. H. (1987) Chem. Eng., NY 94 (March 16) 89. “How to solve it” revisited!: Engineering problem
solving approach.
DANO, S. (1965) Linear Programming in Industry (Springer-Verlag).
DANTZIG, G. B. (1963) Linear Programming and Extensions (Princeton University Press).
DRIEBEEK, N. J. (1969) Applied Linear Programming (Addison-Wesley).
EDGAR, T. E. and HIMMELBLAU, D. M., 2nd edn (2001) Optimization of Chemical Processes (McGraw-Hill).
HENLEY, E. J. and ROSEN, E. M. (1969) Material and Energy Balance Computations (Wiley).
HIMMELBLAU, D. M. (1963) Ind. Eng. Chem. Process Design and Development 2, 296. Process optimisation by
search techniques.
JONES, C. J. (1970) Design Methods: Seeds of Human Futures (Wiley).
KWAUK, M. (1956) AIChE Jl 2, 240. A system for counting variables in separation processes.
LEE, W. CHRISTENSEN J. H. and RUDD, D. F. (1966): AIChE Jl 12, 1104. Design variable selection to simplify
process calculations.
LEE, W. and RUDD, D. F. (1966) AIChE Jl 12, 1185. On the ordering of recycle calculations.
NEMHAUSER, G. L. (1966) Introduction to Dynamic Programming (Wiley).
PETERS, M. S. and TIMMERHAUS, K. D. (1991) Plant Design and Economics for Chemical Engineers, 4th edn
(McGraw-Hill).
POLYA, G. (1957) How to Solve It, 2nd edn (Doubleday).
RASE H. F and BARROW, M. H. (1964) Project Engineering (Wiley).
RUDD, D. F. and WATSON, C. C. (1968) Strategy of Process Design (Wiley).
SMITH, B. D. (1963) Design of Equilibrium Stage Processes (McGraw-Hill).
STOECKER, W. F. (1989) Design of Thermal Systems 3rd edn (McGraw-Hill).
URBANIEC, K. (1986) Optimal Design of Process Equipment (Ellis Horwood).
WELLS, G. L. (1973) Process Engineering with Economic Objective (Leonard Hill).
WILDE, D. J. (1964) Optimum Seeking Methods (Prentice-Hall).
WILLIAMS, N. (1967) Linear and Non-linear Programming in Industry (Pitman).
1.12. NOMENCLATURE
Dimensions
in MLTq
C
D
F
f
fi
f1 , f2 . . .
L
Nd
N0d
Nr
Nv
P
Pp
q
T
vj
v1 , v2 . . .
x1 , x2 . . .
Suffixes
1
2
3
Number of components
Diameter
Stream flow rate
General function
General function (design relationship)
General functions (design relationships)
Length
Degrees of freedom in a design problem
Degrees of freedom (variables free to be selected as design variables)
Number of design relationships
Number of variables
Pressure
Inequality constraints
Heat input, flash distillation
Temperature
Variables
Variables
Variables
Equality constraint function
Inequality constraint function
Inlet, flash distillation
Vapour outlet, flash distillation
Liquid outlet, flash distillation
L
MT1
L
ML1 T2
ML2 T3
q
32
CHEMICAL ENGINEERING
1.13 PROBLEMS
1.1. Given that 1 in D 25.4 mm; 1 lbm D 0.4536 kg; 1 Ž F D 0.556 Ž C; 1 cal D 4.1868 J;
g D 9.807 m s2 , calculate conversion factors to SI units for the following
terms:
i.
ii.
iii.
iv.
v.
vi.
vii.
viii.
ix.
x.
feet
pounds mass
pounds force
horse power (1 HP D 550 foot pounds per second)
psi (pounds per square inch)
lb ft1 s1 (viscosity)
poise (gm cm1 s1 )
Btu (British Thermal Unit)
CHU (Centigrade Heat Unit) also known as PCU (Pound Centigrade Unit)
Btu ft2 h1 Ž F1 (heat transfer coefficient).
1.2. Determine the degrees of freedom available in the design of a simple heat
exchanger. Take the exchanger as a double-pipe exchanger transferring heat
between two single-phase streams.
1.3. A separator divides a process stream into three phases: a liquid organic stream, a
liquid aqueous stream, and a gas stream. The feed stream contains three components, all of which are present to some extent in the separated steams. The composition and flowrate of the feed stream are known. All the streams will be at the same
temperature and pressure. The phase equilibria for the three phases is available.
How many design variables need to be specified in order to calculate the output
stream compositions and flow rates?
1.4. A rectangular tank with a square base is constructed from 5 mm steel plates. If
the capacity required is eight cubic metres determine the optimum dimensions if
the tank has:
i. a closed top
ii. an open top.
1.5. Estimate the optimum thickness of insulation for the roof of a house, given the
following information. The insulation will be installed flat on the attic floor.
Overall heat transfer coefficient for the insulation as a function of thickness, U
values (see Chapter 12):
thickness, mm
U, Wm2 Ž C1
0
20
25
0.9
50
0.7
100
0.3
150
0.25
200
0.20
250
0.15
Average temperature difference between inside and outside of house 10 Ž C; heating
period 200 days in a year.
Cost of insulation, including installation, £70/m3 . Capital charges (see Chapter 6)
15 per cent per year. Cost of fuel, allowing for the efficiency of the heating
system, 6p/MJ.
Note: the rate at which heat is being lost is given by U ð T, W/m2 , where U
is the overall coefficient and T the temperature difference; see Chapter 12.
33
INTRODUCTION TO DESIGN
1.6. (US version) Estimate the optimum thickness of insulation for the roof of a house
given the following information. The insulation will be installed flat on the attic
floor.
Overall heat transfer coefficient for the insulation as a function of thickness, U
values (see Chapter 12):
thickness, mm
U, Wm2 Ž C1
0
20
25
0.9
50
0.7
100
0.3
150
0.25
200
0.20
250
0.15
Average temperature difference between inside and outside of house 12 Ž C; heating
period 250 days in a year. Cost of insulation, including installation, $120/m3 .
Capital charges (see chapter 6) 20 per cent per year. Cost of fuel, allowing for the
efficiency of the heating system, 9c/MJ.
Note: the rate at which heat is being lost is given by U ð T, W/m2 , where U
is the overall coefficient and T the temperature difference; see Chapter 12.
1.7. What is the optimum practical shape for a dwelling, to minimise the heat losses
through the building fabric?
Why is this optimum shape seldom used?
What people do use the optimum shape for their winter dwellings? Is heat retention
their only consideration in their selection of this shape?
1.8. You are part of the design team working on a project for the manufacture of
cyclohexane.
The chief engineer calls you into his office and asks you to prepare an outline
design for an inert gas purging and blanketing system for the reactors and other
equipment, on shutdown. This request arises from a report into an explosion and
fire at another site manufacturing a similar product.
Following the steps given in Figure 1.2, find what you consider the best solution
to this design problem.
CHAPTER 2
Fundamentals of Material Balances
2.1. INTRODUCTION
Material balances are the basis of process design. A material balance taken over the
complete process will determine the quantities of raw materials required and products
produced. Balances over individual process units set the process stream flows and
compositions.
A good understanding of material balance calculations is essential in process design.
In this chapter the fundamentals of the subject are covered, using simple examples to
illustrate each topic. Practice is needed to develop expertise in handling what can often
become very involved calculations. More examples and a more detailed discussion of the
subject can be found in the numerous specialist books written on material and energy
balance computations. Several suitable texts are listed under the heading of “Further
Reading” at the end of this chapter.
The application of material balances to more complex problems is discussed in “Flowsheeting”, Chapter 4.
Material balances are also useful tools for the study of plant operation and trouble
shooting. They can be used to check performance against design; to extend the often
limited data available from the plant instrumentation; to check instrument calibrations;
and to locate sources of material loss.
2.2. THE EQUIVALENCE OF MASS AND ENERGY
Einstein showed that mass and energy are equivalent. Energy can be converted into mass,
and mass into energy. They are related by Einstein’s equation:
E D mc2
⊲2.1⊳
where E D energy, J,
m D mass, kg,
c D the speed of light in vacuo, 3 ð 108 m/s.
The loss of mass associated with the production of energy is significant only in nuclear
reactions. Energy and matter are always considered to be separately conserved in chemical
reactions.
2.3. CONSERVATION OF MASS
The general conservation equation for any process system can be written as:
Material out D Material in C Generation Consumption Accumulation
34
FUNDAMENTALS OF MATERIAL BALANCES
35
For a steady-state process the accumulation term will be zero. Except in nuclear processes,
mass is neither generated nor consumed; but if a chemical reaction takes place a particular
chemical species may be formed or consumed in the process. If there is no chemical
reaction the steady-state balance reduces to
Material out D Material in
A balance equation can be written for each separately identifiable species present, elements,
compounds or radicals; and for the total material.
Example 2.1
2000 kg of a 5 per cent slurry of calcium hydroxide in water is to be prepared by diluting
a 20 per cent slurry. Calculate the quantities required. The percentages are by weight.
Solution
Let the unknown quantities of the 20% slurry and water be X and Y respectively.
Material balance on Ca(OH)2
In
Out
20
5
X
D 2000 ð
100
100
⊲a⊳
Balance on water
X
⊲100 5⊳
⊲100 20⊳
C Y D 2000
100
100
⊲b⊳
From equation ⊲a⊳ X D 500 kg.
Substituting into equation ⊲b⊳ gives Y D 1500 kg
Check material balance on total quantity:
X C Y D 2000
500 C 1500 D 2000, correct
2.4. UNITS USED TO EXPRESS COMPOSITIONS
When specifying a composition as a percentage it is important to state clearly the basis:
weight, molar or volume.
The abbreviations w/w and v/v are used to designate weight basis and volume basis.
Example 2.2
Technical grade hydrochloric acid has a strength of 28 per cent w/w, express this as a
mol fraction.
36
CHEMICAL ENGINEERING
Solution
Basis of calculation 100 kg of 28 per cent w/w acid.
Molecular mass: water 18, HCl 36.5
Mass HCl D 100 ð 0.28 D 28 kg
Mass water D 100 ð 0.72 D 72 kg
28
kmol HCl D
D 0.77
36.5
72
kmol water D
D 4.00
18
Total mols
D 4.77
0.77
D 0.16
4.77
4.00
mol fraction water D
D 0.84
4.77
mol fraction HCl D
Check total
1.00
Within the accuracy needed for technical calculations, volume fractions can be taken
as equivalent to mol fractions for gases, up to moderate pressures (say 25 bar).
Trace quantities are often expressed as parts per million (ppm). The basis, weight or
volume, needs to be stated.
ppm D
quantity of component
ð 106
total quantity
Note. 1 ppm D 104 per cent.
Minute quantities are sometimes quoted in ppb, parts per billion. Care is needed here,
as the billion is usually an American billion (109 ), not the UK billion (1012 ).
2.5. STOICHIOMETRY
Stoichiometry (from the Greek stoikeion element) is the practical application of the
law of multiple proportions. The stoichiometric equation for a chemical reaction states
unambiguously the number of molecules of the reactants and products that take part; from
which the quantities can be calculated. The equation must balance.
With simple reactions it is usually possible to balance the stoichiometric equation by
inspection, or by trial and error calculations. If difficulty is experienced in balancing
complex equations, the problem can always be solved by writing a balance for each
element present. The procedure is illustrated in Example 2.3.
Example 2.3
Write out and balance the overall equation for the manufacture of vinyl chloride from
ethylene, chlorine and oxygen.
FUNDAMENTALS OF MATERIAL BALANCES
37
Solution
Method: write out the equation using letters for the unknown number of molecules of
each reactant and product. Make a balance on each element. Solve the resulting set of
equations.
A⊲C2 H4 ⊳ C B⊲Cl2 ⊳ C C⊲O2 ⊳ D D⊲C2 H3 Cl⊳ C E⊲H2 O⊳
Balance on carbon
on hydrogen
2A D 2D,
ADD
4A D 3D C 2E
on chlorine
on oxygen
substituting D D A gives E D
2B D D, hence B D
2C D E,
CD
A
2
A
2
E
A
D
2
4
putting A D 1, the equation becomes
C2 H4 C 21 Cl2 C 41 O2 D C2 H3 Cl C 12 H2 O
multiplying through by the largest denominator to remove the fractions
4C2 H4 C 2Cl2 C O2 D 4C2 H3 Cl C 2H2 O
2.6. CHOICE OF SYSTEM BOUNDARY
The conservation law holds for the complete process and any sub-division of the process.
The system boundary defines the part of the process being considered. The flows into
and out of the system are those crossing the boundary and must balance with material
generated or consumed within the boundary.
Any process can be divided up in an arbitrary way to facilitate the material balance
calculations. The judicious choice of the system boundaries can often greatly simplify
what would otherwise be difficult and tortuous calculations.
No hard and fast rules can be given on the selection of suitable boundaries for all types
of material balance problems. Selection of the best sub-division for any particular process
is a matter of judgement, and depends on insight into the structure of the problem, which
can only be gained by practice. The following general rules will serve as a guide:
1. With complex processes, first take the boundary round the complete process and if
possible calculate the flows in and out. Raw materials in, products and by-products
out.
2. Select the boundaries to sub-divide the process into simple stages and make a balance
over each stage separately.
3. Select the boundary round any stage so as to reduce the number of unknown streams
to as few as possible.
38
CHEMICAL ENGINEERING
4. As a first step, include any recycle streams within the system boundary (see
Section 2.14).
Example 2.4
Selection of system boundaries and organisation of the solution.
The diagram shows the main steps in a process for producing a polymer. From the
following data, calculate the stream flows for a production rate of 10,000 kg/h.
Reactor, yield on polymer
100 per cent
slurry polymerisation
20 per cent monomer/water
conversion
90 per cent
catalyst 1 kg/1000 kg monomer
short stopping agent
0.5 kg/1000 kg unreacted monomer
Filter, wash water approx. 1 kg/1 kg polymer
Recovery column, yield 98 per cent (percentage recovered)
Dryer, feed ¾5 per cent water, product specification 0.5 per cent H2 O
Polymer losses in filter and dryer ¾1 per cent
Short stop
Monomer
water
catalyst
Polymer
Filter
Dryer
Reactor
Recycle
monomer
Recovery
column
Effluent
Solution
Only those flows necessary to illustrate the choice of system boundaries and method of
calculation are given in the Solution.
Basis: 1 hour
Take the first system boundary round the filter and dryer.
Input
Water
+ monomer
Filter
and
dryer
Product
10,000 kg polymer
0.5% water
Losses
FUNDAMENTALS OF MATERIAL BALANCES
39
With 1 per cent loss, polymer entering sub-system
D
10,000
D 10,101 kg
0.99
Take the next boundary round the reactor system; the feeds to the reactor can then be
calculated.
Short stop
Water
Reactor
Monomer
10,101 kg
polymer
Cat.
Recycle
At 90 per cent conversion, monomer feed
D
10,101
D 11,223 kg
0.9
Unreacted monomer D 11,223 10,101 D 1122 kg
Short-stop, at 0.5 kg/1000 kg unreacted monomer
D 1122 ð 0.5 ð 103 D 0.6 kg
Catalyst, at 1 kg/1000 kg monomer
D 11,223 ð 1 ð 103 D 11 kg
Let water feed to reactor be F1 , then for 20 per cent monomer
0.2 D
F1 D
11,223
F1 C 11,223
11,223⊲1 0.2⊳
D 44,892 kg
0.2
Now consider filter-dryer sub-system again.
Water in polymer to dryer, at 5 per cent (neglecting polymer loss)
D 10,101 ð 0.05 D 505 kg
Balance over reactor-filter-dryer sub-system gives flows to recovery column.
water, 44,892 C 10,101 505 D 54,448 kg
monomer, unreacted monomer, D 1122 kg
40
CHEMICAL ENGINEERING
Water
54,488 kg
monomer
1122 kg
Column
Now consider recovery system
Monomer
Effluent
With 98 per cent recovery, recycle to reactor
D 0.98 ð 1122 D 1100 kg
Composition of effluent 23 kg monomer, 54,488 kg water.
Consider reactor monomer feed
Fresh
feed
Reactor
feed
Recycle
1100 kg
Balance round tee gives fresh monomer required
D 11,223 1100 D 10,123 kg
2.7. CHOICE OF BASIS FOR CALCULATIONS
The correct choice of the basis for a calculation will often determine whether the calculation proves to be simple or complex. As with the choice of system boundaries, no
all-embracing rules or procedures can be given for the selection of the right basis for any
problem. The selection depends on judgement gained by experience. Some guide rules
that will help in the choice are:
1. Time: choose the time basis in which the results are to be presented; for example
kg/h, tonne/y.
2. For batch processes use one batch.
3. Choose as the mass basis the stream flow for which most information is given.
4. It is often easier to work in mols, rather than weight, even when no reaction is
involved.
5. For gases, if the compositions are given by volume, use a volume basis, remembering
that volume fractions are equivalent to mol fractions up to moderate pressures.
2.8. NUMBER OF INDEPENDENT COMPONENTS
A balance equation can be written for each independent component. Not all the components in a material balance will be independent.
41
FUNDAMENTALS OF MATERIAL BALANCES
Physical systems, no reaction
If there is no chemical reaction the number of independent components is equal to the
number of distinct chemical species present.
Consider the production of a nitration acid by mixing 70 per cent nitric and 98 per cent
sulphuric acid. The number of distinct chemical species is 3; water, sulphuric acid, nitric
acid.
H2SO4/H2O
Mixer
HNO3/H2O
H2O
HNO3
H2SO4
Nitration
acid
Chemical systems, reaction
If the process involves chemical reaction the number of independent components will
not necessarily be equal to the number of chemical species, as some may be related by
the chemical equation. In this situation the number of independent components can be
calculated by the following relationship:
Number of independent components D Number of chemical species
Number of independent
chemical equations
⊲2.2⊳
Example 2.5
If nitration acid is made up using oleum in place of the 98 per cent sulphuric acid, there
will be four distinct chemical species: sulphuric acid, sulphur trioxide, nitric acid, water.
The sulphur trioxide will react with the water producing sulphuric acid so there are only
three independent components
Oleum
H2SO4/H2O/SO3
HNO3/H2O
H2O
HNO3
H2SO4
Nitration
acid
Reaction equation SO3 C H2 O ! H2 SO4
No. of chemical species
No. of reactions
4
1
No. of independent equations
3
2.9. CONSTRAINTS ON FLOWS AND COMPOSITIONS
It is obvious, but worth emphasising, that the sum of the individual component flows
in any stream cannot exceed the total stream flow. Also, that the sum of the individual
molar or weight fractions must equal 1. Hence, the composition of a stream is completely
defined if all but one of the component concentrations are given.
42
CHEMICAL ENGINEERING
The component flows in a stream (or the quantities in a batch) are completely defined
by any of the following:
1. Specifying the flow (or quantity) of each component.
2. Specifying the total flow (or quantity) and the composition.
3. Specifying the flow (or quantity) of one component and the composition.
Example 2.6
The feed stream to a reactor contains: ethylene 16 per cent, oxygen 9 per cent, nitrogen 31
per cent, and hydrogen chloride. If the ethylene flow is 5000 kg/h, calculate the individual
component flows and the total stream flow. All percentages are by weight.
Solution
Percentage HCl D 100 ⊲16 C 9 C 31⊳
5000
Percentage ethylene D
ð 100
total
100
hence total flow D 5000 ð
16
9
so, oxygen flow D
ð 31,250
100
31
nitrogen D 31,250 ð
100
44
hydrogen chloride D 31,250 ð
100
D 44
D 16
D 31,250 kg/h
D 2813 kg/h
D 9687 kg/h
D 13,750 kg/h
General rule: the ratio of the flow of any component to the flow of any other component
is the same as the ratio of the compositions of the two components.
The flow of any component in Example 2.6 could have been calculated directly from
the ratio of the percentage to that of ethylene, and the ethylene flow.
Flow of hydrogen chloride D
44
ð 5000 D 13,750 kg/h
16
2.10. GENERAL ALGEBRAIC METHOD
Simple material-balance problems involving only a few streams and with a few unknowns
can usually be solved by simple direct methods. The relationship between the unknown
quantities and the information given can usually be clearly seen. For more complex
problems, and for problems with several processing steps, a more formal algebraic
approach can be used. The procedure is involved, and often tedious if the calculations
have to be done manually, but should result in a solution to even the most intractable
problems, providing sufficient information is known.
43
FUNDAMENTALS OF MATERIAL BALANCES
Algebraic symbols are assigned to all the unknown flows and compositions. Balance
equations are then written around each sub-system for the independent components
(chemical species or elements).
Material-balance problems are particular examples of the general design problem
discussed in Chapter 1. The unknowns are compositions or flows, and the relating
equations arise from the conservation law and the stoichiometry of the reactions. For
any problem to have a unique solution it must be possible to write the same number of
independent equations as there are unknowns.
Consider the general material balance problem where there are Ns streams each
containing Nc independent components. Then the number of variables, Nv , is given by:
Nv D Nc ð Ns
⊲2.3⊳
If Ne independent balance equations can be written, then the number of variables, Nd ,
that must be specified for a unique solution, is given by:
Nd D ⊲Ns ð Nc ⊳ Ne
⊲2.4⊳
Consider a simple mixing problem
1
2
Mixer
4
3
Let Fn be the total flow in stream n, and xn,m the concentration of component m in
stream n. Then the general balance equation can be written
F1 x1,m C F2 x2,m C F3 x3,m D F4 x4,m
⊲2.5⊳
A balance equation can also be written for the total of each stream:
F1 C F2 C F3 D F4
⊲2.6⊳
but this could be obtained by adding the individual component equations, and so is not
an additional independent equation. There are m independent equations, the number of
independent components.
Consider a separation unit, such as a distillation column, which divides a process stream
into two product streams. Let the feed rate be 10,000 kg/h; composition benzene 60 per
cent, toluene 30 per cent, xylene 10 per cent.
Overhead
product
Feed
System
boundary
Bottom
product
44
CHEMICAL ENGINEERING
There are three streams, feed, overheads and bottoms, and three independent components in each stream.
Number of variables (component flow rates) D 9
Number of independent material balance
equations
D3
Number of variables to be specified for
a unique solution
D 93D6
Three variables are specified; the feed flow and composition fixes the flow of each
component in the feed.
Number of variables to be specified by designer D 6 3 D 3. Any three component
flows can be chosen.
Normally the top composition and flow or the bottom composition and flow would be
chosen.
If the primary function of the column is to separate the benzene from the other components, the maximum toluene and xylene in the overheads would be specified; say, at
5 kg/h and 3 kg/h, and the loss of benzene in the bottoms also specified; say, at not
greater than 5 kg/h. Three flows are specified, so the other flows can be calculated.
Benzene in overheads D benzene in feed benzene in bottoms.
0.6 ð 10,000 5 D 5995 kg/h
Toluene in bottoms D toluene in feed toluene in overheads
0.3 ð 10,000 5 D 2995 kg/h
Xylene in bottoms D xylene in feed xylene in overheads
0.1 ð 10,000 3 D 997 kg/h
2.11. TIE COMPONENTS
In Section 2.9 it was shown that the flow of any component was in the same ratio to the
flow of any other component, as the ratio of the concentrations of the two components.
If one component passes unchanged through a process unit it can be used to tie the inlet
and outlet compositions.
This technique is particularly useful in handling combustion calculations where the
nitrogen in the combustion air passes through unreacted and is used as the tie component.
This is illustrated in Example 2.8.
This principle can also be used to measure the flow of a process stream by introducing
a measured flow of some easily analysed (compatible) material.
Example 2.7
Carbon dioxide is added at a rate of 10 kg/h to an air stream and the air is sampled at a
sufficient distance downstream to ensure complete mixing. If the analysis shows 0.45 per
cent v/v CO2 , calculate the air-flow rate.
FUNDAMENTALS OF MATERIAL BALANCES
45
Solution
Normal carbon dioxide content of air is 0.03 per cent
CO2 10kg/h
air
0.45 per cent CO2
air
0.03 per cent CO2
Basis: kmol/h, as percentages are by volume.
kmol/h CO2 introduced D
Let X be the air flow.
Balance on CO2 , the tie component
CO2 in
CO2 out
X⊲0.0045 0.0003⊳
X D 0.2273/0.0042
D
D
D
D
D
10
D 0.2273
44
0.0003 X C 0.2273
0.0045 X
0.2273
54 kmol/h
54 ð 29 D 1560 kg/h
Example 2.8
In a test on a furnace fired with natural gas (composition 95 per cent methane, 5 per
cent nitrogen) the following flue gas analysis was obtained: carbon dioxide 9.1 per cent,
carbon monoxide 0.2 per cent, oxygen 4.6 per cent, nitrogen 86.1 per cent, all percentages
by volume.
Calculate the percentage excess air flow (percentage above stoichiometric).
Solution
Reaction: CH4 C 2O2 ! CO2 C 2H2 O
Note: the flue gas analysis is reported on the dry basis, any water formed having been
condensed out.
Nitrogen is the tie component.
Basis: 100 mol, dry flue gas; as the analysis of the flue gas is known, the mols of each
element in the flue gas (flow out) can be easily calculated and related to the flow into the
system.
Let the quantity of fuel (natural gas) per 100 mol dry flue gas be X.
Balance on carbon, mols in fuel D mols in flue gas
0.95 X D 9.1 C 0.2, hence X D 9.79 mol
Balance on nitrogen (composition of air O2 21 per cent, N2 79 per cent).
Let Y be the flow of air per 100 mol dry flue gas.
N2 in air C N2 in fuel D N2 in flue gas
0.79 Y C 0.05 ð 9.79 D 86.1, hence Y D 108.4 mol
46
CHEMICAL ENGINEERING
Stoichiometric air; from the reaction equation 1 mol methane requires 2 mol oxygen,
100
D 88.6 mol
21
⊲air supplied stoichiometric air⊳
ð 100
Percentage excess air D
stoichiometric air
108.4 88.6
D
D 22 per cent
88.6
so, stoichiometric air D 9.79 ð 0.95 ð 2 ð
2.12. EXCESS REAGENT
In industrial reactions the components are seldom fed to the reactor in exact stoichiometric
proportions. A reagent may be supplied in excess to promote the desired reaction; to
maximise the use of an expensive reagent; or to ensure complete reaction of a reagent,
as in combustion.
The percentage excess reagent is defined by the following equation:
Per cent excess D
quantity supplied stoichiometric
ð 100
stoichiometric quantity
⊲2.7⊳
It is necessary to state clearly to which reagent the excess refers. This is often termed the
limiting reagent.
Example 2.9
To ensure complete combustion, 20 per cent excess air is supplied to a furnace burning
natural gas. The gas composition (by volume) is methane 95 per cent, ethane 5 per cent.
Calculate the mols of air required per mol of fuel.
Solution
Basis: 100 mol gas, as the analysis is volume percentage.
Reactions: CH4 C 2O2 ! CO2 C 2H2 O
C2 H6 C 3 12 O2 ! 2CO2 C 3H2 O
Stoichiometric mols O2 required D 95 ð 2 C 5 ð 3 12 D 207.5
120
D 249
With 20 per cent excess, mols O2 required D 207.5 ð
100
100
D 1185.7
Mols air (21 per cent O2 ) D 249 ð
21
1185.7
Air per mol fuel D
D 11.86 mol
100
FUNDAMENTALS OF MATERIAL BALANCES
47
2.13. CONVERSION AND YIELD
It is important to distinguish between conversion and yield (see Volume 3, Chapter 1).
Conversion is to do with reactants (reagents); yield with products.
Conversion
Conversion is a measure of the fraction of the reagent that reacts.
To optimise reactor design and to minimise by-product formation, the conversion of a
particular reagent is often less than 100 per cent. If more than one reactant is used, the
reagent on which the conversion is based must be specified.
Conversion is defined by the following expression:
Conversion D
D
amount of reagent consumed
amount supplied
(amount in feed stream) (amount in product stream)
(amount in feed stream)
⊲2.8⊳
This definition gives the total conversion of the particular reagent to all products.
Sometimes figures given for conversion refer to one specific product, usually the desired
product. In this instance the product must be specified as well as the reagent. This is
really a way of expressing yield.
Example 2.10
In the manufacture of vinyl chloride (VC) by the pyrolysis of dichloroethane (DCE), the
reactor conversion is limited to 55 per cent to reduce carbon formation, which fouls the
reactor tubes.
Calculate the quantity of DCE needed to produce 5000 kg/h VC.
Solution
Basis: 5000 kg/h VC (the required quantity).
Reaction: C2 H4 Cl2 ! C2 H3 Cl + HCl
mol weights DCE 99, VC 62.5
kmol/h VC produced D
5000
D 80
62.5
From the stoichiometric equation, 1 kmol DCE produces 1 kmol VC. Let X be DCE feed
kmol/h:
80
ð 100
X
80
D 145.5 kmol/h
XD
0.55
Per cent conversion D 55 D
48
CHEMICAL ENGINEERING
In this example the small loss of DCE to carbon and other products has been neglected.
All the DCE reacted has been assumed to be converted to VC.
Yield
Yield is a measure of the performance of a reactor or plant. Several different definitions
of yield are used, and it is important to state clearly the basis of any yield figures. This
is often not done when yield figures are quoted in the literature, and the judgement has
to be used to decide what was intended.
For a reactor the yield (i.e. relative yield, Volume 3, Chapter 1) is defined by:
Yield D
mols of product produced ð stoichiometric factor
mols of reagent converted
⊲2.9⊳
Stoichiometric factor D Stoichiometric mols of reagent required per mol
of product produced
With industrial reactors it is necessary to distinguish between “Reaction yield” (chemical
yield), which includes only chemical losses to side products; and the overall “Reactor
yield” which will include physical losses.
If the conversion is near 100 per cent it may not be worth separating and recycling
the unreacted material; the overall reactor yield would then include the loss of unreacted
material. If the unreacted material is separated and recycled, the overall yield taken over
the reactor and separation step would include any physical losses from the separation
step.
Plant yield is a measure of the overall performance of the plant and includes all chemical
and physical losses.
Plant yield (applied to the complete plant or any stage)
D
mols product produced ð stoichiometric factor
mols reagent fed to the process
⊲2.10⊳
Where more than one reagent is used, or product produced, it is essential that product
and reagent to which the yield figure refers is clearly stated.
Example 2.11
In the production of ethanol by the hydrolysis of ethylene, diethyl ether is produced as a
by-product. A typical feed stream composition is: 55 per cent ethylene, 5 per cent inerts,
40 per cent water; and product stream: 52.26 per cent ethylene, 5.49 per cent ethanol, 0.16
per cent ether, 36.81 per cent water, 5.28 per cent inerts. Calculate the yield of ethanol
and ether based on ethylene.
Solution
Reactions:
C2 H4 C H2 O ! C2 H5 OH
2C2 H5 OH ! ⊲C2 H5 ⊳2 O C H2 O
Basis: 100 mols feed (easier calculation than using the product stream)
⊲a⊳
⊲b⊳
FUNDAMENTALS OF MATERIAL BALANCES
C2H4 52.26%
C2H4 55%
Inerts 5%
49
C2H5OH 5.49%
(C2H5)2O 0.16%
H2O 36.81%
Reactor
H2O 40%
Inerts 5.28%
Note: the flow of inerts will be constant as they do not react, and it can be used to
calculate the other flows from the compositions.
Feed stream
ethylene
inerts
water
55 mol
5 mol
40 mol
Product stream
52.26
ð 5 D 49.49 mol
5.28
5.49
ð 5 D 5.20 mol
D
5.28
0.16
D
ð 5 D 0.15 mol
5.28
D 55.0 49.49 D 5.51 mol
5.2 ð 1
D
ð 100 D 94.4 per cent
5.51
ethylene D
ethanol
ether
Amount of ethylene reacted
Yield of ethanol based on ethylene
As 1 mol of ethanol is produced per mol of ethylene the stoichiometric factor is 1.
Yield of ether based on ethylene D
0.15 ð 2
ð 100 D 5.44 per cent
5.51
The stoichiometric factor is 2, as 2 mol of ethylene produce 1 mol of ether.
Note: the conversion of ethylene, to all products, is given by:
Conversion D
mols fed mols out
55 49.49
D
ð 100
mols fed
55
D 10 per cent
The yield based on water could also be calculated but is of no real interest as water
is relatively inexpensive compared with ethylene. Water is clearly fed to the reactor in
considerable excess.
Example 2.12
In the chlorination of ethylene to produce dichloroethane (DCE), the conversion of
ethylene is reported as 99.0 per cent. If 94 mol of DCE are produced per 100 mol of
ethylene fed, calculate the overall yield and the reactor (reaction) yield based on ethylene.
The unreacted ethylene is not recovered.
50
CHEMICAL ENGINEERING
Solution
Stoichiometric factor 1.
Reaction: C2 H4 C Cl2 ! C2 H4 Cl2
Overall yield (including physical losses) D
D
Chemical yield (reaction yield) D
D
mols DCE produced ð 1
ð 100
mols ethylene fed
94
ð 100 D 94 per cent
100
mols DCE produced
ð 100
mols ethylene converted
94
ð 100 D 94.5 per cent
99
The principal by-product of this process is trichloroethane.
2.14. RECYCLE PROCESSES
Processes in which a flow stream is returned (recycled) to an earlier stage in the processing
sequence are frequently used. If the conversion of a valuable reagent in a reaction process
is appreciably less than 100 per cent, the unreacted material is usually separated and
recycled. The return of reflux to the top of a distillation column is an example of a
recycle process in which there is no reaction.
In mass balance calculations the presence of recycle streams makes the calculations
more difficult.
Without recycle, the material balances on a series of processing steps can be carried
out sequentially, taking each unit in turn; the calculated flows out of one unit become
the feeds to the next. If a recycle stream is present, then at the point where the recycle
is returned the flow will not be known as it will depend on downstream flows not yet
calculated. Without knowing the recycle flow, the sequence of calculations cannot be
continued to the point where the recycle flow can be determined.
Two approaches to the solution of recycle problems are possible:
1. The cut and try method. The recycle stream flows can be estimated and the calculations continued to the point where the recycle is calculated. The estimated flows
are then compared with the calculated and a better estimate made. The procedure
is continued until the difference between the estimated and the calculated flows is
within acceptable limits.
2. The formal, algebraic, method. The presence of recycle implies that some of the
mass balance equations will have to be solved simultaneously. The equations are
set up with the recycle flows as unknowns and solved using standard methods for
the solution of simultaneous equations.
With simple problems, with only one or two recycle loops, the calculation can often be
simplified by the careful selection of the basis of calculation and the system boundaries.
This is illustrated in Examples 2.4 and 2.13.
51
FUNDAMENTALS OF MATERIAL BALANCES
The solution of more complex material balance problems involving several recycle
loops is discussed in Chapter 4.
Example 2.13
The block diagram shows the main steps in the balanced process for the production of
vinyl chloride from ethylene. Each block represents a reactor and several other processing
units. The main reactions are:
Block A, chlorination
C2 H4 C Cl2 ! C2 H4 Cl2 , yield on ethylene 98 per cent
Block B, oxyhydrochlorination
C2 H4 C 2HCl C 21 O2 ! C2 H4 Cl2 C H2 O, yields: on ethylene 95 per cent,
on HCl 90 per cent
Block C, pyrolysis
C2 H4 Cl2 ! C2 H3 Cl C HCl, yields: on DCE 99 per cent, on HCl 99.5 per cent
The HCl from the pyrolysis step is recycled to the oxyhydrochlorination step. The flow
of ethylene to the chlorination and oxyhydrochlorination reactors is adjusted so that the
production of HCl is in balance with the requirement. The conversion in the pyrolysis
reactor is limited to 55 per cent, and the unreacted dichloroethane (DCE) separated and
recycled.
Cl2
A
Chlorination
Recycle DCE
C
Pyrolysis
Ethylene
Oxygen
VC
B
Oxyhydrochlorination
Recycle HCL
Using the yield figures given, and neglecting any other losses, calculate the flow of
ethylene to each reactor and the flow of DCE to the pyrolysis reactor, for a production
rate of 12,500 kg/h vinyl chloride (VC).
Solution
Molecular weights: vinyl chloride 62.5, DCE 99.0, HCl 36.5.
12,500
D 200 kmol/h
62.5
Draw a system boundary round each block, enclosing the DCE recycle within the
boundary of step C.
VC per hour D
52
CHEMICAL ENGINEERING
Let flow of ethylene to block A be X and to block B be Y, and the HCl recycle be Z.
Then the total mols of DCE produced D 0.98X C 0.95Y, allowing for the yields, and
the mols of HCl produced in block C
D ⊲0.98X C 0.95Y⊳0.995 D Z
⊲a⊳
Consider the flows to and product from block B
C2H4
O2
Block
B
DCE
(Z) HCL
The yield of DCE based on HCl is 90 per cent, so the mols of DCE produced
0.90Z
2
Note: the stoichiometric factor is 2 (2 mol HCl per mol DCE).
The yield of DCE based on ethylene is 95 per cent, so
D
0.9Z
D 0.95Y
2
0.95 ð 2Y
ZD
0.9
Substituting for Z into equation (a) gives
Y D ⊲0.98X C 0.95Y⊳0.995 ð
Y D 0.837X
0.9
2 ð 0.95
⊲b⊳
Total VC produced D 0.99 ð total DCE, so
0.99⊲0.98X C 0.95Y⊳ D 200 kmol/h
Substituting for Y from equation (b) gives X D 113.8 kmol/h
and
Y D 0.837 ð 113.8 D 95.3 kmol/h
HCl recycle from equation (a)
Z D ⊲0.98 ð 113.8 C 0.95 ð 95.3⊳0.995 D 201.1 kmol/h
Note: overall yield on ethylene D
200
ð 100 D 96 per cent
⊲113.8 C 95.3⊳
2.15. PURGE
It is usually necessary to bleed off a portion of a recycle stream to prevent the build-up of
unwanted material. For example, if a reactor feed contains inert components that are not
53
FUNDAMENTALS OF MATERIAL BALANCES
separated from the recycle stream in the separation units these inerts would accumulate in
the recycle stream until the stream eventually consisted entirely of inerts. Some portion
of the stream would have to be purged to keep the inert level within acceptable limits. A
continuous purge would normally be used. Under steady-state conditions:
Loss of inert in the purge D Rate of feed of inerts into the system
The concentration of any component in the purge stream will be the same as that in
the recycle stream at the point where the purge is taken off. So the required purge rate
can be determined from the following relationship:
[Feed stream flow-rate] ð [Feed stream inert concentration] D
[Purge stream flow-rate] ð [Specified (desired) recycle inert concentration]
Example 2.14
In the production of ammonia from hydrogen and nitrogen the conversion, based on either
raw material, is limited to 15 per cent. The ammonia produced is condensed from the
reactor (converter) product stream and the unreacted material recycled. If the feed contains
0.2 per cent argon (from the nitrogen separation process), calculate the purge rate required
to hold the argon in the recycle stream below 5.0 per cent. Percentages are by volume.
Solution
Basis: 100 mols feed (purge rate will be expressed as mols per 100 mol feed, as the
production rate is not given).
Process diagram
Recycle
Feed
0.2%
argon
Purge 5% argon
Reactor
Condenser
Liquid
NH3
Volume percentages are taken as equivalent to mol per cent.
Argon entering system with feed D 100 ð 0.2/100 D 0.2 mol.
Let purge rate per 100 mol feed be F.
Argon leaving system in purge D F ð 5/100 D 0.05F.
At the steady state, argon leaving D argon entering
0.05F D 0.2
0.2
D4
FD
0.05
Purge required: 4 mol per 100 mol feed.
2.16. BY-PASS
A flow stream may be divided and some part diverted (by-passed) around some units.
This procedure is often used to control stream composition or temperature.
54
CHEMICAL ENGINEERING
Material balance calculations on processes with by-pass streams are similar to those
involving recycle, except that the stream is fed forward instead of backward. This usually
makes the calculations easier than with recycle.
2.17. UNSTEADY-STATE CALCULATIONS
All the previous material balance examples have been steady-state balances. The accumulation term was taken as zero, and the stream flow-rates and compositions did not vary
with time. If these conditions are not met the calculations are more complex. Steadystate calculations are usually sufficient for the calculations of the process flow-sheet
(Chapter 4). The unsteady-state behaviour of a process is important when considering the
process start-up and shut-down, and the response to process upsets.
Batch processes are also examples of unsteady-state operation; though the total material
requirements can be calculated by taking one batch as the basis for the calculation.
The procedure for the solution of unsteady-state balances is to set up balances over
a small increment of time, which will give a series of differential equations describing
the process. For simple problems these equations can be solved analytically. For more
complex problems computer methods would be used.
The general approach to the solution of unsteady-state problems is illustrated in
Example 2.15. Batch distillation is a further example of an unsteady-state material balance
(see Volume 2, Chapter 11).
The behaviour of processes under non-steady-state conditions is a complex and
specialised subject and beyond the scope of this book. It can be important in process design
when assessing the behaviour of a process from the point of view of safety and control.
The use of material balances in the modelling of complex unsteady-state processes is
discussed in the books by Myers and Seider (1976) and Henley and Rosen (1969).
Example 2.15
A hold tank is installed in an aqueous effluent-treatment process to smooth out fluctuations
in concentration in the effluent stream. The effluent feed to the tank normally contains no
more than 100 ppm of acetone. The maximum allowable concentration of acetone in the
effluent discharge is set at 200 ppm. The surge tank working capacity is 500 m3 and it
can be considered to be perfectly mixed. The effluent flow is 45,000 kg/h. If the acetone
concentration in the feed suddenly rises to 1000 ppm, due to a spill in the process plant,
and stays at that level for half an hour, will the limit of 200 ppm in the effluent discharge
be exceeded?
Solution
Capacity 500 m3
45,000 kg/h
100
1000 ppm
100
(?) ppm
FUNDAMENTALS OF MATERIAL BALANCES
55
Basis: increment of time t.
To illustrate the general solution to this type of problem, the balance will be set up in
terms of symbols for all the quantities and then actual values for this example substituted.
Let, Material in the tank D M,
Flow-rate D F,
Initial concentration in the tank D C0 ,
Concentration at time t after the feed concentration is increased D C,
Concentration in the effluent feed D C1 ,
Change in concentration over time increment t D C,
Average concentration in the tank during the time increment D Cav .
Then, as there is no generation in the system, the general material balance (Section 2.3)
becomes:
Input Output D Accumulation
Material balance on acetone.
Note: as the tank is considered to be perfectly mixed the outlet concentration will be
the same as the concentration in the tank.
Acetone in Acetone out D Acetone accumulated in the tank
FC1 t FCav t D M⊲C C C⊳ MC
F⊲C1 Cav ⊳ D M
C
t
Taking the limit, as t ! 0
dC
C
D
, Cav D C
t
dt
dC
F⊲C1 C⊳ D M
dt
Integrating
t
0
C
dC
⊲C
1 C⊳
C0
C1 C
M
t D ln
F
C1 C0
dt D
M
F
Substituting the values for the example, noting that the maximum outlet concentration
will occur at the end of the half-hour period of high inlet concentration.
t
C1
C0
M
F
D
D
D
D
D
0.5 h
1000 ppm
100 ppm (normal value)
500 m3 D 500,000 kg
45,000 kg/h
56
CHEMICAL ENGINEERING
500,000
1000 C
ln
45,000
1000 100
1000 C
0.045 D ln
900
0.5 D
e0.045 ð 900 D 1000 C
C D 140 ppm
So the maximum allowable concentration will not be exceeded.
2.18. GENERAL PROCEDURE FOR MATERIAL-BALANCE
PROBLEMS
The best way to tackle a problem will depend on the information given; the information
required from the balance; and the constraints that arise from the nature of the problem.
No all embracing, best method of solution can be given to cover all possible problems.
The following step-by-step procedure is given as an aid to the efficient solution of material
balance problems. The same general approach can be usefully employed to organise the
solution of energy balance, and other design problems.
Procedure
Step 1. Draw a block diagram of the process.
Show each significant step as a block, linked by lines and arrows to show the
stream connections and flow direction.
Step 2. List all the available data.
Show on the block diagram the known flows (or quantities) and stream compositions.
Step 3. List all the information required from the balance.
Step 4. Decide the system boundaries (see Section 2.6).
Step 5. Write out all the chemical reactions involved for the main products and byproducts.
Step 6. Note any other constraints,
such as: specified stream compositions,
azeotropes,
phase equilibria,
tie substances (see Section 2.11).
The use of phase equilibrium relationships and other constraints in determining stream
compositions and flows is discussed in more detail in Chapter 4.
Step 7. Note any stream compositions and flows that can be approximated.
Step 8. Check the number of conservation (and other) equations that can be written, and
compare with the number of unknowns. Decide which variables are to be design
variables; see Section 2.10.
This step would be used only for complex problems.
57
FUNDAMENTALS OF MATERIAL BALANCES
Step 9. Decide the basis of the calculation; see Section 2.7.
The order in which the steps are taken may be varied to suit the problem.
2.19. REFERENCES (FURTHER READING)
Basic texts
CHOPEY, N. P. (ed.) Handbook of Chemical Engineering Calculations (McGraw-Hill, 1984).
FELDER, R. M. and ROUSSEAU, R. W. Elementary Principles of Chemical Processes, 6th edn (Pearson, 1995).
HIMMELBLAU, D. M. Basic Principles and Calculations in Chemical Engineering (Prentice-Hall, 1982).
RUDD, D. F., POWERS, G. J. and SIIROLA, J. J. Process Synthesis (Prentice-Hall, 1973).
WHITWELL, J. C. and TONER, R. K. Conservation of Mass and Energy (McGraw-Hill, 1969).
WILLIAMS, E. T. and JACKSON, R. C. Stoichiometry for Chemical Engineers (McGraw-Hill, 1958).
Advanced texts
HENLEY, E. J. and ROSEN, E. M. (1969) Material and Energy Balance Computations (Wiley).
MYERS, A. L. and SEIDER, W. D. (1976) Introduction to Chemical Engineering and Computer Calculations
(Prentice-Hall).
2.20. NOMENCLATURE
Dimensions
in MLT
C
Cav
C0
C1
C
F
Fn
F1
M
Nc
Nd
Ne
Ns
Nv
t
t
X
xn,m
Y
Z
Concentration after time t, Example 2.15
Average concentration, Example 2.15
Initial concentration, Example 2.15
Concentration in feed to tank, Example 2.15
Incremental change in concentration, Example 2.15
Flow-rate
Total flow in stream n
Water feed to reactor, Example 2.4
Quantity in hold tank, Example 2.15
Number of independent components
Number of variables to be specified
Number of independent balance equations
Number of streams
Number of variables
Time, Example 2.15
Incremental change in time, Example 2.15
Unknown flow, Examples 2.8, 2.10, 2.13
Concentration of component m in stream n
Unknown flow, Examples 2.8, 2.13
Unknown flow, Example 2.13
MT1
MT1
MT1
M
T
T
MT1
MT1
MT1
2.21. PROBLEMS
2.1. The composition of a gas derived by the gasification of coal is, volume percentage:
carbon dioxide 4, carbon monoxide 16, hydrogen 50, methane 15, ethane 3,
benzene 2, balance nitrogen. If the gas is burnt in a furnace with 20 per cent
excess air, calculate:
(a) the amount of air required per 100 kmol of gas,
(b) The amount of flue gas produced per 100 kmol of gas,
58
CHEMICAL ENGINEERING
(c) the composition of the flue gases, on a dry basis.
Assume complete combustion.
2.2. Ammonia is removed from a stream of air by absorption in water in a packed
column. The air entering the column is at 760 mmHg pressure and 20 Ž C. The
air contains 5.0 per cent v/v ammonia. Only ammonia is absorbed in the column.
If the flow rate of the ammonia air mixture to the column is 200 m3 /s and the
stream leaving the column contains 0.05 per cent v/v ammonia, calculate:
(a) The flow-rate of gas leaving the column.
(b) The mass of ammonia absorbed.
(c) The flow-rate of water to the column, if the exit water contains 1% w/w
ammonia.
2.3. The off-gases from a gasoline stabiliser are fed to a reforming plant to produce
hydrogen.
The composition of the off-gas, molar per cent, is: CH4 77.5, C2 H6 9.5, C3 H8 8.5,
C4 H10 4.5.
The gases entering the reformer are at a pressure of 2 bara and 35 Ž C and the feed
rate is 2000 m3 /h.
The reactions in the reformer are:
1. C2 H2nC2 C n⊲H2 O⊳ ! n⊲CO⊳ C ⊲2n C 1⊳H2
2. CO C H2 O ! CO2 C H2
The molar conversion of C2 H2nC2 in reaction (1) is 96 per cent and of CO in
reaction (2) 92 per cent.
Calculate:
(a) the average molecular mass of the off-gas,
(b) the mass of gas fed to the reformer, kg/h,
(c) the mass of hydrogen produced, kg/h.
2.4. Allyl alcohol can be produced by the hydrolysis of allyl chloride. Together with
the main product, allyl alcohol, di-ally ether is produced as a by-product. The
conversion of allyl chloride is typically 97 per cent and the yield to alcohol 90
per cent, both on a molar basis. Assuming that there are no other significant side
reactions, calculate masses of alcohol and ether produced, per 1000 kg of allyl
chloride fed to the reactor.
2.5. Aniline is produced by the hydrogenation of nitrobenzene. A small amount of
cyclo-hexylamine is produced as a by-product. The reactions are:
1. C6 H5 NO2 C 3H2 ! C6 H5 NH2 C 2H2 O
2. C6 H5 NO2 C 6H2 ! C6 H11 NH2 C 2H2 O
Nitrobenzene is fed to the reactor as a vapour, with three times the stoichiometric
quantity of hydrogen. The conversion of the nitrobenzene, to all products, is 96
per cent, and the yield to aniline 95 per cent.
The unreacted hydrogen is separated from the reactor products and recycled to
the reactor. A purge is taken from the recycle stream to maintain the inerts in the
FUNDAMENTALS OF MATERIAL BALANCES
59
recycle stream below 5 per cent. The fresh hydrogen feed is 99.5 per cent pure,
the remainder being inerts. All percentages are molar.
For a feed rate of 100 kmol/h of nitrobenzene, calculate:
(a) the fresh hydrogen feed,
(b) the purge rate required,
(c) the composition of the reactor outlet stream.
2.6. In the manufacture of aniline by the hydrogenation of nitrobenzene, the offgases from the reactor are cooled and the products and unreacted nitrobenzene
condensed. The hydrogen and inerts, containing only traces of the condensed
materials, are recycled.
Using the typical composition of the reactor off-gas given below, estimate the
stream compositions leaving the condenser.
Composition, kmol/h: aniline 950, cyclo-hexylamine 10, water 1920, hydrogen
5640, nitrobenzene 40, inerts 300.
2.7. In the manufacture of aniline, the condensed reactor products are separated in a
decanter. The decanter separates the feed into an organic phase and an aqueous
phase. Most of the aniline in the feed is contained in the organic phase and most of
the water in the aqueous phase. Using the data given below, calculate the stream
compositions.
Data:
Typical feed composition, including impurities and by-products, weight per cent:
water 23.8, aniline 72.2, nitrobenzene 3.2, cyclo-hexylamine 0.8.
Density of aqueous layer 0.995, density of organic layer 1.006. Therefore, the
organic layer will be at the bottom.
Solubility of aniline in water 3.2 per cent w/w, and water in aniline 5.15 per cent
w/w.
Partition coefficient of nitrobenzene between the aqueous and organic phases:
Corganic /Cwater D 300
Solubility of cyclo-hexylamine in the water phase 0.12 per cent w/w and in the
organic phase 1.0 per cent w/w.
2.8. In the manufacture of aniline from nitrobenzene the reactor products are condensed
and separated into an aqueous and organic phases in a decanter. The organic
phase is fed to a striping column to recover the aniline. Aniline and water form
an azeotrope, composition 0.96 mol fraction aniline. For the feed composition
given below, make a mass balance round the column and determine the stream
compositions and flow-rates. Take as the basis for the balance 100 kg/h feed and
a 99.9 percentage recovery of the aniline in the overhead product. Assume that
the nitrobenzene leaves with the water stream from the base of the column.
Feed composition, weight percentage: water 2.4, aniline 73.0, nitrobenzene 3.2,
cyclo-hexylamine trace.
Note: Problems 2.5 to 2.8 can be taken together as an exercise in the calculation of a preliminary material
balance for the manufacture of aniline by the process described in detail in Appendix F, Problem F.8.
CHAPTER 3
Fundamentals of Energy Balances
(and Energy Utilisation)
3.1. INTRODUCTION
As with mass, energy can be considered to be separately conserved in all but nuclear
processes.
The conservation of energy, however, differs from that of mass in that energy can be
generated (or consumed) in a chemical process. Material can change form, new molecular
species can be formed by chemical reaction, but the total mass flow into a process unit
must be equal to the flow out at the steady state. The same is not true of energy. The
total enthalpy of the outlet streams will not equal that of the inlet streams if energy is
generated or consumed in the processes; such as that due to heat of reaction.
Energy can exist in several forms: heat, mechanical energy, electrical energy, and it is
the total energy that is conserved.
In process design, energy balances are made to determine the energy requirements of
the process: the heating, cooling and power required. In plant operation, an energy balance
(energy audit) on the plant will show the pattern of energy usage, and suggest areas for
conservation and savings.
In this chapter the fundamentals of energy balances are reviewed briefly, and examples
given to illustrate the use of energy balances in process design. The methods used for
energy recovery and conservation are also discussed.
More detailed accounts of the principles and applications of energy balances are given
in the texts covering material and energy balance calculations which are cited at the end
of Chapter 2.
3.2. CONSERVATION OF ENERGY
As for material (Section 2.3), a general equation can be written for the conservation of
energy:
Energy out D Energy in C generation consumption accumulation
This is a statement of the first law of thermodynamics.
An energy balance can be written for any process step.
Chemical reaction will evolve energy (exothermic) or consume energy (endothermic).
For steady-state processes the accumulation of both mass and energy will be zero.
60
61
FUNDAMENTALS OF ENERGY BALANCES
Energy can exist in many forms and this, to some extent, makes an energy balance
more complex than a material balance.
3.3. FORMS OF ENERGY (PER UNIT MASS OF MATERIAL)
3.3.1. Potential energy
Energy due to position:
Potential energy D gz
⊲3.1⊳
where z D height above some arbitrary datum, m,
g D gravitational acceleration (9.81 m/s2 ).
3.3.2. Kinetic energy
Energy due to motion:
Kinetic energy D
u2
2
⊲3.2⊳
where u D velocity, m/s.
3.3.3. Internal energy
The energy associated with molecular motion. The temperature T of a material is a
measure of its internal energy U:
U D f⊲T⊳
⊲3.3⊳
3.3.4. Work
Work is done when a force acts through a distance:
1
WD
F dx
⊲3.4⊳
0
where F D force, N,
x and l D distance, m.
Work done on a system by its surroundings is conventionally taken as negative; work
done by the system on the surroundings as positive.
Where the work arises from a change in pressure or volume:
2
P dv
⊲3.5⊳
WD
1
where P D pressure, Pa (N/m2 ),
v D volume per unit mass, m3 /kg.
To integrate this function the relationship between pressure and volume must be known.
In process design an estimate of the work done in compressing or expanding a gas is
62
CHEMICAL ENGINEERING
often required. A rough estimate can be made by assuming either reversible adiabatic
(isentropic) or isothermal expansion, depending on the nature of the process.
For isothermal expansion (expansion at constant temperature):
Pv D constant
For reversible adiabatic expansion (no heat exchange with the surroundings):
Pv D constant
where
D ratio of the specific heats, Cp /Cv .
The compression and expansion of gases is covered more fully in Section 3.13.
3.3.5. Heat
Energy is transferred either as heat or work. A system does not contain “heat”, but the
transfer of heat or work to a system changes its internal energy.
Heat taken in by a system from its surroundings is conventionally taken as positive
and that given out as negative.
3.3.6. Electrical energy
Electrical, and the mechanical forms of energy, are included in the work term in an energy
balance. Electrical energy will only be significant in energy balances on electrochemical
processes.
3.4. THE ENERGY BALANCE
Consider a steady-state process represented by Figure 3.1. The conservation equation can
be written to include the various forms of energy.
W
1
Q
Outlet
Inlet
2
z2
z1
Figure 3.1.
General steady-state process
For unit mass of material:
U1 C P1 v1 C u12 /2 C z1 g C Q D U2 C P2 v2 C u22 /2 C z2 g C W
⊲3.6⊳
The suffixes 1 and 2 represent the inlet and outlet points respectively. Q is the heat
transferred across the system boundary; positive for heat entering the system, negative
FUNDAMENTALS OF ENERGY BALANCES
63
for heat leaving the system. W is the work done by the system; positive for work going
from the system to the surroundings, and negative for work entering the system from the
surroundings.
Equation 3.6 is a general equation for steady-state systems with flow.
In chemical processes, the kinetic and potential energy terms are usually small compared
with the heat and work terms, and can normally be neglected.
It is convenient, and useful, to take the terms U and Pv together; defining the term
enthalpy, usual symbol H, as:
H D U C Pv
Enthalpy is a function of temperature and pressure. Values for the more common
substances have been determined experimentally and are given in the various handbooks
(see Chapter 8).
Enthalpy can be calculated from specific and latent heat data; see Section 3.5.
If the kinetic and potential energy terms are neglected equation 3.6 simplifies to:
H2 H1 D Q W
⊲3.7⊳
This simplified equation is usually sufficient for estimating the heating and cooling requirements of the various unit operations involved in chemical processes.
As the flow-dependent terms have been dropped, the simplified equation is applicable
to both static (non-flow) systems and flow systems. It can be used to estimate the energy
requirement for batch processes.
For many processes the work term will be zero, or negligibly small, and equation 3.7
reduces to the simple heat balance equation:
Q D H2 H1
⊲3.8⊳
Where heat is generated in the system; for example, in a chemical reactor:
Q D Qp C Qs
⊲3.9⊳
Qs D heat generated in the system. If heat is evolved (exothermic processes) Qs is taken
as positive, and if heat is absorbed (endothermic processes) it is taken as negative.
Qp D process heat added to the system to maintain required system temperature.
Hence:
Q p D H 2 H1 Q s
⊲3.10⊳
H1 D enthalpy of the inlet stream,
H2 D enthalpy of the outlet stream.
Example 3.1
Balance with no chemical reaction. Estimate the steam and the cooling water required for
the distillation column shown in the figure.
Steam is available at 25 psig (274 kN/m2 abs), dry saturated.
The rise in cooling water temperature is limited to 30Ž C.
Column operates at 1 bar.
64
CHEMICAL ENGINEERING
Distillate (D)
99% Acetone
1% Water
25°C
Feed (F)
1000 kg/h
10% Acetone
90% Water
35°C
All compositions
by weight
reflux ratio 10
Bottoms (W)
< 100 ppm acetone
100°C
Solution
Material balance
It is necessary to make a material balance to determine the top and bottoms product
flow rates.
Balance on acetone, acetone loss in bottoms neglected.
1000 ð 0.1 D D ð 0.99
Distillate, D D 101 kg/h
Bottoms, W D 1000 101 D 899 kg/h
Energy balance
The kinetic and potential energy of the process streams will be small and can be neglected.
Take the first system boundary to include the reboiler and condenser.
HD
QC
HF
System
QB
HW
Inputs: reboiler heat input QB C feed sensible heat HF .
Outputs: condenser cooling QC C top and bottom product sensible heats HD C HW .
The heat losses from the system will be small if the column and exchangers are properly
lagged (typically less than 5 per cent) and will be neglected.
Basis 25Ž C, 1h.
FUNDAMENTALS OF ENERGY BALANCES
Heat capacity data, from Volume 1, average values.
Acetone: 25Ž C to 35Ž C
Ž
Water:
Ž
25 C to 100 C
2.2 kJ/kg K
4.2 kJ/kg K
Heat capacities can be taken as additive.
Feed, 10 per cent acetone D 0.1 ð 2.2 C 0.9 ð 4.2 D 4.00 kJ/kg K
Tops, 99 per cent acetone, taken as acetone, 2.2 kJ/kg K
Bottoms, as water, 4.2 kJ/kg K.
QC must be determined by taking a balance round the condenser.
QC
HV
V
D = 101 kg/h
HD
HL
L
V = Vapour flow
L = Reflux flow
H = Enthalpy
Reflux ratio (see Chapter 11)
L
D 10
D
L D 10 ð 101 D 1010 kg/h
RD
V D L C D D 1111 kg/h
From vapour liquid equilibrium data:
boiling point of 99 per cent acetone/water D 56.5Ž C
At steady state:
input D output
HV D HD C HL C Q C ,
Q C D H V H D HL
Hence
Assume complete condensation.
Enthalpy of vapour HV D latent C sensible heat.
65
66
CHEMICAL ENGINEERING
There are two ways of calculating the specific enthalpy of the vapour at its boiling
point.
(1) Latent heat of vaporisation at the base temperature C sensible heat to heat the
vapour to the boiling point.
(2) Latent heat of vaporisation at the boiling point C sensible heat to raise liquid to
the boiling point.
Values of the latent heat of acetone and water as functions of temperature are given in
Volume 1, so the second method will be used.
Latent heat acetone at 56.5Ž C (330 K) D 620 kJ/kg
Water at 56.5Ž C (330 K) D 2500 kJ/kg
Taking latent heats as additive:
HV D 1111[⊲0.01 ð 2500 C 0.99 ð 620⊳ C ⊲56.5 25⊳2.2]
D 786,699 kJ/h
The enthalpy of the top product and reflux are zero, as they are both at the base
temperature. Both are liquid, and the reflux will be at the same temperature as the product.
Hence
QC D HV D 786,699 kJ/h
⊲218.5 kW⊳
QB is determined from a balance over complete system
Input
Output
Q B C H F D Q C C HD C H W
HF D 1000 ð 4.00⊲35 25⊳ D 40,000 kJ/h
HW D 899 ð 4.2⊲100 25⊳ D 283,185 kJ/h
(boiling point of bottom product taken as 100Ž C).
hence
Q B D Q C C H W C H D HF
D 786,699 C 283,185 C 0 40,000
D 1,029,884 kJ/h
⊲286.1 kW⊳
QB is supplied by condensing steam.
Latent heat of steam (Volume 1) D 2174 kJ/kg at 274 kN/m2
Steam required D
1,029,884
D 473.7 kg/h
2174
QC is removed by cooling water with a temperature rise of 30Ž C
QC D water flow ð 30 ð 4.2
Water flow D
786,699
D 6244 kg/h
4.2 ð 30
67
FUNDAMENTALS OF ENERGY BALANCES
3.5. CALCULATION OF SPECIFIC ENTHALPY
Tabulated values of enthalpy are available only for the more common materials. In the
absence of published data the following expressions can be used to estimate the specific
enthalpy (enthalpy per unit mass).
For pure materials, with no phase change:
T
HT D
Cp dT
⊲3.11⊳
Td
where HT D specific enthalpy at temperature T,
Cp D specific heat capacity of the material, constant pressure,
Td D the datum temperature.
If a phase transition takes place between the specified and datum temperatures, the
latent heat of the phase transition is added to the sensible-heat change calculated by
equation 3.11. The sensible-heat calculation is then split into two parts:
Tp
T
HT D
Cp1 dT C
Cp2 dT
⊲3.12⊳
Td
Tp
where Tp D phase transition temperature,
Cp1 D specific heat capacity first phase, below Tp ,
Cp2 D specific heat capacity second phase, above Tp .
The specific heat at constant pressure will vary with temperature and to use equations
3.11 and 3.12, values of Cp must be available as a function of temperature. For solids
and gases Cp is usually expressed as an empirical power series equation:
Cp D a C bT C cT2 C dT3
or
Cp D a C bT C cT1/2
⊲3.13a⊳
⊲3.13b⊳
Absolute (K) or relative (Ž C) temperature scales may be specified when the relationship
is in the form given in equation 3.13a. For equation 3.13b absolute temperatures must
be used.
Example 3.2
Estimate the specific enthalpy of ethyl alcohol at 1 bar and 200Ž C, taking the datum
temperature as 0Ž C.
Cp liquid 0Ž C 24.65 cal/molŽ C
100Ž C 37.96 cal/molŽ C
Cp gas ⊲tŽ C⊳ 14.66 C 3.758 ð 102 t 2.091 ð 105 t2 C 4.740 ð 109 t3 cal/mol
Boiling point of ethyl alcohol at 1 bar D 78.4Ž C.
Latent heat of vaporisation D 9.22 kcal/mol.
68
CHEMICAL ENGINEERING
Solution
Note: as the data taken from the literature are given in cal/mol the calculation is carried
out in these units and the result converted to SI units.
As no data are given on the exact variation of the Cp of the liquid with temperature,
use an equation of the form Cp D a C bt, calculating a and b from the data given; this
will be accurate enough over the range of temperature needed.
37.96 24.65
D 0.133
100
200
78.4
⊲14.66 C 3.758 ð 102 t
⊲24.65 C 0.133t⊳ dt C 9.22 ð 103 C
D
a D value of Cp at 0Ž C,
H200Ž C
bD
78.4
0
5 2
9 3
2.091 ð 10 t C 4.740 ð 10 t ⊳ dt
78.4
200
D [ 24.65t C 0.133t2 /2] C 9.22 ð 103 C [ 14.66t C 3.758 ð 102 t2 /2 2.091
0
78.4
5 3
9 4
ð 10 t /3 C 4.740 ð 10 t /4]
D 13.95 ð 103 cal/mol
D 13.95 ð 103 ð 4.18 D 58.31 ð 103 J/mol
Specific enthalpy D 58.31 kJ/mol.
Molecular weight of ethyl alcohol, C2 H5 OH D 46
Specific enthalpy D 58.31 ð 103 /46 D 1268 kJ/kg
3.6. MEAN HEAT CAPACITIES
The use of mean heat capacities often facilitates the calculation of sensible-heat changes;
mean heat capacity over the temperature range t1 to t2 is defined by the following equation:
t2
t2
Cp dt ł
dt
⊲3.14⊳
Cpm D
t1
t1
Mean specific heat values are tabulated in various handbooks. If the values are for
unit mass, calculated from some standard reference temperature, tr , then the change in
enthalpy between temperatures t1 and t2 is given by:
H D Cpm,t2 ⊲t2 tr ⊳ Cpm,t1 ⊲t1 tr ⊳
⊲3.15⊳
where tr is the reference temperature from which the values of Cpm were calculated.
If Cp is expressed as a polynomial of the form: Cp D a C bt C ct2 C dt3 , then the
integrated form of equation 3.14 will be:
Cpm
c
d
b
a⊲t tr ⊳ C ⊲t2 tr2 ⊳ C ⊲t3 tr3 ⊳ C ⊲t4 tr4 ⊳
2
3
4
D
t tr
where t is the temperature at which Cpm is required.
⊲3.16⊳
69
FUNDAMENTALS OF ENERGY BALANCES
Ž
If the reference temperature is taken at 0 C, equation 3.16 reduces to:
Cpm D a C
bt ct2
dt3
C
C
2
3
4
⊲3.17⊳
and the enthalpy change from t1 to t2 becomes
H D Cpm,t2 t2 Cpm,t1 t1
⊲3.18⊳
The use of mean heat capacities is illustrated in Example 3.3.
Example 3.3
The gas leaving a combustion chamber has the following composition: CO2 7.8, CO 0.6,
O2 3.4, H2 O 15.6, N2 72.6, all volume percentage. Calculate the heat removed if the gas
is cooled from 800 to 200Ž C.
Solution
Mean heat capacities for the combustion gases are readily available in handbooks and
texts on heat and material balances. The following values are taken from K. A. Kobe,
Thermochemistry of Petrochemicals, reprint No. 44, Pet. Ref. 1958; converted to SI units,
J/molŽ C, reference temperature 0Ž C.
Ž
C
N2
O2
CO2
CO
H2 O
200
800
29.24
30.77
29.95
32.52
40.15
47.94
29.52
31.10
34.12
37.38
Heat extracted from the gas in cooling from 800 to 200Ž C, for each component:
D Mc ⊲Cpm,800 ð 800 Cpm,200 ð 200⊳
where Mc D mols of that component.
Basis 100 mol gas (as analysis is by volume), substitution gives:
CO2
CO
O2
H2 O
N2
7.8⊲47.94 ð 800 40.15 ð 200⊳ D 236.51 ð 103
0.6⊲31.10 ð 800 29.52 ð 200⊳ D 11.39 ð 103
3.4⊲32.52 ð 800 29.95 ð 200⊳ D 68.09 ð 103
15.6⊲37.38 ð 800 34.12 ð 200⊳ D 360.05 ð 103
72.6⊲30.77 ð 800 29.24 ð 200⊳ D 1362.56 ð 103
D 2038.60 kJ/100 mol
D
20.39 kJ/mol
70
CHEMICAL ENGINEERING
3.7. THE EFFECT OF PRESSURE ON HEAT CAPACITY
The data on heat capacities given in the handbooks, and in Appendix A, are, usually for
the ideal gas state. Equation 3.13a should be written as:
CŽp D a C bT C cT2 C dT3
⊲3.19⊳
where the superscript Ž refers to the ideal gas state.
The ideal gas values can be used for the real gases at low pressures. At high pressures
the effect of pressure on the specific heat may be appreciable.
Edmister (1948) published a generalised plot showing the isothermal pressure correction
for real gases as a function of the reduced pressure and temperature. His chart, converted
2000
1000
800
600
400
200
1.0
1.05
1.10
40
1.20
1.30
20
1.6
Cp − Cp° (J mol
−1
−1
K )
100
80
60
1.8
2.0
10
8
6
4
2.2
2.5
60
Tr
=
0.
70
0
0.8 0
9
0. .95
0 .0
1 05
1. 1.1 2
1. .3
1 .4
1 .5
1 .6
1 .8
1
0.
2
4.0
2.
0
1.0
0.8
0.6
3.0
0.4
5
2.
0
3. 25
3. 5
3. 0
4.
0.2
0.1
0.08
0.06
0.04
0.01
0.02
0.04 0.06 0.1
0.2
0.4 0.6 0.8 1.0
2
4
6
8 10
Pr
Tr = Reduced temperature
Pr = Reduced pressure
Figure 3.2.
Excess heat capacity chart (reproduced from Sterbacek et al. (1979), with permission)
71
FUNDAMENTALS OF ENERGY BALANCES
to SI units, is shown as Figure 3.2. Edmister’s chart was based on hydrocarbons, but can
be used for other materials to give an indication of the likely error if the ideal gas specific
heat values are used without corrections.
The method is illustrated in Example 3.4.
Example 3.4
The ideal state heat capacity of ethylene is given by the equation:
CŽp D 3.95 C 15.6 ð 102 T 8.3 ð 105 T2 C 17.6 ð 109 T3 J/mol K
Estimate the value at 10 bar and 300 K.
Solution
Ethylene: critical pressure
50.5 bar
critical temperature 283 K
CŽp D 3.95 C 15.6 ð 102 ð 300 8.3 ð 105 ð 3002 C 17.6 ð 109 ð 3003
D 43.76 J/mol K
10
D 0.20
50.5
300
Tr D
D 1.06
283
From Figure 3.2:
Pr D
Cp CŽp ' 5 J/mol K
So
Cp D 43.76 C 5 D ³ 49 J/mol K
The error in Cp if the ideal gas value were used uncorrected would be approximately 10
per cent.
3.8. ENTHALPY OF MIXTURES
For gases, the heats of mixing are usually negligible and the heat capacities and enthalpies
can be taken as additive without introducing any significant error into design calculations;
as was done in Example 3.3.
Cp ⊲mixture⊳ D xa Cpa C xb Cpb C xc Cpc C Ð Ð Ð .
⊲3.20⊳
where xa , xb , xc , etc., are the mol fractions of the components a, b, c.
For mixtures of liquids and for solutions, the heat of mixing (heat of solution) may be
significant, and so must be included when calculating the enthalpy of the mixture.
For binary mixtures, the specific enthalpy of the mixture at temperature t is given by:
Hmixture,t D xa Ha,t C xb Hb,t C Hm,t
⊲3.21⊳
where Ha,t and Hb,t are the specific enthalpies of the components a and b and Hm,t
is the heat of mixing when 1 mol of solution is formed, at temperature t.
72
CHEMICAL ENGINEERING
Heats of mixing and heats of solution are determined experimentally and are available
in the handbooks for the more commonly used solutions.
If no values are available, judgement must be used to decide if the heat of mixing for
the system is likely to be significant.
For organic solutions the heat of mixing is usually small compared with the other heat
quantities, and can usually be neglected when carrying out a heat balance to determine
the process heating or cooling requirements.
The heats of solution of organic and inorganic compounds in water can be large,
particularly for the strong mineral acids and alkalies.
3.8.1. Integral heats of solution
Heats of solution are dependent on concentration. The integral heat of solution at any
given concentration is the cumulative heat released, or absorbed, in preparing the solution
from pure solvent and solute. The integral heat of solution at infinite dilution is called
the standard integral heat of solution.
Tables of the integral heat of solution over a range of concentration, and plots of the
integral heat of solution as a function of concentration, are given in the handbooks for
many of the materials for which the heat of solution is likely to be significant in process
design calculations.
The integral heat of solution can be used to calculate the heating or cooling required
in the preparation of solutions, as illustrated in Example 3.5.
Example 3.5
A solution of NaOH in water is prepared by diluting a concentrated solution in an agitated,
jacketed, vessel. The strength of the concentrated solution is 50 per cent w/w and 2500 kg
of 5 per cent w/w solution is required per batch. Calculate the heat removed by the cooling
water if the solution is to be discharged at a temperature of 25Ž C. The temperature of the
solutions fed to the vessel can be taken to be 25Ž C.
Solution
Integral heat of solution of NaOH H2 O, at 25Ž C
mols H2 O/mol NaOH
2
4
5
10
infinite
HŽsoln kJ/mol NaOH
22.9
34.4
37.7
42.5
42.9
Conversion of weight per cent to mol/mol:
50 per cent w/w D 50/18 ł 50/40 D 2.22 mol H2 O/mol NaOH
5 per cent w/w D 95/18 ł 5/40 D 42.2 mol H2 O/mol NaOH
FUNDAMENTALS OF ENERGY BALANCES
73
From a plot of the integral heats of solution versus concentration,
HŽsoln 2.22 mol/mol D 27.0 kJ/mol NaOH
42.2 mol/mol D 42.9 kJ/mol NaOH
Heat liberated in the dilution per mol NaOH
D 42.9 27.0 D 15.9 kJ
Heat released per batch D mol NaOH per batch ð 15.9
D
2500 ð 103 ð 0.05
ð 15.9 D 49.7 ð 103 kJ
40
Heat transferred to cooling water, neglecting heat losses,
49.7 MJ per batch
In Example 3.5 the temperature of the feeds and final solution have been taken as the
same as the standard temperature for the heat of solution, 25Ž C, to simplify the calculation.
Heats of solution are analogous to heats of reaction, and examples of heat balances on
processes where the temperatures are different from the standard temperature are given
in the discussion of heats of reaction, Section 3.10.
3.9. ENTHALPY-CONCENTRATION DIAGRAMS
The variation of enthalpy for binary mixtures is conveniently represented on a diagram.
An example is shown in Figure 3.3. The diagram shows the enthalpy of mixtures of
ammonia and water versus concentration; with pressure and temperature as parameters.
It covers the phase changes from solid to liquid to vapour, and the enthalpy values given
include the latent heats for the phase transitions.
The enthalpy is per kg of the mixture (ammonia C water)
Reference states: enthalpy ammonia at 77Ž C D zero
enthalpy water at 0Ž C D zero
Enthalpy-concentration diagrams greatly facilitate the calculation of energy balances
involving concentration and phase changes; this is illustrated in Example 3.6.
Example 3.6
Calculate the maximum temperature when liquid ammonia at 40Ž C is dissolved in water
at 20Ž C to form a 10 per cent solution.
Solution
The maximum temperature will occur if there are no heat losses (adiabatic process). As
no heat or material is removed, the problem can be solved graphically in the enthalpyconcentration diagram (Figure 3.3). The mixing operation is represented on the diagram
74
CHEMICAL ENGINEERING
700
700
650
650
2800
Dew
600
600
line
s
2400
(19
(58
61
(19 8) (981) ) kN/m 2
6) (39
2)
(39
.2) (98
.1)
(9.8
1)
(1.9
6)
550
500
550
500
2000
450
450
400
400
350
350
300
300
250
250
1200
200°C
200
200
800
180
160
150
140
150
120
61)
(13 xN/m 2
(98 73)
(58 1)
80°
(39 8)
2
(19 )
60°
6
(98 )
40°
(49 .1)
.
20°
(19 0)
.
(9. 6)
0°C
81
)
(1.
−20°
96)
−40°
80
60
40
50
20
Water,
0 deg. C.
m.
q. c
g./s
k
20
40°
Boiling lines
20°
14.0
10.0
0°C
6.0
20°
0
.
4
40°
2.0
1.0
60°
Liquid
5
.
0
80°
0.2
e
0.1
lin
ing
2
z
0
.
0
ee
Fr
(19
100
100
Enthalpy, kJ/kg
Enthalpy, k cal/kg
1600
0°C
−50
Ice,
0 deg. C.
−60°
−80°
−100
100
400
50
0
NH3 liquid
−77 °C
−50
NH3 solid
−77 °C
−100
−400
e
lin
zing
e
Solid
Fre
Solid
−150
−150
−800
−200
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
−200
1.0
Ammonia concentration, weight fraction
Figure 3.3. Enthalpy-concentration diagram for aqueous ammonia. Reference states: enthalpies of liquid water
at 0° C and liquid ammonia at 77° C are zero. (Bosniakovic, Technische Thermodynamik, T. Steinkopff,
Leipzig, 1935)
by joining the point A representing pure ammonia at 40Ž C with the point B representing
pure water at 20Ž C. The value of the enthalpy of the mixture lies on a vertical line at the
required concentration, 0.1. The temperature of the mixture is given by the intersection
of this vertical line with the line AB. This method is an application of the “lever rule” for
phase diagrams. For a more detailed explanation of the method and further examples see
75
FUNDAMENTALS OF ENERGY BALANCES
Himmelbau (1995) or any of the general texts on material and energy balances listed at the
end of Chapter 2. The Ponchon-Savarit graphical method used in the design of distillation
columns, described in Volume 2, Chapter 11, is a further example of the application of
the lever rule, and the use of enthalpy-concentration diagrams.
40°
20°
0°
−20
80
60
40
B 0°C
Water
at
20°C
20
A
NH3
at
40°C
Solution
at 40°C
0.1% NH3
3.10. HEATS OF REACTION
If a process involves chemical reaction, heat will normally have to be added or removed.
The amount of heat given out in a chemical reaction depends on the conditions under
which the reaction is carried out. The standard heat of reaction is the heat released when
the reaction is carried out under standard conditions: pure components, pressure 1 atm
(1.01325 bar), temperature usually, but not necessarily, 25Ž C.
Values for the standard heats of reactions are given in the literature, or may be calculated
by the methods given in Sections 3.11 and 3.12.
When quoting heats of reaction the basis should be clearly stated. Either by giving the
chemical equation, for example:
NO C 12 O2 ! NO2
HŽr D 56.68 kJ
(The equation implies that the quantity of reactants and products are mols)
Or, by stating to which quantity the quoted value applies:
HŽr D 56.68 kJ per mol NO2
The reaction is exothermic and the enthalpy change HŽr is therefore negative. The heat
of reaction HŽr is positive. The superscript Ž denotes a value at standard conditions
and the subscript r implies that a chemical reaction is involved.
The state of the reactants and products (gas, liquid or solid) should also be given, if
the reaction conditions are such that they may exist in more than one state; for example:
H2 (g) C 21 O2 (g) ! H2 O(g), HŽr D 241.6 kJ
H2 (g) C 21 O2 (g) ! H2 O (l), HŽr D 285.6 kJ
The difference between the two heats of reaction is the latent heat of the water formed.
76
CHEMICAL ENGINEERING
In process design calculations it is usually more convenient to express the heat of
reaction in terms of the mols of product produced, for the conditions under which the
reaction is carried out, kJ/mol product.
Standard heats of reaction can be converted to other reaction temperatures by making a
heat balance over a hypothetical process, in which the reactants are brought to the standard
temperature, the reaction carried out, and the products then brought to the required reaction
temperature; as illustrated in Figure 3.4.
Hr,t D HŽr C Hprod. Hreact.
Reactants
t°C
Reaction at
temp. t
∆Hr, t
⊲3.22⊳
Products
t°C
∆Ηreact.
∆Hprod.
Reactants
25°C
Figure 3.4.
Reaction at
25°C
∆H°r
Products
25°C
Hr at temperature t
where Hr,t D heat of reaction at temperature t,
Hreact. D enthalpy change to bring reactants to standard temperature,
Hprod. D enthalpy change to bring products to reaction temperature, t.
For practical reactors, where the reactants and products may well be at temperatures
different from the reaction temperature, it is best to carry out the heat balance over
the actual reactor using the standard temperature (25Ž C) as the datum temperature; the
standard heat of reaction can then be used without correction.
It must be emphasised that it is unnecessary to correct a heat of reaction to the reaction
temperature for use in a reactor heat-balance calculation. To do so is to carry out two heat
balances, whereas with a suitable choice of datum only one need be made. For a practical
reactor, the heat added (or removed) Qp to maintain the design reactor temperature will
be given by (from equation 3.10):
Qp D Hproducts Hreactants Qr
where
⊲3.23⊳
Hproducts is the total enthalpy of the product streams, including unreacted
materials and by-products, evaluated from a datum temperature of 25Ž C;
Hreactants is the total enthalpy of the feed streams, including excess reagent and
inerts, evaluated from a datum of 25Ž C;
FUNDAMENTALS OF ENERGY BALANCES
77
Qr is the total heat generated by the reactions taking place, evaluated from the
standard heats of reaction at 25Ž C (298 K).
Qr D
HŽr ð (mol of product formed)
⊲3.24⊳
where HŽr is the standard heat of reaction per mol of the particular product.
Note: A negative sign is necessary in equation 3.24 as Qr is positive when heat is
evolved by the reaction, whereas the standard enthalpy change will be negative for
exothermic reactions. Qp will be negative when cooling is required (see Section 3.4).
3.10.1. Effect of pressure on heats of reaction
Equation 3.22 can be written in a more general form:
P
∂Hreact.
∂Hprod.
Ž
dP
Hr,P,T D Hr C
∂P
∂P
1
T
T
T
∂Hprod.
∂Hreact.
dT
C
∂T
∂T
298
P
P
⊲3.25⊳
If the effect of pressure is likely to be significant, the change in enthalpy of the products
and reactants, from the standard conditions, can be evaluated to include both the effects
of temperature and pressure (for example, by using tabulated values of enthalpy) and the
correction made in a similar way to that for temperature only.
Example 3.7
Illustrates the manual calculation of a reactor heat balance.
Vinyl chloride (VC) is manufactured by the pyrolysis of 1,2,dichloroethane (DCE). The
reaction is endothermic. The flow-rates to produce 5000 kg/h at 55 per cent conversion
are shown in the diagram (see Example 2.13).
The reactor is a pipe reactor heated with fuel gas, gross calorific value 33.5 MJ/m3 .
Estimate the quantity of fuel gas required.
DCE 145.5 kmol/h
liquid 20°C
Reactor
2 bar
500°C
VC 80 kmol/h
DCE 65.5
HCL 80
Q
Solution
Reaction: C2 H4 Cl2 (g) ! C2 H3 Cl(g) C HCl(g)
HŽr D 70,224 kJ/kmol.
The small quantity of impurities, less than 1 per cent, that would be present in the feed
have been neglected for the purposes of this example. Also, the yield of VC has been
taken as 100 per cent. It would be in the region of 99 per cent at 55 per cent conversion.
78
CHEMICAL ENGINEERING
Heat capacity data, for vapour phase
CŽp D a C bT C cT2 C dT3
2
b ð 10
a
VC
HCl
DCE
5.94
30.28
20.45
kJ/kmolK
c ð 105
d ð 109
15.34
1.325
14.36
20.16
0.761
23.07
47.65
4.305
33.83
for liquid phase: DCE at 20Ž C, Cp D 116 kJ/kmol K,
taken as constant over temperature rise from 20 to 25Ž C.
Latent heat of vaporisation of DCE at 25Ž C D 34.3 MJ/kmol.
At 2 bar pressure the change in Cp with pressure will be small and will be neglected.
Take base temperature as 25Ž C (298 K), the standard state for HŽr .
Enthalpy of feed D 145.5 ð 116⊲293 298⊳ D 84,390 kJ/h D 84.4 MJ/h
Enthalpy of product stream D
Component
VC
HCl
DCE
ni Cp
773
298
D
773
298
⊲ni Cp ⊳ dT
ni
(mol/h)
ni a
ni b ð 102
ni c ð 105
ni d ð 109
80
80
65.5
475.2
2422.4
1339.5
1612.8
60.88
1511.0
1227.2
106.0
940.6
3812.0
344.4
2215.9
4237.1
3063.0
2061.8
5683.5
ni Cp dT
773
298
⊲4237.1 C 3063.0 ð 102 T 2061.8 ð 105 T2 C 5683.5 ð 109 T3 ⊳ dT
D 7307.3 MJ/h
Heat consumed in system by the endothermic reaction D HŽr ð mols produced
D 70,224 ð 80 D 5,617,920 kJ/h D 5617.9 MJ/h
Heat to vaporise feed (gas phase reaction)
D 34.3 ð 145.5 D 4990.7 MJ/h
Heat balance:
Output D Input C consumed C Q
Q D Hproduct Hfeed C consumed
D 7307.3 ⊲84.4⊳ C ⊲5617.9 C 4990.7⊳ D 18,002.3 MJ/h
FUNDAMENTALS OF ENERGY BALANCES
79
Taking the overall efficiency of the furnace as 70% the gas rate required
D
D
Heat input
⊲calorific value ð efficiency⊳
18,002.3
D 768 m3 /h
33.5 ð 0.7
3.11. STANDARD HEATS OF FORMATION
The standard enthalpy of formation HŽf of a compound is defined as the enthalpy change
when one mol of the compound is formed from its constituent elements in the standard
state. The enthalpy of formation of the elements is taken as zero. The standard heat of
any reaction can be calculated from the heats of formation HŽf of the products and
reactants; if these are available or can be estimated.
Conversely, the heats of formation of a compound can be calculated from the heats of
reaction; for use in calculating the standard heat of reaction for other reactions.
The relationship between standard heats of reaction and formation is given by
equation 3.26 and illustrated by Examples 3.8 and 3.9
HŽr D
HŽf , products
HŽf , reactants
⊲3.26⊳
A comprehensive list of enthalpies of formation is given in Appendix D.
As with heats of reaction, the state of the materials must be specified when quoting
heats of formation.
Example 3.8
Calculate the standard heat of the following reaction, given the enthalpies of formation:
4NH3 (g) C 5O2 (g) ! 4NO(g) C 6H2 O(g)
Standard enthalpies of formation kJ/mol
NH3 (g)
NO(g)
H2 O(g)
46.2
C90.3
241.6
Solution
Note: the enthalpy of formation of O2 is zero.
HŽf , products
HŽf , reactants
HŽr D
D ⊲4 ð 90.3 C 6 ð ⊲241.6⊳⊳ ⊲4 ð ⊲46.2⊳⊳
D 903.6 kJ/mol
Heat of reaction HŽr D 904 kJ/mol
80
CHEMICAL ENGINEERING
3.12. HEATS OF COMBUSTION
The heat of combustion of a compound HŽc is the standard heat of reaction for complete
combustion of the compound with oxygen. Heats of combustion are relatively easy to
determine experimentally. The heats of other reactions can be easily calculated from the
heats of combustion of the reactants and products.
The general expression for the calculation of heats of reaction from heats of
combustion is
⊲3.27⊳
HŽc , products
HŽc , reactants
HŽr D
Note: the product and reactant terms are the opposite way round to that in the expression
for the calculation from heats of formation (equation 3.26).
For compounds containing nitrogen, the nitrogen will not be oxidised to any significant
extent in combustion and is taken to be unchanged in determining the heat of combustion.
Caution. Heats of combustion are large compared with heats of reaction. Do not round
off the numbers before subtraction; round off the difference.
Two methods of calculating heats of reaction from heats of combustion are illustrated
in Example 3.9.
Example 3.9
Calculate the standard heat of reaction for the following reaction: the hydrogenation of
benzene to cyclohexane.
(1)
(2)
(3)
(4)
(5)
C6 H6 (g) C 3H2 (g) ! C6 H12 (g)
C6 H6 (g) C 7 21 O2 (g) ! 6CO2 (g) C 3H2 O(l)
C6 H12 (g) C 9O2 ! 6CO2 (g) C 6H2 O(l)
C(s) C O2 (g) ! CO2 (g)
H2 (g) C 21 O2 (g) ! H2 O(l)
HŽc
HŽc
HŽc
HŽc
D 3287.4
D 3949.2
D 393.12
D 285.58
kJ
kJ
kJ
kJ
Note: unlike heats of formation, the standard state of water for heats of combustion is
liquid. Standard pressure and temperature are the same 25Ž C, 1 atm.
Solution
Method 1
Using the more general equation 3.26
HŽf , products
HŽf reactants
HŽr D
the enthalpy of formation of C6 H6 and C6 H12 can be calculated, and from these values
the heat of reaction (1).
From reaction (2)
HŽc ⊲C6 H6 ⊳ D 6 ð HŽc ⊲CO2 ⊳ C 3 ð HŽc ⊲H2 O⊳ HŽf ⊲C6 H6 ⊳
3287.4 D 6⊲393.12⊳ C 3⊲285.58⊳ HŽf ⊲C6 H6 ⊳
HŽf ⊲C6 H6 ⊳ D 3287.4 3215.52 D 71.88 kJ/mol
81
FUNDAMENTALS OF ENERGY BALANCES
From reaction (3)
HŽc ⊲C6 H12 ⊳ D 3949.2 D 6⊲393.12⊳ C 6⊲285.58⊳ HŽf ⊲C6 H12 ⊳
HŽf ⊲C6 H12 ⊳ D 3949.2 4072.28 D 123.06 kJ/mol
HŽr D HŽf ⊲C6 H12 ⊳ HŽf ⊲C6 H6 ⊳
HŽr D ⊲123.06⊳ ⊲71.88⊳ D 195 kJ/mol
Note: enthalpy of formation of H2 is zero.
Method 2
Using equation 3.27
HŽr D ⊲HŽc ⊲C6 H6 ⊳ C 3 ð HŽc ⊲H2 ⊳⊳ HŽc ⊲C6 H12 ⊳
D ⊲3287.4 C 3⊲285.88⊳⊳ ⊲3949.2⊳ D 196 kJ/mol
Heat of reaction HŽr D 196 kJ/mol
3.13. COMPRESSION AND EXPANSION OF GASES
The work term in an energy balance is unlikely to be significant unless a gas is expanded
or compressed as part of the process. To compute the pressure work term:
W D
2
P dv
⊲equation 3.5⊳
1
a relationship between pressure and volume during the expansion is needed.
If the compression or expansion is isothermal (at constant temperature) then for unit
mass of an ideal gas:
Pv D constant
and the work done,
W D P1 v1 ln
P2
RT1 P2
D
ln
P1
M
P1
⊲3.28⊳
⊲3.29⊳
where P1 D initial pressure,
P2 D final pressure,
v1 D initial volume.
In industrial compressors or expanders the compression or expansion path will be
“polytropic”, approximated by the expression:
Pvn D constant
⊲3.30⊳
82
CHEMICAL ENGINEERING
The work produced (or required) is given by the general expression (see Volume 1,
Chapter 8):
P2 ⊲n1⊳/n
P2 ⊲n1⊳/n
RT1 n
n
W D P1 v1
1 DZ
1
⊲3.31⊳
n1
P1
M n1
P1
where Z
R
T1
M
W
D
D
D
D
D
compressibility factor (1 for an ideal gas),
universal gas constant, 8.314 JK1 mol1 ,
inlet temperature, K,
molecular mass (weight) of gas,
work done, J/kg.
The value of n will depend on the design and operation of the machine.
The energy required to compress a gas, or the energy obtained from expansion, can be
estimated by calculating the ideal work and applying a suitable efficiency value. For reciprocating compressors the isentropic work is normally used (n D ) (see Figure 3.7); and
for centrifugal or axial machines the polytropic work (see Figure 3.6 and Section 3.13.2).
3.13.1. Mollier diagrams
If a Mollier diagram (enthalpy-pressure-temperature-entropy) is available for the working
fluid the isentropic work can be easily calculated.
W D H1 H2
⊲3.32⊳
where H1 is the specific enthalpy at the pressure and temperature corresponding to
point 1, the initial gas conditions,
H2 is the specific enthalpy corresponding to point 2, the final gas condition.
Point 2 is found from point 1 by tracing a path (line) of constant entropy on the diagram.
The method is illustrated in Example 3.10.
Example 3.10
Methane is compressed from 1 bar and 290 K to 10 bar. If the isentropic efficiency is 0.85,
calculate the energy required to compress 10,000 kg/h. Estimate the exit gas temperature.
Solution
From the Mollier diagram, shown diagrammatically in Figure 3.5
H1 D 4500 cal/mol,
H2 D 6200 cal/mol (isentropic path),
Isentropic work D 6200 4500
D 1700 cal/mol
FUNDAMENTALS OF ENERGY BALANCES
p = 10
Enthalpy
480 K
H′2 = 6500
460 K
H2 = 6200
p=1
Actual path
Isentropic
path
290 K
H1 = 4500
Entropy
Figure 3.5.
Mollier diagram, methane
90
%
Efficiency, Ep,
Axial - flow
80
70
Centrifugal
60
1.0
100
10
Volumetric flow rate (suction conditions),
Figure 3.6.
m3/s
Approximate polytropic efficiencies centrifugal and axial-flow compressors
For an isentropic efficiency of 0.85:
Actual work done on gas D
1700
D 2000 cal/mol
0.85
So, actual final enthalpy
H02 D H1 C 2000 D 6500 cal/mol
83
84
CHEMICAL ENGINEERING
Range
Isentropic efficiency
100
90
80
70
60
1
1.5
2.0
2.5
3.0
3.5
4.0
Compression ratio
Figure 3.7.
Typical efficiencies for reciprocating compressors
From Mollier diagram, if all the extra work is taken as irreversible work done on the gas,
the exit gas temperature D 480 K
Molecular weight methane D 16
Energy required D (mols per hour) ð (specific enthalpy change)
10,000
D
ð 2000 ð 103
16
D 1.25 ð 109 cal/h
D 1.25 ð 109 ð 4.187
D 5.23 ð 109 J/h
5.23 ð 109
D 1.45 MW
Power D
3600
3.13.2. Polytropic compression and expansion
If no Mollier diagram is available, it is more difficult to estimate the ideal work in
compression or expansion processes. Schultz (1962) gives a method for the calculation of
the polytropic work, based on two generalised compressibility functions, X and Y; which
supplement the familiar compressibility factor Z.
T ∂V
1
⊲3.33⊳
XD
V ∂T P
P ∂V
⊲3.34⊳
YD
V ∂P T
His charts for X and Y as functions of reduced temperature and pressure are reproduced
as Figures 3.9 and 3.10. The functions are used to determine the polytropic exponent n
85
FUNDAMENTALS OF ENERGY BALANCES
for use in equation 3.31; and a polytropic temperature exponent m for use in the following
equation:
m
P2
⊲3.35⊳
T2 D T1
P1
ZR 1
where
mD
C X for compression,
⊲3.36⊳
C p Ep
ZR
⊲Ep C X⊳ for expansion
Cp
Ep is the polytropic efficiency, defined by:
polytropic work
for compression Ep D
actual work required
mD
⊲3.37⊳
actual work obtained
polytropic work
An estimate of Ep can be obtained from Figure 3.6.
1
⊲3.38⊳
nD
Y m⊲1 C X⊳
At conditions well removed from the critical conditions equations 3.36, 3.37 and 3.38
reduce to:
⊲ 1⊳
mD
⊲3.36a⊳
Ep
for expansion Ep D
mD
⊲ 1⊳Ep
⊲3.37a⊳
1
⊲3.38a⊳
1m
These expressions can be used to calculate the polytropic work and outlet temperature
by substitution in equations 3.31 and 3.35. They can also be used to make a first estimate
of T2 in order to estimate the mean reduced temperature for use with Figures 3.9 and 3.10.
The use of Schultz’s method is illustrated in Examples 3.11 and 3.16.
nD
Example 3.11
Estimate the power required to compress 5000 kmol/h of HCl at 5 bar, 15Ž C, to 15 bar.
Solution
For HCl, Pc D 82 bar, Tc D 324.6 K
CŽp D 30.30 0.72 ð 102 T C 12.5 ð 106 T2 3.9 ð 109 T3 kJ/kmol K
Estimate T2 from equations 3.35 and 3.36a.
For diatomic gases ' 1.4.
Note:
could be estimated from the relationship
D
Cp
Cp
D
Cv
Cp R
86
CHEMICAL ENGINEERING
At the inlet conditions, the flow rate in m3 /s
288 1
5000
ð 22.4 ð
ð D 6.56
D
3600
273 5
From Figure 3.6 Ep D 0.73
1.4 1
From equations 3.36a and 3.35
mD
D 0.39
1.4 ð 0.73
0.39
15
D 442 K
T2 D 288
5
442 C 228
D 1.03
2 ð 324.6
5 C 15
Pr ⊲mean⊳ D
D 0.12
2 ð 82
At T⊲mean⊳ CŽp D 29.14 kJ/kmol K
Tr
⊲mean⊳
D
Correction for pressure from Figure 3.2, 2 kJ/kmol K
Cp D 29.14 C 2 ' 31 kJ/kmol K
From Figures 3.8, 3.9 and 3.10 at mean conditions:
X D 0.18,
Y D 1.04,
Z D 0.97
Z at inlet conditions D 0.98
From equations 3.36 and 3.38
0.97 ð 8.314
1
mD
C 0.18 D 0.40
31
0.73
nD
From equation 3.31
1
D 1.76
1.04 0.4⊲1 C 0.18⊳
W polytropic D 0.98 ð 288 ð 8.314 ð
1.76
1.76 1
D 3299 kJ/kmol
polytropic work
Ep
3299
D 4520 kJ/kmol
D
0.73
4520
ð 5000 D 6275 kW
Power D
3600
Say, 6.3 MW
0.4
15
T2 D 288
D 447 K
5
Actual work required D
15
5
⊲1.761⊳/1.76
1
1.1
1.2
1.4
1.6
3
Reduced temperature, Tr = 1.0
2
1.5
2.0
1.8
1.6
Compressibility factor, Z
1.0
0.8
0.70
0.75
0.6
1.4
1.3
0.80
1.0
1.2
0.85
0.90
0.95
0.6
0.9
1.1
0.4
1.2
0.5
1.15
1.1
0.7
1.05
1.0
1.03
0.3
1.0
0.8
1.01
0.8
0.9
0.2
0.7
Reduced temperature, Tr
0
0.1
0.2
0.3
FUNDAMENTALS OF ENERGY BALANCES
15
2.0
3
4
6
8
10
0.4
Low pressure range, Pr
0.10
0.1
0.2
0.3
0.4
0.6
0.8
1.0
2
3
4
6
7 8 9 10
20
25
30
Reduced pressure, Pr
Figure 3.8.
Compressibility factors of gases and vapours
87
0.95
88
2.8
12
T ∂V
( ) −1
V ∂T P
P
Pr =
Pc
X=
2.0
0
Tr = T
Tc
9
1.0
1.6
=0
1.2
T
r
1.
05
X
0
0.9
10
2.4
.85
11
, Tr = 1.0
0
0.
80
0.6
0
0.7
0
0.4
1.0 5
Reduced
temperatu
re
0
1.1
0
6
0
1.1
5
1
.
1 0
1.2
1.30
1.50
2.00
.00
1.6 5
5
0.1
0.2
0.3
0.4
1.5
1.0
4
5
15
1.
1.
1.2
1.1
10
3
0
5
0
1.2
1.30
2
1.50
1.30
1
1.50
2.00
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
5.00
2.2
Reduced pressure, Pr
Figure 3.9.
Generalised compressibility function X
2.4
2.6
2.8
3.0
CHEMICAL ENGINEERING
7
0.8
1.00
Compressibility function, X
8
4
P ∂V
V ∂Pr
Pr =
P
Pc
Tr =
P
Tc
1.6
1.5
00
0.9
0
Y=−
0.9
5
1.7
5
1.
1.4
1.05
1.1
1.0
0
5
2
0.60
0.
70
0.
80
1.2
3
1.0
Compressibility function, Y
T
r
1.3
0.1
0.2
10
1.
5
1.0
0.4
0.5
Pr
1.1
0
ced T r =
Redu
,
rature
e
p
m
te
0.3
1.20
1.30
1.50
2.00
5.00
1
1.30
1.10
1.15
1.20
1.30
1.50
2.00
5.00
0.6
FUNDAMENTALS OF ENERGY BALANCES
=0
.85
Y
1.20
1.15
1.10
1.05
1.00
0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
Reduced pressure, Pr
Generalised compressibility function Y
89
Figure 3.10.
94
CHEMICAL ENGINEERING
TABLE 3.2.
ENERGY 1, a simple energy balance program
10 REM SHORT ENERGY PROGRAM, REWRITTEN IN GWBASIC, MARCH 92
20 PRINT "HEAT BALANCE PROGRAM, BASIS kmol/h, TEMP K, DATUM 298 K"
30 PRINT "INPUT THE NUMBER OF COMPONENTS, MAXIMUM 10"
40 INPUT N1
50 PRINT "INPUT HEAT CAPACITY DATA FOR EQUATION A+BT+CT^2+DT^3"
60 FOR I = 1 TO N1
70 PRINT
80 PRINT "FOR COMPONENT"; I; "INPUT A, B, C, D, INCLUDING ANY ZERO VALUES"
90 INPUT A(I), B(I), C(I), D(I)
100 NEXT I
110 H4=H5=H6=Q1=0
120 PRINT "INPUT THE NUMBER OF FEED STREAMS"
130 INPUT S1
140 FOR I = 1 TO S1
150 PRINT "FOR FEED STREAM"; I; "INPUT STREAM TEMP AND NUMBER OF COMPONENTS"
160 INPUT T1, N2
170 GOSUB 580
180 PRINT "STREAM SENSIBLE HEAT ="; H4; "kJ/h"
190 REM TOTAL SENSIBLE HEAT FEED STREAMS
200 H5 = H5 + H4
210 NEXT I
220 PRINT "INPUT NUMBER OF PRODUCT STREAMS"
230 INPUT S1
240 FOR I = 1 TO S1
250 PRINT "FOR PRODUCT STREAM"; I; "INPUT STREAM TEMP AND NUMBER OF COMPONENTS"
260 INPUT T1, N2
270 GOSUB 580
280 PRINT "STREAM SENSIBLE HEAT ="; H4; "kJ/h"
290 REM TOTAL SENSIBLE HEAT PRODUCT STREAMS
300 H6 = H6 + H4
310 NEXT I
320 PRINT "INPUT THE NUMBER OF REACTIONS AND PHASE CHANGES"
330 INPUT N4
340 IF N4 = 0 THEN 450
350 PRINT "FOR EACH REACTION OR PHASE CHANGE INPUT THE HEAT OF REACTION"
360 PRINT "OR THE LATENT HEAT, kJ/kmol; AND QUANTITY INVOLVED kmol/h"
370 PRINT "REMEMBER: HEAT ENVOLVED:POSITIVE; HEAT ABSORBED:NEGATIVE"
380 FOR I = 1 TO N4
390 PRINT
400 PRINT "NEXT REACTION/PHASE CHANGE: INPUT VALUES"
410 INPUT R, F2
420 H7 = F2*R
430 Q1 = Q1 + H7
440 NEXT I
450 REM HEAT BALANCE
460 Q = H6-H5-Q1
470 IF Q < 0 THEN 500
480 PRINT "HEATING REQUIRED ="; Q; "kJ/h"
490 GOTO 510
500 PRINT "COOLING REQUIRED ="; Q; "kJ/h"
510 PRINT "REPEAT CALCULATION WANTED ? TYPE Y FOR YES, N FOR NO"
520 INPUT P$
530 IF P$ = "N" THEN 560
540 PRINT "REPEAT CALCULATION"
550 GOTO 110
560 PRINT "CALCULATIONS FINISHED"
570 STOP
580 REM SUBROUTINE TO CALCULATE STREAM SENSIBLE HEATS
590 PRINT
600 PRINT "FOR EACH COMPONENT, INPUT THE COMPONENT NUMBER AND FLOW-RATE"
610 H4 = 0
620 FOR I1 = 1 TO N2
630 PRINT "NEXT COMPONENT"
640 INPUT J, F
650 REM HEAT CAPACITY EQUATION SPLIT OVER 2 LINES
660 H1 = A(J)*(T1-298) + B(J)*(T1^2-298^2)/2
670 H2 = C(J)*(T1^3-298^3)/3 + D(J)*(T1^4-298^4)/4
680 H3 = F*(H1+H2)
690 H4 = H4+H3
700 NEXT I1
710 RETURN
90
CHEMICAL ENGINEERING
3.13.3. Multistage compressors
Single-stage compressors can only be used for low pressure ratios. At high pressure ratios,
the temperature rise will be too high for efficient operation.
To cope with the need for high pressure generation, the compression is split into a
number of separate stages, with intercoolers between each stage. The interstage pressures
are normally selected to give equal work in each stage.
For a two-stage compressor the interstage pressure is given by:
Pi D
⊲P1 ð P2 ⊳
⊲3.39⊳
where Pi is the intermediate-stage pressure.
Example 3.12
Estimate the power required to compress 1000 m3 /h air from ambient conditions to
700 kN/m2 gauge, using a two-stage reciprocating compressor with an intercooler.
Solution
Take the inlet pressure, P1 , as 1 atmosphere D 101.33 kN/m2 , absolute.
Outlet pressure, P2 , D 700 C 101.33 D 801.33 kN/m2 , absolute.
For equal work in each stage the intermediate pressure, Pi ,
D
⊲1.0133 ð 105 ð 8.0133 ð 105 ⊳ D 2.8495 ð 105 N/m2
For air, take ratio of the specific heats, , to be 1.4.
For equal work in each stage the total work will be twice that in the first stage.
Take the inlet temperature to be 20 Ž C, At that temperature the specific volume is
given by
v1 D
Work done,
293
29
ð
D 1.39 m3 /kg
22.4 273
1.4
W D 2 ð 1.0133 ð 10 ð 1.39 ð
1.4 1
5
2.8495
1.0133
⊲1.41⊳/1.4
1
D 338,844 J/kg D 339 kJ/kg
From Figure 3.7, for a compression ratio of 2.85 the efficiency is approximately 84%. So
work required
D 339/0.84 D 404 kJ/kg
Mass flow-rate
Power required
1000
D 0.2 kg/s
1.39 ð 3600
D 404 ð 0.2 D 80 kW
D
91
FUNDAMENTALS OF ENERGY BALANCES
Example 3.13
In the high-pressure process for the production of polyethylene, ethylene is compressed in
a two-step process. In the primary step, the gas is compressed in a two-stage compressor to
25 to 30 MPa. This is followed by compression in a hypercompressor to 150 to 320 MPa.
Estimate the work required to compress ethylene to 25 MPa in a two-stage compressor.
A reciprocating compressor will be used. The gas is at an initial temperature of 15Ž C and
is cooled to 25Ž C after the first-stage compression.
Solution
As the calculations will be repetitive, use a spreadsheet.
Tin 288 K Pin 1 bar Pout 250 ba R D 8.1345 J/mol K
Data
Tc 282.4 K Pc 50.4 bar M 28.05 Cp data from Appendix D
First stage
Intermediate pressure P2 D 15.811388 bar
eqn 3.39
Compression ratio D P2 /P1 D 15.814
Tin D 288 use eqn 3.11a
A
B
C
3.806
0.15359
8.35E-05
3.806
44.23392
6.924165
41.535011 kJ/kmol K
Cp for ethylene
Coeff.
Cp
sum, Cp D
D
1.755E-08
0.419256
Cp /⊲Cp R⊳ D 1.2502821
gamma D
From Figure 3.7, extrapolated, Ep D 0.86.
mD
T2 D
0.232768
eqn 3.36a
547.52197
eqn 3.35
Mean temp D ⊲T1 C T2 ⊳/2 D 417.76099
Cp at mean temp of 419.6 K
3.806
0.15359
3.806 64.446364
8.35E-05
14.69784 1.2966068
sum, Cp D 54.851135 kJ/kmol K
new gamma D
1.1786657
revised m D
0.1811049
revised T2 D
474.76117
revised mean temp D 381.38058
little change so leave Tmean at
Tr D Tmean /Tc D
1.755E-08
419.6 K
1.4858357 ⊲1.5⊳
92
CHEMICAL ENGINEERING
Pmean D ⊲P1 Ł P2 ⊳/2 D 0.5
Pr D Pmean /Pc D 0.0099206 ⊲0.17⊳
From Figure 3.2 correction to Cp for pressure is negligible.
From Figures 3.8, 3.9, 3.10
Z D 1.0
XD0
YD0
Essentially ideal at this pressure
mD
0.1762593
eqn 3.36a
nD
1.2139743
eqn 3.38a
W D
303.47285 kJ/kmol
eqn 3.31
Actual work required D polytropic work/efficiency D
Say
352.87541
353 kJ/kmol
Second stage work
As the intermediate pressure was selected to give equal work in each stage the second
stage work could be taken as equal to the first stage work. This will be checked.
Tin D 298 K
compression ratio D
P3 /P2 D
15.822785, i.e. same as first stage
So, take gamma and efficiency as for first stage
mD
0.1811049
T3 D
491.24593 K
Tmean D 394.62296 K
Cp at mean temp
Coeff.
3.806
0.15359
8.35E-05
1.755E-08
Cp
3.806
60.610141
13.00011
1.0785715
sum, Cp D 52.494599 kJ/kmol K
Little change from first stage, so use same gamma and Tmean
Tr D
1.5
Pmean D 20.4 bar
Pr D
0.4047619 (0.4)
From Figure 3.2 correction to Cp for pressure is approximately 2.5 J/mol.
This is less than 5 per cent, so neglect.
From Figures 3.8, 3.9, 3.10
Z D 1.0
X D 0.1 approx.
YD0
So, gas can be taken as ideal
W D 314.01026 slightly higher as Tin is higher
FUNDAMENTALS OF ENERGY BALANCES
Actual work D
93
365.12821 365 kJ/kmol
Total work required first step D 718 kJ/kmol
The spreadsheet used for this example was Microsoft Works. A copy of the solution using
Microsoft Excel can be found on the Butterworth-Heinemann web site: bh.com/companions/0750641428.
3.13.4. Electrical drives
The electrical power required to drive a compressor (or pump) can be calculated from a
knowledge of the motor efficiency:
Power D
W ð mass flow-rate
Ee
⊲3.40⊳
where W D work of compression per unit mass (equation 3.31),
Ee D electric motor efficiency.
The efficiency of the drive motor will depend on the type, speed and size. The values
given in Table 3.1 can be used to make a rough estimate of the power required.
Table 3.1.
Approximate efficiencies
of electric motors
Size(kW)
Efficiency (%)
5
15
75
200
750
>4000
80
85
90
92
95
97
3.14. ENERGY BALANCE CALCULATIONS
Energy balance calculations are best solved using spreadsheets or by writing a short
computer program. A suitable program is listed in Table 3.2 and its use described below.
The use of a spreadsheet is illustrated in Example 3.14b.
Energy 1, a simple computer program
This program can be used to calculate the heat input or cooling required for a process
unit, where the stream enthalpies relative to the datum temperature can be calculated from
the specific heat capacities of the components (equation 3.11).
The datum temperature in the program is 25Ž C (298 K), which is standard for most
heat of reaction data. Specific heats are represented by a cubic equation in temperature:
Cp D A C BT C CT 2 C DT 3
Any unspecified constants are typed in as zero.
If the process involves a reaction, the heat generated or consumed is computed from
the heat of reaction per kmol of product (at 25Ž C) and the kmols of product produced.
95
FUNDAMENTALS OF ENERGY BALANCES
If any component undergoes a phase change in the unit, the heat required is computed
from the latent heat (at 25Ž C) and the quantity involved.
The component specific heat capacity coefficients, A, B, C, D, are stored as a matrix.
If an energy balance is to be made on several units, the specific heat coefficients for all
the components can be entered at the start, and the program rerun for each unit.
The program listing contains sufficient remark statements for the operation of the
program to be easily followed. It is written in GW-BASIC for personal computers. It
can easily be adapted for other forms of BASIC and for use on programmable calculators. The use of the program is illustrated in Example 3.14a. It has also been used for
other examples in this chapter and in the flow-sheeting, Chapter 4.
Example 3.14a
Use of computer program ENERGY 1
A furnace burns a liquid coal tar fuel derived from coke-ovens. Calculate the heat transferred in the furnace if the combustion gases leave at 1500 K. The burners operate with
20 per cent excess air.
Take the fuel supply temperature as 50Ž C (323 K) and the air temperature as 15Ž C
(288 K).
The properties of the fuel are:
Carbon
Hydrogen
Oxygen
Nitrogen
Sulphur
Ash
87.5 per cent w/w
8.0
3.5
1.0
trace
balance
Net calorific value
Latent heat of vaporisation
Heat capacity
39,540 kJ/kg
350 kJ/kg
1.6 kJ/kg K
CŽp of gases, kJ/kmol K,
Component
1
CO2
2
H2 O
3
O2
4
N2
Cp D A C BT C CT2 C DT3
A
19.763
32.190
28.06
31.099
B
7.332E-2
19.207E-4
3.674E-6
1.354E-2
C
5.518E-5
10.538E-6
17.431E-6
26.752E-6
Solution
Material balance
Basis: 100 kg (as analysis is by weight).
Assume complete combustion: maximum heat release.
D
17.125E-9
3.591E-9
10.634E-9
11.662E-9
96
CHEMICAL ENGINEERING
Reactions: C C O2 ! CO2
H2 C 12 O2 ! H2 O
Element
kg
kmol
Stoichiometric O2
kmol
C
H2
O2
N2
87.5
8.0
3.5
1.0
7.29
4.0
0.11
0.04
7.29
2.0
11.44
9.29
Total
kmol, products
7.29, CO2
4.0, H2 O
0.11
0.04
O2 required with 20 per cent excess D 9.29 ð 1.2 D 11.15 kmol.
Unreacted O2 from combustion air D 11.15 9.29 D 1.86 kmol.
79
N2 with combustion air D 11.15 ð
D 41.94 kmol.
21
Composition of combustion gases:
CO2
H2 O
O2 0.11 C 1.86
N2 0.04 C 41.94
D
D
D
D
7.29 kmol
4.0
1.97
41.98
Presentation of data to the program:
Cp of fuel (component 5), taken as constant,
A D 1.6,
BDCDDD0
Heat of reaction and latent heat, taken to be values at datum temperature of 298 K.
There is no need to convert to kJ/kmol, providing quantities are expressed in kg. For
the purposes of this example the dissociation of CO2 and H2 O at 1500 K is ignored.
Computer print-out
Data inputs shown after the symbol (?)
RUN
HEAT BALANCE PROGRAM, BASIS kmol/h, TEMP K, DATUM 298 K
INPUT THE NUMBER OF COMPONENTS, MAXIMUM 10
? 5
INPUT HEAT CAPACITY DATA FOR EQUATION A+BT+CT^2+DT^3
FOR COMPONENT 1 INPUT A, B, C, D, INCLUDING ANY ZERO VALUES
? 19.763, 7.332E-2, -5.518E-5, 1.7125E-8
FOR COMPONENT 2 INPUT A, B, C, D, INCLUDING ANY ZERO VALUES
? 32.19, 1.9207E-3, 1.0538E-5, -3.591E-9
FOR COMPONENT 3 INPUT A, B, C, D, INCLUDING ANY ZERO VALUES
? 28.06, -3.67E-6, 1.74E-5, -1.0634E-8
FOR COMPONENT 4 INPUT A, B, C, D, INCLUDING ANY ZERO VALUES
? 31.099, -1.354E-2, 2.6752E-5, -1.1662E-8
FOR COMPONENT 5 INPUT A, B, C, D, INCLUDING ANY ZERO VALUES
? 1.6, 0 0, 0, 0
FUNDAMENTALS OF ENERGY BALANCES
97
INPUT THE NUMBER OF FEED STREAMS
? 2
FOR FEED STREAM 1 INPUT STREAM TEMP AND NUMBER OF COMPONENTS
? 323, 1
FOR EACH COMPONENT, INPUT THE COMPONENT NUMBER AND FLOW-RATE
NEXT COMPONENT
? 5, 100
STREAM SENSIBLE HEAT = 4000 kJ/h
FOR FEED STREAM 2 INPUT STREAM TEMP AND NUMBER OF COMPONENTS
? 288, 2
FOR EACH COMPONENT, INPUT THE COMPONENT NUMBER AND FLOW-RATE
NEXT COMPONENT
? 3, 11.15
NEXT COMPONENT
? 4, 41.94
STREAM SENSIBLE HEAT = -15,484.61 kJ/h
INPUT NUMBER OF PRODUCT STREAMS
? 1
FOR PRODUCT STREAM 1 INPUT STREAM TEMP AND NUMBER OF COMPONENTS
? 1500, 4
FOR EACH COMPONENT, INPUT THE COMPONENT NUMBER AND FLOW-RATE
NEXT COMPONENT
? 1, 7.29
NEXT COMPONENT
? 2, 4.0
NEXT COMPONENT
? 3, 1.97
NEXT COMPONENT
? 4, 41.98
STREAM SENSIBLE HEAT = 2319620 kJ/h
INPUT THE NUMBER OF REACTIONS AND PHASE CHANGES
? 2
FOR EACH REACTION OR PHASE CHANGE INPUT THE HEAT OF REACTION
OR THE LATENT HEAT, kJ/kmol; AND QUANTITY INVOLVED kmol/h
REMEMBER: HEAT ENVOLVED:POSITIVE; HEAT ABSORBED:NEGATIVE
NEXT REACTION/PHASE CHANGE: INPUT VALUES
? +39540, 100
NEXT REACTION/PHASE CHANGE: INPUT VALUES
? -350, 100
COOLING REQUIRED = -1587896 kJ/h
REPEAT CALCULATION WANTED ? TYPE Y FOR YES, N FOR NO
? N
CALCULATIONS FINISHED
Heat transferred (cooling required) D 1,590,000 kJ/100 kg
Note: though the program reports kJ/h, any consistent set of units can be used. For the
example the basis used was 100 kg.
Use of spreadsheets
A spreadsheet can be used for repetitive calculations as a simpler alternative to writing a
program. The procedure is set out below and illustrated in Example 13.14b.
From equation 13.11 the enthalpy of a stream, due to sensible heat, is given by
HDm
mDn
T2
AT C BT2 /2 C CT3 /3 C DT4 /4
mD1 T1
where H D the stream sensible heat/enthalpy
m D flowrate of the steam component kg/s or kmol/s
n D number of stream components
⊲13.11a⊳
98
CHEMICAL ENGINEERING
Procedure
1. Set up the specific heat coefficients as a matrix.
2. Use equation 3.11a to calculate the enthalpy of each component. Tabulate the results.
Sum the columns to find the total stream sensible enthalpy.
3. Repeat for all the inlet and exit streams.
4. Calculate and add the enthalpy from any reaction or phase change and add to the
stream enthalpies.
5. Subtract the total enthalpy of the outlet streams from the inlet to find the change
in enthalpy.
Example 13.14b
Repeat the calculations for the solution of Example 13.4a using a spreadsheet.
Solution
The spreadsheet used for this example is Microsoft Works. A copy of the example using
Microsoft Excel can be found on the companion web site: http://books.elsevier.com/
companions.
Example 3.14b
Data
Fuel oil
Cp kJ/kg, K
%C D
87.5
%oO2 D
3.5
1.6 CV kJ/kg
%H2 D
8
39540
%N2 D
1
lat. heat kJ/kg
350
Specific heats gases
comp.
A
CO2
H2O
O2
N2
Tin fuel, K
B
19.763
32.19
28.06
31.099
323 Tin
C
D
5.52E-05
1.713E-08
1.054E-05
3.59E-09
1.743E-05
1.06E-08
2.675E-05
1.17E-08
288 Tout, K
0.0733
0.0019207
3.67E-06
0.01354
air, K
1500
Basis 100 kg, as analysis is by weight.
MATERIAL BALANCE
Reactions C C O2 D CO2
element
kg
kmol
C
87.5
7.29
H2
8
4.00
O2
3.5
0.11
N2
1
0.04
Totals
100
11.44
O2 with 20% excess, kmol D
N2 with combustion air, kmol D
H2 C 1/2 O2 D H2O
stoichiometric O2, kmol
7.29
2.00
9.29
11.15
41.95
products, kmol
7.29 CO2
4.00 H2O
0.11
0.04
11.44
unreacted O2, kmol D
1.86
99
FUNDAMENTALS OF ENERGY BALANCES
Composition of combustion gases
CO2
H2O
O2
N2
7.29
4.00
1.97
41.98
ENERGY BALANCE
Take datum temp, To be
298 K
In
mols
Air
O2
N2
mols ð Cp
O2
N2
SUM
Energy kJ
Fuel
A
11.15
41.95
Tin
To
28.06
31.099
312.869
1304.455
1617.324
B
3.67E-06
0.01354
4.1E-05
0.567939
0.567979
C
1.743E-05
2.675E-05
0.0001944
0.0011221
0.0013165
D
1.06E-08
1.17E-08
1.19E-07
4.89E-07
6.08E-07
465789.30
481962.54
23555.25
25219.43
10482.593
11612.883
1045.259
1198.17
mass ð Cp ð ⊲Tin To⊳ D
mas ð cv D
sensible heat
combustion
total
Total energy in
Out
CO2
H2O
O2
N2
3958000
sensible C combustion: 3942513.6 kJ
mols A
B
C
7.29
19.763
0.0733 5.52E-05
4.00
32.19 0.0019207 1.054E-05
1.97
28.06 3.67E-06 1.743E-05
41.98
31.099 0.01354 2.675E-05
mols ð Cp CO2
H2O
O2
N2
SUM
Energy
Tout
To
144.07227
128.76
55.2782
1305.536
1633.6465
2.45EC06
486826.65
latent heat mass ð Lv D
35000
Total out D sensible C latent D
Cooling required D Heat in heat out D
Diff
4000
3954000
total
451671.39
467157.83
15486.44
D
1.713E-08
3.59E-09
1.06E-08
1.17E-08
0.534357 0.000402 1.248E-07
0.0076828 4.215E-05 1.44E-08
7.24E-06 3.434E-05 2.09E-08
0.568409
0.001123
4.9E-07
0.026377
0.0008
4.0E-7
29673.72 896937.56 506303.8 total
1171.175 7032.9451 788.6988
Diff
2811429.8
491899.72
2319530.1
2354530.1
1587983.5 kJ/100 kg fuel
3.15. UNSTEADY STATE ENERGY BALANCES
All the examples of energy balances considered previously have been for steady-state
processes; where the rate of energy generation or consumption did not vary with time and
the accumulation term in the general energy balance equation was taken as zero.
If a batch process is being considered, or if the rate of energy generation or removal
varies with time, it will be necessary to set up a differential energy balance, similar to the
differential material balance considered in Chapter 2. For batch processes the total energy
requirements can usually be estimated by taking as the time basis for the calculation 1
batch; but the maximum rate of heat generation will also have to be estimated to size any
heat-transfer equipment needed.
100
CHEMICAL ENGINEERING
The application of a differential energy balance is illustrated in Example 3.13.
Example 3.15
Differential energy balance
In the batch preparation of an aqueous solution the water is first heated to 80Ž C in a jacketed,
agitated vessel; 1000 Imp. gal. (4545 kg) is heated from 15Ž C. If the jacket area is 300 ft2
(27.9 m2 ) and the overall heat-transfer coefficient can be taken as 50 Btu ft2 h1 Ž F1
(285 W m2 K1 ), estimate the heating time. Steam is supplied at 25 psig (2.7 bar).
Solution
The rate of heat transfer from the jacket to the water will be given by the following
expression (see Volume 1, Chapter 9):
dQ
⊲a⊳
D UA⊲ts t⊳
dt
where dQ is the increment of heat transferred in the time interval dt, and
U D the overall-heat transfer coefficient,
ts D the steam-saturation temperature,
t D the water temperature.
The incremental increase in the water temperature dt is related to the heat transferred
dQ by the energy-balance equation:
dQ D WCp dt
⊲b⊳
where WCp is the heat capacity of the system.
Equating equations (a) and (b)
dt
D UA⊲ts t⊳
dt
tB
WCp t2 dt
dt D
UA t1 ⊲ts t⊳
0
WCp
Integrating
Batch heating time
tB D
WCp ts t2
ln
UA
ts t1
For this example WCp D 4.18 ð 4545 ð 103 JK1
UA D 285 ð 27 WK1
t1 D 15Ž C, t2 D 80Ž C, ts D 130Ž C
4.18 ð 4545 ð 103 130 80
ln
tB D
285 ð 27.9
130 15
D 1990s D 33.2 min
In this example the heat capacity of the vessel and the heat losses have been neglected
for simplicity. They would increase the heating time by 10 to 20 per cent.
FUNDAMENTALS OF ENERGY BALANCES
101
3.16. ENERGY RECOVERY
Process streams at high pressure or temperature, and those containing combustible
material, contain energy that can be usefully recovered. Whether it is economic to recover
the energy content of a particular stream will depend on the value of the energy that can
be usefully extracted and the cost of recovery. The value of the energy will depend on
the primary cost of energy at the site. It may be worth while recovering energy from a
process stream at a site where energy costs are high but not where the primary energy
costs are low. The cost of recovery will be the capital and operating cost of any additional
equipment required. If the savings exceed the operating cost, including capital charges,
then the energy recovery will usually be worthwhile. Maintenance costs should be included
in the operating cost (see Chapter 6).
Some processes, such as air separation, depend on efficient energy recovery for
economic operation, and in all processes the efficient utilisation of energy recovery
techniques will reduce product cost.
Some of the techniques used for energy recovery in chemical process plants are
described briefly in the following sections. The references cited give fuller details of
each technique. Miller (1968) gives a comprehensive review of process energy systems;
including heat exchange, and power recover from high-pressure fluid streams.
Kenney (1984) reviews the application of thermodynamic principles to energy recovery
in the process industries.
3.16.1. Heat exchange
The most common energy-recovery technique is to utilise the heat in a high-temperature
process stream to heat a colder stream: saving steam costs; and also cooling water, if
the hot stream requires cooling. Conventional shell and tube exchangers are normally
used. More total heat-transfer area will be needed, over that for steam heating and water
cooling, as the overall driving forces will be smaller.
The cost of recovery will be reduced if the streams are located conveniently close.
The amount of energy that can be recovered will depend on the temperature, flow,
heat capacity, and temperature change possible, in each stream. A reasonable temperature driving force must be maintained to keep the exchanger area to a practical size.
The most efficient exchanger will be the one in which the shell and tube flows are
truly countercurrent. Multiple tube pass exchangers are usually used for practical reasons.
With multiple tube passes the flow will be part counter-current and part co-current and
temperature crosses can occur, which will reduce the efficiency of heat recovery (see
Chapter 12).
The hot process streams leaving a reactor or a distillation column are frequently used
to preheat the feedstreams.
3.16.2. Heat-exchanger networks
In an industrial process there will be many hot and cold streams and there will be
an optimum arrangement of the streams for energy recovery by heat exchange. The
problem of synthesising a network of heat exchangers has been studied by many workers,
102
CHEMICAL ENGINEERING
Sh1
Sh2
Sh3
Sh4
Sh5
Sh6
E1
E2
E3
E4
E5
E6
E6
E7
SC1
E8
Su 2
Su1
Su 1
Sh 1
Sh 2
Sh 3
Sh 4
Sh 5
Sh 6
Sc 1
and Su 2
Figure 3.11.
D
D
D
D
D
D
D
D
residue (360° C)
reflux stream (260° C)
heavy gas oil (340° C)
light gas oil (260° C)
reflux steam (180° C)
reflux stream (165° C)
crude oil (15° C)
cooling water (50° C)
Typical heat-exchanger network
particularly in respect of optimising heat recovery in crude petroleum distillation. An
example of crude preheat train is shown in Figure 3.11. The general problem of the
synthesis and optimisation of a network of heat exchangers has been defined by Masso
and Rudd (1969).
Consider that there are M hot streams, Shi ⊲i D 1, 2, 3, . . . , M⊳ to be cooled and N cold
streams Scj ⊲j D 1, 2, 3, . . . , N⊳ to be heated; each stream having an inlet temperature tf ,
or an outlet temperature t0 , and a stream heat capacity Wi . There may also be Suk ⊲k D
1, 2, 3, . . . , L⊳ auxiliary steam heated or water-cooled exchangers.
The problem is to create a minimum cost network of exchangers, that will also meet the
design specifications on the required outlet temperature t0 of each stream. If the strictly
mathematical approach is taken of setting up all possible arrangements and searching for
the optimum, the problem, even for a small number of exchangers, would require an
inordinate amount of computer time. Boland and Linnhoff (1979) point out that for a
process with four cold and three hot streams, 2.4 ð 1018 arrangements are possible. Most
workers have taken a more pragmatic, “heuristic”, approach to the problem, using “rules
of thumb” to generate a limited number of feasible networks, which are then evaluated.
Porton and Donaldson (1974) suggest a simple procedure that involves the repeated
matching of the hottest stream (highest tf ) against the cold stream with the highest
required outlet temperature (highest t0 ).
A general survey of computer and manual methods for optimising exchanger networks
is given by Nishida et al. (1977); see also Siirola (1974).
The design of heat exchanger networks is covered in more detail is Section 3.17.
3.16.3. Waste-heat boilers
If the process streams are at a sufficiently high temperature the heat recovered can be
used to generate steam.
FUNDAMENTALS OF ENERGY BALANCES
103
Waste-heat boilers are often used to recover heat from furnace flue gases and the process
gas streams from high-temperature reactors. The pressure, and superheat temperature, of
the stream generated will depend on the temperature of the hot stream and the approach
temperature permissible at the boiler exit (see Chapter 12). As with any heat-transfer
equipment, the area required will increase as the mean temperature driving force (log
mean T) is reduced. The permissible exit temperature may also be limited by process
considerations. If the gas stream contains water vapour and soluble corrosive gases, such
as HCl or SO2 , the exit gases temperature must be kept above the dew point.
Hinchley (1975) discusses the design and operation of waste heat boilers for chemical
plant. Both fire tube and water tube boilers are used. A typical arrangement of a water tube
boiler on a reformer furnace is shown in Figure 3.12 and a fire tube boiler in Figure 3.13.
The application of a waste-heat boiler to recover energy from the reactor exit streams in
a nitric acid plant is shown in Figure 3.14.
Water in
Gas outlet
Steam / Water out
Metal shroud
Refractory
lining
Gas inlet
Figure 3.12. Reformed gas waste-heat boiler arrangement of vertical U-tube water-tube boiler (Reprinted by
permission of the Council of the Institution of Mechanical Engineers from the Proceedings of the Conference
on Energy Recovery in the Process Industries, London, 1975.)
The selection and operation of waste heat boilers for industrial furnaces is discussed
in the Efficient Use of Energy, Dryden (1975).
3.16.4. High-temperature reactors
If a reaction is highly exothermic, cooling will be needed and, if the reactor temperature is high enough, the heat removed can be used to generate steam. The lowest steam
pressure normally used in the process industries is 2.7 bar (25 psig) and steam is normally
104
CHEMICAL ENGINEERING
Ferrule wrapped with
insulating fibre
Process gas
outlet 550°C
Steam / Water
riser pipes
Alloy 800 ferrule
Concrete
Alloy 800
production plate
External insulation
Water downcomer pipes
Process gas
1200 / 1000°C
Blowdown connection
Refractory concrete
Insulating concrete
Figure 3.13. Reformed gas waste-heat boiler, principal features of typical natural circulation fire-tube boilers
(Reprinted by permission of the Council of the Institution of Mechanical Engineers from the Proceedings of
the Conference on Energy Recovery in the Process Industries, London, 1975.)
Air
To stack
From absorption
tower no. 5
1
Secondary Air
Air from
bleacher
4
;
3
Ammonia
13
9
....
....
8
14
11
....
....
15
16
10
2
;
5
Stream
7
12
17
To oxidation
tower
;;
;
6
202 HNO3
10.
11.
12.
13.
14.
15.
16.
17.
Water
Water
1.
2.
3.
4.
5.
Air entry
Ammonia vaporiser
Ammonia filter
Control valves
Air-scrubbing tower
6.
7.
8.
9.
Air preheater
Gas mixer
Gas filters
Converters
12 HNO3
Lamont boilers
Steam drum
Gas cooler No. 1
Exhaust turbine
To absorption
Compressor
Steam turbine
Heat exchanger
Gas cooler No. 2
(From Nitric Acid Manufacture, Miles (1961), with permission)
Figure 3.14.
Connections of a nitric acid plant, intermediate pressure type
distributed at a header pressure of around 8 bar (100 psig); so any reactor with a temperature above 200Ž C is a potential steam generator.
Three systems are used:
1. Figure 3.15a. An arrangement similar to a conventional water-tube boiler. Steam is
generated in cooling pipes within the reactor and separated in a steam drum.
105
FUNDAMENTALS OF ENERGY BALANCES
2. Figure 3.15b. Similar to the first arrangement but with the water kept at high pressure
to prevent vaporisation. The high-pressure water is flashed to steam at lower pressure
in a flash drum. This system would give more responsive control of the reactor
temperature.
3. Figure 3.15c. In this system a heat-transfer fluid, such as Dowtherm (see Perry and
Green (1984) and Singh (1985) for details of heat-transfer fluids), is used to avoid
the need for high-pressure tubes. The steam is raised in an external boiler.
Steam
Steam
Flash drum
Steam drum
Feed pump
Reactor
Reactor
(a)
(b)
Steam
Boiler
Feed
water
Reactor
(c)
Figure 3.15.
Steam generation
3.16.5. Low-grade fuels
The waste products from any process (gases, liquids and solids) which contain significant
quantities of combustible material can be used as low-grade fuels; for raising steam or
direct process heating. Their use will only be economic if the intrinsic value of the fuel
justifies the cost of special burners and other equipment needed to burn the waste. If the
combustible content of the waste is too low to support combustion, the waste will have
to be supplemented with higher calorific value primary fuels.
Reactor off-gases
The off-gases (vent gas) from reactors, and recycle stream purges are often of high enough
calorific value to be used as fuels.
The calorific value of a gas can be calculated from the heats of combustion of its
constituents; the method is illustrated in Example 3.14.
Other factors which, together with the calorific value, will determine the economic
value of an off-gas as a fuel are the quantity available and the continuity of supply.
Waste gases are best used for steam raising, rather than for direct process heating, as this
decouples the source from the use and gives greater flexibility.
106
CHEMICAL ENGINEERING
Example 3.16
Calculation of a waste-gas calorific value
The typical vent-gas analysis from the recycle stream in an oxyhydrochlorination process
for the production of dichloroethane (DCE) (British patent BP 1,524,449) is given below,
percentages on volume basis.
O2 7.96, CO2 C N2 87.6, CO 1.79, C2 H4 1.99, C2 H6 0.1, DCE 0.54
Estimate the vent gas calorific value.
Solution
Component calorific values, from Perry and Chilton (1973)
CO 67.6 kcal/mol D 283 kJ/mol
C2 H4 372.8
D 1560.9
C2 H6 337.2
D 1411.9
The value for DCE can be estimated from the heats of formation.
Combustion reaction:
C2 H4 Cl2 (g) C 2 21 O2 (g) ! 2CO2 (g) C H2 O(g) C 2HCl(g)
HŽf from Appendix D
CO2
H2 O
HCl
DCE
HŽc
D
D
D
D
D
D
D
393.8 kJ/mol
242.0
92.4
130.0
HŽf products HŽf reactants
[2⊲393.8⊳ 242.0 C 2⊲92.4⊳] [130.0]
1084.4 kJ
Estimation of vent gas c.v., basis 100 mols.
Component
CO
C 2 H4
C 2 H6
DCE
mols/100 mols
Calorific value
(kJ/mol)
ð
1.79
1.99
0.1
0.54
283.0
1560.9
1411.9
1084.4
Heating value
D
506.6
3106.2
141.2
585.7
Total
4339.7
4339.7
D 43.4 kJ/mol
100
43.4
D
ð 103 D 1938 kJ/m3 ⊲52 Btu/ft3 ⊳ at 1 bar, 0Ž C
22.4
Calorific value of vent gas D
107
FUNDAMENTALS OF ENERGY BALANCES
Barely worth recovery, but if the gas has to be burnt to avoid pollution it could be used
in an incinerator such as that shown in Figure 3.16, giving a useful steam production to
offset the cost of disposal.
Formaldehyde off-gas
Oxychlorination
vent fume
;
NaOH
soln.
Steam
VCM waste fume
Feed water
Liquid
chlorinated H.C.
Mono-chem.
fume
Nat. gas
1090°C
min.
Fume
incinerator
Combustion
air
Figure 3.16.
Waste heat
boiler
88°C
85°C
H 2O
316°C
Primary
scrubber
HCL
soln.
Secondary
scrubber
Typical incinerator-heat recovery-scrubber system for vinyl-chloride-monomer process waste
(Courtesy of John Thurley Ltd.)
Liquid and solid wastes
Combustible liquid and solid waste can be disposed of by burning, which is usually
preferred to dumping. Incorporating a steam boiler in the incinerator design will enable
an otherwise unproductive, but necessary operation, to save energy. If the combustion
products are corrosive, corrosion-resistant materials will be needed, and the flue gases
scrubbed to reduce air pollution. An incinerator designed to handle chlorinated and
other liquid and solid wastes is shown in Figure 3.16. This incinerator incorporates a
steam boiler and a flue-gas scrubber. The disposal of chlorinated wastes is discussed by
Santoleri (1973).
Dunn and Tomkins (1975) discuss the design and operation of incinerators for process
wastes. They give particular attention to the need to comply with the current clean-air
legislation, and the problem of corrosion and erosion of refractories and heat-exchange
surfaces.
3.16.6. High-pressure process streams
Where high-pressure gas or liquid process streams are throttled to lower pressures, energy
can be recovered by carrying out the expansion in a suitable turbine.
Gas streams
The economic operation of processes which involve the compression and expansion
of large quantities of gases, such as ammonia synthesis, nitric acid production and air
108
CHEMICAL ENGINEERING
separation, depends on the efficient recovery of the energy of compression. The energy
recovered by expansion is often used to drive the compressors directly; as shown in
Figure 3.14. If the gas contains condensible components it may be advisable to consider
heating the gas by heat exchange with a higher temperature process stream before
expansion. The gas can then be expanded to a lower pressure without condensation and
the power generated increased.
An interesting process incorporating an expansion turbine is described by Barlow (1975)
who discusses energy recovery in an organic acids plant (acetic and propionic). In this
process a thirteen-stage turbo-expander is used to recover energy from the off-gases. The
pressure range is deliberately chosen to reduce the off-gases to a low temperature at the
expander outlet (60Ž C), for use for low-temperature cooling, saving refrigeration.
The energy recoverable from the expansion of a gas can be estimated by assuming
polytropic expansion; see Section 3.13.2 and Example 3.17.
The design of turboexpanders for the process industries is discussed by Bloch et al.
(1982).
Example 3.17
Consider the extraction of energy from the tail gases from a nitric acid adsorption tower,
such as that described in Chapter 4, Example 4.4.
Gas composition, kmol/h:
O2
N2
NO
NO2
H2 O
371.5
10,014.7
21.9
Trace
saturated at 250Ž C
If the gases leave the tower at 6 atm, 25Ž C, and are expanded to, say, 1.5 atm, calculate
the turbine exit gas temperatures without preheat, and if the gases are preheated to
400Ž C with the reactor off-gas. Also, estimate the power recovered from the preheated
gases.
Solution
For the purposes of this calculation it will be sufficient to consider the tail gas as all
nitrogen, flow 10,410 kmol/h.
Pc D 33.5 atm,
Tc D 126.2 K
Figure 3.6 can be used to estimate the turbine efficiency.
Exit gas volumetric flow-rate D
10,410
1
ð 22.4 ð
3600
1.5
' 43 m3 /s
FUNDAMENTALS OF ENERGY BALANCES
109
from Figure 3.6 EP D 0.75
6
D 0.18
33.5
298
Tr inlet D
D 2.4
126.2
Pr inlet D
For these values the simplified equations can be used, equations 3.37a and 3.38a.
For N2 D 1.4
1.4 1
ð 0.75 D 0.21
1.4
1
1
nD
D
D 1.27
1m
1 0.21
1.5 0.21
D 223 K
without preheat T2 D 298
6.0
mD
D 50Ž C (acidic water would condense out)
with preheat T2 D 673
1.5
6.0
0.21
D 503 K
D 230Ž C
From equation 3.31, work done by gases as a result of polytropic expansion
1.27
1.5 ⊲1.271⊳/1.27
1
D 1 ð 673 ð 8.314 ð
1.27 1
6.0
D 6718 kJ/kmol
Actual work D polytropic work ð Ep
D 6718 ð 0.75 D 5039 kJ/kmol
Power output D work/kmol ð kmol/s D 5039 ð
10,410
3600
D 14,571 kJ/s D 14.6 MW
Liquid streams
As liquids are essentially incompressible, less energy is stored in a compressed liquid than
a gas. However, it is worth considering power recovery from high-pressure liquid streams
(>15 bar) as the equipment required is relatively simple and inexpensive. Centrifugal
pumps are used as expanders and are often coupled directly to pumps. The design,
operation and cost of energy recovery from high-pressure liquid streams is discussed
by Jenett (1968), Chada (1984) and Buse (1985).
110
CHEMICAL ENGINEERING
3.16.7. Heat pumps
A heat pump is a device for raising low grade heat to a temperature at which the heat can
be utilised. It pumps the heat from a low temperature source to the higher temperature
sink, using a small amount of energy relative to the heat energy recovered.
Heat pumps are increasingly finding applications in the process industries. A typical
application is the use of the low grade heat from the condenser of a distillation column
to provide heat for the reboiler; see Barnwell and Morris (1982) and Meili (1990). Heat
pumps are also used with dryers, heat being abstracted from the exhaust air and used
to preheat the incoming air. The use of a heat pump with an evaporator is described in
Volume 2, Chapter 14.
Details of the thermodynamic cycles used for heat pumps can be found in most
textbooks on Engineering Thermodynamics, and in Reay and MacMichael (1988). In
the process industries heat pumps operating on the mechanical vapour compression cycle
would normally be used. A vapour compression heat pump applied to a distillation column
is shown in Figure 3.17a. The working fluid, usually a commercial refrigerant, is fed to
the reboiler as a vapour at high pressure and condenses, giving up heat to vaporise the
process fluid. The liquid refrigerant from the reboiler is then expanded over a throttle
valve and the resulting wet vapour fed to the column condenser. In the condenser the
wet refrigerant is dried, taking heat from the condensing process vapour. The refrigerant
vapour is then compressed and recycled to the reboiler, completing the working cycle.
If the conditions are suitable the process fluid can be used as the working fluid for the
heat pump. This arrangement is shown in Figure 3.17b. The hot process liquid at high
Feed
Vapour
Compressor
Expansion
valve
Condenser
Low
press
High
press
Reboiler
Liquid
(a)
Figure 3.17.
(b)
Distillation column with heat pump (a) Separate refrigerant circuit (b) Using column fluid as the
refrigerant
FUNDAMENTALS OF ENERGY BALANCES
111
pressure is expanded over the throttle value and fed to the condenser, to provide cooling
to condense the vapour from the column. The vapour from the condenser is compressed
and returned to the base of the column. In an alternative arrangement, the process vapour
is taken from the top of the column, compressed and fed to the reboiler to provide heating.
The “efficiency” of a heat pump is measured by the coefficient of performance, COP:
COP D
energy delivered at higher temperature
energy input compressor
The COP will depend principally on the working temperatures.
The economics of the application of heat pumps in the process industries is discussed
by Holland and Devotta (1986). Details of the application of heat pumps in a wide range
of industries are given by Moser and Schnitzer (1985).
3.17. PROCESS INTEGRATION AND PINCH TECHNOLOGY
Process integration can lead to a substantial reduction in the energy requirements of a
process. In recent years much work has been done on developing methods for investigating
energy integration and the efficient design of heat exchanger networks; see Gundersen
and Naess (1988). One of the most successful and generally useful techniques is that
developed by Bodo Linnhoff and other workers: pinch technology. The term derives from
the fact that in a plot of the system temperatures versus the heat transferred, a pinch
usually occurs between the hot stream and cold stream curves, see Figure 3.22. It has
been shown that the pinch represents a distinct thermodynamic break in the system and
that, for minimum energy requirements, heat should not be transferred across the pinch,
Linnhoff and Townsend (1982).
In this section the fundamental principles of the pinch technology method for energy
integration will be outlined and illustrated with reference to a simple problem. The method
and its applications are described fully in a guide published by the Institution of Chemical
Engineers, IChemE (1994); see also Douglas (1988).
3.17.1. Pinch technology
The development and application of the method can be illustrated by considering the
problem of integrating the utilisation of energy between 4 process streams. Two hot
streams which require cooling, and two cold streams that have to be heated. The process
data for the streams is set out in Table 3.3. Each stream starts from a source temperature
Ts , and is to be heated or cooled to a target temperature Tt . The heat capacity of each
stream is shown as CP. For streams where the specific heat capacity can be taken as
constant, and there is no phase change, CP will be given by:
CP D mCp
where m D mass flow-rate, kg/s
Cp D average specific heat capacity between Ts and Tt kJ kg1Ž C1
112
CHEMICAL ENGINEERING
Table 3.3.
Data for heat integration problem
Stream
number
Heat capacity
CP, kW/° C
°C
Tt
Type
°C
Heat load
kW
1
2
3
4
hot
hot
cold
cold
3.0
1.0
2.0
4.5
180
150
20
80
60
30
135
140
360
120
230
270
Ts
The heat load shown in the table is the total heat required to heat, or cool, the stream
from the source to target temperature.
The four streams are shown diagrammatically below, Figure 3.18:
There is clearly scope for energy integration between these four streams. Two require
heating and two cooling; and the stream temperatures are such that heat can be transferred
from the hot to the cold streams. The task is to find the best arrangement of heat exchangers
to achieve the target temperatures.
CP = 3.0 kW/°C
Stream 1 180°C
Stream 2 150°C
Stream 3 20°C
1.0
2.0
4.5
Stream 4 80°C
Figure 3.18.
60°C
30°C
135°C
140°C
Diagrammatic representation of process streams
Simple two-stream problem
Before investigating the energy integration of the four streams shown in Table 3.3, the
use of a temperature-enthalpy diagram will be illustrated for a simple problem involving
only two streams. The general problem of heating and cooling two streams from source to
target temperatures is shown in Figure 3.19. Some heat is exchanged between the streams
in the heat exchanger. Additional heat, to raise the cold stream to the target temperature,
is provided by the hot utility (usually steam) in the heater; and additional cooling to bring
the hot stream to its target temperature, by the cold utility (usually cooling water) in the
cooler.
Cold
utility
Tt
Ts
Hot
stream
Tt
Hot
utility
Figure 3.19.
Exchanger
Ts
Two-stream exchanger problem
Cold
stream
113
FUNDAMENTALS OF ENERGY BALANCES
In Figure 3.20 the stream temperatures are plotted on the y-axis and the enthalpy change
in each stream on the x-axis. For heat to be exchanged a minimum temperature difference
must be maintained between the two streams. This is shown as Tmin on the diagram. The
practical minimum temperature difference in a heat exchanger will usually be between
10 and 20Ž C; see Chapter 12.
∆Hhot
∆Hhot
Temperature
Cold stream
Hot
stream
∆Tmin
∆Tmin
∆Hex
∆Hcold
∆Hex
∆Hcold
Enthalpy
Enthalpy
(a)
(b)
Figure 3.20.
Temperature-enthalpy for 2-stream example
The heat transferred between the streams is shown on the diagram as Hex , and the
heat transferred from the utilities as Hcold and Hhot :
H D CP ð ⊲temperature change⊳
It can be seen by comparing Figure 3.20a and b that the amount of heating and cooling
needed will depend on the minimum temperature difference. Decreasing Tmin will
increase the amount of heat exchanged between the two streams and so decrease the
consumption of the hot and cold utilities.
Four stream problem
In Figure 3.21a the hot streams given in Table 3.3 are shown plotted on a temperatureenthalpy diagram.
As the diagram shows changes in the enthalpy of the streams, it does not matter where
a particular curve is plotted on the enthalpy axis; as long as the curve runs between
the correct temperatures. This means that where more than one stream appears in a
temperature interval, the stream heat capacities can be added to give the composite curve
shown in Figure 3.21b.
In Figure 3.22, the composite curve for the hot streams and the composite curve for
cold streams are drawn with a minimum temperature difference, the displacement between
the curves, of 10Ž C. This implies that in any of the exchangers to be used in the network
the temperature difference between the streams will not be less than 10Ž C.
114
CHEMICAL ENGINEERING
200
140
120
Stre
am
2
Temperature, °C
180
160
100
80
60
40
am
Streams 1
CP = 3.0
1
re
St
Streams 1 + 2
CP = 3.0 + 1.0 = 4.0
Stream 2 CP = 1.0 kW/°C
20
0
0
100
200
300
400
500
600 0
100
200
Enthalpy, kW
400
500
600
Enthalpy, kW
(a)
Figure 3.21.
300
(b)
Hot stream temperature v. enthalpy (a) Separate hot streams (b) Composite hot streams
Hot utility
50 kW
200
180
Temperature, °C
160
ms
ea
140
tr
ts
Ho
120
100
d
Col
Pinch
80
s
am
stre
∆Tmin = 10°C
60
40
30 kW
Cold utility
20
0
0
100
200
300
400
500
600
Enthalpy, kW
Figure 3.22.
Hot and cold stream composite curves
As for the two-stream problem, the displacement of the curves at the top and bottom
of the diagram gives the hot and cold utility requirements. These will be the minimum
values needed to satisfy the target temperatures. This is valuable information. It gives the
designer target values for the utilities to aim for when designing the exchanger network.
Any design can be compared with the minimum utility requirements to check if further
improvement is possible.
In most exchanger networks the minimum temperature difference will occur at only
one point. This is termed the pinch. In the problem being considered, the pinch occurs at
between 90Ž C on the hot stream curve and 80Ž C on the cold stream curve.
115
FUNDAMENTALS OF ENERGY BALANCES
Significance of the pinch
The pinch divides the system into two distinct thermodynamic regions. The region above
the pinch can be considered a heat sink, with heat flowing into it, from the hot utility,
but not out of it. Below the pinch the converse is true. Heat flows out of the region to
the cold utility. No heat flows across the pinch.
If a network is designed that requires heat to flow across the pinch, then the consumption
of the hot and cold utilities will be greater than the minimum values that could be achieved.
3.17.2. The problem table method
The problem table is the name given by Linnhoff and Flower to a numerical method for
determining the pinch temperatures and the minimum utility requirements; Linnhoff and
Flower (1978). Once understood, it is the preferred method, avoiding the need to draw the
composite curves and manoeuvre the composite cooling curve using, for example, tracing
paper or cut-outs, to give the chosen minimum temperature difference on the diagram.
The procedure is as follows:
1. Convert the actual stream temperatures Tact into interval temperatures Tint by
subtracting half the minimum temperature difference from the hot stream temperatures,
and by adding half to the cold stream temperatures:
Tmin
2
Tmin
D Tact C
2
hot streams Tint D Tact
cold streams Tint
The use of the interval temperature rather than the actual temperatures allows the
minimum temperature difference to be taken into account. Tmin D 10Ž C for the problem
being considered; see Table 3.4.
Table 3.4.
Stream
1
2
3
4
Interval temperatures for Tmin D 10° C
Actual temperature
Interval temperature
180
150
20
80
175
145
(25)
85
60
30
135
140
55
25
140
(145)
2. Note any duplicated interval temperatures. These are bracketed in Table 3.4.
3. Rank the interval temperatures in order of magnitude, showing the duplicated temperatures only once in the order; see Table 3.5.
4. Carry out a heat balance for the streams falling within each temperature interval:
For the nth interval:
Hn D ⊲CPc CPh ⊳ ⊲Tn ⊳
where Hn
CPc
CPh
Tn
D
D
D
D
net heat required in the nth interval
sum of the heat capacities of all the cold streams in the interval
sum of the heat capacities of all the hot streams in the interval
interval temperature difference D ⊲Tn1 Tn ⊳
116
CHEMICAL ENGINEERING
See Table 3.6.
Table 3.5.
Ranked order of interval temperatures
Rank
Interval
Tn ° C
Streams in
interval
175° C
145
140
85
55
25
30
5
55
30
30
1
4 ⊲2 C 1⊳
⊲3 C 4⊳ ⊲1 C 2⊳
3 ⊲1 C 2⊳
32
Note: Duplicated temperatures are omitted. The interval
T and streams in the intervals are included as they are
needed for Table 3.6.
Table 3.6.
Problem table
Interval
Interval
temp. ° C
Tn
°C
CPc CPh Ł
kW/° C
H
kW
Surplus or
Deficit
1
2
3
4
5
175
145
140
85
55
25
30
5
55
30
30
3.0
0.5
2.5
2.0
1.0
90
2.5
137.5
60
30
s
d
d
s
d
Ł Note:
The streams in each interval are given in Table 3.5.
5. “Cascade” the heat surplus from one interval to the next down the column of interval
temperatures; Figure 3.23a.
Cascading the heat from one interval to the next implies that the temperature difference
is such that the heat can be transferred between the hot and cold streams. The presence
Interval
temp.
0 kW
50 kW
175° C
145° C
90 kW
90 kW
2.5 kW
140° C
87.5 kW
85° C
60 kW
135.5 kW
137.5 kW
50 kW
10 kW
30 kW
25° C
140 kW
2.5 kW
137.5 kW
55° C
90 kW
0.0 kW
60 kW
60 kW
30 kW
20 kW
(a)
30 kW
(b)
From (b) pinch occurs at interval temperature D 85° C.
Figure 3.23.
Heat cascade
FUNDAMENTALS OF ENERGY BALANCES
117
of a negative value in the column indicates that the temperature gradient is in the wrong
direction and that the exchange is not thermodynamically possible.
This difficulty can be overcome if heat is introduced into the top of the cascade:
6. Introduce just enough heat to the top of the cascade to eliminate all the negative
values; see Figure 3.23b.
Comparing the composite curve, Figure 3.22, with Figure 3.23b shows that the heat
introduced to the cascade is the minimum hot utility requirement and the heat removed at
the bottom is the minimum cold utility required. The pinch occurs in Figure 3.23b where
the heat flow in the cascade is zero. This is as would be expected from the rule that for
minimum utility requirements no heat flows across the pinch. In Figure 3.23b the pinch
temperatures are 80 and 90Ž C, as was found using the composite stream curves.
It is not necessary to draw up a separate cascade diagram. This was done in Figure 3.23
to illustrate the principle. The cascaded values can be added to the problem table as two
additional columns; see example 3.16.
Summary
For maximum heat recovery and minimum use of utilities:
1. Do not transfer heat across the pinch
2. Do not use hot utilities below the pinch
3. Do not use cold utilities above the pinch
3.17.3. The heat exchanger network
Grid representation
It is convenient to represent a heat exchanger network as a grid; see Figure 3.24. The
process streams are drawn as horizontal lines, with the stream numbers shown in square
boxes. Hot streams are drawn at the top of the grid, and flow from left to right. The cold
streams are drawn at the bottom, and flow from right to left. The stream heat capacities
CP are shown in a column at the end of the stream lines.
Cooler
Hot stream
no. n
A
n
A
m
Exchanger
Figure 3.24.
Cold stream
no. m
Grid representation
Heat exchangers are drawn as two circles connected by a vertical line. The circles
connect the two streams between which heat is being exchanged; that is, the streams that
would flow through the actual exchanger. Heater and coolers are drawn as a single circle,
connected to the appropriate utility.
118
CHEMICAL ENGINEERING
Network design for maximum energy recovery
The analysis carried out in Figure 3.22, and Figure 3.23, has shown that the minimum
utility requirements for the problem set out in Table 3.3 are 50 kW of the hot and 30 kW
of the cold utility; and that the pinch occurs where the cold streams are at 80 and the
hot 90Ž C.
The grid representation of the streams is shown in Figure 3.25. The vertical dotted lines
represent the pinch and separate the grid into the regions above and below the pinch.
CP
(kW/°C)
90°C 80°C
60°C
180°C
3.0
1
30°C
150°C
1.0
2
135°C
20°C
3
140°C
2.0
80°C
4
Figure 3.25.
4.5
Grid for 4 stream problem
For maximum energy recovery (minimum utility consumption) the best performance is
obtained if no cooling is used above the pinch. This means that the hot streams above
the pinch should be brought to the pinch temperature solely by exchange with the cold
streams. The network design is therefore started at the pinch; finding feasible matches
between streams to fulfil this aim. In making a match adjacent to the pinch the heat
capacity CP of the hot stream should be equal to or less than that of the cold stream. This
is to ensure that the minimum temperature difference between the curves is maintained.
The slope of a line on the temperature-enthalpy diagram is equal to the reciprocal of the
heat capacity. So, above the pinch the lines will converge if CPhot exceeds CPcold and as
the streams start with a separation at the pinch equal to Tmin , the minimum temperature
condition would be violated.
Below the pinch the procedure is the same; the aim being to bring the cold streams
to the pinch temperature by exchange with the hot streams. For streams adjacent to the
pinch the criterion for matching streams is that the heat capacity of the cold stream must
be equal to or greater than the hot stream, to avoid breaking the minimum temperature
difference condition.
The network design above the pinch
CPhot CPcold
1. Applying this condition at the pinch, stream 1 can be matched with stream 4, but
not with 3.
119
FUNDAMENTALS OF ENERGY BALANCES
Matching streams 1 and 4 and transferring the full amount of heat required to bring
stream 1 to the pinch temperature gives:
Hex D CP⊲Ts Tpinch ⊳
Hex D 3.0⊲180 90⊳ D 270 kW
This will also satisfy the heat load required to bring stream 4 to its target temperature:
Hex D 4.5⊲140 80⊳ D 270 kW
2. Stream 2 can be matched with stream 3, whilst satisfying the heat capacity restriction.
Transferring the full amount to bring stream 3 to the pinch temperature:
Hex D 1.0⊲150 90⊳ D 60 kW
3. The heat required to bring stream 3 to its target temperature, from the pinch temperature, is:
H D 2.0⊲135 80⊳ D 110 kW
So a heater will have to be included to provide the remaining heat load:
Hhot D 110 60 D 50 kW
This checks with the value given by the problem table, Figure 3.23b.
The proposed network design above the pinch is shown in Figure 3.26.
CP
kW/°C
90°C 80°C
180°C
60°C
3.0
1
30°C
150°C
1.0
2
20°C
135°C
2.0
3
140°C 50 kW
60 kW
80°C
4.5
4
270 kW Pinch
Figure 3.26.
Network design above pinch
Network design below the pinch
CPhot ½ CPcold
4. Stream 4 is at the pinch temperature, Ts D 80Ž C.
5. A match between stream 1 and 3 adjacent to the pinch will satisfy the heat capacity
restriction but not one between streams 2 and 3. So 1 is matched with 3 transferring the
full amount to bring stream 1 to its target temperature; transferring:
Hex D 3.0⊲90 60⊳ D 90 kW
120
CHEMICAL ENGINEERING
6. Stream 3 requires more heat to bring it to the pinch temperature; amount needed:
H D 2.0⊲80 20⊳ 90 D 30 kW
This can be provided from stream 2, as the match will now be away from the pinch.
The rise in temperature of stream 3 will be given by:
T D H/CP
So transferring 30 kW will raise the temperature from the source temperature to:
20 C 30/2.0 D 35Ž C
and this gives a stream temperature difference on the outlet side of the exchanger of:
90 35 D 55Ž C
So the minimum temperature difference condition, 10Ž C, will not be violated by this
match.
7. Stream 2 will need further cooling to bring it to its target temperature, so a cooler
must be included; cooling required.
Hcold D 1.0⊲90 30⊳ 30 D 30 kW
Which is the amount of the cold utility predicted by the problem table.
The proposed network for maximum energy recovery is shown in Figure 3.27.
CP
90°C 80°C
180°C
B
1
150°C
135°C
50 kW
360
1.0
120
2.0
230
4.5
270
30°C
30 kW
Heater
A
140°C
kW
3.0
Cooler
D
A
2
kW/°C
60°C
C
∆H
C
60 kW
90 kW
B
270 kW
Figure 3.27.
D
30 kW
20°C
3
80°C
4
Pinch
Proposed heat exchanger network Tmin D 10° C
Stream splitting
If the heat capacities of streams are such that it is not possible to make a match at the pinch
without violating the minimum temperature difference condition, then the heat capacity
can be altered by splitting a stream. Dividing the stream will reduce the mass flow-rates
in each leg and hence the heat capacities. This is illustrated in Example 3.16.
Guide rules for stream matching and splitting are given in the Institution of Chemical
Engineers Guide, IChemE (1994).
FUNDAMENTALS OF ENERGY BALANCES
121
Summary
The heuristics (guide rules) for devising a network for maximum heat recovery are given
below:
1. Divide the problem at the pinch.
2. Design away from the pinch.
3. Above the pinch match streams adjacent to the pinch, meeting the restriction:
CPhot CPcold
4. Below the pinch match streams adjacent to the pinch, meeting the restriction:
CPhot ½ CPcold
5. If the stream matching criteria can not be satisfied split a stream.
6. Maximise the exchanger heat loads.
7. Supply external heating only above the pinch, and external cooling only below the
pinch.
3.17.4. Minimum number of exchangers
The network shown in Figure 3.27 was designed to give the maximum heat recovery, and
will therefore give the minimum consumption, and cost, of the hot and cold utilities.
This will not necessarily be the optimum design for the network. The optimum design
will be that which gives the lowest total annual costs: taking into account the capital
cost of the system, in addition to the utility and other operating costs. The number of
exchangers in the network, and their size, will determine the capital cost.
In Figure 3.27 it is clear that there is scope for reducing the number of exchangers.
Exchanger D can be deleted and the heat loads of the cooler and heater increased to
bring streams 2 and 3 to their target temperatures. Heat would cross the pinch and the
consumption of the utilities would be increased. Whether the revised network would be
better, more economic, would depend on the relative cost of capital and utilities. For any
network there will be an optimum design that gives the least annual cost: capital charges
plus utility and other operating costs. The estimation of capital and operating costs are
covered in Chapter 6.
To find the optimum design it will be necessary to cost a number of alternative designs,
seeking a compromise between the capital costs, determined by the number and size of
the exchangers, and the utility costs, determined by the heat recovery achieved.
For simple networks Holmann (1971) has shown that the minimum number of
exchangers is given by:
Zmin D N0 1
⊲3.41⊳
where Zmin D minimum number of exchangers needed, including heaters and coolers
N0 D the number of streams, including the utilities
122
CHEMICAL ENGINEERING
For complex networks a more general expression is needed to determine the minimum
number of exchangers:
⊲3.42⊳
Zmin D N0 C L 0 S
where L 0 D the number of internal loops present in the network
S D the number of independent branches (subsets) that exist in the network.
A loop exists where a close path can be traced through the network. There is a loop in
the network shown in Figure 3.27. The loop is shown in Figure 3.28. The presence of a
loop indicates that there is scope for reducing the number of exchangers.
B
1
C
A
D
2
A
C
D
B
3
4
Pinch
Figure 3.28.
Loop in network
For a full discussion of equation 3.42 and its applications see Linnhoff et al. (1979),
and IChemE (1994).
In summary, to seek the optimum design for a network:
1. Start with the design for maximum heat recovery. The number of exchangers needed
will be equal to or less than the number for maximum energy recovery.
2. Identify loops that cross the pinch. The design for maximum heat recovery will
usually contain loops.
3. Starting with the loop with the least heat load, break the loops by adding or
subtracting heat.
4. Check that the specified minimum temperature difference Tmin has not been
violated, and revise the design as necessary to restore the Tmin .
5. Estimate the capital and operating costs, and the total annual cost.
6. Repeat the loop breaking and network revision to find the lowest cost design.
7. Consider the safety, operability and maintenance aspects of the proposed design.
Importance of the minimum temperature difference
In a heat exchanger, the heat-transfer area required to transfer a specified heat load is
inversely proportional to the temperature difference between the streams; see Chapter 12.
FUNDAMENTALS OF ENERGY BALANCES
123
This means that the value chosen for Tmin will determine the size of the heat
exchangers in a network. Reducing Tmin will increase the heat recovery, decreasing
the utility consumption and cost, but at the expense of an increase in the exchanger size
and capital cost.
For any network there will be a best value for the minimum temperature difference
that will give the lowest total annual costs. The effect of changes in the specified Tmin
need to be investigated when optimising a heat recovery system.
3.17.5. Threshold problems
Problems that show the characteristic of requiring only either a hot utility or a cold
utility (but not both) over a range of minimum temperature differences, from zero up to
a threshold value, are known as threshold problems. A threshold problem is illustrated in
Figure 3.29.
Temperature
Hot utlity
∆TMIN = Threshold
Cold utility = zero
Enthalpy
Figure 3.29.
Threshold problem
To design the heat exchanger network for a threshold problem, it is normal to start at
the most constrained point. The problem can often be treated as one half of a problem
exhibiting a pinch.
Threshold problems are encountered in the process industries. A pinch can be introduced
in such problems if multiple utilities are used, as in the recovery of heat to generate steam.
124
CHEMICAL ENGINEERING
The procedures to follow in the design of threshold problems are discussed by Smith
(1995) and IChemE (1994).
3.17.6. Multiple pinches and multiple utilities
The use of multiple utilities can lead to more than one pinch in a problem. In introducing multiple utilities the best strategy is to generate at the highest level and use at the
lowest level. For a detailed discussion of this type of problem refer to Smith (1995) and
IChemE (1994).
3.17.7. Process integration: integration of other process operations
The use of the pinch technology method in the design of heat exchanger networks has been
outlined in Sections 3.17.1 to 3.17.6. The method can also be applied to the integration
of other process units; such as, separation column, reactors, compressors and expanders,
boilers and heat pumps. The wider applications of pinch technology are discussed in the
Institution of Chemical Engineers Guide, IChemE (1994) and by Linnhoff et al. (1983),
and Townsend and Linnhoff (1982), (1983), (1993).
Some guide rules for process integration:
1. Install combined heat and power (co-generation) systems across the pinch; see
Chapter 14.
2. Install heat engines either above or below the pinch.
3. Install distillation columns above or below the pinch.
4. Install heat pumps across the pinch; see Section 3.16.7.
The techniques of process integration have been expanded for use in optimising mass
transfer operations, and have been applied in waste reduction, water conservation, and
pollution control, see Dunn and El-Halwagi (2003).
Example 3.18
Determine the pinch temperatures and the minimum utility requirements for the streams
set out in the table below, for a minimum temperature difference between the streams of
20Ž C. Devise a heat exchanger network to achieve the maximum energy recovery.
Stream
number
1
2
3
4
Type
hot
hot
cold
cold
Heat capacity
kW/Ž C
40.0
30.0
60.0
20.0
Source
temp. Ž C
180
150
30
80
Target
temp. Ž C
40
60
180
160
Heat
load kW
5600
2700
9000
1600
Solution
The construction of the problem table to find the minimum utility requirement and the
pinch temperature is facilitated by using a spreadsheet. The calculations in each cell are
repetitive and the formula can be copied from cell to cell using the cell copy commands.
125
FUNDAMENTALS OF ENERGY BALANCES
The spreadsheet AS-EASY-AS (TRIUS Inc) was used to develop the tables for this
problem.
First calculate the interval temperatures, for Tmin D 20Ž C
hot streams Tint D Tact 10Ž C
cold streams Tint D Tact C 10Ž C
Stream
1
2
3
4
Actual temp. Ž C
Source
Target
180
40
150
60
30
180
80
160
Interval temp. Ž C
Source
Target
170
30
140
50
40
190
90
⊲170⊳
Next rank the interval temperatures, ignoring any duplicated values. Show which
streams occur in each interval to aid in the calculation of the combined stream heat
capacities:
190°C
170
Interval 1
1
180°C
2
140
180°C
160°C
2 150°C
3
90
4
50
4 80°C
60°C
5
40
40°C
6
30
Figure 3.30.
3 30°C
Intervals and streams
Now set out the problem table:
Interval
1
2
3
4
5
6
Interval
temp. Ž C
190
170
140
90
50
40
30
T
Ž
C
CPc ð CPh
kW/Ž C
H
kW
20
30
50
40
10
10
60.0
40.0
10.0
10.0
20.0
40.0
1200
1200
500
400
200
400
Cascade
0
2900
1200
1700
2400
500
2900
0
2500
400
2700
200
2300
600
In the last column 2900 kW of heat have been added to eliminate the negative values
in the previous column.
So, the hot utility requirement is 2900 kW and the cold, the bottom value in the column,
is 600 kW.
The pinch occurs where the heat transferred is zero, that is at interval number 3, 90Ž C.
126
CHEMICAL ENGINEERING
So at the pinch hot streams will be at:
90 C 10 D 100Ž C
and the cold at:
90 10 D 80Ž C
To design the network for maximum energy recovery: start at the pinch and match
streams following the rules on stream heat capacities for matches adjacent to the pinch.
Where a match is made: transfer the maximum amount of heat.
The proposed network is shown in Figure 3.31.
100°C
80°C
1800 kW
3200 kW
180°C
600 kW
40°C
1
1500 kW
1200 kW
60°C
150°C
2
1300 kW
180°C
30°C
3
160°C
80°C
4
1600 kW
Pinch
Figure 3.31.
Network, example 3.17
The methodology followed in devising this network was:
Above pinch
1. CPhot CPcold
2. Can match stream 1 and 2 with stream 3 but not with stream 4.
3. Check the heat available in bringing the hot streams to the pinch temperature.
stream 1 H D 40.0⊲180 100⊳ D 3200 kW
stream 2 H D 30.0⊲150 100⊳ D 1500 kW
4. Check the heat required to bring the cold streams from the pinch temperature to
their target temperatures.
stream 3 H D 60.0⊲180 80⊳ D 6000 kW
stream 4 H D 20.0⊲160 80⊳ D 1600 kW
5. Match stream 1 with 3 and transfer 3200 kW, that satisfies (ticks off) stream 1.
6. Match stream 2 with 3 and transfer 1500 kW, that ticks off stream 2.
7. Include a heater on stream 3 to provide the balance of the heat required:
Hhot D 6000 4700 D 1300 kW
8. Include a heater on stream 4 to provide heat load required, 1600 kW.
FUNDAMENTALS OF ENERGY BALANCES
127
Below pinch
9. CPhot ½ CPcold
10. Note that stream 4 starts at the pinch temperature so can not provide any cooling
below the pinch.
11. Cannot match stream 1 or 2 with stream 3 at the pinch.
12. So, split stream 3 to reduce CP. An even split will allow both streams 1 and 2 to
be matched with the split streams adjacent to the pinch, so try this:
13. Check the heat available from bringing the hot streams from the pinch temperature
to their target temperatures.
stream 1 H D 40.0⊲100 40⊳ D 2400 kW
stream 2 H D 30.0⊲100 60⊳ D 1200 kW
14. Check the heat required to bring the cold streams from their source temperatures
to the pinch temperature:
stream 3 H D 60.0⊲80 30⊳ D 3000 kW
stream 4 is at the pinch temperature.
15. Note that stream 1 can not be brought to its target temperature of 40Ž C by full
interchange with stream 3 as the source temperature of stream 3 is 30Ž C, so Tmin
would be violated. So transfer 1800 kW to one leg of the split stream 3.
16. Check temperature at exit of this exchanger:
1800
D 55Ž C, satisfactory
40
17. Provide cooler on stream 1 to bring it to its target temperature, cooling needed:
Temp out D 100
Hcold D 2400 1800 D 600 kW
18. Transfer the full heat load from stream 2 to second leg of stream 3; this satisfies
both streams.
Note that the heating and cooling loads, 2900 kW and 600 kW, respectively, match
those predicted from the problem table.
3.18. REFERENCES
BARLOW, J. A. (1975) Inst. Mech. Eng. Conference on Energy Recovery in the Process Industries, London.
Energy recovery in a petro-chemical plant: advantages and disadvantages.
BARNWELL, J. and MORRIS, C. P. (1982) Hyd. Proc. 61 (July) 117. Heat pump cuts energy use.
BLOCH, H. P., CAMERON, J. A., DANOWSKY, F. M., JAMES, R., SWEARINGEN, J. S. and WEIGHTMAN, M. E.
(1982) Compressors and Expanders: Selection and Applications for the Process Industries (Dekker).
BOLAND, D. and LINNHOFF, B. (1979) Chem. Engr, London No. 343 (April) 222. The preliminary design of
networks for heat exchangers by systematic methods.
BUSE, F. (1981) Chem. Eng., NY 88 (Jan 26th) 113. Using centrifugal pumps as hydraulic turbines.
CHADA, N. (1984) Chem. Eng., NY 91 (July 23rd) 57. Use of hydraulic turbines to recover energy.
DOUGLAS, J. M. (1988) Conceptual Design of Chemical Processes (McGraw-Hill).
DRYDEN, I. (ed.) (1975) The Efficient Use of Energy (IPC Science and Technology Press).
DUNN, K. S. and TOMKINS, A. G. (1975) Inst. Mech. Eng. Conference on Energy Recovery in the Process Industries, London. Waste heat recovery from the incineration of process wastes.
DUNN, R. F. and EL-HALWAGI, M. M. (2003) J. Chem. Technol. Biotechol. 78, 1011. Process integration
technology review: background and applications in the chemical process industry.
EDMISTER, W. C. (1948) Pet. Ref. 27 (Nov.) 129 (609). Applications of thermodynamics to hydrocarbon
processing, part XIII heat capacities.
128
CHEMICAL ENGINEERING
GUNDERSEN, T. and NAESS, L. (1988). Comp. and Chem. Eng., 12, No. 6, 503. The synthesis of cost optimal
heat-exchanger networks an industrial review of the state of the art.
HIMMELBLAU, D. M. (1995) Basic Principles and Calculations in Chemical Engineering, 6th edn (Pearson).
HINCHLEY, P. (1975) Inst. Mech. Eng. Conference on Energy Recovery in the Process Industries, London. Waste
heat boilers in the chemical industry.
HOLMANN, E. C. (1971) PhD Thesis, University of South California, Optimum networks for heat exchangers.
HOLLAND, F. A. and DEVOTTA, S. (1986) Chem. Engr, London, No. 425 (May) 61. Prospects for heat pumps
in process applications.
ICHEME (1994) User Guide on Process Integration for Efficient Use of Energy, revised edn (Institution of
Chemical Engineers, London).
JENETT, E. (1968) Chem. Eng., NY 75 (April 8th) 159, (June 17th) 257 (in two parts). Hydraulic power recovery
systems.
KENNEY, W. F. (1984) Energy Conversion in the Process Industries, Academic Press.
LINNHOFF, B. and FLOWER, J. R. (1978) AIChEJI 24, 633 (2 parts) synthesis of heat exchanger networks.
LINNHOFF, B., MASON, D. R. and WARDLE, I. (1979) Comp. and Chem. Eng. 3, 295, Understanding heat
exchanger networks.
LINNHOFF, B., DUNFORD, H. and SMITH R. (1983) Chem. Eng. Sci. 38, 1175. Heat integration of distillation
columns into overall processes.
LINNHOFF, B. (1993) Trans IChemE 71, Part A, 503. Pinch Analysis a state-of-the-art overview.
MASSO, A. H. and RUDD, D. F. (1969) AIChEJl 15, 10. The synthesis of system design: heuristic structures.
MEILI, A. (1990) Chem. Eng. Prog. 86(6) 60. Heat pumps for distillation columns.
MILES, F. D. (1961) Nitric Acid Manufacture and Uses (Oxford U.P.)
MILLER, R. (1968) Chem. Eng., NY 75 (May 20th) 130. Process energy systems.
MOSER, F. and SCHNITZER, H. (1985) Heat Pumps in Industry (Elsevier).
NISHIDA, N., LIU, Y. A. and LAPIDUS, L. (1977) AIChEJl 23, 77. Studies in chemical process design and
synthesis.
PERRY, R. H. and CHILTON, C. H. (eds) (1973) Chemical Engineers Handbook, 5th edn (McGraw-Hill).
PERRY, R. H. and GREEN, D. W. (eds) (1984) Perry’s Chemical Engineers Handbook, 6th edn (McGraw-Hill).
PORTON, J. W. and DONALDSON, R. A. B. (1974) Chem. Eng. Sci. 29, 2375. A fast method for the synthesis of
optimal heat exchanger networks.
REAY, D. A. and MACMICHAEL, D. B. A. (1988) Heat Pumps: Design and Application, 2nd edn (Pergamon
Press).
SANTOLERI, J. J. (1973) Chem. Eng. Prog. 69 (Jan.) 69. Chlorinated hydrocarbon waste disposal and recovery
systems.
SIIROLA, J. J. (1974) AIChE 76th National Meeting, Tulsa, Oklahoma. Studies of heat exchanger network
synthesis.
SINGH, J. (1985) Heat Transfer Fluids and Systems for Process and Energy Applications, Marcel Dekker.
STERBACEK, Z., BISKUP, B. and TAUSK, P. (1979) Calculation of Properties Using Corresponding-state Methods
(Elsevier).
SHULTZ, J. M. (1962) Trans. ASME 84 (Journal of Engineering for Power) (Jan.) 69, (April) 222 (in two parts).
The polytropic analysis of centrifugal compressors.
SMITH, R. (1995) Chemical Process Design (McGraw-Hill)
TOWNSEND, D. W. and LINNHOFF, B. (1983) AIChEJl 29, 742. Heat and power networks in processes design.
TOWNSEND, D. W. and LINNHOFF, B. (1982) Chem. Engr., London, No. 378 (March) 91. Designing total energy
systems by systematic methods.
3.19. NOMENCLATURE
Dimensions
in MLTq
a
b
CP
Cp
Cpa
Cpb
Cpc
Cpm
Cp1
Constant in specific heat equation (equation 3.13)
Constant in specific heat equation (equation 3.13)
Stream heat capacity
Specific heat at constant pressure
Specific heat component a
Specific heat component b
Specific heat component c
Mean specific heat
Specific heat first phase
L2 T2 q1
L2 T2 q2
ML2 T2 q1
L2 T2 q1
L2 T2 q1
L2 T2 q1
L2 T2 q1
L2 T2 q1
L2 T2 q1
129
FUNDAMENTALS OF ENERGY BALANCES
Cp2
Cv
Cop
c
CPc
CPh
Ee
Ep
F
g
H
Ha
Hb
Hd
Hf
HT
Hw
H
Hcold
Hex
Hhot
Hn
Hm,t
Hr,t
H°c
H°f
H°m
H°r
L
L0
l
M
M
m
m
m
N
N0
n
P
Pi
Pr
P1
P2
Q
Qb
Qc
Qp
Qr
Qs
R
S
Scj
Shi
Suk
T
Tact
Specific heat second phase
Specific heat at constant volume
Ideal gas state specific heat
Constant in specific heat equation (equation 3.13)
Sum of heat capacities of cold streams
Sum of heat capacities of hot streams
Efficiency, electric motors
Polytropic efficiency, compressors and turbines
Force
Gravitational acceleration
Enthalpy
Specific enthalpy of component a
Specific enthalpy of component b
Enthalpy top product stream (Example 3.1)
Enthalpy feed stream (Example 3.1)
Specific enthalpy at temperature T
Enthalpy bottom product stream (Example 3.1)
Change in enthalpy
Heat transfer from cold utility
Heat transfer in exchanger
Heat transfer from hot utility
Heat available in nth interval
Heat of mixing at temperature t
Heat of reaction at temperature t
Standard heat of combustion
Standard enthalpy of formation
Standard heat of mixing
Standard heat of reaction
Number of auxiliary streams, heat exchanger networks
Number of internal loops in network
Distance
Number of hot streams, heat-exchanger networks
Molecular mass (weight)
Polytropic temperature exponent
Mass
Mass flow-rate
Number of cold streams, heat-exchanger networks
Number of streams
Expansion or compression index (equation 3.30)
Pressure
Inter-stage pressure
Reduced pressure
Initial pressure
Final pressure
Heat transferred across system boundary
Reboiler heat load (Example 3.1)
Condenser heat load (Example 3.1)
Heat added (or subtracted) from a system
Heat from reaction
Heat generated in the system
Universal gas constant
Number of independent branches
Cold streams, heat-exchanger networks
Hot streams, heat-exchanger networks
Auxiliary streams, heat-exchanger networks
Temperature, absolute
Actual stream temperature
L2 T2 q1
L2 T2 q1
L2 T2 q1
L2 T2 q3 or L2 T2 q1/2
ML2 T2 q1
ML2 T2 q1
MLT2
LT2
ML2 T2
L2 T2
L2 T2
ML2 T3
ML2 T3
L2 T2
ML2 T3
ML2 T2
ML2 T3
ML2 T3
ML2 T3
ML2 T3
L2 T2
L2 T2
L2 T2
L2 T2
L2 T2
L2 T2
L
M
MT1
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML2 T2 or
ML2 T3
ML2 T3
ML2 T2 or
ML2 T2 or
ML2 T2 or
L2 T2 q1
q
q
ML2 T3
ML2 T3
ML2 T3
ML2 T3
130
Td
Tint
Tn
Tp
Tr
Ts
Tt
Tmin
Tn
t
t
tr
tf
to
U
u
V1
V2
v
X
x
xa
xb
xc
Y
W
Wi
Z
z
Zmin
CHEMICAL ENGINEERING
Datum temperature for enthalpy calculations
Interval temperature
Temperature in nth interval
Phase-transition temperature
Reduced temperature
Source temperature
Target temperature
Minimum temperature difference in heat exchanger
Internal temperature difference
Temperature, relative scale
Time
Reference temperature, mean specific heat
Inlet-stream temperatures, heat-exchanger networks
Outlet-stream temperatures, heat-exchanger networks
Internal energy per unit mass
Velocity
Initial volume
Final volume
Volume per unit mass
Compressibility function defined by equation 3.33
Distance
Mol fraction component a in a mixture
Mol fraction component b in a mixture
Mol fraction component c in a mixture
Compressibility function defined by equation 3.34
Work per unit mass
Heat capacity of streams in a heat-exchanger network
Compressibility factor
Height above datum
Minimum number of heat exchangers in network
q
q
q
q
q
q
q
q
q
T
q
q
q
L2 T2
LT1
L3
L3
M1 L3
L
L2 T2
ML2 T3 q1
L
3.20. PROBLEMS
3.1. A liquid stream leaves a reactor at a pressure of 100 bar. If the pressure is reduced
to 3 bar in a turbine, estimate the maximum theoretical power that could be
obtained from a flow-rate of 1000 kg/h. The density of the liquid is 850 kg/m3 .
3.2. Calculate the specific enthalpy of water at a pressure of 1 bar and temperature of
200 Ž C. Check your value using steam tables. The specific heat capacity of water
can be calculated from the equation:
Cp D 4.2 2 ð 103 t; where t is in Ž C and Cp in kJ/kg.
Take the other data required from Appendix C.
3.3. A gas produced as a by-product from the carbonisation of coal has the following
composition, mol per cent: carbon dioxide 4, carbon monoxide 15, hydrogen 50,
methane 12, ethane 2, ethylene 4, benzene 2, balance nitrogen. Using the data
given in Appendix C, calculate the gross and net calorific values of the gas. Give
your answer in MJ/m3 , at standard temperature and pressure.
3.4. In the manufacture of aniline, liquid nitrobenzene at 20 Ž C is fed to a vaporiser
where it is vaporised in a stream of hydrogen. The hydrogen stream is at 30 Ž C,
and the vaporiser operates at 20 bar. For feed-rates of 2500 kg/h nitrobenzene and
366 kg/h hydrogen, estimate the heat input required. The nitrobenzene vapour is
not superheated.
FUNDAMENTALS OF ENERGY BALANCES
131
3.5. Aniline is produced by the hydrogenation of nitrobenzene. The reaction takes
place in a fluidised bed reactor operating at 270 Ž C and 20 bar. The excess heat of
reaction is removed by a heat transfer fluid passing through tubes in the fluidised
bed. Nitrobenzene vapour and hydrogen enter the reactor at a temperature of
260 Ž C. A typical reactor off-gas composition, mol per cent, is: aniline 10.73,
cyclo-hexylamine 0.11, water 21.68, nitrobenzene 0.45, hydrogen 63.67, inerts
(take as nitrogen) 3.66. Estimate the heat removed by the heat transfer fluid, for
a feed-rate of nitrobenzene to the reactor of 2500 kg/h.
The specific heat capacity of nitrobenzene can be estimate using the methods given
in Chapter 8. Take the other data required from Appendix C.
3.6. Hydrogen chloride is produced by burning chlorine with an excess of hydrogen.
The reaction is highly exothermic and reaches equilibrium very rapidly. The
equilibrium mixture contains approximately 4 per cent free chlorine but this is
rapidly combined with the excess hydrogen as the mixture is cooled. Below 200Ž C
the conversion of chlorine is essentially complete.
The burner is fitted with a cooling jacket, which cools the exit gases to 200 Ž C.
The gases are further cooled, to 50 Ž C, in an external heat exchanger.
For a production rate of 10,000 tonnes per year of hydrogen chloride, calculate
the heat removed by the burner jacket and the heat removed in the external cooler.
Take the excess hydrogen as 1 per cent over stoichiometric. The hydrogen supply
contains 5 per cent inerts (take as nitrogen) and is fed to the burner at 25Ž C. The
chlorine is essentially pure and is fed to the burner as a saturated vapour. The
burner operates at 1.5 bar.
3.7. A supply of nitrogen is required as an inert gas for blanketing and purging vessels.
After generation, the nitrogen is compressed and stored in a bank of cylinders,
at a pressure of 5 barg. The inlet pressure to the compressor is 0.5 barg, and
temperature 20 Ž C. Calculate the maximum power required to compress 100 m3 /h.
A single-stage reciprocating compressor will be used.
3.8. Hydrogen chloride gas, produced by burning chlorine with hydrogen, is required
at a supply pressure of 600 kN/m2 , gauge. The pressure can be achieved by either
operating the burner under pressure or by compressing the hydrogen chloride
gas. For a production rate of hydrogen chloride of 10,000 kg/h, compare the
power requirement of compressing the hydrogen supply to the burner, with that
to compress the product hydrogen chloride. The chlorine feed will be supplied at
the required pressure from a vaporiser. Both the hydrogen and chlorine feeds are
essentially pure. Hydrogen will be supplied to the burner one percent excess of
over the stoichiometric requirement.
A two-stage centrifugal compressor will be used for both duties. Take the polytropic efficiency for both compressors as 70 per cent. The hydrogen supply pressure
is 120 kN/m2 and the temperature 25 Ž C. The hydrogen chloride is cooled to 50 Ž C
after leaving the burner. Assume that the compressor intercooler cools the gas to
50 Ž C, for both duties.
Which process would you select and why?
132
CHEMICAL ENGINEERING
3.9. Estimate the work required to compress ethylene from 32 MPa to 250 MPa in a
two-stage reciprocating compressor where the gas is initially at 30 Ž C and leaves
the intercooler at 30 Ž C. See Example 3.13.
3.10. Determine the pinch temperature and the minimum utility requirements for the
process set out below. Take the minimum approach temperature as 15 Ž C. Devise
a heat exchanger network to achieve maximum energy recovery.
Stream
number
1
2
3
4
Type
hot
hot
cold
cold
Heat capacity
kW/Ž C
13.5
27.0
53.5
23.5
Source
Temp. Ž C
180
135
60
35
Target
Temp. Ž C
80
45
100
120
3.11. Determine the pinch temperature and the minimum utility requirements for the
process set out below. Take the minimum approach temperature as 15Ž C. Devise
a heat exchanger network to achieve maximum energy recovery.
Stream
number
1
2
3
4
5
Type
hot
hot
hot
cold
cold
Heat capacity
kW/Ž C
10.0
20.0
40.0
30.0
8.0
Source
Temp. Ž C
200
155
90
60
35
Target
Temp. Ž C
80
50
35
100
90
3.12. To produce a high purity product two distillation columns are operated in series.
The overhead stream from the first column is the feed to the second column.
The overhead from the second column is the purified product. Both columns are
conventional distillation columns fitted with reboilers and total condensers. The
bottom products are passed to other processing units, which do not form part of this
problem. The feed to the first column passes through a preheater. The condensate
from the second column is passed through a product cooler. The duty for each
stream is summarised below:
No.
1
2
3
4
5
6
Stream
Type
Feed preheater
First condenser
Second condenser
First reboiler
Second reboiler
Product cooler
cold
hot
hot
cold
cold
hot
Source
temp. Ž C.
20
70
65
85
75
55
Target
temp. Ž C
50
60
55
87
77
25
Duty, kW
900
1350
1100
1400
900
30
Find the minimum utility requirements for this process, for a minimum approach
temperature of 10 Ž C.
Note: the stream heat capacity is given by dividing the exchanger duty by the
temperature change.
CHAPTER 4
Flow-sheeting
4.1. INTRODUCTION
This chapter covers the preparation and presentation of the process flow-sheet. The flowsheet is the key document in process design. It shows the arrangement of the equipment
selected to carry out the process; the stream connections; stream flow-rates and compositions; and the operating conditions. It is a diagrammatic model of the process.
The flow-sheet will be used by the specialist design groups as the basis for their designs.
This will include piping, instrumentation, equipment design and plant layout. It will also
be used by operating personnel for the preparation of operating manuals and operator
training. During plant start-up and subsequent operation, the flow-sheet forms a basis for
comparison of operating performance with design.
The flow-sheet is drawn up from material balances made over the complete process
and each individual unit. Energy balances are also made to determine the energy flows
and the service requirements.
Manual flow-sheeting calculations can be tedious and time consuming when the process
is large or complex, and computer-aided flow-sheeting programs are being increasingly
used to facilitate this stage of process design. Their use enables the designer to consider
different processes, and more alterative processing schemes, in his search for the best
process and optimum process conditions. Some of the proprietary flow-sheeting programs
available are discussed in this chapter. A simple linear flow-sheeting program is presented
in detail and listed in the appendices.
In this chapter the calculation procedures used in flow-sheeting have for convenience
been divided into manual calculation procedures and computer-aided procedures.
The next step in process design after the flow-sheet is the preparation of Piping
and Instrumentation diagrams (abbreviated to P & I diagrams) often also called the
Engineering Flow-sheet or Mechanical Flow-sheet. The P & I diagrams, as the name
implies, show the engineering details of the process, and are based on the process flowsheet. The preparation and presentation of P & I diagrams is discussed in Chapter 5. The
abbreviation PFD (for Process Flow Diagram) is often used for process flow-sheets, and
PID for Piping and Instrumentation Diagrams.
4.2. FLOW-SHEET PRESENTATION
As the process flow-sheet is the definitive document on the process, the presentation
must be clear, comprehensive, accurate and complete. The various types of flow-sheet are
discussed below.
133
134
CHEMICAL ENGINEERING
4.2.1. Block diagrams
A block diagram is the simplest form of presentation. Each block can represent a single
piece of equipment or a complete stage in the process. Block diagrams were used to
illustrate the examples in Chapters 2 and 3. They are useful for showing simple processes.
With complex processes, their use is limited to showing the overall process, broken
down into its principal stages; as in Example 2.13 (Vinyl Chloride). In that example each
block represented the equipment for a complete reaction stage: the reactor, separators and
distillation columns.
Block diagrams are useful for representing a process in a simplified form in reports
and textbooks, but have only a limited use as engineering documents.
The stream flow-rates and compositions can be shown on the diagram adjacent to the
stream lines, when only a small amount of information is to be shown, or tabulated
separately.
The blocks can be of any shape, but it is usually convenient to use a mixture of squares
and circles, drawn with a template.
4.2.2. Pictorial representation
On the detailed flow-sheets used for design and operation, the equipment is normally
drawn in a stylised pictorial form. For tender documents or company brochures, actual
scale drawings of the equipment are sometimes used, but it is more usual to use
a simplified representation. The symbols given in British Standard, BS 1553 (1977)
“Graphical Symbols for General Engineering” Part 1, “Piping Systems and Plant” are
recommended; though most design offices use their own standard symbols. A selection of
symbols from BS 1553 is given in Appendix A. The American National Standards Institute
(ANSI) has also published a set of symbols for use on flow-sheets. Austin (1979) has
compared the British Standard, ANSI, and some proprietary flow-sheet symbols.
In Europe, the German standards organisation has published a set of guide rules and
symbols for flow-sheet presentation, DIN 28004 (1988). This is available in an English
translation from the British Standards Institution.
4.2.3. Presentation of stream flow-rates
The data on the flow-rate of each individual component, on the total stream flow-rate,
and the percentage composition, can be shown on the flow-sheet in various ways. The
simplest method, suitable for simple processes with few equipment pieces, is to tabulate
the data in blocks alongside the process stream lines, as shown in Figure 4.1. Only a
limited amount of information can be shown in this way, and it is difficult to make neat
alterations or to add additional data.
A better method for the presentation of data on flow-sheets is shown in Figure 4.2.
In this method each stream line is numbered and the data tabulated at the bottom of the
sheet. Alterations and additions can be easily made. This is the method generally used by
professional design offices. A typical commercial flow-sheet is shown in Figure 4.3. Guide
rules for the layout of this type of flow-sheet presentation are given in Section 4.2.5.
135
FLOW-SHEETING
AN
500
Water 2500
Total 3000
H1
Water 5000
Total 5000
15°C
60°C
DM water
Steam
From
storages
15°C
F1
40°C
60°C
To dryer
CW
60°C
R1
Cat.
5
Water 100
Total 105
AN
Water
Polymer
Salts
Total
From
catalyst
prep
Figure 4.1.
50
2600
450
5
3105
Water
AN
Polymer
Salts
Total
7300
45
2
5
7352
AN
Water
Polymer
Salts
Total
5
300
448
trace
753
Equipment key
R1 Polymer reactor
H1 Water heater
F1 Vacuum filter
Flow-sheet: polymer production
4.2.4. Information to be included
The amount of information shown on a flow-sheet will depend on the custom and practice
of the particular design office. The list given below has therefore been divided into
essential items and optional items. The essential items must always be shown, the optional
items add to the usefulness of the flow-sheet but are not always included.
Essential information
1. Stream composition, either:
(i) the flow-rate of each individual component, kg/h, which is preferred, or
(ii) the stream composition as a weight fraction.
2. Total stream flow-rate, kg/h.
3. Stream temperature, degrees Celsius preferred.
4. Nominal operating pressure (the required operating pressure).
Optional information
1. Molar percentages composition.
2. Physical property data, mean values for the stream, such as:
(i) density, kg/m3 ,
(ii) viscosity, mN s/m2 .
3. Stream name, a brief, one or two-word, description of the nature of the stream, for
example “ACETONE COLUMN BOTTOMS”.
4. Stream enthalpy, kJ/h.
The stream physical properties are best estimated by the process engineer responsible for
the flow-sheet. If they are then shown on the flow-sheet, they are available for use by
the specialist design groups responsible for the subsequent detailed design. It is best that
each group use the same estimates, rather than each decide its own values.
136
Tail gas
To
sheet no 9317 1
10
Water
11
2
Air
Filter
8
Absorber
Compressor
2A
1A
Steam
3
Cooler
5
1
9
6
4
Vaporiser
Filter
W. H. B.
Reactor
(Oxidiser)
12
7
Mixer
Condenser
13
Product
Flows kg/h Pressures nominal
Line no.
1
1A
Stream
Ammonia Ammonia
Component feed
vapour
NH3
O2
N2
NO
NO2
HNO3
H2 O
731.0
Total
731.0
731.0
8
15
8
20
Press bar
Temp. ° C
2
Filtered
air
2A
Oxidiser
air
3
Oxidiser
feed
4
Oxidiser
outlet
2628.2
8644.7
731.0
2628.2
8644.7
Nil
935.7
8668.8
1238.4
731.0
3036.9
9990.8
Trace
13,027.7
1
15
5
W.H.B.
outlet
(1)
(935.7)
8668.8
(1)
(1238.4)
Trace
Nil
1161.0
11,272.9
12,003.9
12,003.9
12,003.9
8
230
8
204
8
907
8
234
Figure 4.2.
6
7
8
9
Condenser Condenser Secondary Absorber
gas
acid
air
feed
275.2
8668.8
202.5
(1)
(?)
Nil
1161.0
Trace
Trace
10,143.1
1860.7
1754.8
1
40
8
40
8
40
408.7
1346.1
683.9
10,014.7
202.5
967.2
29.4
850.6
1010.1
10
Tail(2)
gas
11
Water
feed
371.5
10,014.7
21.9
(1)
967.2 (Trace)
1376.9
Trace
Trace
Trace
Trace
1704.0
1136.0
1376.9
2840.0
4700.6
8
25
1
40
1
43
29.4
11,897.7
8
40
10,434.4
12
13
Absorber Product C & R Construction Inc
acid
acid
26.3
1
25
Flow-sheet: simplified nitric acid process (Example 4.2)
(1) See example
Trace
Trace
Trace
Nitric acid 60 per cent
100,000 t/y
Client BOP Chemicals
SLIGO
Trace
Sheet no. 9316
2554.6
2146.0
Dwg by Date
Checked 25/7/1980
CHEMICAL ENGINEERING
Ammonia
14
From
sheet no 9315
FLOW-SHEETING
137
Figure 4.2a.
Flow-sheet drawn using FLOSHEET
Figure 4.3.
A typical flow-sheet
FLOW-SHEETING
139
4.2.5. Layout
The sequence of the main equipment items shown symbolically on the flow-sheet follows
that of the proposed plant layout. Some licence must be exercised in the placing of
ancillary items, such as heat exchangers and pumps, or the layout will be too congested.
But the aim should be to show the flow of material from stage to stage as it will occur,
and to give a general impression of the layout of the actual process plant.
The equipment should be drawn approximately to scale. Again, some licence is allowed
for the sake of clarity, but the principal equipment items should be drawn roughly in the
correct proportion. Ancillary items can be drawn out of proportion. For a complex process,
with many process units, several sheets may be needed, and the continuation of the process
streams from one sheet to another must be clearly shown. One method of indicating a
line continuation is shown in Figure 4.2; those lines which are continued over to another
are indicated by a double concentric circle round the line number and the continuation
sheet number written below.
The table of stream flows and other data can be placed above or below the equipment
layout. Normal practice is to place it below. The components should be listed down the
left-hand side of the table, as in Figure 4.2. For a long table it is good practice to repeat
the list at the right-hand side, so the components can be traced across from either side.
The stream line numbers should follow consecutively from left to right of the layout,
as far as is practicable; so that when reading the flow-sheet it is easy to locate a particular
line and the associated column containing the data.
All the process stream lines shown on the flow-sheet should be numbered and the data
for the stream given. There is always a temptation to leave out the data on a process
stream if it is clearly just formed by the addition of two other streams, as at a junction,
or if the composition is unchanged when flowing through a process unit, such as a
heat exchanger; this should be avoided. What may be clear to the process designer is
not necessarily clear to the others who will use the flow-sheet. Complete, unambiguous
information on all streams should be given, even if this involves some repetition. The
purpose of the flow-sheet is to show the function of each process unit; even to show when
it has no function.
4.2.6. Precision of data
The total stream and individual component flows do not normally need to be shown
to a high precision on the process flow-sheet; at most one decimal place is all that is
usually justified by the accuracy of the flow-sheet calculations, and is sufficient. The
flows should, however, balance to within the precision shown. If a stream or component
flow is so small that it is less than the precision used for the larger flows, it can be
shown to a greater number of places, if its accuracy justifies this and the information
is required. Imprecise small flows are best shown as “TRACE”. If the composition of
a trace component is specified as a process constraint, as, say, for an effluent stream or
product quality specification, it can be shown in parts per million, ppm.
A trace quantity should not be shown as zero, or the space in the tabulation left blank,
unless the process designer is sure that it has no significance. Trace quantities can be
important. Only a trace of an impurity is needed to poison a catalyst, and trace quantities
140
CHEMICAL ENGINEERING
can determine the selection of the materials of construction; see Chapter 7. If the space in
the data table is left blank opposite a particular component the quantity may be assumed
to be zero by the specialist design groups who take their information from the flow-sheet.
4.2.7. Basis of the calculation
It is good practice to show on the flow-sheet the basis used for the flow-sheet calculations.
This would include: the operating hours per year; the reaction and physical yields; and
the datum temperature used for energy balances. It is also helpful to include a list of the
principal assumptions used in the calculations. This alerts the user to any limitations that
may have to be placed on the flow-sheet information.
4.2.8. Batch processes
Flow-sheets drawn up for batch processes normally show the quantities required to
produce one batch. If a batch process forms part of an otherwise continuous process,
it can be shown on the same flow-sheet, providing a clear break is made when tabulating
the data between the continuous and batch sections; the change from kg/h to kg/batch.
A continuous process may include batch make-up of minor reagents, such as the catalyst
for a polymerisation process.
4.2.9. Services (utilities)
To avoid cluttering up the flow-sheet, it is not normal practice to show the service headers
and lines on the process flow-sheet. The service connections required on each piece of
equipment should be shown and labelled. The service requirements for each piece of
equipment can be tabulated on the flow-sheet.
4.2.10. Equipment identification
Each piece of equipment shown on the flow-sheet must be identified with a code number
and name. The identification number (usually a letter and some digits) will normally be
that assigned to a particular piece of equipment as part of the general project control
procedures, and will be used to identify it in all the project documents.
If the flow-sheet is not part of the documentation for a project, then a simple, but
consistent, identification code should be devised. The easiest code is to use an initial letter
to identify the type of equipment, followed by digits to identify the particular piece. For
example, H heat exchangers, C columns, R reactors. The key to the code should
be shown on the flow-sheet.
4.2.11. Computer aided drafting
Most design offices now use computer aided drafting programs for the preparation of
flow-sheets and other process drawings. When used for drawing flow-sheets, and piping
and instrumentation diagrams (see Chapter 5), standard symbols representing the process
equipment, instruments and control systems are held in files and called up as required.
FLOW-SHEETING
141
To illustrate the use of a commercial computer aided design program, Figure 4.2 has
been redrawn using the program FLOSHEET and is shown as Figure 4.2a. FLOSHEET is
a versatile flow-sheet drafting program. It is used by many chemical engineering departments in the UK; see Preece (1986) and Preece and Stephens (1989).
FLOSHEET is part of a suite of programs called PROCEDE which has been developed
for the efficient handling of all the information needed in process design. It aims to
cover the complete process environment, using graphical user interfaces to facilitate the
transfer of information, Preece et al. (1991). The equipment specification sheets given in
Appendix G are from the PROCEDE package.
4.3. MANUAL FLOW-SHEET CALCULATIONS
This section is a general discussion of the techniques used for the preparation of flowsheets from manual calculations. The stream flows and compositions are calculated from
material balances; combined with the design equations that arise from the process and
equipment design constraints.
As discussed in Chapter 1, there will be two kinds of design constraints:
External constraints: not directly under the control of the designer, and which cannot
normally be relaxed. Examples of this kind of constraint are:
(i) Product specifications, possibly set by customer requirements.
(ii) Major safety considerations, such as flammability limits.
(iii) Effluent specifications, set by government agencies.
Internal constraints: determined by the nature of the process and the equipment
functions. These would include:
(i)
(ii)
(iii)
(iv)
(v)
The process stoichiometry, reactor conversions and yields.
Chemical equilibria.
Physical equilibria, involved in liquid-liquid and gas/vapour-liquid separations.
Azeotropes and other fixed compositions.
Energy-balance constraints. Where the energy and material balance interact, as for
example in flash distillation.
(vi) Any general limitations on equipment design.
The flow-sheet is usually drawn up at an early stage in the development of the project. A
preliminary flow-sheet will help clarify the designer’s concept of the process; and serve
as basis for discussions with other members of the design team.
The extent to which the flow-sheet can be drawn up before any work is done on
the detailed design of the equipment will depend on the complexity of the process and
the information available. If the design is largely a duplication of an existing process,
though possibly for a different capacity, the equipment performance will be known and
the stream flows and compositions can be readily calculated. For new processes, and for
major modifications of existing processes, it will only be possible to calculate some of
142
CHEMICAL ENGINEERING
the flows independently of the equipment design considerations; other stream flows and
compositions will be dependent on the equipment design and performance. To draw up
the flow-sheet the designer must use his judgement in deciding which flows can be calculated directly; which are only weakly dependent on the equipment design; and which are
determined by the equipment design.
By weakly dependent is meant those streams associated with equipment whose performance can be assumed, or approximated, without introducing significant errors in the
flow-sheet. The detailed design of these items can be carried out later, to match the
performance then specified by the flow-sheet. These will be items which in the designer’s
estimation do not introduce any serious cost penalty if not designed for their optimum
performance. For example, in a phase separator, such as a decanter, if equilibrium between
the phases is assumed the outlet stream compositions can be often calculated directly,
independent of the separator design. The separator would be designed later, to give sufficient residence time for the streams to approach the equilibrium condition assumed in the
flow-sheet calculation.
Strong interaction will occur where the stream flows and compositions are principally determined by the equipment design and performance. For example, the optimum
conversion in a reactor system with recycle of the unreacted reagents will be determined
by the performance of the separation stage, and reactor material balance cannot be made
without considering the design of the separation equipment. To determine the stream
flows and compositions it would be necessary to set up a mathematical model of the
reactor-separator system, including costing.
To handle the manual calculations arising from complex processes, with strong interactions between the material balance calculations and the equipment design, and where
physical recycle streams are present, it will be necessary to sub-divide the process into
manageable sub-systems. With judgement, the designer can isolate those systems with
strong interactions, or recycle, and calculate the flows sequentially, from sub-system
to sub-system, making approximations as and where required. Each sub-system can be
considered separately, if necessary, and the calculations repeatedly revised till a satisfactory flow-sheet for the complete process is obtained. To attempt to model a complex
process without subdivision and approximation would involve too many variables and
design equations to be handled manually. Computer flow-sheeting programs should be
used if available.
When sub-dividing the process and approximating equipment performance to produce a
flow-sheet, the designer must appreciate that the resulting design for the complete process,
as defined by the flow-sheet, will be an approximation to the optimum design. He must
continually be aware of, and check, the effect of his approximations on the performance
of the complete process.
4.3.1. Basis for the flow-sheet calculations
Time basis
No plant will operate continuously without shut-down. Planned shut-down periods will be
necessary for maintenance, inspection, equipment cleaning, and the renewal of catalysts
FLOW-SHEETING
143
and column packing. The frequency of shut-downs, and the consequent loss of production
time, will depend on the nature of the process. For most chemical and petrochemical
processes the plant attainment will typically be between 90 to 95 per cent of the total
hours in a year (8760). Unless the process is known to require longer shut-down periods,
a value of 8000 hours per year can be used for flow-sheet preparation.
Scaling factor
It is usually easiest to carry out the sequence of flow-sheet calculations in the same order
as the process steps; starting with the raw-material feeds and progressing stage by stage,
where possible, through the process to the final product flow. The required production
rate will usually be specified in terms of the product, not the raw-material feeds, so it
will be necessary to select an arbitrary basis for the calculations, say 100 kmol/h of the
principal raw material. The actual flows required can then be calculated by multiplying
each flow by a scaling factor determined from the actual production rate required.
Scaling factor D
mols product per hour specified
mols product produced per 100 kmol
of the principal raw material
4.3.2. Flow-sheet calculations on individual units
Some examples of how design constraints can be used to determine stream flows and
compositions are given below.
1. Reactors
(i) Reactor yield and conversion specified.
The reactor performance may be specified independently of the detailed design
of the reactor. The conditions for the optimum, or near optimum, performance may
be known from the operation of existing plant or from pilot plant studies.
For processes that are well established, estimates of the reactor performance can
often be obtained from the general and patent literature; for example, the production
of nitric and sulphuric acids.
If the yields and conversions are known, the stream flows and compositions can
be calculated from a material balance; see Example 2.13.
(ii) Chemical equilibrium.
With fast reactions, the reaction products can often be assumed to have
reached equilibrium. The product compositions can then be calculated from the
equilibrium data for the reaction, at the chosen reactor temperature and pressure;
see Example 4.1.
2. Equilibrium stage
In a separation or mixing unit, the anticipated equipment performance may be such that
it is reasonable to consider the outlet streams as being in equilibrium; the approach to
equilibrium being in practice close enough that no significant inaccuracy is introduced
144
CHEMICAL ENGINEERING
by assuming that equilibrium is reached. The stream compositions can then be calculated
from the phase equilibrium data for the components. This approximation can often be
made for single-stage gas-liquid and liquid-liquid separators, such as quench towers,
partial condensers and decanters. It is particularly useful if one component is essentially
non-condensable and can be used as a tie substance (see Section 2.11). Some examples
of the use of this process constraint are given in Examples 4.2 and 4.4.
3. Fixed stream compositions
If the composition (or flow-rate) of one stream is fixed by “internal” or “external”
constraints, this may fix the composition and flows of other process streams. In Chapter 1,
the relationship between the process variables, the design variables and design equations
was discussed. If sufficient design variables are fixed by external constraints, or by the
designer, then the other stream flows round a unit will be uniquely determined. For
example, if the composition of one product stream from a distillation column is fixed
by a product specification, or if an azeotrope is formed, then the other stream composition can be calculated directly from the feed compositions; see Section 2.10. The feed
composition would be fixed by the outlet composition of the preceding unit.
4. Combined heat and material balances
It is often possible to make a material balance round a unit independently of the heat
balance. The process temperatures may be set by other process considerations, and the
energy balance can then be made separately to determine the energy requirements to
maintain the specified temperatures. For other processes the energy input will determine
the process stream flows and compositions, and the two balances must be made simultaneously; for instance, in flash distillation or partial condensation; see also Example 4.1.
Example 4.1
An example illustrating the calculation of stream composition from reaction equilibria,
and also an example of a combined heat and material balance.
In the production of hydrogen by the steam reforming of hydrocarbons, the classic
water-gas reaction is used to convert CO in the gases leaving the reforming furnace to
hydrogen, in a shift converter.
CO(g) C H2 O(g) ! CO2 (g) C H2 (g)
HŽ298 41,197 kJ/kmol
In this example the exit gas stream composition from a converter will be determined for
a given inlet gas composition and steam ratio; by assuming that in the outlet stream the
gases reach chemical equilibrium. In practice the reaction is carried out over a catalyst,
and the assumption that the outlet composition approaches the equilibrium composition
is valid. Equilibrium constants for the reaction are readily available in the literature.
A typical gases composition obtained by steam reforming methane is:
CO2 8.5,
CO 11.0,
Ž
H2 76.5 mol per cent dry gas
If this is fed to a shift converter at 500 K, with a steam ratio of 3 mol H2 O to 1 mol CO,
estimate the outlet composition and temperature.
145
FLOW-SHEETING
Solution
Basis: 100 mol/h dry feed gas.
H2 O in feed stream D 3.0 ð 11.0 D 33 mol.
2
1
500°K
Shift converter
Let fractional conversion of CO to H2 be C. Then mols of CO reacted D 11.0 ð C. From
the stoichiometric equation and feed composition, the exit gas composition will be:
CO D 11.0⊲1 C⊳
CO2 D 8.5 C 11.0 ð C
H2 O D 33 11.0 ð C
H2 D 76.5 C 11.0 ð C
PCO ð PH2 O
Kp D
PCO2 ð PH2
At equilibrium
The temperature is high enough for the gases to be considered ideal, so the equilibrium
constant is written in terms of partial pressure rather than fugacity, and the constant will
not be affected by pressure. Mol fraction can be substituted for partial pressure. As the
total mols in and out is constant, the equilibrium relationship can be written directly in
mols of the components.
Kp D
Expanding and rearranging
11⊲1 C⊳⊲33 11C⊳
⊲8.5 C 11C⊳⊲76.5 C 11C⊳
⊲Kp 121 121⊳C2 C ⊲Kp 935 C 484⊳C C ⊲Kp 650 363⊳ D 0
⊲1⊳
Kp is a function of temperature.
For illustration, take T out D 700Ž K, at which Kp D 1.11 ð 101
107.6C2 C 587.8C 290.85 D 0
C D 0.57
The reaction is exothermic and the operation can be taken as adiabatic, as no cooling is
provided and the heat losses will be small.
The gas exit temperature will be a function of the conversion. The exit temperature
must satisfy the adiabatic heat balance and the equilibrium relationship.
A heat balance was carried over a range of values for the conversion C, using the
program Energy 1, Chapter 3. The value for which the program gives zero heat input or
146
CHEMICAL ENGINEERING
output required (adiabatic) is the value that satisfies the conditions above. For a datum
temperature of 25Ž C:
Data for energy-balance program
C°p (kJ/kmol)
Stream (mol)
Component
1
2
3
4
CO2
CO
H2 O
H2
1
2
a
8.5
11.0
33.0
76.5
8.5 C 11C
11⊲1 C⊳
33 11C
76.5 C 11C
19.80
30.87
32.24
27.14
b
7.34
1.29
l9.24
9.29
c
5.6
27.9
10.56
13.81
E-2
E-2
E-4
E-3
d
E-5
E-6
E-6
E-6
17.15
12.72
3.60
7.65
E-9
E-9
E-9
E-9
Results
Outlet
temp.
(K)
550
600
650
Outlet composition, mol
Kp
C
Mols
converted
1.86 ð 102
0.88
0.79
0.68
9.68
8.69
7.48
3.69 ð 102
6.61 ð 102
CO
CO2
H2 O
H2
Heat
required
Q
1.32
2.31
3.52
18.18
17.19
15.98
23.32
24.31
25.52
86.18
85.19
83.98
175,268
76,462
337,638
The values for the equilibrium constant Kp were taken from Technical Data on Fuel,
Spiers.
The outlet temperature at which Q D 0 was found by plotting temperature versus Q to
be 580 K.
At 580 K, Kp D 2.82 ð 102 .
From equation (1)
117.6C2 C 510.4 C 344.7 D 0,
C D 0.83
Outlet gas composition
CO2
CO
H2 O
H2
D
D
D
D
8.5 C 11 ð 0.83
11⊲1 0.83⊳
33.0 11 ð 0.83
76.5 C 11 ð 0.83
D 17.6
D 1.9
D 23.9
D 85.6
129.0 mol
In this example the outlet exit gas composition has been calculated for an arbitrarily
chosen steam: CO ratio of 3. In practice the calculation would be repeated for different
steam ratios, and inlet temperatures, to optimise the design of the converter system. Two
converters in series are normally used, with gas cooling between the stages. For large units
a waste-heat boiler could be incorporated between the stages. The first stage conversion
is normally around 80 per cent.
Example 4.2
This example illustrates the use of phase equilibrium relationships (vapour-liquid) in
material balance calculations.
147
FLOW-SHEETING
In the production of dichloroethane (EDC) by oxyhydrochlorination of ethylene, the
products from the reaction are quenched by direct contact with dilute HCl in a quench
tower. The gaseous stream from this quench tower is fed to a condenser and the uncondensed vapours recycled to the reactor. A typical composition for this stream is shown
in the diagram below; operating pressure 4 bar. Calculate the outlet stream compositions
leaving the condenser.
3
1
Recycle gas
Gas in
EDC
Ethylene
Inerts
Water
Temp
6350 kg/h
150
6640
1100
95°C
2
35°C
Condensate
Partial
condenser
The EDC flow includes some organic impurities and a trace of HCl. The inerts are
mainly N2 , CO, O2 non-condensable.
Solution
In order to calculate the outlet stream composition it is reasonable, for a condenser, to
assume that the gas and liquid streams are in equilibrium at the outlet liquid temperature
of 35Ž C.
The vapour pressures of the pure liquids can be calculated from the Antoine equation
(see Chapter 8):
At 35Ž C (308 K)
EDC
0.16 bar
Ethylene
70.7
H2 O
0.055
From the vapour pressures it can be seen that the EDC and water will be essentially
totally condensed, and that the ethylene remains as vapour. Ethylene will, however, tend
to be dissolved in the condensed EDC. As a first trial, assume all the ethylene stays in
the gas phase.
Convert flows to mol/h.
Mol wt.
EDC
C 2 H4
Inerts
H2 O
99
28
32 (estimated)
18
kmol/h
64
5.4 213.4
208
61
Take the “non-condensables” (ethylene and inerts) as the tie substance. Treat gas phase
as ideal, and condensed EDC-water as immiscible.
148
CHEMICAL ENGINEERING
Partial pressure of
non-condensables
D (total pressure) (vapour pressure of EDC C vapour
pressure of water)
D 4 0.16 0.055 D 3.79 bar
vapour press. EDC
ð flow non-condensables
partial press.
non-condensables
0.16
D
ð 213.4 D 9 kmol/h
3.79
0.055
Similarly, flow of H2 O
D
ð 213.4 D 3.1 kmol/h
in vapour
3.79
Flow of EDC in vapour D
So composition of gas streams is
EDC
H2 O
Inerts
C 2 H4
kmol/h
9
3.1
208
5.4
Per cent mol
4.0
1.4
92.3
2.3
kg/h
891
56
6640
150
Check on dissolved ethylene
Partial pressure of ethylene D total pressure ð mol fraction
2.3
D 4ð
D 0.092 bar
100
By assuming EDC and C2 H4 form an ideal solution, the mol fraction of ethylene
dissolved in the liquid can be estimated, from Raoults Law (see Chapter 8).
yA D
yA
xA
PAŽ
P
D
D
D
D
xA PAŽ
P
gas phase mol fraction,
liquid phase mol fraction,
sat. vapour pressure,
total pressure,
Substituting
2.3
xA 70.7
D
100
4
xA D 1.3 ð 103
hence quantity of ethylene in liquid D kmol EDC ð xA
D ⊲64 9⊳ ð 1.3 ð 103 D 0.07 kmol/h
so kmol ethylene in gas phase
D 5.4 0.07 D 5.33 kmol/h
149
FLOW-SHEETING
This is little different from calculated value and shows that initial assumption that
no ethylene was condensed or dissolved was reasonable; so report ethylene in liquid
as “trace”.
Material balance
Stream no.:
Title
EDC
H2 O
Ethylene
Inerts
Total
Flows (kg/h)
1
2
3
Condenser feed
Condensate
Recycle gas
6350
1100
150
6640
14,240
5459
1044
Trace
6503
891
56
150
6640
7737
95
4
35
4
35
4
Temp.Ž C
Pressure bar:
Example 4.3
This example illustrates the use of liquid-liquid phase equilibria in material balance calculations. The condensate stream from the condenser described in Example 4.2 is fed to a
decanter to separate the condensed water and dichloroethane (EDC). Calculate the decanter
outlet stream compositions.
2
1
Water
phase
Feed
EDC 5459 kg/h
Water 1075
3
Organic
phase
Solution
Assume outlet phases are in equilibrium.
The solubilities of the components at 20Ž C are:
EDC in water
Water in EDC
0.86 kg/100 kg
0.16 kg/100 kg
Note the water will contain a trace of HCl, but as data on the solubility of EDC in dilute
HCl are not available, the solubility in water will be used.
As the concentrations of dissolved water and EDC are small, the best approach to this
problem is by successive approximation; rather than by setting up and solving equations
for the unknown concentrations.
150
CHEMICAL ENGINEERING
As a first approximation take organic stream flow D EDC flow in.
Then water in EDC D
0.16
ð 5459 D 8.73 kg/h
100
So water flow out D 1075 8.73 D 1066.3 kg/h
and EDC dissolved in the water stream D
1066.3
ð 0.86 D 9.2 kg/h
100
so, revised organic stream flow D 5459 9.2 D 5449.8 kg/h
and quantity of water dissolved D
in the stream
5449.8
ð 0.16 D 8.72 kg/h
100
Which is not significantly lower than the first approximation. So stream flows, kg/h,
will be:
Stream no.
Title
1
Decanter
feed
2
Organic
phase
3
Aqueous
phase
EDC
H2 O
5459
1075
5449.8
8.7
9.2
1066.3
Total
6534
5458.5
1075.5
Example 4.4
This example illustrates the manual calculation of a material and energy balance for a
process involving several processing units.
Draw up a preliminary flow-sheet for the manufacture of 20,000 t/y nitric acid (basis
100 per cent HNO3 ) from anhydrous ammonia, concentration of acid required 50 to 60
per cent.
The technology of nitric acid manufacture is well established and has been reported in
several articles:
1. R. M. Stephenson: Introduction to the Chemical Process Industries (Reinhold, 1966).
2. C. H. Chilton: The Manufacture of Nitric Acid by the Oxidation of Ammonia
(American Institute of Chemical Engineers).
3. S. Strelzoff: Chem. Eng. NY 63(5), 170 (1956).
4. F. D. Miles: Nitric Acid Manufacture and Uses (Oxford University Press, 1961).
Three processes are used:
1. Oxidation and absorption at atmospheric pressure.
2. Oxidation and absorption at high pressure (approx. 8 atm).
3. Oxidation at atmospheric pressure and absorption at high pressure.
The relative merits of the three processes are discussed by Chilton (2), and Strelzoff (3).
151
FLOW-SHEETING
For the purposes of this example the high-pressure process has been selected. A typical
process is shown in the block diagram.
Air
Air
Water
Product
~60% HNO3
NH3
Vaporiser
Reactor
(Oxidiser)
Waste heat
boiler
Coolercondenser
Absorber
Schematic (block) diagram; production of nitric acid by oxidation of ammonia
The principal reactions in the reactor (oxidiser) are:
Reaction 1.
NH3 (g) C 45 O2 (g) ! NO(g) C 23 H2 O(g) HŽ298 D 226,334 kJ/kmol
Reaction 2.
NH3 (g) C 34 O2 (g) ! 21 N2 (g) C 32 H2 O(g)
The nitric oxide formed can also react with ammonia:
Reaction 3.
HŽ298 D 316,776 kJ/kmol
NH3 (g) C 32 NO(g) ! 45 N2 (g) C 23 H2 O(g) HŽ298 D 452,435 kJ/kmol
The oxidation is carried out over layers of platinum-rhodium catalyst; and the reaction
conditions are selected to favour reaction 1. Yields for the oxidation step are reported to
be 95 to 96 per cent.
Solution
Basis of the flow-sheet calculations
Typical values, taken from the literature cited:
1.
2.
3.
4.
5.
8000 operating hours per year.
Overall plant yield on ammonia 94 per cent.
Oxidiser (reactor) chemical yield 96 per cent.
Acid concentration produced 58 per cent w/w HNO3 .
Tail gas composition 0.2 per cent v/v NO.
Material balances
Basis: 100 kmol NH3 feed to reactor.
Oxidiser
Oxidiser
1
NH3
4
3
Air
2
152
CHEMICAL ENGINEERING
From reaction 1, at 96 per cent yield,
96
D 96 kmol
100
NO produced D 100 ð
oxygen required D 96 ð
5
4
D 120 kmol
water produced D 96 ð
3
2
D 144 kmol
The remaining 4 per cent ammonia reacts to produce nitrogen; production of 1 mol of N2
requires 23 mol of O2 , by either reaction 2 or 1 and 3 combined.
nitrogen produced D
4
2
D 2 kmol
oxygen required D 2 ð
3
2
D 3 kmol
All the oxygen involved in these reactions produces water,
water produced D 3 ð 2 D 6 kmol
So, total oxygen required and water produced;
water D 144 C 6 D 150 kmol
oxygen (stoichiometric) D 120 C 3 D 123 kmol
Excess air is supplied to the oxidiser to keep the ammonia concentration below the
explosive limit (see Chapter 9), reported to be 12 to 13 per cent (Chilton), and to provide
oxygen for the oxidation of NO to NO2 .
Reaction 4.
NO(g) C 21 O2 ! NO2 (g)
HŽ298 D 57,120 kJ/kmol
The inlet concentration of ammonia will be taken as 11 per cent v/v.
So, air supplied D
100
ð 100 D 909 kmol
11
Composition of air: 79 per cent N2 , 21 per cent O2 , v/v.
So, oxygen and nitrogen flows to oxidiser:
21
D 191 kmol
100
79
nitrogen D 909 ð
D 718 kmol
100
oxygen D 909 ð
And the oxygen unreacted (oxygen in the outlet stream) will be given by:
oxygen unreacted D 191 123 D 68 kmol
The nitrogen in the outlet stream will be the sum of the nitrogen from the air and that
produced from ammonia:
nitrogen in outlet D 718 C 2 D 720 kmol
153
FLOW-SHEETING
Summary, stream compositions:
Feed (3)
NH3
NO
H2 O
O2
N2
Outlet (4)
kmol
kg
kmol
kg
100
nil
trace
191
718
1700
nil
96
150
68
720
2880
2700
2176
20,016
6112
20,104
Total
27,916
27,916
Notes
(1) The small amount of water in the inlet air is neglected.
(2) Some NO2 will be present in the outlet gases, but at the oxidiser temperature used,
1100 to 1200 K, the amount will be small, typically <1 per cent.
(3) It is good practice always to check the balance across a unit by calculating the
totals; total flow in must equal total flow out.
Waste-heat boiler (WHB) and cooler-condenser
The temperature of the gases leaving the oxidiser is reduced in a waste-heat boiler and
cooler-condenser. There will be no separation of material in the WHB but the composition
will change, as NO is oxidised to NO2 as the temperature falls. The amount oxidised
will depend on the residence time and temperature (see Stephenson). The oxidation is
essentially complete at the cooler-condenser outlet. The water in the gas condenses in the
cooler-condenser to form dilute nitric acid, 40 to 50 per cent w/w.
Balance on cooler-condenser
5
6
7
The inlet stream (5) will be taken as having the same composition as the reactor outlet
stream (4).
Let the cooler-condenser outlet temperature be 40Ž C. The maximum temperature of the
cooling water will be about 30Ž C, so this gives a 10Ž C approach temperature.
If the composition of the acid leaving the unit is taken as 45 per cent w/w (a typical
value) the composition of the gas phase can be estimated by assuming that the gas and
condensed liquid are in equilibrium at the outlet temperature.
154
CHEMICAL ENGINEERING
Ž
At 40 C the vapour pressure of water over 45 per cent HNO3 is 29 mmHg (Perry’s
Chemical Engineers Handbook, 5th edn, pp. 3 65). Take the total pressure as 8 atm. The
mol fraction of water in the outlet gas stream will be given by the ratio of the vapour
pressure to the total pressure:
mol fraction water D
29
D 4.77 ð 103
760 ð 8
As a first trial, assume that all the water in the inlet stream is condensed, then:
water condensed D 150 kmol D 2700 kg
NO2 combines with this water to produce a 45 per cent solution:
Reaction 5. 3NO2 C H2 O ! 2HNO3 C NO
For convenience, take as a subsidiary basis for this calculation 100 kmol of HNO3 (100
per cent basis) in the condensate.
From reaction 5, the mols of water required to form 100 kmol HNO3 will be:
50 kmol D 900 kg
mass of 100 kmol HNO3 D 100 ð 63 D 6300 kg
water to dilute this to 45 per cent D
6300 ð 55
D 7700 kg
45
So, total water to form dilute acid D 900 C 7700 D 8600 kg.
Changing back to the original basis of 100 kmol NH3 feed:
HNO3 formed D 100 ð
D 100 ð
Water condensed per 100 kmol NH3 feed
Total water to form 45 per cent acid, per 100 kmol HNO3
2700
D 31.4 kmol
8600
NO2 consumed (from reaction 5) D 31.4 ð
3
2
1
2
D 47.1 kmol
NO formed D 31.4 ð D 15.7 kmol
H2 O reacted D 15.7 kmol
Condensed water not reacted with NO2 D 150 15.7 D 134.3 kmol.
The quantity of unoxidised NO in the gases leaving the cooler-condenser will depend
on the residence time and the concentration of NO and NO2 in the inlet stream. For
simplicity in this preliminary balance the quantity of NO in the outlet gas will be taken
as equal to the quantity formed from the absorption of NO2 in the condensate to form
nitric acid:
NO in outlet gas D 15.7 kmol
The unreacted oxygen in the outlet stream can be calculated by making a balance over
the unit on the nitric oxides, and on oxygen.
FLOW-SHEETING
155
Balance on oxides
Total ⊲NO C NO2 ⊳ entering D NO in stream 4 D 96 kmol
Of this, 31.4 kmol leaves as nitric acid, so (NO C NO2 ) left in the gas stream
D 96 31.4 D 64.6 kmol.
Of this, 15.7 kmol is assumed to be NO, so NO2 in exit gas D 64.6 15.7
D 48.9 kmol.
Balance on oxygen
Let unreacted O2 be x kmol. Then oxygen out of the unit will be given by:
H2 O
NO
3
C HNO3 C
C NO2 C x
gas
2
2
2 acid
stream ⊲7⊳
stream ⊲6⊳
3
15.7
134.3
D ⊲171 C x⊳ kmol
D
C 48.9 C x C
ð 31.4 C
2
2
2
NO
Oxygen into the unit D
C O2 C H2 O
2
stream ⊲5⊳
D
96
150
C 68 C
D 191 kmol
2
2
Equating O2 in and out:
unreacted O2 , x, D 191 171 D 20.0 kmol
As a first trial, all the water vapour was assumed to condense; this assumption will
now be checked.
The quantity of water in the gas stream will be given by:
mol fraction ð total flow.
The total flow of gas (neglecting water) = 804.6 kmol, and the mol fraction of water
was estimated to be 4.77 ð 103 .
So, water vapour D 4.77 ð 103 ð 804.6 D 3.8 kmol
And, mols of water condensed D 134.3 3.8 D 130.5 kmol.
The calculations could be repeated using this adjusted value for the quantity of water
condensed, to get a better approximation, but the change in the acid, nitric oxides, oxygen
and water flows will be small. So, the only change that will be made to the original
estimates will be to reduce the quantity of condensed water by that estimated to be in the
gas stream:
Water in stream ⊲6⊳ 3.8 kmol D 68.4 kg
So, water in stream (7) D 134.3 3.8 D 130.5 kmol D 2349 kg.
156
CHEMICAL ENGINEERING
Summary, stream compositions:
Gas (6)
NO
NO2
O2
N2
HNO3
H2 O
Acid (7)
kmol
kg
kmol
15.7
48.9
20.0
720
471.0
2249.4
640
20,160
Trace
Trace
3.8
68.4
Total
31.4
130.5
23,588.4
kg
1978.2
2349.0
4327.2
Total, stream ⊲6⊳ C ⊲7⊳ D 23,588.4 C 4327.2 D 27,915.6 kg, checks with inlet stream (4)
total of 27,915.
Absorber
In the absorber the NO2 in the gas stream is absorbed in water to produce acid of about
60 per cent w/w. Sufficient oxygen must be present in the inlet gases to oxidise the NO
formed to NO2 . The rate of oxidation will be dependent on the concentration of oxygen,
so an excess is used. For satisfactory operation the tail gases from absorber should contain
about 3 per cent O2 (Miles).
Tail
gas
10
11
Water
6
8
9
12
Secondary
air
From stream (6) composition:
NO in inlet stream to absorber D 15.7 kmol and O2 D 20.0 kmol
Note: Though the NO/NO2 ratio in this stream is not known exactly, this will not affect
the calculation of the oxygen required; the oxygen is present in the stream either as free,
uncombined oxygen or combined in the NO2 .
157
FLOW-SHEETING
So, O2 required to oxidise the NO in the inlet to stream to NO2 , from reaction 4, D
15.7 ð 21 D 7.85 kmol.
Hence, the “free” oxygen in the inlet stream D 20.0 7.85 D 12.15 kmol.
Combining reactions (4) and (5) gives the overall reaction for the absorption of NO2
to produce HNO3 .
Reaction 6.
4NO2 C 2H2 O C O2 ! 4HNO3
Using this reaction, the oxygen required to oxidise the NO formed in the absorber can be
calculated:
O2 required to oxidise NO formed D f⊲NO C NO2 ⊳ in stream ⊲6⊳g ð
D ⊲48.9 C 15.7⊳ ð
1
4
1
4
D 16.15 kmol
So O2 required for complete oxidation, in addition to that in inlet gas
D 16.15 12.15 D 4 kmol
Let the secondary air flow be y kmol. Then the O2 in the secondary air will be D
0.21 y kmol. Of this, 4 kmol react with NO in the absorber, so the free O2 in the tail
gases will be D 0.21 y 4 kmol.
N2 passes through the absorber unchanged, so the N2 in the tail gases D the N2 entering
the absorber from the cooler-condenser and the secondary air. Hence:
N2 in tail gas D 720 C 0.79 y kmol.
The tail gases are essentially all N2 and O2 (the quantity of other constituents is
negligible) so the percentage O2 in the tail gas will be given by:
O2 per cent D 3 D
from which
⊲0.21 y 4⊳100
⊲720 C 0.79 y⊳ C ⊲0.21 y 4⊳
y D 141.6 kmol
and the O2 in the tail gases D 141.6 ð 0.21 4 D 25.7 kmol
and the N2 in the tail gases D 720 C 111.8 D 831.8 kmol.
Tail gas composition, the tail gases will contain from 0.2 to 0.3 per cent NO, say 0.2
per cent, then:
0.2
D ⊲N2 C O2 ⊳ flow ð 0.002
100
D ⊲831.8 C 25.7⊳0.002 D 1.7 kmol
NO in tail gas D total flow ð
The quantity of the secondary air was based on the assumption that all the nitric oxides
were absorbed. This figure will not be changed as it was calculated from an assumed
(approximate) value for the concentration of the O2 in the tail gases. The figure for O2
in the tail gases must, however, be adjusted to maintain the balance.
The unreacted O2 can be calculated from Reactions (4) and (6). 1.7 kmol of NO are not
oxidised or absorbed, so the adjusted O2 in tail gases D 25.7 C 1.7⊲ 14 C 12 ⊳ D 27.0 kmol.
158
CHEMICAL ENGINEERING
The tail gases will be saturated with water at the inlet water temperature, say 25Ž C.
Partial pressure of water at 25Ž C D 0.032 atm. The absorber pressure will be approximately 8 atm, so mol fraction water D 0.032/8 D 4 ð 103 and H2 O in tail gas D
857.5 ð 4 ð 103 D 3.4 kmol.
Water required, stream (11).
The nitrogen oxides absorbed, allowing for the NO in the tail gases, will equal the
HNO3 formed
D ⊲48.9 C 15.7⊳ 1.7 D 62.9 kmol D 3962.7 kg
Stoichiometric H2 O required, from reaction 6
62.9
ð 2 D 31.5 kmol
4
The acid strength leaving the absorber will be taken as 60 per cent w/w. Then, water
required for dilution
D
3962.7
ð 0.4 D 2641.8 kg D 146.8 kmol
0.6
So, total water required, allowing for the water vapour in the inlet stream (6), but
neglecting the small amount in the secondary air
D
D 31.5 C 146.8 C 3.4 3.8 D 177.9 kmol
Summary, stream compositions:
Stream
Secondary air (8)
kmol
NO
NO2
O2
N2
HNO3
H2 O
29.7
111.8
Check on totals:
Acid (12)
kg
kmol
kg
950.4
3130.4
15.7
48.9
49.7
831.8
471.0
2249.4
1590.4
23,290.0
3.8
68.4
trace
Total
Inlet (9)
4080.8
kmol
kg
Tail gas (10)
kmol
kg
1.7
51.0
27.0
831.8
864
23,290.4
3.4
61.2
Water feed (11)
kmol
kg
177.9
3202.2
trace
62.9
146.8
27,669.2
3962.7
2641.8
6604.5
24,266.6
Stream ⊲6⊳ C ⊲8⊳ D ⊲9⊳? 4080.8 C 23,588.4 D 27,669.2
27,669.2 D 27,669.2 checks
Stream ⊲9⊳ C ⊲11⊳ D ⊲10⊳ C ⊲12⊳? 27,669.2 C 3203.2 D 24,266.6 C 6604.5
30,871.4 D 30,871.1 near enough.
Acid produced
12
7
Mixer
13
Product
3202.6
159
FLOW-SHEETING
From cooler-condenser HNO3
H2 O
From absorber
HNO3
H2 O
Totals
HNO3
H2 O
D
D
D
D
D
D
31.4
130.5
62.9
146.8
1978.2
2349.0
kmol
kmol
kmol
kmol
C 3962.7
C 2641.8
D
D
D
D
D
D
1978.2
2349.0
3962.7
2641.8
5940.9
4990.8
kg
kg
kg
kg
kg
kg
10,931.7 kg
So, concentration of mixed acids D
5940.9
ð 100 D 54 per cent.
10,931.7
Summary, stream composition:
Acid product (13)
Stream
kmol
HNO3
H2 O
94.3
277.3
kg
5940.3
4990.8
10,931.7
Overall plant yield
The overall yield can be calculated by making a balance on the combined nitrogen:
Yield D
94.3/2
mols N2 in HNO3 produced
D
D 94.3 per cent
mols N2 in NH3 feed
100/2
Note: the acid from the cooler-condenser could be added to the acid flow in the absorber,
on the appropriate tray, to produce a more concentrated final acid. The secondary air flow
is often passed through the acid mixer to strip out dissolved NO.
Scale-up to the required production rate
Production rate, 20,000 t/y HNO3 (as 100 per cent acid).
With 8000 operating hours per year
kg/h D
20,000 ð 103
D 2500 kg/h
8000
From calculations on previous basis:
100 kmol NH3 produces 5940.9 kg HNO3 .
So, scale-up factor D
2500
D 0.4208
5940.9
To allow for unaccounted physical yield losses, round off to 0.43
160
CHEMICAL ENGINEERING
All the stream flows, tabulated, were multiplied by this factor and are shown on the
flowsheet, Figure 4.2. A sample calculation is given below:
Stream (6) gas from condenser
NO
NO2
O2
N2
H2 O
Total
Mass 100 kmol NH3 basis
(kg)
471
2249.4
640.0
20,160.0
68.4
ð0.43 D
23,588.8
Mass flow for 20,000 t/y
(kg/h)
202.5
967.2
275.2
8668.0
29.4
10,143.1
Energy balance
Basis 1 hour.
Compressor
Calculation of the compressor power and energy requirements (see Chapter 3).
Inlet flow rate, from flow sheet D
Volumetric flow rate
13,027.7
D 0.125 kmol/s
29 ð 3600
288
D 2.95 m3 /s
273
From Figure 3.6, for this flow rate a centrifugal compressor would be used, Ep D 74 per
cent.
⊲n1⊳/n
n
P2
Work (per kmol) D Z1 T1 R
1
(3.31)
n1
P1
m
P2
(3.35)
Outlet temperature, T2 D T1
P1
at inlet conditions, 15Ž C, 1 bar D 0.125 ð 22.4 ð
As the conditions are well away from the critical conditions for air, equations (3.36a) and
(3.38a) can be used
⊲ 1⊳
⊲3.36a⊳
mD
Ep
nD
for air can be taken as 1.4
1
1m
1.4 1
D 0.39
1.4 ð 0.74
1
nD
D 1.64
1 0.39
mD
⊲3.38a⊳
161
FLOW-SHEETING
Ž
The inlet air will be at the ambient temperature, take as 15 C. With no intercooling
T2 D 288 ð 80.39 D 648 K
This is clearly too high and intercooling will be needed. Assume compressor is divided
into two sections, with approximately equal work in each section. Take the intercooler
gas outlet temperature as 60Ž C (which gives a reasonable approach to the normal cooling
water temperature of 30Ž C).
For equal work in each section the interstage pressure
p
Pout
D 8 D 2.83
D
Pin
Taking the interstage pressure as 2.83 atm will not give exactly equal work in each section,
as the inlet temperatures are different; however, it will be near enough for the purposes
of this example.
1.64
First section work, inlet 15Ž C D 1 ð 288 ð 8.314 ð
⊲2.83⊳⊲1.641⊳/1.64 1
1.64 1
D 3072.9 kJ/kmol
1.64
Second section work, inlet 60Ž C D 1 ð 333 ð 8.314 ð
⊲2.83⊳⊲1.641⊳/1.64 1
1.64 1
D 3552.6 kJ/kmol
Total work D 3072.9 C 3552.6 D 6625.5 kJ/kmol
work/kmol ð kmol/s
6625.5 ð 0.125
Compressor power D
D
efficiency
0.74
D 1119 kJ/s D 1.12 MW
Energy required per hour D 1.12 ð 3600 D 4032 MJ
Compressor outlet temperature D 333⊲2.83⊳0.39 D 500 K
say, 230Ž C
This temperature will be high enough for no preheating of the reactor feed to be needed
(Strelzoff).
Ammonia vaporiser
The ammonia will be stored under pressure as a liquid. The saturation temperature at
8 atm is 20Ž C. Assume the feed to the vaporiser is at ambient temperature, 15Ž C.
Specific heat at 8 bar D 4.5 kJ/kgK
Latent heat at 8 bar D 1186 kJ/kg
Flow to vaporiser D 731.0 kg/h
Heat input required to raise to 20Ž C and vaporise
D 731.0[4.5⊲20 15⊳ C 1186] D 883,413.5 kJ/h
add 10 per cent for heat losses D 1.1 ð 883,413.5 D 971,754.9 kJ/h
say, 972 MJ
162
CHEMICAL ENGINEERING
Mixing tee
air
230°C
11,272.9 kg/h
t3
NH3 vapour 731.0 kg/h
20°C
Cp air D 1 kJ/kgK,
Cp ammonia vapour 2.2 kJ/kgK.
Note: as the temperature of the air is only an estimate, there is no point in using other
than average values for the specific heats at the inlet temperatures.
Energy balance around mixing tee, taking as the datum temperature the inlet temperature
to the oxidiser, t3 .
11,272.9 ð 1⊲230 t3 ⊳ C 731 ð 2.2⊲20 t3 ⊳ D 0
t3 D 204Ž C
Oxidiser
The program ENERGY 1 (see Chapter 3) was used to make the balance over on the
oxidiser. Adiabatic operation was assumed (negligible heat losses) and the outlet temperature found by making a series of balances with different outlet temperatures to find the
value that reduced the computed cooling required to zero (adiabatic operation). The data
used in the program are listed below:
HŽr reaction 1 D 226,334 kJ/kmol (per kmol NH3 reacted)
HŽr reaction 2 D 316,776 kJ/kmol (per kmol NH3 reacted)
All the reaction yield losses were taken as caused by reaction 2.
NH3 reacted, by reaction 1
731.0 ð 0.96
D 41.3 kmol/h
Flow of NH3 to oxidiser ð reactor yield D
17
731.0 ð 0.04
balance by reaction 2 D
D 1.7 kmol/h
17
Summary, flows and heat capacity data:
Stream
component
NH3
O2
N2
NO
H2 O
Temp. K
Feed
(3)
kmol/h
43
82.1
308.7
477
Product
(4)
kmol/h
29.2
309.6
41.3
64.5
T4
CŽp kJ/kmol K
a
b
c
d
27.32
28.11
31.15
29.35
32.24
23.83E-3
3.68E-6
1.36E-2
0.94E-3
19.24E-4
17.07E-6
17.46E-6
26.80E-6
9.75E-6
10.5E-6
11.85E-9
10.65E-9
11.68E-9
4.19E-9
3.60E-9
The outlet temperature T4 was found to be 1180 K D 907Ž C.
163
FLOW-SHEETING
Waste-heat boiler (WHB)
As the amount of NO oxidised to NO2 in this unit has not been estimated, it is not possible
to make an exact energy balance over the unit. However, the maximum possible quantity
of steam generated can be estimated by assuming that all the NO is oxidised; and the
minimum quantity by assuming that none is. The plant steam pressure would be typically
150 to 200 psig ³ 11 bar, saturation temperature 184Ž C. Taking the approach temperature
of the outlet gases (difference between gas and steam temperature) to be 50Ž C, the gas
outlet temperature will be D 184 C 50 D 234Ž C (507 K).
1238.4
From the flow-sheet, NO entering WHB D
D 41.3 kmol
30
935.7
D 29.2 kmol/h
O2 entering D
32
If all the NO is oxidised, reaction 4, the oxygen leaving the WHB will be reduced to
41.3
29.2
D 8.6 kmol/h
2
HŽr D 57,120 kJ/kmol, NO oxidised
If no NO is oxidised the composition of the outlet gas will be the same as the inlet. The
inlet gas has the same composition as the reactor outlet, which is summarised above.
Summarised below are the flow changes if the NO is oxidised:
CŽp (kJ/kmol K)
O2
NO2
Temp.
(kmol/h)
a
b
7.46
41.3
507K
24.23
4.84 E-2
c
as above
20.81 E-2
d
0.29 E-9
Using the program ENERGY 1, the following values were calculated for the heat transferred to the steam:
no NO oxidised
9.88 GJ/h
all NO oxidised 12.29 GJ/h
Steam generated; take feed water temperature as 20Ž C,
enthalpy of saturated steam at 11 bar D 2781 kJ/kg
enthalpy of water at 20Ž C D 84 kJ/kg
heat to form 1 kg steam D 2781 84 D 2697 kJ
steam generated D
heat transferred
enthalpy change per kg
so, minimum quantity generated D
maximum D
9,880,000
D 3662 kg/h
2697
12,290,000
D 4555 kg/h
2697
164
CHEMICAL ENGINEERING
Note: in practice superheated steam would probably be generated, for use in a turbine
driving the air compressor.
Cooler-condenser
The sources of heat to be considered in the balance on this unit are:
1. Sensible heat: cooling the gases from the inlet temperature of 234Ž C to the required
outlet temperature (the absorber inlet temperature) 40Ž C.
2. Latent heat of the water condensed.
3. Exothermic oxidation of NO to NO2 .
4. Exothermic formation of nitric acid.
5. Heat of dilution of the nitric acid formed, to 40 per cent w/w.
6. Sensible heat of the outlet gas and acid streams.
So that the magnitude of each source can be compared, each will be calculated separately.
Take the datum temperature as 25Ž C.
1. Gas sensible heat
The program ENERGY 1 was used to calculate the sensible heat in the inlet and outlet
gas streams. The composition of the inlet stream and the heat capacity data will be
the same as that for the WHB outlet given above. Outlet stream flows from flow-sheet,
converted to kmol/h:
Condenser outlet (6)
O2
N2
NO
NO2
H2 O
kmol/h
8.6
309.6
6.75
21.03
1.63
Temp. 313 K
Sensible heat inlet stream (5) D 2.81 GJ/h,
outlet stream (6) D 0.15 GJ/h.
2. Condensation of water
Water condensed D ⊲inlet H2 O outlet H2 O⊳ D ⊲1161 29⊳ D 1131.6 kg/h
Latent heat of water at the inlet temperature, 230Ž C D 1812 kJ/kg
The steam is considered to condense at the inlet temperature and the condensate then
cooled to the datum temperature.
Heat from condensation D 1131.6 ð 1812 D 2.05 ð 106 kJ/h
Sensible heat to cool condensate D 1131.6 ð 4.18⊲230 25⊳
D 0.97 ð 106 kJ/h
Total, condensation and cooling D ⊲2.05 C 0.97⊳106 kJ/h
D 3.02 GJ/h
165
FLOW-SHEETING
3. Oxidation of NO
The greatest heat load will occur if all the oxidation occurs in the cooler-condenser (i.e.
none in the WHB) which gives the worst condition for the cooler-condenser design.
Mols of NO oxidised D mols in mols out D 41.3 6.75 D 34.55 kmol/h
From reaction 4, heat generated D 34.55 ð 57,120
D 1.97 ð 106 kJ/h D 1.97 GJ/h
4. Formation of nitric acid
850.6
D 13.50 kmol/h
63
The enthalpy changes in the various reactions involved in the formation of aqueous nitric
acid are set out below (Miles):
HNO3 formed, from flow sheet, D
2NO2 ⊲g⊳ ! N2 O4 ⊲g⊳
N2 O4 ⊲g⊳ C H2 O⊲l⊳ C 12 O2 ⊲g⊳ ! 2HNO3 ⊲g⊳
HNO3 ⊲g⊳ ! HNO3 ⊲l⊳
H D 57.32 kJ
H D C 9.00 kJ
H D 39.48 kJ
⊲6a⊳
⊲6b⊳
⊲7⊳
Combining reactions 6a, 6b and 7.
Reaction 8.
2NO2 ⊲g⊳ C H2 O⊲l⊳ C 12 O2 ! 2HNO3 ⊲l⊳
overall enthalpy change D 57.32 C 9.00 C 2⊲39.48⊳
D 127.28 kJ
127.28
ð 103
2
D 63,640 kJ
heat generated D 13.50 ð 63,640 D 0.86 ð 106 kJ/h
D 0.86 GJ/h
heat generated per kmol of HNO3 (l) formed D
Note, the formation of N2 O4 and the part played by N2 O4 in the formation of nitric acid
was not considered when preparing the flow-sheet, as this does not affect the calculation
of the components flow-rates.
5. Heat of dilution of HNO3
The heat of dilution was calculated from an enthalpy concentration diagram given in
Perry’s Chemical Engineers Handbook, 5th edn, p. 3.205, Figure 3.42.
The reference temperature for this diagram is 32Ž F (0Ž C). From the diagram:
enthalpy of 100 per cent HNO3 D 0
enthalpy of 45 per cent HNO3 D 80 Btu/lb solution
specific heat 45 per cent HNO3 D 0.67
So, heat released on dilution, at 32Ž F D 80 ð 4.186/1.8 D 186 kJ/kg soln.
Heat to raise solution to calculation datum temperature of 25Ž C D 0.67⊲25 0⊳4.186
D 70.1 kJ/kg.
So, heat generated on dilution at 25Ž C D 186 70.1 D 115.9 kJ/kg soln.
166
CHEMICAL ENGINEERING
63
ð 100
45
D 140 kg,
Quantity of solution produced by dilution of 1 kmol 100 per cent HNO3 D
so, heat generated on dilution of 1 kmol D 140 ð 115.9 D 16,226 kJ,
so, total heat generated D 13.5 ð 16,226 D 219,051 kJ/h
D 0.22 GJ/h.
6. Sensible heat of acid
Acid outlet temperature was taken as 40Ž C, which is above the datum temperature.
Sensible heat of acid D 0.67 ð 4.186⊲40 25⊳ ð 1860.7 D 78,278 kJ/h D 0.08 GJ/h
Heat balance (GJ/h)
Heat to cooling
water
Gas in
2.81
Oxidation
1.97
Condensation
3.02
HNO3 formation 0.86
Dilution
0.22
Total
6.07
Gas out
0.15
Liquid out
0.08
Heat transferred to cooling water D 2.81 C 6.07 0.15 0.08
D 8.65 GJ/h
Air cooler
The secondary air from the compressor must be cooled before mixing with the process
gas stream at the absorber inlet; to keep the absorber inlet temperature as low as possible.
Take the outlet temperature as the same as exit gases from the cooler condenser, 40Ž C.
Secondary air flow, from flow-sheet, 1754.8 kg/h
Specific heat of air 1 kJ/kgK
Heat removed from secondary air D 1754.8 ð 1 ð ⊲230 40⊳
D 333,412 kJ/h D 0.33 GJ/h
Absorber
The sources of heat in the absorber will be the same as the cooler-condenser and the same
calculation methods have been used. The results are summarised below:
Sensible
Sensible
Sensible
Sensible
heat
heat
heat
heat
in
in
in
in
inlet gases from cooler-condenser D 0.15 GJ/h
secondary air D 1754.8 ð 1.0⊲40 25⊳ D 0.018 GJ/h
tail gases (at datum) D 0
water feed (at datum) D 0
167
FLOW-SHEETING
202.5 21.9
D 6.02 kmol/h
30
Heat generated D 6.02 ð 57,120 D 0.34 GJ/h
1704
HNO3 formed D
D 27.05 kmol/h
63
Heat generated D 27.05 ð 63,640 D 1.72 GJ/h
NO oxidised
D
Heat of dilution to 60 per cent at 25Ž C D 27.05 ð 14,207 D 0.38 GJ/h
Water condensed D 29.4 26.3 D 3.1 kg/h
Latent heat at 40Ž C D 2405 kJ/h
Sensible heat above datum temperature D 4.18 (40 25) D 63 kJ/kg
Heat released D 3.1⊲2405 C 63⊳ D 7.6 ð 103 GJ/h (negligible)
Sensible heat in acid out, specific heat 0.64, take temperature out as same as gas
inlet, 40Ž C
D 0.64⊲40 25⊳4.18 ð 2840 D 0.11 GJ/h
Heat balance (GJ/h)
Tail gas
0.0
Oxidation
HNO3
Dilution
Condensation
0.34
1.72
0.38
2.44
Gas
in
0.15
Water
0.0
Heat to
cooling
water
Sec. air
0.018
0.11
Acid out
Heat transferred to cooling water D 0.15 C 0.018 C 2.44 0.11 D 2.5 GJ/h
Mixer
Calculation of mixed acid temperature.
Taking the datum as 0Ž C for this calculation, so the enthalpy-concentration diagram
can be used directly.
From diagram:
enthalpy 45 per cent acid at 0Ž C D 186 kJ/kg
specific heat D 0.67 kcal/kgŽ C
enthalpy 60 per cent acid at 0Ž C D 202 kJ/kg
specific heat D 0.64 kcal/kgŽ C
168
CHEMICAL ENGINEERING
So, enthalpy 45 per cent acid at 40Ž C D 186 C 0.67 ð 4.186⊲40⊳ D 73.8 kJ/kg
and enthalpy 60 per cent acid at 40Ž C D 202 C 0.64 ð 4.186⊲40⊳ D 94.8 kJ/kg
⊲73.8 ð 1860.7⊳ C ⊲94.8 ð 2840.0⊳
⊲1860.7 C 2840.0⊳
D 86.5 kJ/kg
Enthalpy of mixed acid D
From enthalpy-concentration diagram, enthalpy of mixed acid
(54 per cent) at 0Ž C D 202 kJ/kg; specific heat D 0.65 kcal/kgŽ C
so, “sensible” heat in mixed acid above datum of 0Ž C
D 86.5 ⊲202⊳ D 115.5 kJ/kg
and, mixed acid temperature D
115.5
D 43Ž C
0.65 ð 4.186
Energy recovery
In an actual nitric acid plant the energy in the tail gases would normally be recovered
by expansion through a turbine coupled to the air compressor. The tail gases would be
preheated before expansion, by heat exchange with the process gas leaving the WHB.
4.4. COMPUTER-AIDED FLOW-SHEETING
The computer programs available for flow-sheeting in process design can be classified
into two basic types:
1. Full simulation programs, which require powerful computing facilities.
2. Simple material balance programs requiring only a relatively small core size.
The full simulation programs are capable of carrying out rigorous simultaneous heat and
material balances, and preliminary equipment design: producing accurate and detailed
flow-sheets. In the early stages of a project the use of a full simulation package is often
not justified and a simple material balance program is more suitable. These are an aid
to manual calculations and enable preliminary flow-sheets to be quickly, and cheaply,
produced.
4.5. FULL STEADY-STATE SIMULATION PROGRAMS
Complex flow-sheeting programs, that simulate the operation and a complete process,
or individual units, have been developed by several commercial software organisations.
The names of the principal packages available, and the contact address, are listed in
Table 4.1. Many of the commercial programs have been made available by the proprietors
to university and college departments for use in teaching, at nominal cost.
169
FLOW-SHEETING
Table 4.1.
Simulation packages
Acronym
Type
Source
Internet address
http//www.—
ASPEN
steady-state
Aspen Technology Inc.
Ten Canal Park,
Cambridge, MA
02141-2201,
USA
WinSim Inc.
P.O. Box 1885,
Houston,
TX 77251-1885, USA
Hyprotech
Suite 900, 125-9 Avenue SE,
Calgary, Alberta,
T2G-OP6, Canada
Merged with Aspen Tech
SimSci-Esscor
5760 Fleet Street,
Suite 100, Carlsbad,
CA 92009, USA
Chemstations Inc.
2901 Wilcrest, Suite 305,
Houston, TX 77042
USA
Aspentech.com
Aspen DPS
DESIGN II
steady-state
HYSYS
steady-state
dynamic
PRO/II
steady-state
DYNSIM
dynamic
CHEMCAD
steady-state
winsim.com
hyprotech.com
simsci.com
chemstations.net
Note: Contact the web site to check the full features of the current versions of the programs.
Detailed discussion of these programs is beyond the scope of this book. For a general
review of the requirements, methodology and application of process simulation programs
the reader is referred to the books by: Husain (1986), Wells and Rose (1986), Leesley
(1982), Benedek (1980), Mah and Seider (1980), Westerberg et al. (1979) and Crowe
et al. (1971); and the paper by Panelides (1988).
Process simulation programs can be divided into two basic types:
Sequential-modular programs: in which the equations describing each process unit
(module) are solved module-by-module in a stepwise manner; and iterative techniques
used to solve the problems arising from the recycle of information.
They simulate the steady-state operation of the process and can be used to draw-up
the process flow sheet, and to size individual items of equipment, such as distillation
columns.
Equation based programs: in which the entire process is described by a set of differential
equations, and the equations solved simultaneously: not stepwise, as in the sequential
approach. Equation based programs can simulate the unsteady-state operation of processes
and equipment.
In the past, most simulation programs available to designers were of the sequentialmodular type. They were simpler to develop than the equation based programs, and
required only moderate computing power. The modules are processed sequentially, so
essentially only the equations for a particular unit are in the computer memory at one
time. Also, the process conditions, temperature, pressure, flow-rate, are fixed in time.
170
CHEMICAL ENGINEERING
But, computational difficulties can arise due to the iterative methods used to solve recycle
problems and obtain convergence. A major limitation of modular-sequential simulators is
the inability to simulate the dynamic, time dependent, behaviour of a process.
Equation based, dynamic, simulators require appreciably more computing power than
steady-state simulators; to solve the thousands of differential equations needed to describe
a process, or even a single item of equipment. However, with the development of fast
powerful machines this is no longer a restriction. By their nature, equation based programs
do not experience the problems of recycle convergence inherent in sequential simulators.
But, as temperature, pressure and flow-rate are not fixed and the input of one unit is not
determined by the calculated output from the previous unit in the sequence, as with steadystate simulators, equation based programs are more time demanding on computer time.
This has led to the development of hybrid programs in which the steady-state simulator
is used to generate the initial conditions for the dynamic simulation.
The principal advantage of equation based, dynamic, simulators is their ability to model
the unsteady-state conditions that occur at start-up and during fault conditions. Dynamic
simulators are being increasingly used for safety studies and in the design of control
systems.
The structure of a typical simulation program is shown in Figure 4.4.
Data input
Thermodynamic
sub-routines
Convergence
promotion
sub-routines
Physical
property
data files
Cost data
files
Figure 4.4.
Executive program (organisation of the problem)
Equipment
sub-routines
Library and
specials
Data
output
A typical simulation program
The program consists of:
1. A main executive program; which controls and keeps track of the flow-sheet calculations and the flow of information to and from the sub-routines.
FLOW-SHEETING
171
2. A library of equipment performance sub-routines (modules); which simulate the
equipment and enable the output streams to be calculated from information on the
inlet streams.
3. A data bank of physical properties. To a large extent the utility of a sophisticated flow-sheeting program will depend on the comprehensiveness of the physical
property data bank. The collection of the physical property data required for the
design of a particular process, and its transformation into a form suitable for a
particular flow-sheeting program can be very time-consuming.
4. Sub-programs for thermodynamic routines; such as the calculation of vapour-liquid
equilibria and stream enthalpies.
5. Sub-programs and data banks for costing; the estimation of equipment capital costs
and operating costs. Full simulation flow-sheeting programs enable the designer to
consider alternative processing schemes, and the cost routines allow quick economic
comparisons to be made. Some programs include optimisation routines. To make use
of a costing routine, the program must be capable of producing at least approximate
equipment designs.
In a sequential-modular program the executive program sets up the flow-sheet sequence,
identifies the recycle loops, and controls the unit operation calculations: interacting with
the unit operations library, physical property data bank and the other sub-routines. It will
also contain procedures for the optimum ordering the calculations and routines to promote
convergence.
In an equation based simulators the executive program sets up the flow-sheet and the
set of equations that describe the unit operations, and then solves the equations; taking
data from the unit operations library and physical property data bank and the file of
thermodynamic sub-routines.
Many of the proprietary flow-sheeting packages are now front-ended with a graphical
user interface to display the flow-sheet and facilitate the input of information to the package.
4.5.1. Information flow diagrams
To present the problem to the computer, the basic process flow diagram, which shows
the sequence of unit operations and stream connections, must be transformed into an
information flow diagram, such as that shown in Figure 4.5b. Each block represents a
calculation module in the simulation program; usually a process unit or part of a unit. Units
in which no change of composition, or temperature or pressure, occurs are omitted from
the information flow diagram. But other operations not shown on the process flow diagram
as actual pieces of equipment, but which cause changes in the stream compositions, such
as mixing tees, must be shown.
The lines and arrows connecting the blocks show the flow of information from one
subprogram to the next. An information flow diagram is a form of directed graph (a
diagraph).
The calculation topology defined by the information diagram is transformed into a
numerical form suitable for input into the computer, usually as a matrix.
172
CHEMICAL ENGINEERING
Purge
Compressor
Decanter
Condenser
Decanter
Hydrogen
Nitrobenzene
Vaporiser
Reactor
2
Hydrogen
1
Mixing
tee
Nitrobenzene
3
Distillation
column
(a)
Purge
Crude
aniline
Splitting
tee
4
5
6
Reactor Condenser Decanter
Vaporiser
7
Mixing
tee
(b)
8
9
Decanter
Crude
aniline
Note: (1) Modules have been added to represent mixing and separation tees.
(2) The compressor is omitted.
(3) The distillation module includes the condenser and reboiler.
Figure 4.5.
(a) Process flow diagram: hydrogenation of nitrobenzene to aniline (b) Information flow diagram
hydrogenation of nitrobenzene to aniline (Figure 4.5a)
4.6. MANUAL CALCULATIONS WITH RECYCLE STREAMS
If a proprietary simulation program is not available, problems involving recycle streams
can be solved on a spreadsheet using the procedure described below.
The procedure is based on the theory of recycle processes published by Nagiev (1964).
The concept of split-fractions is used to set up the set of simultaneous equations that
define the material balance for the process. This method has also been used by Rosen
(1962) and is described in detail in the book by Henley and Rosen (1969).
4.6.1. The split-fraction concept
In an information flow diagram, such as that shown in Figure 4.5b, each block represents a calculation module; that is, the set of equations that relate the outlet stream
component flows to the inlet flows. The basic function of most chemical processing units
(unit operations) is to divide the inlet flow of a component between two or more outlet
173
FLOW-SHEETING
streams; for example, a distillation column divides the components in the feed between
the overhead and bottom product streams, and any side streams. It is therefore convenient, when setting up the equations describing a unit operation, to express the flow of
any component in any outlet stream as a fraction of the flow of that component in the
inlet stream.
The block shown in Figure 4.6 represents any unit in an information flow diagram, and
shows the nomenclature that will be used in setting up the material balance equations.
Total flow
Flows from
other units
Unit
i
λ ik
Flows from
outside
system
g
Flows out
to other units
λ ik . α jik
αj
ik
i0k
To
unit j
From Component
unit i
Figure 4.6.
i D the unit number,
i,k D the total flow into the unit i of the component k,
˛j,i,k D the fraction of the total flow of component k entering unit i that leaves in the
outlet stream connected to the unit j; the “split-fraction coefficient”,
gi,0,k D any fresh feed of component k into unit i; flow from outside the system (from
unit 0).
The flow of any component from unit i to unit j will equal the flow into unit i multiplied
by the split-fraction coefficient.
D i,k ð ˛j,i,k
The value of the split-fraction coefficient will depend on the nature of the unit and the
inlet stream composition.
The outlet streams from a unit can feed forward to other units, or backward (recycle).
An information flow diagram for a process consisting of three units, with two recycle
streams is shown in Figure 4.7. The nomenclature defined in Figure 4.6 is used to show
the stream flows.
α13k λ 3k
α31k λ 1k
λ1k
λ 2k
α32k λ 2k
1
2
3
α21k λ 1k
λ 3k
g
10k
g
α12k λ 2k
30k
Figure 4.7.
174
CHEMICAL ENGINEERING
Consider the streams entering unit 1.
α13k λ 3k
λ
1k
1
g
α12k λ2k
10k
Figure 4.8.
A material balance gives:
g10k C ˛13k 3k C ˛12k 2k D 1k
⊲4.1⊳
A similar material balance can be written at the inlet to each unit:
unit 2: ˛21k 1k D 2k
⊲4.2⊳
unit 3: ˛32k 2k C g30k C ˛31k 1k D 3k
⊲4.3⊳
Rearranging each equation
1k ˛12k 2k ˛13k 3k D g10k
⊲4.1a⊳
˛21k 1k C 2k D 0
⊲4.2b⊳
˛31k 1k ˛32k 2k C 3k D g30k
⊲4.3c⊳
This is simply a set of three simultaneous equations in the unknown flows 1k , 2k , 3k .
These equations are written in matrix form:
i
1
1
1
j 2 ˛21k
3 ˛31k
2
˛12k
1
˛32k
3
˛13k
1k
g10
0 ð 2k D 0
1
g30
3k
There will be a set of such equations for each component.
This procedure for deriving the set of material balance equations is quite general. For
a process with n units there will be a set of n equations for each component.
The matrix form of the n equations will be as shown in Figure 4.9.
⊲1 ˛11k ⊳ ˛12k ˛13k
˛21k ⊲1 ˛22k ⊳ ˛23k
˛n 1k . . . . . . . . . . . . . . . .
Figure 4.9.
...
...
˛1nk
˛2nk
...
⊲1 ˛⊳nnk
1k
2k
ð
nk
g10k
g20k
D
Matrix form of equations for n units
gn 0k
175
FLOW-SHEETING
For practical processes most of the split-fraction coefficients are zero and the matrix is
sparse.
In general, the equations will be non-linear, as the split-fractions coefficients (˛’s)
will be functions of the inlet flows, as well as the unit function. However, many of the
coefficients will be fixed by the process constraints, and the remainder can usually be
taken as independent of the inlet flows (’s) as a first approximation.
The fresh feeds will be known from the process specification; so if the split-fraction
coefficients can be estimated, the equations can be solved to determine the flows of
each component to each unit. Where the split-fractions are strongly dependent on the
inlet flows, the values can be adjusted and the calculation repeated until a satisfactory
convergence between the estimated values and those required by the calculated inlet flows
is reached.
Processes with reaction
In a chemical reactor, components in the inlet streams are consumed and new components, not necessarily in the inlet streams, are formed. The components formed cannot
be shown as split-fractions of the inlet flows and must therefore be shown as pseudo
fresh-feeds.
A reactor is represented as two units (Figure 4.10). The split-fractions for the first unit
are chosen to account for the loss of material by reaction. The second unit divides the
reactor output between the streams connected to the other units. If the reactor has only
one outlet stream (one connection to another unit), the second unit forming the reactor
can be omitted.
λ1kα 01K
λ1k
Material
consumed
1
λ 2k
2
λ 2kα j2k
g
20k
Material
formed
Figure 4.10.
λ1k(1-α01k)
Reactor unit
Closed recycle systems
In some processes, a component may be recycled around two or more units in a closed
loop. For example, the solvent in an absorption or liquid extraction process will normally
be recovered by distillation and recycled. In this situation it will be necessary to introduce
the solvent as a pseudo fresh-feed and the to remove it from the recycle loop by introducing
a dummy stream divider, purging one stream.
As, in practice, some of the recycling component will always be lost, the amount purged
should be adjusted to allow for any losses that are identified on the flow-sheet.
176
CHEMICAL ENGINEERING
4.6.2. Illustration of the method
The procedure for setting up the equations and assigning suitable values to the splitfraction coefficients is best illustrated by considering a short problem: the manufacture of
acetone from isopropyl alcohol.
Process description
heat
Reaction:
C3 H7 OH ! ⊲CH3 ⊳2 CO C H2
cat.
Isopropyl alcohol is vaporised, heated and fed to a reactor, where it undergoes catalytic
dehydrogenation to acetone. The reactor exit gases (acetone, water, hydrogen and unreacted
isopropyl alcohol) pass to a condenser where most of the acetone, water and alcohol
condense out. The final traces of acetone and alcohol are removed in a water scrubber.
The effluent from the scrubber is combined with the condensate from the condenser, and
distilled in a column to produce “pure” acetone and an effluent consisting of water and
alcohol. This effluent is distilled in a second column to separate the excess water. The
product from the second column is an azeotrope of water and isopropyl alcohol containing
approximately 91 per cent alcohol. This is recycled to the reactor. Zinc oxide or copper is
used as the catalyst, and the reaction carried out at 400 to 500Ž C and 40 to 50 psig pressure
(4.5 bar). The yield to acetone is around 98 per cent, and the conversion of isopropyl
alcohol per pass through the reactor is 85 to 90 per cent.
Water
H2
;;;;;;
Isopropyl alcohol
feed
Condenser
Preheater
Vaporiser
Reactor
Scrubber
Reflux
condenser
Acetone
Column 2
Column 1
Boiler
Water
Recycle alcohol
Figure 4.11.
Process flow diagram
The process flow diagram is shown in Figure 4.11. This diagram is simplified and
drawn as an information flow diagram in Figure 4.12. Only those process units in which
there is a difference in composition between the inlet and outlet streams are shown. The
177
FLOW-SHEETING
H
vent
Alcohol feed
Reactor
1
Condenser
2
Acetone
product
Water
Scrubber
3
Water
Coln 1
4
Coln 2
5
Bypass
Recycle
Figure 4.12.
Information flow diagram
preheater and vaporiser are not shown, as there is no change in composition in these units
and no division of the inlet stream into two or more outlet streams.
Figure 4.12 is redrawn in Figure 4.13, showing the fresh feeds, split-fraction coefficients and component flows. Note that the fresh feed g20k represents the acetone and
hydrogen generated in the reactor. There are 5 units so there will be 5 simultaneous
equations. The equations can be written out in matrix form (Figure 4.14) by inspection
of Figure 4.13. The fresh feed vector contains three terms.
A
g
10k
B
1
C
2
α54kλ4k
α43kλ3k
α32kλ2k
α21kλ1k
λ5k
λ4k
λ3k
λ2k
λ1k
D
3
E
4
5
α42kλ 2k
g
20k
Acetone
hydrogen
{
}
g
30k
{Water}
α15kλ5k
{Isopropyl
alcohol }
Figure 4.13.
1
1
2
3
4
5
1
˛21k
0
0
0
Split-fractions and fresh feeds
2
3
4
5
0
1
˛32k
˛42k
0
0
0
1
˛43k
0
0
0
0
1
˛54k
˛15k
0
0
0
1
Figure 4.14.
1k
2k
ð
3k
4k
5k
g10k
g20k
D
g30k
0
0
The set of equations
Estimation of the split-fraction coefficients
The values of the split-fraction coefficients will depend on the function of the processing
unit and the constraints on the stream flow-rates and compositions. Listed below are
suggested first trial values, and the basis for selecting the particular value for each
component.
178
CHEMICAL ENGINEERING
Component 1, isopropyl alcohol (k D 1)
Unit 1, Reactor. The conversion per pass is given as 90 per cent, so for each mol entering
only 10 per cent leave, hence ˛211 is fixed at 0.1. For this example it is assumed that
the conversion is independent of the feed stream composition.
Unit 2, Condenser. Most of the alcohol will condense as its boiling point is 82Ž C. Assume
90 per cent condensed, ˛421 D 0.9 (liquid out) and ˛321 D 0.1 (vapour out). The
actual amounts will depend on the condenser design.
Unit 3, Scrubber. To give a high plant yield, the scrubber would be designed to recover
most of the alcohol in the vent stream. Assume 99 per cent recovery, allowing for
the small loss that must theoretically occur, ˛431 D 0.99.
Unit 4, First column. The fraction of alcohol in the overheads would be fixed by the
amount allowed in the acetone product specification. Assume 1 per cent loss to the
acetone is acceptable, which will give less than 1 per cent alcohol in the product;
fraction in the bottoms 99 per cent, ˛541 D 0.99.
Unit 5, Second column. No distillation column can be designed to give complete separation
of the components. However, the volatilities for this system are such that a high
recovery of alcohol should be practicable. Assume 99 per cent recovery, alcohol
recycled, ˛151 D 0.99.
Component 2, Acetone (k D 2)
Unit 1. Assume that any acetone in the feed passes through the reactor unchanged,
˛212 D 1.
Unit 2. Most of the acetone will condense (b.p. 56Ž C) say 80 per cent, ˛322 D 0.2,
˛422 D 0.8.
Unit 3. As for alcohol, assume 99 per cent absorbed, allows for a small loss, ˛432 D 0.99.
Unit 4. Assume 99 per cent recovery of acetone as product, ˛542 D 0.01.
Unit 5. Because of its high volatility in water all but a few ppm of the acetone will go
overhead, put ˛152 D 0.01.
Component 3, Hydrogen (k D 3)
Unit 1. Passes through unreacted, ˛213 D 1.
Unit 2. Non-condensable, ˛323 D 1, ˛423 D 0.
Unit 3. None absorbed, ˛433 D 0.
Unit 4. Any present in the feed would go out with the overheads, ˛543 D 1.
Unit 5. As for unit 4, ˛153 D 1.
Component 4, Water (k D 4)
Unit 1. Passes through unreacted, ˛214 D 1.
Unit 2. A greater fraction of the water will condense than the alcohol or acetone
(b.p. 100Ž C) assume 95 per cent condensed, ˛324 D 0.05, ˛423 D 0.95.
Unit 3. There will be a small loss of water in the vent gas stream, assume 1 per cent lost,
˛434 D 0.99.
Unit 4. Some water will appear in the acetone product; as for the alcohol this will be
fixed by the acetone product specification. Putting ˛544 D 0.99 will give less than 1
per cent water in the product.
Unit 5. The overhead composition will be close to the azeotropic composition, approximately 9 per cent water. The value of ˛154 (recycle to the reactor) must be selected
179
FLOW-SHEETING
so that the overheads from this unit approximate to the azeotropic composition, as a
first try put ˛154 D 0.05.
Estimation of fresh feeds
1. Isopropyl alcohol, take the basis of the flow sheet as 100 mol feed, g101 D 100.
2. Acetone formed in the reaction. The overall yield to acetone is approximately 98
per cent, so acetone formed D 100 ð 98
2 D 980 mol, g202 D 98 mol.
3. Hydrogen, it is formed in equimolar proportion to acetone, so g203 D 98 mol.
4. Water, the feed of water to the scrubber will be dependent on the scrubber design. A
typical design value for mGm /Lm for a scrubber is 0.7 (see Volume 2, Chapter 4). For
the acetone absorption this would require a value of Lm of 200 mol, g304 D 200 mol.
Matrices
Substituting the values for alcohol (k D 1) into the matrix (Figure 4.14) gives the following
set of equations for the flow of alcohol into each unit;
1
0
0
0 0.99
11
100
0
0
0 21 0
0.1 1
0
0 ð 31 D 0
0 0.1 1
0 0.9 0.99 1
0
0
41
0
0
0 0.99 1
0
51
Substitution of the values of the split-fraction coefficients for the other components will
give the sets of equations for the component flows to each unit. The values of the splitfraction coefficients and fresh feeds are summarised in Table 4.2.
Table 4.2.
˛
kD
21k
32k
42k
43k
54k
15k
Mol
Split-fraction coefficients and feeds
1
2
3
4
0.1
0.1
0.9
0.99
0.99
0.99
1
0.2
0.8
0.99
0.01
0.01
1
1
0
0
1
1
1.0
0.05
0.95
0.99
0.99
0.05
g101
100
g202
98
g203
98
g304
200
Solution of the equations
The most convenient way to set up and solve the equations is to use a spreadsheet; but any
of the standard procedures and programs available for the solution of linear simultaneous
equations can be used; Westlake (1968), Mason (1984).
Most proprietary spreadsheets include a routine for the inversion of matrices and the
solution of sets of linear simultaneous equations. By using cell references, with cell
copying and cell pointing, it is a simple procedure to set up the split fraction matrices
180
CHEMICAL ENGINEERING
and fresh feed vectors; solve the equations; and use the results to calculate and check the
values of any stream composition.
Once the spreadsheet has been set up it is easy to change the values of the split fractions
and fresh feeds, and iterate until the design constraints for the problem are satisfied.
The sample problem was solved using an inexpensive, but versatile, spreadsheet package
“AS-EASY-AS”⊲1⊳. The procedure used is illustrated below.
Procedure
Step 1: Set up the table of split-fractions and fresh feeds, Figure 4.15.
A] ......
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
. .A/. . . . . . . .B/. . . . . . . .C/. . . . . . . .D/. . . . . . . .E/. . . . . . . .F/. . . . . . . .G/. . . . . . . .H
MASSBAL EXAMPLE USING SPREAD SHEET “AS-EASY-AS”
TO SOLVE EQUATIONS
Split fraction coefficients and fresh feeds
alpha / k
21k
32k
42k
43k
54k
15k
mol
1
2
3
4
0.10
0.10
0.90
0.99
0.99
0.99
1.00
0.20
0.80
0.99
0.01
0.01
1.00
1.00
0.00
0.00
1.00
1.00
1.00
0.05
0.95
0.99
0.99
0.05
g101
g202
g203
g304
100.00
98.00
98.00
200.00
Figure 4.15.
Step 2: Set up an identity matrix of the dimensions needed, n ð n; a matrix with 1’s
on the leading diagonal and 0’s elsewhere. For this problem there are 5 unis so a 5 ð 5
matrix is needed, Figure 4.16.
A ] ....
20
21
22
23
24
25
26
27
28
29
30
31
. . . .A/. . . . . . . .B/. . . . . . . .C/. . . . . . . .D/. . . . . . . .E/. . . . . . . .F/. . . . . . . .G/. . . . . . . .H
Identity matric
1
2
3
4
5
1
2
3
4
5
g
1.00
0.00
0.00
0.00
0.00
0.00
1.00
0.00
0.00
0.00
0.00
0.00
1.00
0.00
0.00
0.00
0.00
0.00
1.00
0.00
0.00
0.00
0.00
0.00
1.00
0.00
0.00
0.00
0.00
0.00
Flows
Figure 4.16.
⊲1⊳ AS-EASY-AS is copyright software developed by TRUIS Inc., North Andover, Massachusetts, USA.
Check their web site to download the latest version: www.truisinc.com.
181
FLOW-SHEETING
Step 3: Make a copy of the identity matrix, one for each component. For this problem
there are 4 components so 4 copies are needed.
Step 4: Copy the appropriate split-fractions and fresh feeds from the table of splitfractions and fresh feeds, Figure 4.15, into the component matrices, Figure 4.17. Copy
the cell references, not the actual values. Using the cell references ensures that subsequent
changes in the values in the primary table, Figure 4.15, will be copied automatically to
the appropriate matrix.
For example, in Figure 4.17 the contents of cell F72 are (F15), not 0.05.
A ] . . . . . . . .A/. . . . . . . .B/. . . . . . . .C/. . . . . . . .D/. . . . . . . .E/. . . . . . . .F/. . . . . . . .G/. . . . . .
31
32
33
Matrix equations
34
35
kD1
36
37
1
2
3
4
5
g
38
39
1
1.00
0.00
0.00
0.00
0.99
100.00
2
0.10
1.00
0.00
0.00
0.00
0.00
40
41
3
0.00
0.10
1.00
0.00
0.00
0.00
42
4
0.00
0.90
0.99
1.00
0.00
0.00
43
5
0.00
0.00
0.00
0.99
1.00
0.00
44
45
46
kD2
47
48
1
2
3
4
5
g
49
50
1
1.00
0.00
0.00
0.00
0.01
0.00
51
2
1.00
1.00
0.00
0.00
0.00
98.00
52
3
0.00
0.20
1.00
0.00
0.00
0.00
4
0.00
0.80
0.99
1.00
0.00
0.00
53
54
5
0.00
0.00
0.00
0.01
1.00
0.00
55
56
57
kD3
58
59
1
2
3
4
5
g
60
61
1
1.00
0.00
0.00
0.00
1.00
0.00
62
2
1.00
1.00
0.00
0.00
0.00
98.00
63
3
0.00
1.00
1.00
0.00
0.00
0.00
4
0.00
0.00
0.00
1.00
0.00
0.00
64
65
5
0.00
0.00
0.00
1.00
1.00
0.00
66
67
68
kD4
69
70
1
2
3
4
5
g
71
72
1
1.00
0.00
0.00
0.00
0.05
0.00
73
2
1.00
1.00
0.00
0.00
0.00
0.00
74
3
0.00
0.05
1.00
0.00
0.00
200.00
75
4
0.00
0.95
0.99
1.00
0.00
0.00
76
5
0.00
0.00
0.00
0.99
1.00
0.00
77
78
Figure 4.17.
. .H
Flows
110.85
11.09
1.11
11.07
10.96
Flows
0.01
98.01
19.60
97.81
0.98
Flows
0.00
98.00
98.00
0.00
0.00
Flows
10.31
10.31
200.52
208.31
206.22
182
CHEMICAL ENGINEERING
Step 5: Use the equation solving routine (E-solve with AS-EASY-AS) to solve the
equations and put the results, the flows into each unit, into a column headed “flows”,
column H in Figure 4.17; repeat for each component matrix.
Step 6: Transfer (COPY) the component flows into a table and use the SUM function
to total the flows in a column, Figure 4.18. Copy the cell references into the table not the
values. Examples, from Figure 4.18:
cell C84 contents:
cell C85 contents:
cell G84 contents:
(H40)
(H41)
SUM(C84. .F84)
A ] . . . . . . . .A/. . . . . . . .B/. . . . . . . .C/. . . . . . . .D/. . . . . . . .E/. . . . . . . .F/. . . . . . . .G/. . . . . . . .H
77
78
79
Flow and Compositions
80
81
Component
1
2
3
4
Totals
Unit
82
1
110.85
0.01
0.00
10.31
121.17
83
2
11.09
98.01
98.00
10.31
217.41
84
3
1.11
19.60
98.00
200.52
319.23
85
4
11.07
97.81
0.00
208.31
317.19
86
5
10.96
0.98
0.00
206.22
218.16
87
88
89
90
Unit
1
2
3
4
5
91
92
Comp.%
1
91.48
5.10
0.35
3.49
5.03
2
0.01
45.08
6.14
30.84
0.45
93
3
0.00
45.08
30.70
0.00
0.00
94
4
8.51
4.74
62.81
65.67
94.53
95
96
97
Total
100.00
100.00
100.00
100.00
100.00
Figure 4.18.
Step 7: Set up a table to calculate the percentage composition of the stream into each
unit; by copying from the table of component flows. The results are shown in Figure 4.18.
Example, from Figure 4.18:
cell C92 contents:
(C83/G83) Ł 100
Step 8: Set up the calculations for any values which are design constraints. For example,
the overheads, recycle flow, from the second column which should approximate to the
azeotropic composition; see Table 4.4. The calculations giving the composition of this
stream are shown in Figure 4.19a.
FLOW-SHEETING
183
A ] . . . . . . . .A/. . . . . . . .B/. . . . . . . .C/. . . . . . . .D/. . . . . . . .E/. . . . . . . .F/. . . . . . . .G/. . . . . . . .H
98
99
100
101
Recycle flow composition
102
103
alpha 1, 5, 4 D 0.05
104
105
Component
1
2
3
4
Total
106
107
Flow
10.85
0.01
0.00
10.31
21.17
108
109
Percent
51.26
0.05
0.00
48.70
110
111
112
Figure 4.19a.
A ] . . . . . . . .A/. . . . . . . .B/. . . . . . . .C/. . . . . . . .D/. . . . . . . .E/. . . . . . . .F/. . . . . . . .G/. . . . . . . .H
98
99
100
101
Recycle flow composition
102
103
alpha 1, 5, 4 D 0.0053
104
105
Component
1
2
3
4
Total
106
107
Flow
10.85
0.01
0.00
1.08
11.94
108
109
Per cent
90.88
0.08
0.00
9.04
110
111
112
Figure 4.19b.
Step 9: Change the values of the appropriate split fractions, or fresh feeds, in the
primary table, Figure 4.15, and observe the changes to the calculated values: which will
carry through the spread sheet automatically. Iterate on the values until the desired result
is obtained.
Comments on the first trial solutions
Table 4.3 shows the feed of each component and the total flow to each unit. The composition of any other stream of interest can be calculated from these values and the splitfraction coefficients. The compositions and flows should be checked for compliance with
the process constraints, the split-fraction values adjusted, and the calculation repeated,
as necessary, until a satisfactory fit is obtained. Some of the constraints to check in this
example are discussed below.
184
CHEMICAL ENGINEERING
Table 4.3.
Solution of equations, feeds to units
Unit
Component
1
2
3
4
Total
1
2
3
4
5
1k
2k
3k
4k
5k
110.85
11.09
1.11
11.07
10.96
0.01
98.01
19.6
97.81
0.98
0.0
98.0
98.0
0.0
0.0
10.31
10.31
200.51
208.3
206.22
121.17
217.41
319.22
317.19
218.16
Recycle flow from the second column
This should approximate to the azeotropic composition (9 per cent alcohol, 91 per cent
water). The flow of any component in this stream is given by multiplying the feed to the
column (5k ) by the split-fraction coefficient for the recycle stream (˛15k ). The calculated
flows for each component are shown in Table 4.4.
Table 4.4.
Component
5k
˛15k
Flow
˛15k 5k
Per cent
Calculation of recycle stream flow
1
2
3
4
10.96
0.99
0.98
0.01
0.0
1
206.22
0.05
10.85
51.3
0.01
0.05
0
0
10.31
48.7
Total
21.17
Calculated percentage alcohol D 51.3 per cent, required value 91 per cent. Clearly
the initial value selected for ˛154 was too high; too much recycle. Iteration, using the
spreadsheet, shows the correct value of ˛154 to be 0.0053, see Figure 4.19b.
Reactor conversion and yield
11 21
110.85 11.09
alcohol in alcohol out
D
D
alcohol in
11
110.85
D 90 per cent, which is the value given
acetone out
98.01
22
Yield D
D
D
alcohol in alcohol out
11 21
110.85 11.09
D 98.3 per cent, near enough.
Conversion D
Condenser vapour and liquid composition
The liquid and vapour streams from the partial condenser should be approximately in
equilibrium.
The component flows in the vapour stream D ˛32k 2k and in the liquid stream D
˛42k 2k . The calculation is shown in Table 4.5.
These compositions should be checked against the vapour-liquid equilibrium data for
acetone-water and the values of the split-fraction coefficients adjusted, as necessary.
185
FLOW-SHEETING
Table 4.5.
Condenser vapour and liquid compositions
Component k
1
2
3
4
Total
2k
˛32k
Vapour flow
˛32k 2k
Per cent
˛42k
Liquid flow
˛42k 2k
Per cent
11.09
0.1
98.01
0.2
98.0
1
10.31
0.05
1.11
0.9
0.9
19.6
16.4
0.8
98.0
82.2
0
0.52
0.4
0.95
119.23
9.98
10.2
78.41
79.9
0
0
9.79
10.0
98.18
4.6.3. Guide rules for estimating split-fraction coefficients
The split-fraction coefficients can be estimated by considering the function of the process
unit, and by making use of any constraints on the stream flows and compositions that
arise from considerations of product quality, safety, phase equilibria, other thermodynamic
relationships; and general process and mechanical design considerations. The procedure
is similar to the techniques used for the manual calculation of material balances discussed
in Section 4.3.
Suggested techniques for use in estimating the split-fraction coefficients for some of
the more common unit operations are given below.
1. Reactors
The split-fractions for the reactants can be calculated directly from the percentage conversion. The conversion may be dependent on the relative flows of the reactants (feed composition) and, if so, iteration may be necessary to determine values that satisfy the feed
condition.
Conversion is not usually very dependent on the concentration of any inert components.
The pseudo fresh feeds of the products formed in the reactor can be calculated from
the specified, or estimated, yields for the process.
2. Mixers
For a unit that simply combines several inlet streams into one outlet stream, the splitfraction coefficients for each component will be equal to 1. ˛j,i,k D 1.
3. Stream dividers
If the unit simply divides the inlet stream into two or more outlet streams, each with the
same composition as the inlet stream, then the split-fraction coefficient for each component
will have the same value as the fractional division of the total stream. A purge stream is
an example of this simple division of a process stream into two streams: the main stream
and the purge. For example, for a purge rate of 10 per cent the split-fraction coefficients
for the purge stream would be 0.1.
186
CHEMICAL ENGINEERING
4. Absorption or stripping columns
The amount of a component absorbed or stripped in a column is dependent on the column
design (the number of stages), the component solubility, and the gas and liquid rates.
The fraction absorbed can be estimated using the absorption factor method, attributed to
Kremser (1930) (see Volume 2, Chapter 12). If the concentration of solute in the solvent
feed to the column is zero, or can be neglected, then for the solute component the fraction
absorbed D
⊲Lm /mGm ⊳sC1 Lm /mGm
⊲Lm /mGm ⊳sC1 1
and for a stripping column, the fraction stripped D
⊲mGm /Lm ⊳sC1 ⊲mGm /Lm ⊳
⊲mGm /Lm ⊳sC1 1
where Gm
Lm
m
s
D
D
D
D
gas flow rate, kmol m2 h1 ,
liquid flow rate, kmol m2 h1 ,
slope of the equilibrium curve,
the number of stages.
For a packed column the chart by Colburn (1939) can be used (see Volume 2, Chapter 11).
This gives the ratio of the inlet and outlet concentrations, y1 /y2 , in terms of the number
of transfer units and mGm /Lm .
The same general approach can be used for solvent extraction processes.
5. Distillation columns
A distillation column divides the feed stream components between the top and bottom
streams, and any side streams. The product compositions are often known; they may be
specified, or fixed by process constraints, such as product specifications, effluent limits
or an azeotropic composition. For a particular stream, “s”, the split-fraction coefficient is
given by:
xsk rs
xfk
where xsk D the concentration of the component k in the stream, s,
xfk D the concentration component k in the feed stream,
rs D the fraction of the total feed that goes to the stream, s.
If the feed composition is fixed, or can be estimated, the value of rs can be calculated
from a mass balance.
The split-fraction coefficients are not very dependent on the feed composition, providing
the reflux flow-rate is adjusted so that the ratio of reflux to feed flow is held constant;
Vela (1961), Hachmuth (1952).
It is not necessary to specify the reflux when calculating a preliminary material balance;
the system boundary can be drawn to include the reflux condenser.
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FLOW-SHEETING
For a column with no side streams the fraction of the total feed flow going to the
overheads is given by:
xfk xwk
roverheads D
xdk xwk
where x is the component composition and the suffixes f, d, w refer to feed, overheads
and bottoms respectively.
6. Equilibrium separators
This is a stream divider with two outlet streams, a and b, which may be considered to be
in equilibrium.
Feed
xf k
Stream a, xak
Stream b, xbk
where xak D concentration of component k in stream a,
xbk D concentration of component k in stream b,
xfk D concentration of component k in the feed stream.
If the equilibrium relationship can be expressed by a simple equilibrium constant, Kk ,
such that:
xak D Kk xbk
Then the split-fraction coefficients can be calculated from a material balance.
Kk ⊲xfk xbk ⊳
Split fraction for stream a D
.
Kk 1
xfk
4.7. REFERENCES
AUSTIN, D. G. (1979) Chemical Engineering Drawing Symbols (George Godwin).
BENEDEK, P. (ed.) (1980) Steady-state Flow-sheeting of Chemical Plants (Elsevier).
BS 1553: . . . Specification for graphical symbols for general engineering
Part 1: 1977 Piping systems and plant.
COLBURN, A. P. (1939) Trans. Am. Inst. Chem. Eng. 35, 211. The simplified calculation of diffusional processes,
general considerations of two-film resistances.
CROWE, C. M., HAMIELEE, A. E., HOFFMAN, T. N., JOHNSON, A. I., SHANNON, P. T. and WOODS, D. R. (1971)
Chemical Plant Simulation (Prentice-Hall).
DIN 28004 (1988) Flow sheets and diagrams of process plants, 4 parts (BSI).
GUNN, D. J. (1977) Inst. Chem. Eng., 4th Annual Research Meeting, Swansea, April. A sparse matrix technique
for the calculation of linear reactor-separator simulations of chemical plant.
GUNN, D. J. (1982) IChemE Symposium Series No. 74, 99, A versatile method of flow sheet analysis for process
evolution and modification.
HACHMUTH, K. H. (1952) Chem. Eng. Prog. 48 (Oct.) 523, (Nov.) 570, (Dec.) 570 (in three parts). Industrial
viewpoints on separation processes.
HENLEY, E. J. and ROSEN, E. M. (1969) Material and Energy Balance Computations (Wiley).
HUSAIN, A. (1986) Chemical Process Simulation (Wiley).
KREMSER, A. (1930) Nat. Petroleum News 22 (21 May) 43. Theoretical analysis of absorption columns.
188
CHEMICAL ENGINEERING
LEESLEY, M. E. (ed.) (1982) Computer Aided Process Plant Design (Gulf).
MAH, S. H. and SEIDER, W. D. (eds) (1980) Foundations of Computer-aided Process Design (2 vols.)
(Engineering Foundation/AIChemE).
MASON, J. C. (1984) BASIC Matrix Methods (Butterworths).
NAGIEV, M. F. (1964) The Theory of Recycle Processes in Chemical Engineering (Pergamon).
PANTELIDES, C. C. (1988) Comp. and Chem. Eng., 12, 745. SpeedUp recent advances in process engineering.
PREECE, P. E. (1986) Chem. Eng., London. No. 426, 87. The making of PFG and PIG.
PREECE, P. E. and STEPHENS, M. B. (1989) IChemE Symposium Series No. 114, 89, PROCEDE opening
windows on the design process.
PREECE, P. E., KIFT, M. H. and GRILLS, D. M. (1991) Computer-Orientated Process Design, Proceedings of
COPE, Barcelona, Spain, Oct. 14 16, 209, A graphical user interface for computer aided process design.
ROSEN, E. M. (1962) Chem. Eng. Prog. 58 (Oct.) 69. A machine computation method for performing material
balances.
VELA, M. A. (1961) Pet. Ref. 40 (May) 247, (June) 189 (in two parts). Use of fractions for recycle balances.
WELLS, G. L. and ROSE, L. M. (1986) The Art of Chemical Process Design (Elsevier).
WESTERBERG, A. W., HUTCHINSON, H. P., MOTARD, R. L. and WINTER, P. (1979) Process Flow-sheeting
(Cambridge U.P.).
WESTLAKE, J. R. (1968) A handbook of numerical matrix inversion and solution of linear equations (Wiley).
4.8. NOMENCLATURE
Dimensions
in MLT
Gm
giok
Kk
Lm
m
rs
s
xak
xbk
xdk
xfk
xwk
ik
˛jik
Molar flow-rate of gas per unit area
Fresh feed to unit i of component k
Equilibrium constant for component k
Liquid flow-rate per unit area
Slope of equilibrium line
Fraction of total feed that goes to stream s
Number of stages
Concentration of component k in stream a
Concentration of component k in stream b
Concentration of component k in distillate
Concentration of component k in feed
Concentration of component k in bottom product
Total flow of component k to unit i
Split-fraction coefficient : fraction of component k flowing from unit i to unit j
ML2 T1
MT1
ML2 T1
MT1
4.9. PROBLEMS
4.1. Monochlorobenzene is produced by the reaction of benzene with chlorine.
A mixture of monochlorobenzene and dichlorobenzene is produced, with a
small amount of trichlorobenzene. Hydrogen chloride is produced as a byproduct. Benzene is fed to the reactor in excess to promote the production of
monochlorobenzene.
The reactor products are fed to a condenser where the chlorobenzenes and
unreacted benzene are condensed. The condensate is separated from the noncondensable gases in a separator. The non-condensables, hydrogen chloride and
unreacted chlorine, pass to an absorption column where the hydrogen chloride is
absorbed in water. The chlorine leaving the absorber is recycled to the reactor.
The liquid phase from the separator, chlorobenzenes and unreacted benzene, is
fed to a distillation column, where the chlorobenzenes are separated from the
unreacted benzene. The benzene is recycle to the reactor.
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FLOW-SHEETING
Using the data given below, calculate the stream flows and draw up a preliminary
flow-sheet for the production of 1.0 tonne monochlorobenzene per day.
Hint: start the material balance at the reactor inlet (after the addition of the recycle
streams) and use a basis of 100 kmol/h benzene at this point.
Data
Reactor
C6 H6 C Cl2 ! C6 H5 C HCl
Reactions:
C6 H6 C 2Cl2 ! C6 H4 Cl2 C 2HCl
mol ratio Cl2 : C6 H6 at inlet to reactor D 0.9
overall conversion of benzene D 55.3 per cent
yield of monochlorobenzene D 73.6 per cent
yield of dichlorobenzene D 27.3 per cent
production of other chlorinated compounds can be neglected.
Condenser
Assume that all the chlorobenzenes and unreacted benzene condenses. Assume
that the vapour pressure of the liquid at the condenser temperature is not significant; i.e. that no chlorobenzene or benzene are carried over in the gas stream.
Separator
Assume complete separation of the liquid and gas phases.
Absorber
Assume 100 per cent absorption of hydrogen chloride, and that 98 per cent of
the chlorine is recycled, the remainder being dissolved in the water. The water
supply to the absorber is set to produce a 30 per cent w/w strength hydrochloric
acid.
Distillation column
Take the recovery of benzene to be 95 per cent, and complete separation of the
chlorobenzenes.
4.2. Methyl tertiary butyl ether (MTBE) is used as an anti-knock additive in petrol
(gasoline).
It is manufactured by the reaction of isobutene with methanol. The reaction is
highly selective and practically any C4 stream containing isobutene can be used
as a feedstock
CH2
C⊲CH3 ⊳2 C CH3 OH ! ⊲CH3 ⊳3
C
O
CH3
A 10 per cent excess of methanol is used to suppress side reactions.
In a typical process, the conversion of isobutene in the reactor stage is 97 per cent.
The product is separated from the unreacted methanol and any C4 ’s by distillation.
The essentially pure, liquid, MTBE leaves the base of the distillation column and
is sent to storage. The methanol and C4 ’s leave the top of the column as vapour
and pass to a column where the methanol is separated by absorption in water. The
C4 ’s leave the top of the absorption column, saturated with water, and are used as
a fuel gas. The methanol is separated from the water solvent by distillation and
recycled to the reactor stage. The water, which leaves the base of the column, is
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CHEMICAL ENGINEERING
recycled to the absorption column. A purge is taken from the water recycle stream
to prevent the build-up of impurities.
1. Draw up an information flow diagram for this process.
2. Estimate the split faction coefficients and fresh feeds for each stage.
3. Set up the resulting material balance equations, in matrix form.
4. Solve the equations using a suitable spread-sheet.
5. Adjust the values chosen for the split-fractions and feeds, so the results meet
the constraints,
6. Draw a flow-sheet for the process.
Treat the C4 ’s, other than isobutene, as one component.
Data:
1. Feedstock composition, mol per cent: n-butane D 2, butene-1 D 31, butene-2 D
18, isobutene D 49.
2. Required production rate of MTBE, 7000 kg/h.
3. Reactor conversion of isobutene, 97 per cent.
4. Recovery of MTBE from the distillation column, 99.5 per cent.
5. Recovery of methanol in the absorption column, 99 per cent.
6. Concentration of methanol in the solution leaving the absorption column, 15
per cent.
7. Purge from the water recycle stream, to waste treatment, 10 per cent of the
flow leaving the methanol recovery column.
8. The gases leave the top of the absorption column saturated with water at 30 Ž C.
9. Both columns operate at essentially atmospheric pressure.
4.3. Water and ethanol form a low boiling point azeotrope. So, water cannot be
completely separated from ethanol by straight distillation. To produce absolute
(100 per cent) ethanol it is necessary to add an entraining agent to break the
azeotrope. Benzene is an effective entrainer and is used where the product is not
required for food products. Three columns are used in the benzene process.
Column 1. This column separates the ethanol from the water. The bottom product
is essentially pure ethanol. The water in the feed is carried overhead as the ternary
azeotrope of ethanol, benzene and water (24 per cent ethanol, 54 per cent benzene,
22 per cent water). The overhead vapour is condensed and the condensate separated
in a decanter into, a benzene-rich phase (22 per cent ethanol, 74 per cent benzene,
4 per cent water) and a water-rich phase (35 per cent ethanol, 4 per cent benzene,
61 per cent water). The benzene-rich phase is recycled to the column as reflux. A
benzene make-up stream is added to the reflux to make good any loss of benzene
from the process. The water-rich phase is fed to the second column.
Column 2. This column recovers the benzene as the ternary azeotrope and recycles
it as vapour to join the overhead vapour from the first column. The bottom product
from the column is essentially free of benzene (29 per cent ethanol, 51 per cent
water). This stream is fed to the third column.
Column 3. In this column the water is separated and sent to waste treatment. The
overhead product consists of the azeotropic mixture of ethanol and water (89 per
cent ethanol, 11 per cent water). The overheads are condensed and recycled to
join the feed to the first column. The bottom product is essentially free of ethanol.
FLOW-SHEETING
191
From the compositions given, calculate the stream flows for the production of
absolute alcohol from 100 kmol/h raw alcohol feed, composition 89 per cent
ethanol, balance water. Take the benzene losses to total 0.1 kmol/h. Draw a preliminary flow-sheet for the process.
All the compositions given are mol percentage.
4.4. A plant is required to produce 10,000 tonnes per year of anhydrous hydrogen
chloride from chlorine and hydrogen. The hydrogen source is impure: 90 per cent
hydrogen, balance nitrogen.
The chlorine is essentially pure chlorine, supplied in rail tankers.
The hydrogen and chlorine are reacted in a burner at 1.5 bar pressure.
H2 C Cl2 ! 2HCl
Hydrogen is supplied to the burner in 3 per cent excess over the stoichiometric
amount. The conversion of chlorine is essentially 100 per cent. The gases leaving
the burner are cooled in a heat exchanger.
The cooled gases pass to an absorption column where the hydrogen chloride gas is
absorbed in dilute hydrochloric acid. The absorption column is designed to recover
99.5 per cent of the hydrogen chloride in the feed.
The unreacted hydrogen and inerts pass from the absorber to a vent scrubber where
any hydrogen chloride present is neutralised by contact with a dilute, aqueous
solution, of sodium hydroxide. The solution is recirculated around the scrubber.
The concentration of sodium hydroxide is maintained at 5 per cent by taking a
purge from the recycle loop and introducing a make up stream of 25 per cent
concentration. The maximum concentration of hydrogen chloride discharged in
the gases vented from the scrubber to atmosphere must not exceed 200 ppm (parts
per million) by volume.
The strong acid from the absorption column (32 per cent HCl) is fed to a stripping
column where the hydrogen chloride gas is recovered from the solution by distillation. The diluted acid from the base of this column (22 per cent HCl), is recycled
to the absorption column.
The gases from the top of the stripping column pass through a partial condenser,
where the bulk of the water vapour present is condensed and returned to the
column as reflux. The gases leaving the column will be saturated with water
vapour at 40 Ž C.
The hydrogen chloride gas leaving the condenser is dried by contact with concentrated sulphuric acid in a packed column. The acid is recirculated over the packing.
The concentration of sulphuric acid is maintained at 70 per cent by taking a purge
from the recycle loop and introducing a make up stream of strong acid (98 per
cent H2 SO4 ).
The anhydrous hydrogen chloride product is compressed to 5 bar and supplied as
a feed to another process.
Using the information provided, calculate the flow-rates and compositions of the
main process streams, and draw a flow-sheet for this process.
There is no need to calculate the reflux flow to the distillation column; that will
be determined by the column design.
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CHEMICAL ENGINEERING
4.5. Ammonia is synthesised from hydrogen and nitrogen. The synthesis gas is usually
produced from hydrocarbons. The most common raw materials are oil or natural
gas; though coal, and even peat can be used.
When produced from natural gas the synthesis gas will be impure, containing up
to 5 per cent inerts, mainly methane and argon. The reaction equilibrium and rate
are favoured by high pressure. The conversion is low, about 15 per cent and so,
after removal of the ammonia produced, the gas is recycled to the converter inlet.
A typical process would consist of: a converter (reactor) operating at 350 bar; a
refrigerated system to condense out the ammonia product from the recycle loop;
and compressors to compress the feed and recycle gas. A purge is taken from the
recycle loop to keep the inert concentration in the recycle gas at an acceptable
level.
Using the data given below, draw an information flow diagram of the process
and calculate the process stream flow-rates and compositions for the production of
600 t/d ammonia. Use either the ‘Nagiev’ split fraction method, with any suitable
spreadsheet; or manual calculations.
Data:
Composition of synthesis gas, mol fraction:
N2
24.5
H2
73.5
CH4
1.7
A
0.3
Temperature and operating pressure of liquid ammonia gas separator, 340 bar
and 28 Ž C.
Inert gas concentration in recycle gas, not greater than 15 per cent mol per cent.
4.6. Methyl ethyl ketone (MEK) is manufactured by the dehydrogenation of 2-butanol.
A simplified description of the processes listing the various units used is given
below:
1. A reactor in which the butanol is dehydrated to produce MEK and hydrogen,
according to the reaction:
CH3 CH2 CH3 CHOH ! CH3 CH2 CH3 CO C H2
The conversion of alcohol to MEK is 88 per cent and the yield can be taken
as 100 per cent.
2. A cooler-condenser, in which the reactor off-gases are cooled and most of the
MEK and unreacted alcohol are condensed. Two exchangers are used but they
can be modelled as one unit. Of the MEK entering the unit 84 per cent is
condensed, together with 92 per cent of the alcohol. The hydrogen is noncondensable. The condensate is fed forward to the final purification column.
3. An absorption column, in which the uncondensed MEK and alcohol are
absorbed in water.
Around 98 per cent of the MEK and alcohol can be considered to be absorbed
in this unit, giving a 10 per cent w/w solution of MEK. The water feed to the
absorber is recycled from the next unit, the extractor. The vent stream from the
absorber, containing mainly hydrogen, is sent to a flare stack.
4. An extraction column, in which the MEK and alcohol in the solution from
the absorber are extracted into trichloroethylane (TCE). The raffinate, water
FLOW-SHEETING
193
containing around 0.5 per cent w/w MEK, is recycled to the absorption column.
The extract, which contains around 20 per cent w/w MEK, and a small amount
of butanol and water, is fed to a distillation column.
5. A distillation column, which separates the MEK and alcohol from the
solvent TCE.
The solvent containing a trace of MEK and water is recycled to the extraction
column.
6. A second distillation column, which produces a pure MEK product from the
crude product from the first column. The residue from this column, which
contains the bulk of the unreacted 2-butanol, is recycled to the reactor.
For a production rate of 1250 kg/h MEK:
1. Draw up an information flow diagram for this process.
2. Estimate the split-faction coefficients and fresh feeds for each stage.
3. Set up the resulting material balance equations, in matrix form.
4. Solve the equations using a suitable spread-sheet.
5. Adjust the values chosen for the split-fractions and feeds, so the results meet
the constraints,
6. Draw a flow-sheet for the process.
Postscript: The design problems given in Appendix F provide more problems in flow-sheeting.
CHAPTER 5
Piping and Instrumentation
5.1. INTRODUCTION
The process flow-sheet shows the arrangement of the major pieces of equipment and their
interconnection. It is a description of the nature of the process.
The Piping and Instrument diagram (P and I diagram or PID) shows the engineering
details of the equipment, instruments, piping, valves and fittings; and their arrangement.
It is often called the Engineering Flow-sheet or Engineering Line Diagram.
This chapter covers the preparation of the preliminary P and I diagrams at the process
design stage of the project.
The design of piping systems, and the specification of the process instrumentation and
control systems, is usually done by specialist design groups, and a detailed discussion
of piping design and control systems is beyond the scope of this book. Only general
guide rules are given. The piping handbook edited by Nayyar et al. (2000) is particularly
recommended for the guidance on the detailed design of piping systems and process
instrumentation and control. The references cited in the text and listed at the end of the
chapter should also be consulted.
5.2. THE P AND I DIAGRAM
The P and I diagram shows the arrangement of the process equipment, piping, pumps,
instruments, valves and other fittings. It should include:
1. All process equipment identified by an equipment number. The equipment should
be drawn roughly in proportion, and the location of nozzles shown.
2. All pipes, identified by a line number. The pipe size and material of construction
should be shown. The material may be included as part of the line identification
number.
3. All valves, control and block valves, with an identification number. The type and
size should be shown. The type may be shown by the symbol used for the valve or
included in the code used for the valve number.
4. Ancillary fittings that are part of the piping system, such as inline sight-glasses,
strainers and steam traps; with an identification number.
5. Pumps, identified by a suitable code number.
6. All control loops and instruments, with an identification number.
For simple processes, the utility (service) lines can be shown on the P and I diagram.
For complex processes, separate diagrams should be used to show the service lines, so
194
PIPING AND INSTRUMENTATION
195
the information can be shown clearly, without cluttering up the diagram. The service
connections to each unit should, however, be shown on the P and I diagram.
The P and I diagram will resemble the process flow-sheet, but the process
information is not shown. The same equipment identification numbers should be used
on both diagrams.
5.2.1. Symbols and layout
The symbols used to show the equipment, valves, instruments and control loops will
depend on the practice of the particular design office. The equipment symbols are usually
more detailed than those used for the process flow-sheet. A typical example of a P and I
diagram is shown in Figure 5.25.
Standard symbols for instruments, controllers and valves are given in the British
Standard BS 1646.
Austin (1979) gives a comprehensive summary of the British Standard symbols, and
also shows the American standard symbols (ANSI) and examples of those used by some
process plant contracting companies.
The German standard symbols are covered by DIN 28004, DIN (1988).
When laying out the diagram, it is only necessary to show the relative elevation of
the process connections to the equipment where these affect the process operation; for
example, the net positive suction head (NPSH) of pumps, barometric legs, syphons and
the operation of thermosyphon reboilers.
Computer aided drafting programs are available for the preparation of P and I diagrams,
see the reference to the PROCEDE package in Chapter 4.
5.2.2. Basic symbols
The symbols illustrated below are those given in BS 1646.
Control valve
Figure 5.1.
This symbol is used to represent all types of control valve, and both pneumatic and
electric actuators.
Failure mode
The direction of the arrow shows the position of the valve on failure of the power
supply.
196
CHEMICAL ENGINEERING
Fails open
Fails shut
Maintains position
Figure 5.2.
Instruments and controllers
Locally mounted
Main panel mounted
Figure 5.3.
Locally mounted means that the controller and display is located out on the plant near
to the sensing instrument location. Main panel means that they are located on a panel
in the control room. Except on small plants, most controllers would be mounted in the
control room.
Type of instrument
This is indicated on the circle representing the instrument-controller by a letter code (see
Table 5.1).
Table 5.1.
Property
measured
Flow-rate
Level
Pressure
Quality, analysis
Radiation
Temperature
Weight
Any other
property (specified
in a note)
Letter Code for Instrument Symbols (Based on BS 1646: 1979)
First
letter
Indicating
only
Recording
only
Controlling
only
Indicating
and controlling
Recording
and controlling
F
L
P
Q
R
T
W
FI
LI
PI
QI
RI
TI
WI
FR
LR
PR
QR
RR
TR
WR
FC
LC
PC
QC
RC
TC
WC
FIC
LIC
PIC
QIC
RIC
TIC
WIC
FRC
LRC
PRC
QRC
RRC
TRC
WRC
X
XI
XR
XC
XIC
XRC
Notes:
(1) The letter A may be added to indicate an alarm; with H or L placed next to the instrument circle to indicate
high or low.
(2) D is used to show difference or differential; eg. PD for pressure differential.
(3) F, as the second letter indicates ratio; eg. FFC indicates a flow ratio controller.
Consult the standard for the full letter code.
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PIPING AND INSTRUMENTATION
The first letter indicates the property measured; for example, F D flow. Subsequent
letters indicate the function; for example,
I D indicating
RC D recorder controller
The suffixes E and A can be added to indicate emergency action and/or alarm functions.
The instrument connecting lines should be drawn in a manner to distinguish them from
the main process lines. Dotted or cross-hatched lines are normally used.
FRC
Figure 5.4.
A typical control loop
5.3. VALVE SELECTION
The valves used for chemical process plant can be divided into two broad classes,
depending on their primary function:
1. Shut-off valves (block valves), whose purpose is to close off the flow.
2. Control valves, both manual and automatic, used to regulate flow.
(a)
Figure 5.5.
(b)
(a) Gate valve (slide valve) (b) Plug valve
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CHEMICAL ENGINEERING
(c)
(d)
Figure 5.5.
(e)
(c) Ball valve (d) Globe valve (e) Diaphragm valve
The main types of valves used are:
Gate
Plug
Ball
Globe
Diaphragm
Butterfly
Figure
Figure
Figure
Figure
Figure
Figure
5.5a
5.5b
5.5c
5.5d
5.5e
5.5f
A valve selected for shut-off purposes should give a positive seal in the closed position and
minimum resistance to flow when open. Gate, plug and ball valves are most frequently
used for this purpose. The selection of values is discussed by Merrick (1986) (1990),
Smith and Vivian (1995) and Smith and Zappe (2003).
If flow control is required, the valve should be capable of giving smooth control over the
full range of flow, from fully open to closed. Globe valves are normally used, though the
199
PIPING AND INSTRUMENTATION
(f)
Figure 5.5.
(g)
(f) Butterfly valve (g) Non-return valve, check valve, hinged disc type
other types can be used. Butterfly valves are often used for the control of gas and vapour
flows. Automatic control valves are basically globe valves with special trim designs (see
Volume 3, Chapter 7).
The careful selection and design of control valves is important; good flow control must
be achieved, whilst keeping the pressure drop as low as possible. The valve must also be
sized to avoid the flashing of hot liquids and the super-critical flow of gases and vapours.
Control valve sizing is discussed by Chaflin (1974).
Non-return valves are used to prevent back-flow of fluid in a process line. They do
not normally give an absolute shut-off of the reverse flow. A typical design is shown in
Figure 5.5g.
Details of valve types and standards can be found in the technical data manual of the
British Valve and Actuators Manufacturers Association, BVAMA (1991). Valve design is
covered by Pearson (1978).
5.4. PUMPS
5.4.1. Pump selection
The pumping of liquids is covered by Volume 1, Chapter 8. Reference should be made
to that chapter for a discussion of the principles of pump design and illustrations of the
more commonly used pumps.
Pumps can be classified into two general types:
1. Dynamic pumps, such as centrifugal pumps.
2. Positive displacement pumps, such as reciprocating and diaphragm pumps.
The single-stage, horizontal, overhung, centrifugal pump is by far the most commonly
used type in the chemical process industry. Other types are used where a high head or
other special process considerations are specified.
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CHEMICAL ENGINEERING
Pump selection is made on the flow rate and head required, together with other process
considerations, such as corrosion or the presence of solids in the fluid.
The chart shown in Figure 5.6 can be used to determine the type of pump required for
a particular head and flow rate. This figure is based on one published by Doolin (1977).
104
Total head, m
Reciprocating
103
Multi-stage
*High speed
single-stage
or
*multi
102
Single - stage
1750 rpm
Single - stage
3500 rpm
10
10
102
103
104
105
Flow rate, m3/h
Figure 5.6.
Centrifugal pump selection guide. Ł Single-stage >1750 rpm, multi-stage 1750 rpm
Centrifugal pumps are characterised by their specific speed (see Volume 1, Chapter 8).
In the dimensionless form, specific speed is given by:
Ns D
where N
Q
h
g
D
D
D
D
NQ1/2
⊲gh⊳3/4
⊲5.1⊳
revolutions per second,
flow, m3 /s,
head, m,
gravitational acceleration m/s2 .
Pump manufacturers do not generally use the dimensionless specific speed, but define
it by the equation:
NQ1/2
⊲5.2⊳
N0s D 3/4
h
where N0s D revolutions per minute (rpm),
Q D flow, US gal/min,
h D head, ft.
Values of the non-dimensional specific speed, as defined by equation 5.1, can be converted
to the form defined by equation 5.2 by multiplying by 1.73 ð 104 .
The specific speed for centrifugal pumps (equation 5.2) usually lies between 400 and
10,000, depending on the type of impeller. Generally, pump impellers are classified as
radial for specific speeds between 400 and 1000, mixed flow between 1500 and 7000, and
PIPING AND INSTRUMENTATION
201
axial above 7000. Doolin (1977) states that below a specific speed of 1000 the efficiency
of single-stage centrifugal pumps is low and multi-stage pumps should be considered.
For a detailed discussion of the factors governing the selection of the best centrifugal
pump for a given duty the reader should refer to the articles by De Santis (1976), Neerkin
(1974), Jacobs (1965) or Walas (1983).
Positive displacement, reciprocating, pumps are normally used where a high head is
required at a low flow-rate. Holland and Chapman (1966) review the various types of
positive displacement pumps available and discuss their applications.
A general guide to the selection, installation and operation of pumps for the processes
industries is given by Davidson and von Bertele (1999) and Jandiel (2000).
The selection of the pump cannot be separated from the design of the complete piping
system. The total head required will be the sum of the dynamic head due to friction
losses in the piping, fittings, valves and process equipment, and any static head due to
differences in elevation.
The pressure drop required across a control valve will be a function of the valve
design. Sufficient pressure drop must be allowed for when sizing the pump to ensure that
the control valve operates satisfactorily over the full range of flow required. If possible,
the control valve and pump should be sized together, as a unit, to ensure that the optimum
size is selected for both. As a rough guide, if the characteristics are not specified, the
control valve pressure drop should be taken as at least 30 per cent of the total dynamic
pressure drop through the system, with a minimum value of 50 kPa (7 psi). The valve
should be sized for a maximum flow rate 30 per cent above the normal stream flow-rate.
Some of the pressure drop across the valve will be recovered downstream, the amount
depending on the type of valve used.
Methods for the calculation of pressure drop through pipes and fittings are given in
Section 5.4.2 and Volume 1, Chapter 3. It is important that a proper analysis is made of
the system and the use of a calculation form (work sheet) to standardize pump-head calculations is recommended. A standard calculation form ensures that a systematic method
of calculation is used, and provides a check list to ensure that all the usual factors have
been considered. It is also a permanent record of the calculation. Example 5.8 has been
set out to illustrate the use of a typical calculation form. The calculation should include
a check on the net positive suction head (NPSH) available; see section 5.4.3.
Kern (1975) discusses the practical design of pump suction piping, in a series of
articles on the practical aspects of piping system design published in the journal Chemical
Engineering from December 1973 through to November 1975. A detailed presentation
of pipe-sizing techniques is also given by Simpson (1968), who covers liquid, gas and
two-phase systems. Line sizing and pump selection is also covered in a comprehensive
article by Ludwig (1960).
5.4.2. Pressure drop in pipelines
The pressure drop in a pipe, due to friction, is a function of the fluid flow-rate, fluid
density and viscosity, pipe diameter, pipe surface roughness and the length of the pipe.
It can be calculated using the following equation:
Pf D 8f⊲L/di ⊳
u2
2
⊲5.3⊳
202
where Pf
f
L
di
u
CHEMICAL ENGINEERING
D
D
D
D
D
D
pressure drop, N/m2 ,
friction factor,
pipe length, m,
pipe inside diameter, m,
fluid density, kg/m3 ,
fluid velocity, m/s.
The friction factor is a dependent on the Reynolds number and pipe roughness. The
friction factor for use in equation 5.3 can be found from Figure 5.7.
The Renolds number is given by Re D ⊲ ð u ð di ⊳/
⊲5.4⊳
Values for the absolute surface roughness of commonly used pipes are given in Table 5.2.
The parameter to use with Figure 5.7 is the relative roughness, given by:
relative roughness, e D absolute roughness/pipe inside diameter
Note: the friction factor used in equation 5.3 is related to the shear stress at the pipe wall,
R, by the equation f D ⊲R/u2 ⊳. Other workers use different relationships. Their charts
for friction factor will give values that are multiples of those given by Figure 5.7. So, it is
important to make sure that the pressure drop equation used matches the friction factor chart.
Table 5.2.
Pipe roughness
Material
Absolute roughness, mm
Drawn tubing
Commercial steel pipe
Cast iron pipe
Concrete pipe
0.0015
0.046
0.26
0.3 to 3.0
Non-Newtonian fluids
In equation 5.3, and when calculating the Reynolds number for use with Figure 5.7, the
fluid viscosity and density are taken to be constant. This will be true for Newtonian liquids
but not for non-Newtonian liquids, where the apparent viscosity will be a function of the
shear stress.
More complex methods are needed to determine the pressure drop of non-Newtonian
fluids in pipelines. Suitable methods are given in Volume 2, Chapter 4, and in Chabbra
and Richardson (1999); see also Darby (2001).
Gases
When a gas flows through a pipe the gas density is a function of the pressure and so is determined by the pressure drop. Equation 5.3 and Figure 5.7 can be used to estimate the pressure
drop, but it may be necessary to divide the pipeline into short sections and sum the results.
Miscellaneous pressure losses
Any obstruction to flow will generate turbulence and cause a pressure drop. So, pipe
fittings, such as: bends, elbows, reducing or enlargement sections, and tee junctions, will
increase the pressure drop in a pipeline.
0.1
0.09
0.08
0.07
0.06
Equation 5.3, ∆p = 8f
f
0.05
ru 2
2
L
d
0.04
0.03
0.02
f
Pipe roughness
Critical
zone
0.015
e/d
0.01
0.0095
0.0090
0.0085
0.0080
0.0075
0.0070
0.0065
0.0060
0.0055
0.0050
0.0045
0.05
0.04
0.03
0.02
0.015
Laminar flow
0.01
0.008
0.006
0.004
0.0040
0.0035
0.0030
0.00275
0.0025
0.00225
0.0020
0.002
0.001
0.0006
Smooth pipes
0.00175
0.0002
0.0015
0.0001
0.00125
0.00001
0.00000
5
0.001
0.0009
0.0008
0.0007
0.0006
0.0005
10
2
2
3
4
5
6
7
8 9
10
3
2
3
4
5
6
7
8 9
4
10
2
3
4
5
6
7
8
9
5
10
udr
Reynolds number Re =
m
Figure 5.7.
Pipe friction versus Reynolds number and relative roughness
2
3
4
5
6
7
8 9
10
6
2
3
4
5
6
7
8 9
10
7
204
CHEMICAL ENGINEERING
There will also be a pressure drop due to the valves used to isolate equipment and
control the fluid flow. The pressure drop due to these miscellaneous losses can be estimated
using either of two methods:
1. As the number of velocity heads, K, lost at each fitting or valve.
A velocity head is u2 /2g, metres of the fluid, equivalent to ⊲u2 /2⊳, N/m2 . The
total number of velocity heads lost due to all the fittings and valves is added to the
pressure drop due to pipe friction.
2. As a length of pipe that would cause the same pressure loss as the fitting or valve.
As this will be a function of the pipe diameter, it is expressed as the number of
equivalent pipe diameters. The length of pipe to add to the actual pipe length is
found by multiplying the total number of equivalent pipe diameters by the diameter
of the pipe being used.
The number of velocity heads lost, or equivalent pipe diameter, is a characteristic of the
particular fitting or type of valve used. Values can be found in handbooks and manufacturers’ literature. The values for a selected number of fittings and valves are given in
Table 5.3.
The two methods used to estimate the miscellaneous losses are illustrated in
Example 5.1.
Pipe fittings are discussed in section 5.5.3, see also Perry et al. (1997). Valve types and
applications are discussed in section 5.3.
Table 5.3.
Pressure loss in pipe fittings and valves (for turbulent flow)
Fitting or valve
45° standard elbow
45° long radius elbow
90° standard radius elbow
90° standard long elbow
90° square elbow
Tee-entry from leg
Tee-entry into leg
Union and coupling
Sharp reduction (tank outlet)
Sudden expansion (tank inlet)
Gate valve
fully open
1/4 open
1/2 open
3/4 open
Globe valve, bevel seatfully open
1/2 open
Plug valve - open
K, number of
velocity heads
number of equivalent
pipe diameters
0.35
0.2
0.6 0.8
0.45
1.5
1.2
1.8
0.04
0.5
1.0
15
10
30 40
23
75
60
90
2
25
50
0.15
16
4
1
7.5
800
200
40
6
8.5
0.4
300
450
18
Example 5.1
A pipeline connecting two tanks contains four standard elbows, a plug valve that is fully
open and a gate valve that is half open. The line is commercial steel pipe, 25 mm internal
diameter, length 120 m.
205
PIPING AND INSTRUMENTATION
The properties of the fluid are: viscosity 0.99 mNM2 s, density 998 kg/m3 .
Calculate the total pressure drop due to friction when the flow rate is 3500 kg/h.
Solution
Cross-sectional area of pipe D
⊲25 ð 103 ⊳2 D 0.491 ð 103 m2
4
Fluid velocity, u D
1
3500
1
ð
D 1.98 m/s
ð
3600 0.491 ð 103
998
Reynolds number, Re D ⊲998 ð 1.98 ð 25 ð 103 ⊳/0.99 ð 103
D 49,900 D 5 ð 104
⊲5.4⊳
Absolute roughness commercial steel pipe, Table 5.2 D 0.046 mm
Relative roughness D 0.046/⊲25 ð 103 ⊳ D 0.0018, round to 0.002
From friction factor chart, Figure 5.7, f D 0.0032
Miscellaneous losses
fitting/valve
entry
elbows
globe valve, open
gate valve, 1/2 open
exit
Total
number of velocity
heads, K
equivalent pipe
diameters
0.5
⊲0.8 ð 4⊳
6.0
4.0
1.0
14.7
25
⊲40 ð 4⊳
300
200
50
735
Method 1, velocity heads
A velocity head D u2 /2g D 1.982 /⊲2 ð 9.8⊳ D 0.20 m of liquid.
Head loss D 0.20 ð 14.7 D 2.94 m
as pressure D 2.94 ð 998 ð 9.8 D 28,754 N/m2
Friction loss in pipe, Pf D 8 ð 0.0032
⊲120⊳
1.982
998
ð
⊲25 ð 103 ⊳
2
D 240,388 N/m2
Total pressure D 28,754 C 240,388 D 269,142 N/m2 D 270 kN/m2
Method 2, equivalent pipe diameters
Extra length of pipe to allow for miscellaneous losses
D 735 ð 25 ð 103 D 18.4 m
⊲5.3⊳
206
CHEMICAL ENGINEERING
So, total length for P calculation D 120 C 18.4 D 138.4 m
Pf D 8 ð 0.0032
D 277 kN/m2
1.982
⊲138.4⊳
998
ð
D 277,247 N/m2
⊲25 ð 103 ⊳
2
⊲5.3⊳
Note: the two methods will not give exactly the same result. The method using velocity
heads is the more fundamentally correct approach, but the use of equivalent diameters is
easier to apply and sufficiently accurate for use in design calculations.
5.4.3. Power requirements for pumping liquids
To transport a liquid from one vessel to another through a pipeline, energy has to be
supplied to:
1. overcome the friction losses in the pipes;
2. overcome the miscellaneous losses in the pipe fittings (e.g. bends), valves, instruments etc.;
3. overcome the losses in process equipment (e.g. heat exchangers);
4. overcome any difference in elevation from end to end of the pipe;
5. overcome any difference in pressure between the vessels at each end of the pipeline.
The total energy required can be calculated from the equation:
where W
z
P
Pf
gz C P/ Pf / W D 0
D
D
D
D
⊲5.5⊳
work done, J/kg,
difference in elevations (z1 z2 ), m,
difference in system pressures (P1 P2 ), N/m2 ,
pressure drop due to friction, including miscellaneous losses,
and equipment losses, (see section 5.4.2), N/m2 ,
D liquid density, kg/m3 ,
g D acceleration due to gravity, m/s2 .
P2
P1
Liquid
Level
Z2
Z1
Vessel 1
Vessel 2
Pump
Datum
Figure 5.8.
Piping system
207
PIPING AND INSTRUMENTATION
If W is negative a pump is required; if it is positive a turbine could be installed to extract
energy from the system.
The head required from the pump D Pf /g P/g z
⊲5.5a⊳
The power is given by:
Power D ⊲W ð m⊳/, for a pump
⊲5.6a⊳
and D ⊲W ð m⊳ ð , for a turbine
⊲5.6b⊳
where m D mass flow-rate, kg/s,
D efficiency = power out/power in.
The efficiency will depend on the type of pump used and the operating conditions. For
preliminary design calculations, the efficiency of centrifugal pumps can be determined
using Figure. 5.9.
75
70
65
125
60
100
75
Capacity, m3/h
Efficiency, %
200
55
50
50
25
45
10
20
30
40
50
60
70
80
90
Head, m
Figure 5.9.
Centrifugal pump efficiency
Example 5.2
A tanker carrying toluene is unloaded, using the ship’s pumps, to an on-shore storage
tank. The pipeline is 225 mm internal diameter and 900 m long. Miscellaneous losses due
to fittings, valves, etc., amount to 600 equivalent pipe diameters. The maximum liquid
level in the storage tank is 30 m above the lowest level in the ship’s tanks. The ship’s
208
CHEMICAL ENGINEERING
tanks are nitrogen blanketed and maintained at a pressure of 1.05 bar. The storage tank
has a floating roof, which exerts a pressure of 1.1 bar on the liquid.
The ship must unload 1000 tonne within 5 hours to avoid demurrage charges. Estimate
the power required by the pump. Take the pump efficiency as 70 per cent.
Physical properties of toluene: density 874 kg/m3 , viscosity 0.62 mNm2 s.
Solution
Cross-sectional area of pipe D
Minimum fluid velocity D
⊲225 ð 103 ⊳2 D 0.0398 m2
4
1000 ð 103
1
1
ð
ð
D 1.6 m/s
5 ð 3600
0.0398 874
Reynolds number D ⊲874 ð 1.6 ð 225 ð 103 ⊳/0.62 ð 103
D 507,484 D 5.1 ð 105
⊲5.4⊳
Absolute roughness commercial steel pipe, Table 5.2 D 0.046 mm
Relative roughness D 0.046/225 D 0.0002
Friction factor from Figure 5.7, f D 0.0019
Total length of pipeline, including miscellaneous losses,
D 900 C 600 ð 225 ð 103 D 1035 m
1.622
1035
ð
874
ð
Friction loss in pipeline, Pf D 8 ð 0.0019 ð
225 ð 103
2
D 78,221 N/m2
⊲5.3⊳
Maximum difference in elevation, ⊲z1 z2 ⊳ D ⊲0 30⊳ D 30 m
Pressure difference, (P1 P2 ⊳ D ⊲1.05 1.1⊳105 D 5 ð 103 N/m2
Energy balance
9.8⊲30⊳ C ⊲5 ð 103⊳/874 ⊲78,221⊳/874 W D 0
⊲5.5⊳
W D 389.2 J/kg,
Power D ⊲389.2 ð 55.56⊳/0.7 D 30,981 W,
say 31 kW .
⊲5.6a⊳
5.4.4. Characteristic curves for centrifugal pumps
The performance of a centrifugal pump is characterised by plotting the head developed
against the flow-rate. The pump efficiency can be shown on the same curve. A typical
plot is shown in Figure 5.10. The head developed by the pump falls as the flow-rate is
increased. The efficiency rises to a maximum and then falls.
For a given type and design of pump, the performance will depend on the impeller
diameter, the pump speed, and the number of stages. Pump manufacturers publish families
of operating curves for the range of pumps they sell. These can be used to select the best
pump for a given duty. A typical set of curves is shown in Figure 5.11.
209
PIPING AND INSTRUMENTATION
2950 rpm
250
30
(a)
Efficiency, %
40
50
200
60
70
80
Head, m
(b)
70
150
60
50
40
(c)
(d)
100
(e)
50
0
0
10
20
40
30
Flow-rate,
50
60
m3/h
Figure 5.10. Pump characteristic for a range of impeller sizes
(a) 250 mm (b) 225 mm (c) 200 (d) 175 mm (e) 150 mm.
200
Each area corresponds
to the performance
characteristics of one
pump over a range of
impeller sizes
150
Head, m
100
80
70
60
50
40
30
20
10
1
2
3
4
5
6
8 10
2
Flow-rate, litres/s
Figure 5.11.
Family of pump curves
3
4
5
6
80
210
CHEMICAL ENGINEERING
5.4.5. System curve (operating line)
There are two components to the pressure head that has to be supplied by the pump in a
piping system:
1. The static pressure, to overcome the differences in head (height) and pressure.
2. The dynamic loss due to friction in the pipe, the miscellaneous losses, and the
pressure loss through equipment.
The static pressure difference will be independent of the fluid flow-rate. The dynamic
loss will increase as the flow-rate is increased. It will be roughly proportional to the flowrate squared, see equation 5.3. The system curve, or operating line, is a plot of the total
pressure head versus the liquid flow-rate. The operating point of a centrifugal pump can be
found by plotting the system curve on the pump’s characteristic curve, see Example 5.3.
When selecting a centrifugal pump for a given duty, it is important to match the pump
characteristic with system curve. The operating point should be as close as is practical to
the point of maximum pump efficiency, allowing for the range of flow-rate over which
the pump may be required to operate.
Most centrifugal pumps are controlled by throttling the flow with a valve on the pump
discharge, see Section 5.8.3. This varies the dynamic pressure loss, and so the position
of the operating point on the pump characteristic curve.
Throttling the flow results in an energy loss, which is acceptable in most applications.
However, when the flow-rates are large, the use of variable speed control on the pump
drive should be considered to conserve energy.
A more detailed discussion of the operating characteristics of centrifugal and other
types of pump is given by Walas (1990) and Karassik et al. (2001).
Example 5.3
A process liquid is pumped from a storage tank to a distillation column, using a centrifugal
pump. The pipeline is 80 mm internal diameter commercial steel pipe, 100 m long.
Miscellaneous losses are equivalent to 600 pipe diameters. The storage tank operates at
atmospheric pressure and the column at 1.7 bara. The lowest liquid level in the tank will be
1.5 m above the pump inlet, and the feed point to the column is 3 m above the pump inlet.
Plot the system curve on the pump characteristic given in Figure A and determine the
operating point and pump efficiency.
Properties of the fluid: density 900 kg/m3 , viscosity 1.36 mN m2 s.
Solution
Static head
Difference in elevation, z D 3.0 1.5 D 1.5 m
Difference in pressure, P D ⊲1.7 1.013⊳105 D 0.7 ð 105 N/m2
as head of liquid D ⊲0.7 ð 105 ⊳/⊲900 ð 9.8⊳ D 7.9 m
Total static ead D 1.5 C 7.9 D 9.4 m
211
PIPING AND INSTRUMENTATION
Dynamic head
As an initial value, take the fluid velocity as 1 m/s, a reasonable value.
Cross-sectional area of pipe D ⊲80 ð 103 ⊳2 D 5.03 ð 103 m2
4
Volumetric flow-rate D 1 ð 5.03 ð 103 ð 3600 D 18.1 m3 /h
900 ð 1 ð 80 ð 103
D 5.3 ð 104
1.36 ð 103
Relative roughness D 0.46/80 D 0.0006
Reynolds number D
⊲5.4⊳
Friction factor from Figure 5.7, f D 0.0027
Length including miscellaneous loses D 100 C ⊲600 ð 80 ð 103 ⊳ D 148 m
Pressure drop, Pf D 8 ð 0.0027
⊲148⊳
12
ð
900
ð
D 17,982 N/m2
⊲80 ð 103 ⊳
2
D 17,982/⊲900 ð 9.8⊳ D 2.03 m liquid
Total head D 9.4 C 2.03 D 11.4 m
30.0
25.0
Pump curve
Efficiency
Liquid head, m
77
20.0
79
80
79
15.0
77
10.0
System
curve
5.0
0.0
0
10
20
30
40
Flow-rate, m3/h
Figure A.
Example 5.3
50
60
70
80
⊲5.3⊳
212
CHEMICAL ENGINEERING
To find the system curve the calculations were repeated for the velocities shown in the
table below:
velocity
m/s
flow-rate
m3 /h
static head
m
dynamic head
m
total head
m
1
1.5
2.0
2.5
3.0
18.1
27.2
36.2
45.3
54.3
9.4
9.4
9.4
9.4
9.4
2.0
4.3
6.8
10.7
15.2
11.4
14.0
16.2
20.1
24.6
Plotting these values on the pump characteristic gives the operating point as 18.5 m at
40.0 m3 /h and the pump efficiency as 79 per cent.
5.4.6. Net positive suction head (NPSH)
The pressure at the inlet to a pump must be high enough to prevent cavitation occurring
in the pump. Cavitation occurs when bubbles of vapour, or gas, form in the pump casing.
Vapour bubbles will form if the pressure falls below the vapour pressure of the liquid.
The net positive suction head available ⊲NPSH a vail ⊳ is the pressure at the pump suction,
above the vapour pressure of the liquid, expressed as head of liquid.
The net positive head required ⊲NPSH reqd ⊳ is a function of the design parameters of
the pump, and will be specified by the pump manufacturer. As a general guide, the NPSH
should be above 3 m for pump capacities up to 100 m3 /h, and 6 m above this capacity.
Special impeller designs can be used to overcome problems of low suction head; see
Doolin (1977).
The net positive head available is given by the following equation:
NPSH a vail D P/ C H Pf / Pv /
⊲5.7⊳
where NPSH a vail D net positive suction head available at the pump suction, m,
P D the pressure above the liquid in the feed vessel, N/m2 ,
H D the height of liquid above the pump suction, m,
Pf D the pressure loss in the suction piping, N/m2 ,
Pv D the vapour pressure of the liquid at the pump suction, N/m2 ,
D the density of the liquid at the pump suction temperature, kg/m3 .
The inlet piping arrangement must be designed to ensure that NPSH a vail exceeds NPSH reqd
under all operating conditions.
The calculation of NPSH a vail is illustrated in Example 5.4.
Example 5.4
Liquid chlorine is unloaded from rail tankers into a storage vessel. To provide the
necessary NPSH, the transfer pump is placed in a pit below ground level. Given the
following information, calculate the NPSH available at the inlet to the pump, at a maximum
flow-rate of 16,000 kg/h.
PIPING AND INSTRUMENTATION
213
The total length of the pipeline from the rail tanker outlet to the pump inlet is 50 m.
The vertical distance from the tank outlet to the pump inlet is 10 m. Commercial steel
piping, 50 mm internal diameter, is used.
Miscellaneous friction losses due to the tanker outlet constriction and the pipe fittings
in the inlet piping, are equivalent to 1000 equivalent pipe diameters. The vapour pressure
of chlorine at the maximum temperature reached at the pump is 685 kN/m2 and its density
and viscosity, 1286 kg/m3 and 0.364 mNm2 s. The pressure in the tanker is 7 bara.
Solution
Friction losses
Miscellaneous losses
D 1000 ð 50 ð 103 D 50 m of pipe
Total length of inlet piping
D 50 C 50 D 100 m
Relative roughness, e/d
D 0.046/50 D 0.001
D ⊲50 ð 103 ⊳2 D 1.96 ð 103 m2
4
1
16,000
1
ð
D 1.76 m/s
D
ð
3
3600
1.96 ð 10
1286
Pipe cross-sectional area
Velocity, u
D
Reynolds number
1286 ð 1.76 ð 50 ð 103
D 3.1 ð 105
0.364 ð 103
⊲5.4⊳
Friction factor from Figure 5.7, f D 0.00225
Pf D 8 ð 0.00225
⊲100⊳
1.762
ð
1286
ð
D 71,703 N/m2
⊲50 ð 103 ⊳
2
71.703
685 ð 103
7 ð 105
C 10
1286 ð 9.8
1286 ð 9.8
1286 ð 9.8
D 55.5 C 10 5.7 54.4 D 5.4 m
NPSH D
⊲5.3⊳
⊲5.7⊳
5.4.7. Pump and other shaft seals
A seal must be made where a rotating shaft passes through the casing of a pump, or the
wall of a vessel. The seal must serve several functions:
1. To keep the liquid contained.
2. To prevent ingress of incompatible fluids, such as air.
3. To prevent escape of flammable or toxic materials.
Packed glands
The simplest, and oldest, form of seal is the packed gland, or stuffing box, Figure 5.12.
Its applications range from: sealing the stems of the water taps in every home, to proving
the seal on industrial pumps, agitator and valve shafts.
214
CHEMICAL ENGINEERING
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Packing
Housing
Figure 5.12.
Bolts
Gland
Follower
Packed gland
Lubricant
Lantern Ring
Figure 5.13.
Packed gland with lantern ring
The shaft runs through a housing (gland) and the space between the shaft and the wall
of the housing is filled with rings of packing. A gland follower is used to apply pressure
to the packing to ensure that the seal is tight. Proprietary packing materials are used. A
summary of the factors to be considered in the selection of packing materials for packed
glands is given by Hoyle (1975). To make a completely tight seal, the pressure on the
packing must be 2 to 3 times the system pressure. This can lead to excessive wear on
rotating shafts and lower pressures are used; allowing some leakage, which lubricates the
packing. So, packed glands should only be specified for fluids that are not toxic, corrosive,
or inflammable.
To provide positive lubrication, a lantern ring is often incorporated in the packing and
lubricant forced through the ring into the packing, see Figure 5.13. With a pump seal, a
flush is often take from the pump discharge and returned to the seal, through the lantern
ring, to lubricate and cool the packing. If any leakage to the environment must be avoided
a separate flush liquid can be used. A liquid must be selected that is compatible with the
process fluid, and the environment; water is often used.
Mechanical seals
In the process industries the conditions at the pump seal are often harsh and more complex
seals are needed. Mechanical face seals are used, Figure 5.14. They are generally referred
to simply as mechanical seals, and are used only on rotating shafts.
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PIPING AND INSTRUMENTATION
Retaining
screw
215
O-rings
Seal
face
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Rotating
seal
Spring
Figure 5.14.
Static
seal
Basic mechanical seal
The seal is formed between two flat faces, set perpendicular to the shaft. One face
rotates with the shaft, the other is stationary. The seal is made, and the faces lubricated
by a very thin film of liquid, about 0.0001m thick. A particular advantage of this type
of seal is that it can provide a very effective seal without causing any wear on the shaft.
The wear is transferred to the special seal faces. Some leakage will occur but it is small,
normally only a few drops per hour.
Unlike a packed gland, a mechanical seal, when correctly installed and maintained, can
be considered leak-tight.
A great variety of mechanical seal designs are available, and seals can be found to suit
virtually all applications. Only the basic mechanical seal is described below. Full details,
and specifications, of the range of seals available and their applications can be obtained
from manufacturers’ catalogues.
The basic mechanical seal
The components of a mechanical seal, Figure 5.14 are:
1. A stationary sealing ring (mating ring).
2. A seal for the stationary ring, O-rings or gaskets.
3. A rotating seal ring (primary ring), mounted so that it can slide along the shaft to
take up wear in the seal faces.
4. A secondary seal for the rotating ring mount; usually O-rings, or or chevron seals.
5. A spring to maintain contact pressure between the seal faces; to push the faces
together.
216
CHEMICAL ENGINEERING
6. A thrust support for the spring; either a collar keyed to the shaft or a step in the
shaft.
The assembled seal is fitted into a gland housing (stuffing box) and held in place by a
retaining ring (gland plate).
Mechanical seals are classified as inside or outside, depending on whether, the primary
(rotating ring) is located inside the housing; running in the fluid, or, outside. Outside seals
are easier to maintain, but inside seals are more commonly used in the process industries,
as it is easier to lubricate and flush this type.
Double seals
Where it is necessary to prevent any leakage of fluid to the atmosphere, a double
mechanical seal is used. The space between the two seals is flushed with a harmless
fluid, compatible with the process fluid, and provides a buffer between the two seals.
Seal-less pumps (canned pumps)
Pumps that have no seal on the shaft between the pump and the drive motor are available.
They are used for severe duties, where it is essential that there is no leakage into the
process fluid, or the environment.
The drive motor and pump are enclosed in a single casing and the stator windings
and armature are protected by metal cans; they are usually referred to as canned pumps.
The motor runs in the process fluid. The use of canned pumps to control environmental
pollution is discussed by Webster (1979).
5.5. MECHANICAL DESIGN OF PIPING SYSTEMS
5.5.1. Wall thickness: pipe schedule
The pipe wall thickness is selected to resist the internal pressure, with an allowance
for corrosion. Processes pipes can normally be considered as thin cylinders; only highpressure pipes, such as high-pressure steam lines, are likely to be classified as thick
cylinders and must be given special consideration (see Chapter 13).
The British Standard 5500 gives the following formula for pipe thickness:
tD
Pd
20d C P
⊲5.8⊳
where P D internal pressure, bar,
d D pipe od, mm,
d D design stress at working temperature, N/mm2 .
Pipes are often specified by a schedule number (based on the thin cylinder formula).
The schedule number is defined by:
Schedule number D
Ps ð 1000
s
⊲5.9⊳
PIPING AND INSTRUMENTATION
217
Ps D safe working pressure, lb/in2 (or N/mm2 ),
s D safe working stress, lb/in2 (or N/mm2 ).
Schedule 40 pipe is commonly used for general purposes.
Full details of the preferred dimensions for pipes can be found in the appropriate
Handbook and Standards. The main United Kingdom code for pipes and piping systems
is the British Standard is BS 1600.
The UK pipe schedule numbers are the same as the American (US). A summary of the
US standards is given in Perry et al. (1997).
Example 5.5
Estimate the safe working pressure for a 4 in. (100 mm) dia., schedule 40 pipe, carbon
steel, butt welded, working temperature 100Ž C. The safe working stress for butt welded
steel pipe up to 120Ž C is 6000 lb/in2 (41.4 N/mm2 ).
Solution
Ps D
⊲schedule no.⊳ ð s
40 ð 6000
D
D 240 lb/in2 D 1656 kN/m2
1000
1000
5.5.2. Pipe supports
Over long runs, between buildings and equipment, pipes are usually carried on pipe racks.
These carry the main process and service pipes, and are laid out to allow easy access to
the equipment.
Various designs of pipe hangers and supports are used to support individual pipes.
Details of typical supports can be found in the books by Perry et al. (1997) and Holmes
(1973). Pipe supports frequently incorporate provision for thermal expansion.
5.5.3. Pipe fittings
Pipe runs are normally made up from lengths of pipe, incorporating standard fittings for
joints, bends and tees. Joints are usually welded but small sizes may be screwed. Flanged
joints are used where this is a more convenient method of assembly, or if the joint will
have to be frequently broken for maintenance. Flanged joints are normally used for the
final connection to the process equipment, valves and ancillary equipment.
Details of the standard pipe fittings, welded, screwed and flanged, can be found in
manufacturer’s catalogues and in the appropriate national standards. The standards for
metal pipes and fittings are discussed by Masek (1968).
5.5.4. Pipe stressing
Piping systems must be designed so as not to impose unacceptable stresses on the
equipment to which they are connected.
218
CHEMICAL ENGINEERING
Loads will arise from:
1.
2.
3.
4.
5.
Thermal expansion of the pipes and equipment.
The weight of the pipes, their contents, insulation and any ancillary equipment.
The reaction to the fluid pressure drop.
Loads imposed by the operation of ancillary equipment, such as relief valves.
Vibration.
Thermal expansion is a major factor to be considered in the design of piping systems. The
reaction load due to pressure drop will normally be negligible. The dead-weight loads
can be carried by properly designed supports.
Flexibility is incorporated into piping systems to absorb the thermal expansion. A piping
system will have a certain amount of flexibility due to the bends and loops required by
the layout. If necessary, expansion loops, bellows and other special expansion devices
can be used to take up expansion.
A discussion of the methods used for the calculation of piping flexibility and stress
analysis are beyond the scope of this book. Manual calculation techniques, and the application of computers in piping stress analysis, are discussed in the handbook edited by
Nayyar et al. (2000).
5.5.5. Layout and design
An extensive discussion of the techniques used for piping system design and specification
is beyond the scope of this book. The subject is covered thoroughly in the books by
Sherwood (1991), Kentish (1982a) (1982b), and Lamit (1981).
5.6. PIPE SIZE SELECTION
If the motive power to drive the fluid through the pipe is available free, for instance when
pressure is let down from one vessel to another or if there is sufficient head for gravity
flow, the smallest pipe diameter that gives the required flow-rate would normally be used.
If the fluid has to be pumped through the pipe, the size should be selected to give the
least annual operating cost.
Typical pipe velocities and allowable pressure drops, which can be used to estimate
pipe sizes, are given below:
Velocity m/s
P kPa/m
1 3
0.5
0.05
0.02 per cent of
line pressure
Liquids, pumped (not viscous)
Liquids, gravity flow
Gases and vapours
15 30
High-pressure steam, >8 bar
30 60
Rase (1953) gives expressions for design velocities in terms of the pipe diameter. His
expressions, converted to SI units, are:
PIPING AND INSTRUMENTATION
Pump discharge
Pump suction
Steam or vapour
219
0.06d C 0.4 m/s
0.02d C 0.1 m/s
0.2d m/s
where d is the internal diameter in mm.
Simpson (1968) gives values for the optimum velocity in terms of the fluid density.
His values, converted to SI units and rounded, are:
Fluid density kg/m3
Velocity m/s
1600
800
160
16
0.16
0.016
2.4
3.0
4.9
9.4
18.0
34.0
The maximum velocity should be kept below that at which erosion is likely to occur.
For gases and vapours the velocity cannot exceed the critical velocity (sonic velocity)
(see Volume 1, Chapter 4) and would normally be limited to 30 per cent of the critical
velocity.
Economic pipe diameter
The capital cost of a pipe run increases with diameter, whereas the pumping costs
decrease with increasing diameter. The most economic pipe diameter will be the one
which gives the lowest annual operating cost. Several authors have published formulae
and nomographs for the estimation of the economic pipe diameter, Genereaux (1937),
Peters and Timmerhaus (1968) (1991), Nolte (1978) and Capps (1995). Most apply to
American practice and costs, but the method used by Peters and Timmerhaus has been
modified to take account of UK prices (Anon, 1971).
The formulae developed in this section are presented as an illustration of a simple
optimisation problem in design, and to provide an estimate of economic pipe diameter
that is based on UK costs and in SI units. The method used is essentially that first
published by Genereaux (1937).
The cost equations can be developed by considering a 1 metre length of pipe.
The purchase cost will be roughly proportional to the diameter raised to some power.
Purchase cost D Bdn £/m
The value of the constant B and the index n depend on the pipe material and schedule.
The installed cost can be calculated by using the factorial method of costing discussed
in Chapter 6.
Installed cost D Bdn ⊲1 C F⊳
where the factor F includes the cost of valves, fittings and erection, for a typical run of
the pipe.
The capital cost can be included in the operating cost as an annual capital charge. There
will also be an annual charge for maintenance, based on the capital cost.
Cp D Bdn ⊲1 C F⊳⊲a C b⊳
⊲5.10⊳
220
CHEMICAL ENGINEERING
where Cp D capital cost portion of the annual operating cost, £,
a D capital charge, per cent/100,
b D maintenance costs, per cent/100.
The power required for pumping is given by:
Power D volumetric flow-rate ð pressure drop.
Only the friction pressure drop need be considered, as any static head is not a function
of the pipe diameter.
To calculate the pressure drop the pipe friction factor needs to be known. This is a
function of Reynolds number, which is in turn a function of the pipe diameter. Several
expressions have been proposed for relating friction factor to Reynolds number. For
simplicity the relationship proposed by Genereaux (1937) for turbulent flow in clean
commercial steel pipes will be used.
f D 0.04Re0.16
where f is the Fanning friction factor D 2⊲R/u2 ⊳.
Substituting this into the Fanning pressure drop equation gives:
P D 4.13 ð 1010 G1.84 0.16 1 d4.84
where P
G
d
D
D
D
D
D
⊲5.11⊳
2
pressure drop, kN/m (kPa),
flow rate, kg/s,
density, kg/m3 ,
viscosity, m Nm2 s
pipe id, mm.
The annual pumping costs will be given by:
Cf D
G
Ap
P
E
where A D plant attainment, hours/year,
p D cost of power, £/kWh,
E D pump efficiency, per cent/100.
Substituting from equation 5.11
Hp
4.13 ð 1010 G2.84 0.16 2 d4.84
⊲5.12⊳
E
The total annual operating cost Ct D Cp C Cf.
Adding equations 5.10 and 5.12, differentiating, and equating to zero to find the pipe
diameter to give the minimum cost gives:
1/⊲4.84Cn⊳
2 ð 1011 ð ApG2.84 0.16 2
⊲5.13⊳
d, optimum D
EnB⊲1 C F⊳⊲a C b⊳
Cf D
Equation 5.13 is a general equation and can be used to estimate the economic pipe
diameter for any particular situation. It can be set up on a spreadsheet and the effect of
the various factors investigated.
PIPING AND INSTRUMENTATION
221
The equation can be simplified by substituting typical values for the constants.
The normal attainment for a chemical process plant will be between
90 95%, so take the operating hours per year as 8000.
E Pump and compressor efficiencies will be between 50 to 70%, so take 0.6.
p Use the current cost of power, 0.055 £/kWh (mid-1992).
F This is the most difficult factor to estimate. Other authors have used
values ranging from 1.5 (Peters and Timmerhaus (1968)) to 6.75 (Nolte
(1978)). It is best taken as a function of the pipe diameter; as has been
done to derive the simplified equations given below.
B, n Can be estimated from the current cost of piping.
a
Will depend on the current cost of capital, around 10% in mid-1992.
b
A typical figure for process plant will be 5%, see Chapter 6.
A
F, B, and n have been estimated from cost data published by the Institution of Chemical
Engineers, IChemE (1987), updated to mid-1992. This includes the cost of fittings, installation and testing. A log-log plot of the data gives the following expressions for the
installed cost:
Carbon steel, 15 to 350 mm
Stainless steel, 15 to 350 mm
27 d0.55 £/m
31 d0.62 £/m
Substitution in equation 5.12 gives, for carbon steel:
d, optimum D 366 G0.53 0.03 0.37
Because the exponent of the viscosity term is small, its value will change very little
over a wide range of viscosity
at
D 105 Nm2 s ⊲0.01 cp⊳, 0.03 D 0.71
D 102 Nm2 s ⊲10 cp⊳, 0.03 D 0.88
Taking a mean value of 0.8, gives the following equations for the optimum diameter,
for turbulent flow:
Carbon steel pipe:
d, optimum D 293 G0.53 0.37
⊲5.14⊳
d, optimum D 260 G0.52 0.37
⊲5.15⊳
Stainless steel pipe:
Equations 5.14 and 5.15 can be used to make an approximate estimate of the economic
pipe diameter for normal pipe runs. For a more accurate estimate, or if the fluid or pipe
run is unusual, the method used to develop equation 5.13 can be used, taking into account
the special features of the particular pipe run.
The optimum diameter obtained from equations 5.14 and 5.15 should remain valid
with time. The cost of piping depends on the cost power and the two costs appear in the
equation as a ratio raised to a small fractional exponent.
Equations for the optimum pipe diameter with laminar flow can be developed by using
a suitable equation for pressure drop in the equation for pumping costs.
222
CHEMICAL ENGINEERING
The approximate equations should not be used for steam, as the quality of steam depends
on its pressure, and hence the pressure drop.
Nolte (1978) gives detailed methods for the selection of economic pipe diameters,
taking into account all the factors involved. He gives equations for liquids, gases, steam
and two-phase systems. He includes in his method an allowance for the pressure drop
due to fittings and valves, which was neglected in the development of equation 5.12, and
by most other authors.
The use of equations 5.14 and 5.15 are illustrated in Examples 5.6 and 5.7, and the
results compared with those obtained by other authors. Peters and Timmerhaus’s formulae
give larger values for the economic pipe diameters, which is probably due to their low
value for the installation cost factor, F.
Example 5.6
Estimate the optimum pipe diameter for a water flow rate of 10 kg/s, at 20Ž C. Carbon
steel pipe will be used. Density of water 1000 kg/m3 .
Solution
d, optimum D 293 ð ⊲10⊳0.53 10000.37
⊲5.14⊳
D 77.1 mm
use 80-mm pipe.
Viscosity of water at 20Ž C D 1.1 ð 103 Ns/m2 ,
Re D
4G
4 ð 10
D 1.45 ð 105
D
d
ð 1.1 ð 103 ð 80 ð 103
>4000, so flow is turbulent.
Comparison of methods:
Economic diameter
Equation 5.14
Peters and Timmerhaus (1991)
Nolte (1978)
180 mm
4 in. (100 mm)
80 mm
Example 5.7
Estimate the optimum pipe diameter for a flow of HCl of 7000 kg/h at 5 bar, 15Ž C,
stainless steel pipe. Molar volume 22.4 m3 /kmol, at 1 bar, 0Ž C.
Solution
Molecular weight HCl D 36.5.
Density at operating conditions D
36.5 5 273
ð ð
D 7.72 kg/m3
22.4 1 288
223
PIPING AND INSTRUMENTATION
Optimum diameter D 260
7000
3600
0.52
7.720.37
⊲5.15⊳
D 172.4 mm
use 180-mm pipe.
Viscosity of HCl 0.013 m Ns/m2
Re D
4
7000
1
D 1.06 ð 106 , turbulent
ð
ð
3
3600 0.013 ð 10 ð 180 ð 103
Comparison of methods:
Economic diameter
Equation 5.15
Peters and Timmerhaus (1991)
Nolte (1978)
180 mm
9 in. (220 mm) carbon steel
7 in. (180 mm) carbon steel
Example 5.8
Calculate the line size and specify the pump required for the line shown in Figure 5.15;
material ortho-dichlorobenzene (ODCB), flow-rate 10,000 kg/h, temperature 20Ž C, pipe
material carbon steel.
2m
5.5 m
6.5 m
7.5 m
m
5m
20
tum
0.5 m
0.5
1.0 m
2.5 m
Da
1m
Preliminary layout
not to scale
4m
tum
Da
Figure 5.15.
Piping isometric drawing (Example 5.8)
224
CHEMICAL ENGINEERING
Solution
ODCB density at 20Ž C D 1306 kg/m3 .
Viscosity: 0.9 mNs/m2 (0.9 cp).
Estimation of pipe diameter required
typical velocity for liquid 2 m/s
10,000
D 2.78 kg/s
3600
2.78
volumetric flow D
D 2.13 ð 103 m3 /s
1306
mass flow D
2.13 ð 103
volumetric flow
D
D 1.06 ð 103 m2
velocity
2
4
3
diameter of pipe D
D 0.037 m
1.06 ð 10 ð
area of pipe D
D 37 mm
Or, use economic pipe diameter formula:
d, optimum D 293 ð 2.780.53 ð 13060.37
⊲5.14⊳
D 35.4 mm
Take diameter as 40 mm
cross-sectional area D
⊲40 ð 103 ⊳ D 1.26 ð 103 m2
4
Pressure drop calculation
fluid velocity D
2.13 ð 103
D 1.70 m/s
1.26 ð 103
Friction loss per unit length, f1 :
Re D
1306 ð 1.70 ð 40 ð 103
D 9.9 ð 104
0.9 ð 103
⊲5.5⊳
Absolute roughness commercial steel pipe, table 5.2 D 0.46 mm
Relative roughness, e/d D 0.046/40 D 0.001
Friction factor from Figure 5.7, f D 0.0027
f1 D 8 ð 0.0027 ð
D 1.02 kPa
1.72
⊲1⊳
ð 1306 ð
D 1019 N/m2
3
⊲40 ð 10 ⊳
2
⊲5.3⊳
225
PIPING AND INSTRUMENTATION
Design for a maximum flow-rate of 20 per cent above the average flow.
Friction loss D 1.02 ð 1.22 D 1.5 kPa/m
Miscellaneous losses
Take as equivalent pipe diameters. All bends will be taken as 90Ž standard radius elbow.
Line to pump suction:
length
D 1.5 m
bend, 1 ð 30 ð 40 ð 103 D 1.2 m
valve, 1 ð 18 ð 40 ð 103 D 0.7 m
3.4 m
entry loss D
u2
⊲see Section 5.4.2⊳
2
at maximum design velocity D
1306⊲1.7 ð 1.2⊳2
D 2.7 kPa
2 ð 103
Control valve pressure drop, allow normal 140 kPa
⊲ð1.22 ⊳ maximum 200 kPa
Heat exchanger, allow normal 70 kPa
⊲ð1.22 ⊳ maximum 100 kPa
Orifice, allow normal 15 kPa
⊲ð1.22 ⊳ maximum 22 kPa
Line from pump discharge:
length D 4 C 5.5 C 20 C 5 C 0.5 C 1 C 6.5 C 2 D 44.5 m
D 7.2 m
bends, 6 ð 30 ð 40 ð 103 D 7.2 m
3
valves, 3 ð 18 ð 40 ð 10 D 2.2 m
D 2.2 m
54.0 m
The line pressure-drop calculation is set out on the calculation sheet shown in Table 5.4.
Pump selection:
flow-rate D 2.13 ð 103 ð 3600 D 7.7 m3 /h
differential head, maximum, 44 m
select single-stage centrifugal (Figure 5.6)
226
CHEMICAL ENGINEERING
Table 5.4.
Job no.
Sheet no.
4415A
1
Fluid
Temperature ° C
By
ODCB
20
Density kg/m3
DISCHARGE CALCULATION
Line size mm
40
1306
Viscosity mNs/m2
Normal flow kg/s
Design max. flow kg/s
0.9
2.78
3.34
SUCTION CALCULATION
Line size mm
40
Flow
Norm.
Max.
u1
Velocity
1.7
2.0
f1
Friction loss
1.0
1.5
L1
Line length
3.4
f1 L1
Line loss
3.4
5.1
u21 /2
Entrance
1.9
2.7
(40 kPa) Strainer
(1) Sub-total
5.3
7.8
Static head
Equip. press
(2) Sub-total
(2) (1) (3) Suction press
(4) VAP. PRESS.
(3) (4) (5) NPSH
(5)/g
u2
f2
L2
f2 L2
30%
Units
m/s
kPa/m
m
kPa
kPa
kPa
kPa
1.5
19.6
100
119.6
1.5
19.6
100
119.6
m
kPa
kPa
kPa
114.3
0.1
114.2
8.7
111.8
0.1
111.7
8.6
kPa
kPa
kPa
m
z2
gz2
(7) C (6)
(3)
Flow
Norm.
Max.
Velocity
Friction loss
Line length
Line loss
Orifice
Control valve
Equipment
(a) Heat ex.
(b)
(c)
(6) Dynamic loss
1.7
1.0
54
54
15
140
2.0
1.5
22
200
70
100
279
403
kPa
kPa
kPa
kPa
Static head
6.5
85
200
None
285
564
114.3
450
85
200
None
285
685
111.8
576
m
kPa
kPa
kPa
kPa
kPa
kPa
kPa
34
44
m
Equip. press (max)
Contingency
(7) Sub-total
Discharge press.
Suction press.
(8) Diff. press.
(8)/g
Valve/(6)
Control valve
% Dyn. loss
50%
C 201
1 bar
C 203
2 bar
7.5 m
2.5 m
H 205
1.0 m
z1
gz1
Line calculation form (Example 5.4)
Pump and line calculation sheet
RKS,
7/7/79
Checked
Z1 = 2.5 − 1 = 1.5 m
Z2 = 7.5 − 1 = 6.5 m
Units
m/s
kPa/m
m
kPa
kPa
kPa
PIPING AND INSTRUMENTATION
Table 5.5.
227
Pump Specification Sheet (Example 5.8)
Pump Specification
Type:
No. stages:
Single/Double suction:
Vertical/Horizontal mounting:
Impeller type:
Casing design press.:
design temp.:
Driver:
Seal type:
Max. flow:
Diff. press.:
Centrifugal
1
Single
Horizontal
Closed
600 kPa
20° C
Electric, 440 V, 50 c/s 3-phase.
Mechanical, external flush
7.7 m3 /h
600 kPa (47 m, water)
5.7. CONTROL AND INSTRUMENTATION
5.7.1. Instruments
Instruments are provided to monitor the key process variables during plant operation.
They may be incorporated in automatic control loops, or used for the manual monitoring
of the process operation. They may also be part of an automatic computer data logging
system. Instruments monitoring critical process variables will be fitted with automatic
alarms to alert the operators to critical and hazardous situations.
Comprehensive reviews of process instruments and control equipment are published
periodically in the journal Chemical Engineering. These reviews give details of all the
instruments and control hardware available commercially, including those for the on-line
analysis of stream compositions (Anon., 1969). Details of process instruments and control
equipment can also be found in various handbooks, Perry et al. (1997) and Lipak (2003).
It is desirable that the process variable to be monitored be measured directly; often,
however, this is impractical and some dependent variable, that is easier to measure, is
monitored in its place. For example, in the control of distillation columns the continuous,
on-line, analysis of the overhead product is desirable but difficult and expensive to achieve
reliably, so temperature is often monitored as an indication of composition. The temperature instrument may form part of a control loop controlling, say, reflux flow; with the
composition of the overheads checked frequently by sampling and laboratory analysis.
5.7.2. Instrumentation and control objectives
The primary objectives of the designer when specifying instrumentation and control
schemes are:
1. Safe plant operation:
(a) To keep the process variables within known safe operating limits.
(b) To detect dangerous situations as they develop and to provide alarms and
automatic shut-down systems.
(c) To provide interlocks and alarms to prevent dangerous operating procedures.
2. Production rate:
To achieve the design product output.
228
CHEMICAL ENGINEERING
3. Product quality:
To maintain the product composition within the specified quality standards.
4. Cost:
To operate at the lowest production cost, commensurate with the other objectives.
These are not separate objectives and must be considered together. The order in which they
are listed is not meant to imply the precedence of any objective over another, other than
that of putting safety first. Product quality, production rate and the cost of production will
be dependent on sales requirements. For example, it may be a better strategy to produce
a better-quality product at a higher cost.
In a typical chemical processing plant these objectives are achieved by a combination
of automatic control, manual monitoring and laboratory analysis.
5.7.3. Automatic-control schemes
The detailed design and specification of the automatic control schemes for a large project
is usually done by specialists. The basic theory underlying the design and specification
of automatic control systems is covered in several texts: Coughanowr (1991), Shinskey
(1984) (1996) and Perry et al. (1997). The books by Murrill (1988) and Shinskey (1996)
cover many of the more practical aspects of process control system design, and are
recommended.
In this chapter only the first step in the specification of the control systems for a process
will be considered: the preparation of a preliminary scheme of instrumentation and control,
developed from the process flow-sheet. This can be drawn up by the process designer
based on his experience with similar plant and his critical assessment of the process
requirements. Many of the control loops will be conventional and a detailed analysis of
the system behaviour will not be needed, nor justified. Judgement, based on experience,
must be used to decide which systems are critical and need detailed analysis and design.
Some examples of typical (conventional) control systems used for the control of specific
process variables and unit operations are given in the next section, and can be used as a
guide in preparing preliminary instrumentation and control schemes.
Guide rules
The following procedure can be used when drawing up preliminary P and I diagrams:
1. Identify and draw in those control loops that are obviously needed for steady plant
operation, such as:
(a) level controls,
(b) flow controls,
(c) pressure controls,
(d) temperature controls.
2. Identify the key process variables that need to be controlled to achieve the specified
product quality. Include control loops using direct measurement of the controlled
variable, where possible; if not practicable, select a suitable dependent variable.
3. Identify and include those additional control loops required for safe operation, not
already covered in steps 1 and 2.
PIPING AND INSTRUMENTATION
229
4. Decide and show those ancillary instruments needed for the monitoring of the plant
operation by the operators; and for trouble-shooting and plant development. It is
well worthwhile including additional connections for instruments which may be
needed for future trouble-shooting and development, even if the instruments are not
installed permanently. This would include: extra thermowells, pressure tappings,
orifice flanges, and extra sample points.
5. Decide on the location of sample points.
6. Decide on the need for recorders and the location of the readout points, local or
control room. This step would be done in conjunction with steps 1 to 4.
7. Decide on the alarms and interlocks needed; this would be done in conjunction with
step 3 (see Chapter 9).
5.8. TYPICAL CONTROL SYSTEMS
5.8.1. Level control
In any equipment where an interface exists between two phases (e.g. liquid vapour),
some means of maintaining the interface at the required level must be provided. This
may be incorporated in the design of the equipment, as is usually done for decanters,
or by automatic control of the flow from the equipment. Figure 5.16 shows a typical
arrangement for the level control at the base of a column. The control valve should be
placed on the discharge line from the pump.
Figure 5.16.
Level control
5.8.2. Pressure control
Pressure control will be necessary for most systems handling vapour or gas. The method
of control will depend on the nature of the process. Typical schemes are shown in
Figures 5.17a, b, c, d (see p. 230). The scheme shown in Figure 5.17a would not be
used where the vented gas was toxic, or valuable. In these circumstances the vent should
be taken to a vent recovery system, such as a scrubber.
5.8.3. Flow control
Flow control is usually associated with inventory control in a storage tank or other
equipment. There must be a reservoir to take up the changes in flow-rate.
To provide flow control on a compressor or pump running at a fixed speed and
supplying a near constant volume output, a by-pass control would be used, as shown
in Figures 5.18a, b (see p. 231).
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CHEMICAL ENGINEERING
(a)
(b)
(c)
(d)
Figure 5.17. (a) Pressure control by direct venting (b) Venting of non-condensables after a condenser
(c) Condenser pressure control by controlling coolant flow (d) Pressure control of a condenser by varying
the heat-transfer area, area dependent on liquid level
5.8.4. Heat exchangers
Figure 5.19a (see p. 232) shows the simplest arrangement, the temperature being controlled by varying the flow of the cooling or heating medium.
If the exchange is between two process streams whose flows are fixed, by-pass control
will have to be used, as shown in Figure 5.19b (see p. 232).
Condenser control
Temperature control is unlikely to be effective for condensers, unless the liquid stream is
sub-cooled. Pressure control is often used, as shown in Figure 5.17d, or control can be
based on the outlet coolant temperature.
Reboiler and vaporiser control
As with condensers, temperature control is not effective, as the saturated vapour temperature is constant at constant pressure. Level control is often used for vaporisers; the
controller controlling the steam supply to the heating surface, with the liquid feed to the
vaporiser on flow control, as shown in Figure 5.20 (see p. 232). An increase in the feed
results in an automatic increase in steam to the vaporiser to vaporise the increased flow
and maintain the level constant.
PIPING AND INSTRUMENTATION
231
(a)
(b)
Figure 5.18. (a) Flow control for a reciprocating pump (b) Alternative scheme for a centrifugal
compressor or pump
Reboiler control systems are selected as part of the general control system for the
column and are discussed in Section 5.8.7.
5.8.5. Cascade control
With this arrangement, the output of one controller is used to adjust the set point of
another. Cascade control can give smoother control in situations where direct control
of the variable would lead to unstable operation. The “slave” controller can be used to
compensate for any short-term variations in, say, a service stream flow, which would upset
the controlled variable; the primary (master) controller controlling long-term variations.
Typical examples are shown in Figure 5.22e (see p. 235) and 5.23 (see p. 235).
5.8.6. Ratio control
Ratio control can be used where it is desired to maintain two flows at a constant ratio; for
example, reactor feeds and distillation column reflux. A typical scheme for ratio control
is shown in Figure 5.21 (see p. 233).
5.8.7. Distillation column control
The primary objective of distillation column control is to maintain the specified composition of the top and bottom products, and any side streams; correcting for the effects of
disturbances in:
1. Feed flow-rate, composition and temperature.
2. Steam supply pressure.
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CHEMICAL ENGINEERING
(a)
(b)
Figure 5.19.
(a) Control of one fluid stream (b) By-pass control
Figure 5.20.
Vaporiser control
3. Cooling water pressure and header temperature.
4. Ambient conditions, which cause changes in internal reflux (see Chapter 11).
The compositions are controlled by regulating reflux flow and boil-up. The column overall
material balance must also be controlled; distillation columns have little surge capacity
(hold-up) and the flow of distillate and bottom product (and side-streams) must match the
feed flows.
Shinskey (1984) has shown that there are 120 ways of connecting the five main parts of
measured and controlled variables, in single loops. A variety of control schemes has been
devised for distillation column control. Some typical schemes are shown in Figures 5.22a,
b, c, d, e (see pp. 234, 235); ancillary control loops and instruments are not shown.
PIPING AND INSTRUMENTATION
Figure 5.21.
233
Ratio control
Distillation column control is discussed in detail by Parkins (1959), Bertrand and Jones
(1961) and Shinskey (1984) Buckley et al. (1985).
Column pressure is normally controlled at a constant value. The use of variable pressure
control to conserve energy has been discussed by Shinskey (1976).
The feed flow-rate is often set by the level controller on a preceding column. It can be
independently controlled if the column is fed from a storage or surge tank.
Feed temperature is not normally controlled, unless a feed preheater is used.
Temperature is often used as an indication of composition. The temperature sensor
should be located at the position in the column where the rate of change of temperature
with change in composition of the key component is a maximum; see Parkins (1959).
Near the top and bottom of the column the change is usually small. With multicomponent
systems, temperature is not a unique function of composition.
Top temperatures are usually controlled by varying the reflux ratio, and bottom temperatures by varying the boil-up rate. If reliable on-line analysers are available they can be
incorporated in the control loop, but more complex control equipment will be needed.
Differential pressure control is often used on packed columns to ensure that the packing
operates at the correct loading; see Figure 5.22d (see p. 234).
Additional temperature indicating or recording points should be included up the column
for monitoring column performance and for trouble shooting.
5.8.8. Reactor control
The schemes used for reactor control depend on the process and the type of reactor. If a
reliable on-line analyser is available, and the reactor dynamics are suitable, the product
composition can be monitored continuously and the reactor conditions and feed flows
controlled automatically to maintain the desired product composition and yield. More
often, the operator is the final link in the control loop, adjusting the controller set points
to maintain the product within specification, based on periodic laboratory analyses.
Reactor temperature will normally be controlled by regulating the flow of the heating
or cooling medium. Pressure is usually held constant. Material balance control will be
necessary to maintain the correct flow of reactants to the reactor and the flow of products
and unreacted materials from the reactor. A typical reactor control scheme is shown in
Figure 5.23 (see p. 235).
234
CHEMICAL ENGINEERING
(a)
(b)
(c)
(d)
Figure 5.22. (a) Temperature pattern control. With this arrangement interaction can occur between the top and
bottom temperature controllers (b) Composition control. Reflux ratio controlled by a ratio controller, or splitter
box, and the bottom product as a fixed ratio of the feed flow (c) Composition control. Top product take-off and
boil-up controlled by feed (d) Packed column, differential pressure control. Eckert (1964) discusses the control
of packed columns
PIPING AND INSTRUMENTATION
235
(e)
Figure 5.22.
(e) Batch distillation, reflux flow cascaded with temperature to maintain constant top composition
Figure 5.23.
A typical stirred tank reactor control scheme, temperature: cascade control, and reagent:
flow control
5.9. ALARMS AND SAFETY TRIPS, AND INTERLOCKS
Alarms are used to alert operators of serious, and potentially hazardous, deviations in
process conditions. Key instruments are fitted with switches and relays to operate audible
and visual alarms on the control panels and annunciator panels. Where delay, or lack
of response, by the operator is likely to lead to the rapid development of a hazardous
situation, the instrument would be fitted with a trip system to take action automatically
to avert the hazard; such as shutting down pumps, closing valves, operating emergency
systems.
236
CHEMICAL ENGINEERING
The basic components of an automatic trip system are:
1. A sensor to monitor the control variable and provide an output signal when a preset
value is exceeded (the instrument).
2. A link to transfer the signal to the actuator, usually consisting of a system of
pneumatic or electric relays.
3. An actuator to carry out the required action; close or open a valve, switch off a
motor.
A description of some of the equipment (hardware) used is given by Rasmussen (1975).
A safety trip can be incorporated in a control loop; as shown in Figure 5.24a. In this
system the high-temperature alarm operates a solenoid valve, releasing the air on the
pneumatic activator, closing the valve on high temperature. However, the safe operation
of such a system will be dependent on the reliability of the control equipment, and for
potentially hazardous situations it is better practice to specify a separate trip system; such
as that shown in Figure 5.24b. Provision must be made for the periodic checking of the
trip system to ensure that the system operates when needed.
(a)
Figure 5.24.
(b)
(a) Trip as part of control system (b) Separate shut-down trip
Interlocks
Where it is necessary to follow a fixed sequence of operations for example, during a
plant start-up and shut-down, or in batch operations interlocks are included to prevent
operators departing from the required sequence. They may be incorporated in the control
system design, as pneumatic or electric relays, or may be mechanical interlocks. Various
proprietary special lock and key systems are available.
5.10. COMPUTERS AND MICROPROCESSORS IN
PROCESS CONTROL
Computers are being increasingly used for data logging, process monitoring and control.
They have largely superseded the strip charts and analogue controllers seen in older
plant. The long instrument panels and “mimic” flow-chart displays have been replaced
by intelligent video display units. These provide a window on the process. Operators
PIPING AND INSTRUMENTATION
237
Figure 5.25.
Piping and instrumentation diagram
238
CHEMICAL ENGINEERING
and technical supervision can call up and display any section of the process to review
the operating parameters and adjust control settings. Abnormal and alarm situations are
highlighted and displayed.
Historical operating data is retained in the computer memory. Averages and trends can
be displayed, for plant investigation and trouble shooting.
Software to continuously update and optimise plant performance can be incorporated
in the computer control systems.
Programmable logic controllers are used for the control and interlocking of processes
where a sequence of operating steps has to be carried out: such as, in batch processes,
and in the start-up and shut down of continuous processes.
A detailed discussion of the application of digital computers and microprocessors in
process control is beyond the scope of this volume. The use of computers and microprocessor based distributed control systems for the control of chemical process is covered
by Kalani (1988).
5.11. REFERENCES
ANON. (1969) Chem. Eng., NY 76 (June 2nd) 136. Process instrument elements.
ANON. (1971) Brit. Chem. Eng. 16, 313. Optimum pipeline diameters by nomograph.
AUSTIN, D. G. (1979) Chemical Engineering Drawing Symbols (George Godwin).
BERTRAND, L. and JONES, J. B. (1961) Chem. Eng., NY 68 (Feb. 20th) 139. Controlling distillation columns.
BUCKLEY, P. S., LUYBEN, W. L. and SHUNTA, J. P. (1985) Design of Distillation Column Control Systems
(Arnold).
BVAMA (1991) Valves and Actuators from Britain, 5th edn (British Valve and Actuator Manufacturers’ Association).
CAPPS, R. W. (1995) Chem. Eng. NY, 102 (July) 102. Select the optimum pipe diameter.
CHABBRA, R. P. and RICHARDSON, J. F. (1999) Non-Newtonian Flow in the Process Industries (ButterworthHeinemann).
CHAFLIN, S. (1974) Chem. Eng., NY 81 (Oct. 14th) 105. Specifying control valves.
COUGHANOWR, D. R. (1991) Process Systems Analysis and Control, 2nd edn. (MacGraw-Hill).
DARBY, R. (2001) Chem. Eng., NY 108 (March) 66. Take the mystery out of non-Newton fluids.
DAVIDSON, J. and VON BERTELE, O. (1999) Process Pump Selection A Systems Approach (I. Mech E.)
DE SANTIS, G. J. (1976) Chem. Eng., NY 83 (Nov. 22nd) 163. How to select a centrifugal pump.
DOOLIN, J. H. (1977) Chem. Eng., NY (Jan. 17th) 137. Select pumps to cut energy cost.
ECKERT, J. S. (1964) Chem. Eng., NY 71 (Mar. 30th) 79. Controlling packed-column stills.
GENEREAUX, R. P. (1937) Ind. Eng. Chem. 29, 385. Fluid-flow design methods.
HOLLAND, F. A. and CHAPMAN, F. S. (1966) Chem. Eng., NY 73 (Feb. 14th) 129. Positive displacement pumps.
HOYLE, R. (1978) Chem. Eng. NY, 85 (Oct 8th) 103. How to select and use mechanical packings.
ICHEME (1988) A New Guide to Capital Cost Estimation 3rd edn (Institution of Chemical Engineers, London).
JACOBS, J. K. (1965) Hydrocarbon Proc. 44 (June) 122. How to select and specify process pumps.
JANDIEL, D. G. (2000) Chem. Eng. Prog. 96 (July) 15. Select the right compressor.
KALANI, G. (1988) Microprocessor Based Distributed Control Systems (Prentice Hall).
KARASSIK, I. J. et al. (2001) Pump Handbook, 3rd edn (McGraw-Hill).
KENTISH, D. N. W. (1982a) Industrial Pipework (McGraw-Hill).
KENTISH, D. N. W. (1982b) Pipework Design Data (McGraw-Hill).
KERN, R. (1975) Chem. Eng., NY 82 (April 28th) 119. How to design piping for pump suction conditions.
LAMIT, L. G. (1981) Piping Systems: Drafting and Design (Prentice Hall).
LIPAK, B. G. (2003) Instrument Engineers’ Handbook, Vol 1: Process Measurement and Analysis, 4th edn (CRC
Press).
LUDWG, E. E. (1960) Chem. Eng., NY 67 (June 13th) 162. Flow of fluids.
MASEK, J. A. (1968) Chem. Eng., NY 75 (June 17th) 215. Metallic piping.
MERRICK, R. C. (1986) Chem. Eng., NY 93 (Sept. 1st) 52. Guide to the selection of manual valves.
MERRICK, R. C. (1990) Valve Selection and Specification Guide (Spon.).
MURRILL, P. W. (1988) Application Concepts of Process Control (Instrument Society of America).
NAYYAR, M. L. et al. (2000) Piping Handbook, 7th edn (McGraw-Hill).
239
PIPING AND INSTRUMENTATION
NEERKIN, R. F. (1974) Chem. Eng., NY 81 (Feb. 18) 104. Pump selection for chemical engineers.
NOLTE, C. B. (1978) Optimum Pipe Size Selection (Trans. Tech. Publications).
PARKINS, R. (1959) Chem. Eng. Prog. 55 (July) 60. Continuous distillation plant controls.
PEARSON, G. H. (1978) Valve Design (Mechanical Engineering Publications).
PERRY, R. H. and CHILTON, C. H. (eds) (1973) Chemical Engineers Handbook, 5th edn (McGraw-Hill).
PERRY, R. H., GREEN, D. W. and MALONEY, J. O. (eds) (1997) Perry’s Chemical Engineers’ Handbook, 7th
edn. (McGraw-Hill).
PETERS, M. S. and TIMMERHAUS, K. D. (1968) Plant Design and Economics for Chemical Engineers, 2nd edn
(McGraw-Hill).
PETERS, M. S. and TIMMERHAUS, K. D. (1991) Plant Design and Economics, 4th edn (McGraw-Hill).
RASE, H. F. (1953) Petroleum Refiner 32 (Aug.) 14. Take another look at economic pipe sizing.
RASMUSSEN, E. J. (1975) Chem. Eng., NY 82 (May 12th) 74. Alarm and shut down devices protect process
equipment.
SHERWOOD, D. R. (1991) The Piping Guide, 2nd edn (Spon.).
SHINSKEY, F. G. (1976) Chem. Eng. Prog. 72 (May) 73. Energy-conserving control systems for distillation units.
SHINSKEY, F. G. (1984) Distillation Control, 2nd edn (McGraw-Hill).
SHINSKEY, F. G. (1996) Process Control Systems, 4th edn (McGraw-Hill).
SIMPSON, L. L. (1968) Chem. Eng., NY 75 (June 17th) 1923. Sizing piping for process plants.
SMITH, E. and VIVIAN, B. E. (1995) Valve Selection (Mechanical Engineering Publications).
SMITH, P. and ZAPPE, R. W. (2003) Valve Selection Handbook, 5th edn (Gulf Publishing).
WALAS S. M. (1990) Chemical Process Equipment (Butterworth-Heinemann).
WEBSTER, G. R. (1979) Chem. Engr. London No. 341 (Feb.) 91. The canned pump in the petrochemical
environment.
British Standards
BS 806: 1986 Ferrous pipes and piping for and in connection with land boilers.
BS 1600: 1991 Dimension of steel pipes for the petroleum industry.
BS 1646: 1984 Symbolic representation for process measurement control functions and instrumentation.
Part 1: 1977 Basic requirements.
Part 2: 1983 Specifications for additional requirements.
Part 3: 1984 Specification for detailed symbols for instrument interconnection diagrams.
Part 4: 1984 Specification for basic symbols for process computer, interface and shared display/control
functions.
American Standards
USAS B31.1.0: The ASME standard code for pressure piping.
ASA B31.3.0: The ASME code for petroleum refinery piping.
5.12. NOMENCLATURE
Dimensions
in MLT£
A
B
a
b
Cf
Cp
Ct
d
di
E
e
Plant attainment (hours operated per year)
Purchased cost factor, pipes
Capital charges factor, piping
Maintenance cost factor, piping
Annual pumping cost, piping
Capital cost, piping
Total annual cost, piping
Pipe diameter
Pipe inside diameter
Pump efficiency
Relative roughness
£L1
£L1 T1
£L1
£L1 T1
L
L
240
CHEMICAL ENGINEERING
F
f
G
g
H
h
K
L
m
N
Ns
n
P
Pf
Ps
Pv
P
Pf
p
Q
R
t
u
W
z
z
d
s
Re
Installed cost factor, piping
Friction factor
Mass flow rate
Gravitational acceleration
Height of liquid above the pump suction
Pump head
Number of velocity heads
Pipe length
Mass flow-rate
Pump speed, revolutions per unit time
Pump specific speed
Index relating pipe cost to diameter
Pressure
Pressure loss in suction piping
Safe working pressure
Vapour pressure of liquid
Difference in system pressures (P1 P2 )
Pressure drop†
Cost of power, pumping
Volumetric flow rate
Shear stress on surface, pipes
Pipe wall thickness
Fluid velocity
Work done
Height above datum
Difference in elevation (z1 z2 )
Pump efficiency
Fluid density
Viscosity of fluid
Design stress
Safe working stress
Reynolds number
NPSH a vail
NPSH reqd
Net positive suction head available at the pump suction
Net positive suction head required at the pump suction
MT1
LT2
L
L
L
MT1
T1
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
L3 T1
ML1 T2
L
LT1
L2 T2
L
L
ML3
ML1 T1
ML1 T2
ML1 T2
L
L
† Note: In Volumes 1 and 2 this symbol is used for pressure difference, and pressure drop (negative pressure
gradient) indicated by a minus sign. In this chapter, as the symbol is only used for pressure drop, the minus
sign is omitted for convenience.
5.13. PROBLEMS
5.1. Select suitable valve types for the following applications:
1. Isolating a heat exchanger.
2. Manual control of the water flow into a tank used for making up batches of
sodium hydroxide solution.
3. The valves need to isolate a pump and provide emergency manual control on
a by-pass loop.
4. Isolation valves in the line from a vacuum column to the steam ejectors
producing the vacuum.
5. Valves in a line where cleanliness and hygiene are an essential requirement.
State the criterion used in the selection for each application.
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PIPING AND INSTRUMENTATION
5.2. Crude dichlorobenzene is pumped from a storage tank to a distillation column.
The tank is blanketed with nitrogen and the pressure above the liquid surface is
held constant at 0.1 bar gauge pressure. The minimum depth of liquid in the tank
is 1 m.
The distillation column operates at a pressure of 500 mmHg (500 mm of mercury,
absolute). The feed point to the column is 12 m above the base of the tank. The
tank and column are connected by a 50 mm internal diameter commercial steel
pipe, 200 m long. The pipe run from the tank to the column contains the following
valves and fittings: 20 standard radius 90Ž elbows; two gate valves to isolate the
pump (operated fully open); an orifice plate and a flow-control valve.
If the maximum flow-rate required is 20,000 kg/h, calculate the pump motor rating
(power) needed. Take the pump efficiency as 70 per cent and allow for a pressure
drop of 0.5 bar across the control valve and a loss of 10 velocity heads across the
orifice.
Density of the dichlorobenzene 1300 kg/m3 , viscosity 1.4 cp.
5.3. A liquid is contained in a reactor vessel at 115 bar absolute pressure. It is transferred to a storage vessel through a 50 mm internal diameter commercial steel pipe.
The storage vessel is nitrogen blanketed and pressure above the liquid surface is
kept constant at 1500 N/m2 gauge. The total run of pipe between the two vessels is
200 m. The miscellaneous losses due to entry and exit losses, fittings, valves, etc.,
amount to 800 equivalent pipe diameters. The liquid level in the storage vessel is
at an elevation 20 m below the level in the reactor.
A turbine is fitted in the pipeline to recover the excess energy that is available,
over that required to transfer the liquid from one vessel to the other. Estimate
the power that can be taken from the turbine, when the liquid transfer rate is
5000 kg/h. Take the efficiency of the turbine as 70%.
The properties of the fluid are: density 895 kg/m3 , viscosity 0.76 mNm2 s.
5.4. A process fluid is pumped from the bottom of one distillation column to another,
using a centrifugal pump. The line is standard commercial steel pipe 75 mm
internal diameter. From the column to the pump inlet the line is 25 m long and
contains six standard elbows and a fully open gate valve. From the pump outlet to
the second column the line is 250 m long and contains ten standard elbows, four
gate valves (operated fully open) and a flow-control valve. The fluid level in the
first column is 4 m above the pump inlet. The feed point of the second column is
6 m above the pump inlet. The operating pressure in the first column is 1.05 bara
and that of the second column 0.3 barg.
Determine the operating point on the pump characteristic curve when the flow is
such that the pressure drop across the control valve is 35 kN/m2 .
The physical properties of the fluid are: density 875 kg/m3 , viscosity
1.46 mN m2 s.
Also, determine the NPSH, at this flow-rate, if the vapour pressure of the fluid at
the pump suction is 25 kN/m2 .
Pump characteristic
Flow-rate, m3 /h
Head, m of liquid
0.0
32.0
18.2
31.4
27.3
30.8
36.3
29.0
45.4
26.5
54.5
23.2
63.6
18.3
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CHEMICAL ENGINEERING
5.5. A polymer is produced by the emulsion polymerisation of acrylonitrile and methyl
methacrylate in a stirred vessel. The monomers and an aqueous solution of catalyst
are fed to the polymerisation reactor continuously. The product is withdrawn from
the base of the vessel as a slurry.
Devise a control system for this reactor, and draw up a preliminary piping and
instrument diagram. The follow points need to be considered:
1.
2.
3.
4.
5.
6.
Close control of the reactor temperature is required.
The reactor runs 90 per cent full.
The water and monomers are fed to the reactor separately.
The emulsion is a 30 per cent mixture of monomers in water.
The flow of catalyst will be small compared with the water and monomer flows.
Accurate control of the catalyst flow is essential.
5.6. Devise a control system for the distillation column described in Chapter 11,
Example 11.2. The flow to the column comes from a storage tank. The product,
acetone, is sent to storage and the waste to an effluent pond. It is essential that
the specifications on product and waste quality are met.
CHAPTER 6
Costing and Project Evaluation
6.1. INTRODUCTION
Cost estimation is a specialised subject and a profession in its own right. The design
engineer, however, needs to be able to make quick, rough, cost estimates to decide between
alternative designs and for project evaluation. Chemical plants are built to make a profit,
and an estimate of the investment required and the cost of production are needed before
the profitability of a project can be assessed.
In this chapter the various components that make up the capital cost of a plant and the
components of the operating costs are discussed, and the techniques used for estimating
reviewed briefly. Simple costing methods and some cost data are given, which can be
used to make preliminary estimates of capital and operating costs at the flow-sheet stage.
They can also be used to cost out alternative processing schemes and equipment.
For a more detailed treatment of the subject the reader should refer to the numerous
specialised texts that have been published on cost estimation. The following books are
particularly recommended: Happle and Jordan (1975) and Guthrie (1974), Page (1984),
Garrett (1989).
6.2. ACCURACY AND PURPOSE OF CAPITAL COST ESTIMATES
The accuracy of an estimate depends on the amount of design detail available: the accuracy
of the cost data available; and the time spent on preparing the estimate. In the early stages
of a project only an approximate estimate will be required, and justified, by the amount
of information by then developed.
Capital cost estimates can be broadly classified into three types according to their
accuracy and purpose:
1. Preliminary (approximate) estimates, accuracy typically š30 per cent, which are
used in initial feasibility studies and to make coarse choices between design alternatives. They are based on limited cost data and design detail.
2. Authorisation (Budgeting) estimates, accuracy typically š10 15 per cent. These are
used for the authorisation of funds to proceed with the design to the point where an
accurate and more detailed estimate can be made. Authorisation may also include
funds to cover cancellation charges on any long delivery equipment ordered at this
stage of the design to avoid delay in the project. In a contracting organisation this
type of estimate could be used with a large contingency factor to obtain a price for
tendering. Normally, however, an accuracy of about š5 per cent would be needed
243
244
CHEMICAL ENGINEERING
and a more detailed estimate would be made, if time permitted. With experience,
and where a company has cost data available from similar projects, estimates of
acceptable accuracy can be made at the flow-sheet stage of the project. A rough P
and I diagram and the approximate sizes of the major items of equipment would
also be needed.
3. Detailed (Quotation) estimates, accuracy š5 10 per cent, which are used for project
cost control and estimates for fixed price contracts. These are based on the completed
(or near complete) process design, firm quotations for equipment, and a detailed
breakdown and estimation of the construction cost.
The cost of preparing an estimate increases from about 0.1 per cent of the total project
cost for š30 per cent accuracy, to about 2 per cent for a detailed estimate with an accuracy
of š5 per cent.
6.3. FIXED AND WORKING CAPITAL
Fixed capital is the total cost of the plant ready for start-up. It is the cost paid to the
contractors.
It includes the cost of:
1.
2.
3.
4.
5.
Design, and other engineering and construction supervision.
All items of equipment and their installation.
All piping, instrumentation and control systems.
Buildings and structures.
Auxiliary facilities, such as utilities, land and civil engineering work.
It is a once-only cost that is not recovered at the end of the project life, other than the
scrap value.
Working capital is the additional investment needed, over and above the fixed capital,
to start the plant up and operate it to the point when income is earned.
It includes the cost of:
1.
2.
3.
4.
5.
Start-up.
Initial catalyst charges.
Raw materials and intermediates in the process.
Finished product inventories.
Funds to cover outstanding accounts from customers.
Most of the working capital is recovered at the end of the project. The total investment
needed for a project is the sum of the fixed and working capital.
Working capital can vary from as low as 5 per cent of the fixed capital for a simple,
single-product, process, with little or no finished product storage; to as high as 30 per
cent for a process producing a diverse range of product grades for a sophisticated market,
such as synthetic fibres. A typical figure for petrochemical plants is 15 per cent of the
fixed capital.
Methods for estimating the working capital requirement are given by Bechtel (1960),
Lyda (1972) and Scott (1978).
COSTING AND PROJECT EVALUATION
245
6.4. COST ESCALATION (INFLATION)
The cost of materials and labour has been subject to inflation since Elizabethan times. All
cost-estimating methods use historical data, and are themselves forecasts of future costs.
Some method has to be used to update old cost data for use in estimating at the design
stage, and to forecast the future construction cost of the plant.
The method usually used to update historical cost data makes use of published cost
indices. These relate present costs to past costs, and are based on data for labour, material
and energy costs published in government statistical digests.
Cost in year A D Cost in year B ð
Cost index in year A
Cost index in year B
⊲6.1⊳
To get the best estimate, each job should be broken down into its components and separate
indices used for labour and materials. It is often more convenient to use the composite
indices published for various industries in the trade journals. These produce a weighted
average index combining the various components in proportions considered typical for
the particular industry. Such an index for the chemical industry in the United Kingdom
is published in the journal Process Engineering, Anon. (2004). The composition of this
index is:
C D 0.45Eq C 0.1Ci C 0.19Cn C 0.26Di
where C
Ci
Cn
Di
D
D
D
D
the composite index
civil engineering index
site engineering index
design index
The base year used for the index is revised about every 5 years. The base for the current
index is January 2000 D 100; see Anon. (2002). Care must be taken when updating costs
over a period that includes a change in the index base; see Example 6.1.
The Process Engineering index, over a ten-year period (January to January), is shown
in Figure 6.1a.
Process Engineering also publishes monthly cost indices for several other countries,
including the United States, Japan, Australia and many of the EU countries.
A composite index for the United States process plant industry is published monthly in
the journal Chemical Engineering, the CPE plant cost index. This journal also publishes
the Marshall and Swift index (M and S equipment cost index), base year 1926. The CPE
index over a ten-year period is shown in Figure 6.1b.
All cost indices should be used with caution and judgement. They do not necessarily
relate the true make-up of costs for any particular piece of equipment or plant; nor the
effect of supply and demand on prices. The longer the period over which the correlation is
made the more unreliable the estimate. Between 1970 and 1990 prices rose dramatically.
Since then the annual rise has slowed down and is now averaging around 2 to 3 per cent
per year.
To estimate the future cost of a plant some prediction has to be made of the future
annual rate of inflation. This can be based on the extrapolation of one of the published
indices, tempered by the engineer’s own assessment of what the future may hold.
246
CHEMICAL ENGINEERING
120
115
Index
110
105
100
95
90
1996 1997 1998 1999 2000 2001 2002
Year
Figure 6.1a.
2003 2004
Process Engineering index
420
410
Index
400
390
380
370
360
1996 1997 1998 1999 2000 2001 2002 2003 2004
Year
Figure 6.1b.
CPE index
COSTING AND PROJECT EVALUATION
247
Example 6.1
The purchased cost of a shell and tube heat exchanger, carbon shell, stainless steel tubes,
heat transfer area 500 m2 , was £7600 in January 1998; estimate the cost in January 2006.
Use the Process Engineering plant index.
Solution
From Figure 6.1:
Index in 1998 D 106
2000 D 108, 100 (change of base)
2004 D 111
So, estimated cost in January 2000 D 7600 ð 108/106 D £7743,
and in 2004 D 7743 ð 111/100 D £8595
From Figure 6.1, the average increase in costs is about 2.5 per cent per year. Use this
value to predict the exchanger cost in 2006.
Cost in 2006 D 8595 ð ⊲1.025⊳2 D £9030
Say £9000.
6.5. RAPID CAPITAL COST ESTIMATING METHODS
6.5.1. Historical costs
An approximate estimate of the capital cost of a project can be obtained from a knowledge
of the cost of earlier projects using the same manufacturing process. This method can be
used prior to the preparation of the flow-sheets to get a quick estimate of the investment
likely to be required.
The capital cost of a project is related to capacity by the equation
n
S2
⊲6.2⊳
C2 D C1
S1
where C2 D capital cost of the project with capacity S2 ,
C1 D capital cost of the project with capacity S1 .
The value of the index n is traditionally taken as 0.6; the well-known six-tenths rule. This
value can be used to get a rough estimate of the capital cost if there are not sufficient data
available to calculate the index for the particular process. Estrup (1972) gives a critical
review of the six-tenths rule. Equation 6.2 is only an approximation, and if sufficient data
are available the relationship is best represented on a log-log plot. Garrett (1989) has
published capital cost-plant capacity curves for over 250 processes.
Example 6.2
Obtain a rough estimate of the cost of a plant to produce 750 tonnes per day of sulphuric
acid, from sulphur. Use the costs given by Garrett (1989) reproduced in Figure 6.2.
248
CHEMICAL ENGINEERING
Figure 6.2.
Capital Cost v. Capacity
Solution
Garret’s units are US dollars and US tons, and refer to 1987 (Chemical Engineering Index
quoted as 320).
1 US ton D 2000 lb D 0.91 tonne ⊲1000 kg⊳
So, 750 tonne per day D 750/0.91 D 824 US t/d
From Figure 6.2 the fixed capital cost for this capacity, for production from sulphur, is
13 ð 106 US dollars.
There are two possible ways to convert to UK costs:
1. Convert at the 1987 exchange rate and update using a UK index.
2. Update using a US index and convert using the current exchange rate.
1. In 1987 (January) the rate of exchange was $1.64 D £1, and UK and US cost can be
taken as roughly equivalent.
13 ð 106
D £7.93 ð 106
1.64
Updating this cost using the index published in Process Engineering (basis 100 at end
1990)
1987 cost D
Index 1987 (January) D 78
2004 (January) D 154 (basis adjusted to 1990)
154
D £15.67 ð 106
78
say, £16,000,000
So, capital cost of plant early 2004 D 7.93 ð 106 ð
2. Garrett quotes the Chemical Engineering Index for his costs as 320 (January 1987).
COSTING AND PROJECT EVALUATION
249
The value in January 2004 was, approximately, 405, so the dollar cost of the plant in
early 2004 will be:
405
D $16.45 ð 106
13 ð 106 ð
320
The rate of exchange in January 2004 was $1.82, so the cost in pounds sterling will be
16.45 ð 106
D £9.04 ð 106
1.82
say, $9,000,000
Widely different from that estimated by method 1. This is not surprising as inflation in
the UK has been very much greater than that in the US over this period.
Where UK, or other local, indexes and historical exchange rates are available, it is
probably better to convert costs to the local currency using the rate of exchange ruling at
the date of the costs and update using the local index: method 1 in the Example 6.2. In
the United Kingdom historical values for exchange rates can be found in the government
publication Economic Trends (Central Statistical Office, HMSO). Current and historical
values for most currencies can be found on the Internet/World Wide Web.
As a rough guide US costs can be taken as equivalent to local prices, converted to local
currency, for Western European countries, but construction costs may be significantly
greater in less developed parts of the world.
Location factors can be used to make allowance for the variation in costs in different
countries; see IChemE (1987).
6.5.2. Step counting methods
Step counting estimating methods provide a way of making a quick, order of magnitude,
estimate of the capital cost of a proposed project.
The technique is based on the premise that the capital cost is determined by a number
of significant processing steps in the overall process. Factors are usually included to allow
for the capacity, and complexity of the process: material of construction, yield, operating
pressure and temperature.
A number of workers have published correlations based on a step counting approach:
Taylor (1977), Wilson (1971). These and other correlations are reviewed and compared
in the Institution of Chemical Engineers booklet, IChemE (1988).
Bridgwater, IChemE (1988), gives a developed relatively simple correlation for plants
that are predominantly liquid and/or solid phase handing processes.
His equation, adjusted to 2004 prices is:
for plant capacities under 60,000 tonne per year:
C D 150,000 N (Q/s)0.30
⊲6.3⊳
C D 170 N (Q/s)0.675
⊲6.4⊳
and above 60,000 t/y:
where C D capital cost in pounds sterling
N D Number of functional units
250
CHEMICAL ENGINEERING
Q D plant capacity, tonne per year
s D reactor conversion
Reactor conversion is defined as:
mass of desired product
sD
mass reactor input
Timms, IChemE (1988) gives a simple equation for gas phase processes; updated to
1998:
C D 9000 N Q0.615
⊲6.5⊳
where the symbols are the same as for equations 6.3 and 6.4.
In US dollars
C0 D 14,000 N Q0.615
(6.5a)
0
Where C D captial cost in US dollars
Example 6.3
Estimate the capital cost for the nitric acid plant shown in Figure 4.2, Chapter 4.
Solution
Number of significant processing steps 6.
Capacity 100,000 tonne per year
C D 9000 ð 6 ð 100,0000.615 D 64.2 ð 106
⊲6.5⊳
say, £65 million.
C0 D 14,000 ð 6 ð 100,0000.615 D 99.8 ð 106
say, $100 million.
Clearly, step counting methods can only, at best, give a very approximate idea of the
probable cost of a plant. They are useful in the conceptual stage of process design, when
comparisons between alternative process routes are being made.
6.6. THE FACTORIAL METHOD OF COST ESTIMATION
Capital cost estimates for chemical process plants are often based on an estimate of the
purchase cost of the major equipment items required for the process, the other costs
being estimated as factors of the equipment cost. The accuracy of this type of estimate
will depend on what stage the design has reached at the time the estimate is made, and
on the reliability of the data available on equipment costs. In the later stages of the
project design, when detailed equipment specifications are available and firm quotations
have been obtained, an accurate estimation of the capital cost of the project can be
made.
COSTING AND PROJECT EVALUATION
251
6.6.1. Lang factors
The factorial method of cost estimation is often attributed to Lang (1948). The fixed
capital cost of the project is given as a function of the total purchase equipment cost by
the equation:
Cf D fL Ce
⊲6.6⊳
where Cf D fixed capital cost,
Ce D the total delivered cost of all the major equipment items: storage tanks,
reaction vessels, columns, heat exchangers, etc.,
fL D the “Lang factor”, which depends on the type of process.
fL D 3.1 for predominantly solids processing plant
fL D 4.7 for predominantly fluids processing plant
fL D 3.6 for a mixed fluids-solids processing plant
The values given above should be used as a guide; the factor is best derived from an
organisation’s own cost files.
Equation 6.6 can be used to make a quick estimate of capital cost in the early stages of
project design, when the preliminary flow-sheets have been drawn up and the main items
of equipment roughly sized.
6.6.2. Detailed factorial estimates
To make a more accurate estimate, the cost factors that are compounded into the
“Lang factor” are considered individually. The direct-cost items that are incurred in the
construction of a plant, in addition to the cost of equipment are:
1.
2.
3.
4.
5.
6.
7.
8.
Equipment erection, including foundations and minor structural work.
Piping, including insulation and painting.
Electrical, power and lighting.
Instruments, local and control room.
Process buildings and structures.
Ancillary buildings, offices, laboratory buildings, workshops.
Storages, raw materials and finished product.
Utilities (Services), provision of plant for steam, water, air, firefighting services (if
not costed separately).
9. Site, and site preparation.
The contribution of each of these items to the total capital cost is calculated by multiplying
the total purchased equipment by an appropriate factor. As with the basic “Lang factor”,
these factors are best derived from historical cost data for similar processes. Typical values
for the factors are given in several references, Happle and Jordan (1975) and Garrett
(1989). Guthrie (1974), splits the costs into the material and labour portions and gives
separate factors for each. In a booklet published by the Institution of Chemical Engineers,
IChemE (1988), the factors are shown as a function of plant size and complexity.
The accuracy and reliability of an estimate can be improved by dividing the process
into sub-units and using factors that depend on the function of the sub-units; see Guthrie
(1969). In Guthrie’s detailed method of cost estimation the installation, piping and
252
CHEMICAL ENGINEERING
instrumentation costs for each piece of equipment are costed separately. Detailed costing
is only justified if the cost data available are reliable and the design has been taken to the
point where all the cost items can be identified and included.
Typical factors for the components of the capital cost are given in Table 6.1. These
can be used to make an approximate estimate of capital cost using equipment cost data
published in the literature.
In addition to the direct cost of the purchase and installation of equipment, the capital
cost of a project will include the indirect costs listed below. These can be estimated as a
function of the direct costs.
Indirect costs
1. Design and engineering costs, which cover the cost of design and the cost of
“engineering” the plant: purchasing, procurement and construction supervision.
Typically 20 per cent to 30 per cent of the direct capital costs.
2. Contractor’s fees, if a contractor is employed his fees (profit) would be added to the
total capital cost and would range from 5 per cent to 10 per cent of the direct costs.
3. Contingency allowance, this is an allowance built into the capital cost estimate to
cover for unforeseen circumstances (labour disputes, design errors, adverse weather).
Typically 5 per cent to 10 per cent of the direct costs.
The indirect cost factors are included in Table 6.1.
The capital cost required for the provision of utilities and other plant services will
depend on whether a new (green field) site is being developed, or if the plant is to be
built on an existing site and will make use of some of the existing facilities. The term
Table 6.1.
Typical factors for estimation of project fixed capital cost
Process type
Item
1. Major equipment, total purchase
cost
f1 Equipment erection
f2 Piping
f3 Instrumentation
f4 Electrical
f5 Buildings, process
Ł f Utilities
6
Ł f Storages
7
Ł f Site development
8
Ł f Ancillary buildings
9
2. Total physical plant cost (PPC)
PPC D PCE (1 C f1 C Ð Ð Ð C f9 )
D PCE ð
f10 Design and Engineering
f11 Contractor’s fee
f12 Contingency
Fixed capital D PPC (1 C f10 C f11 C f12 )
D PPC ð
Ł Omitted
Fluids
Fluids
solids
Solids
PCE
0.4
0.70
0.20
0.10
0.15
0.50
0.15
0.05
0.15
PCE
0.45
0.45
0.15
0.10
0.10
0.45
0.20
0.05
0.20
PCE
0.50
0.20
0.10
0.10
0.05
0.25
0.25
0.05
0.30
3.40
3.15
2.80
0.30
0.05
0.10
0.25
0.05
0.10
0.20
0.05
0.10
1.45
1.40
1.35
for minor extensions or additions to existing sites.
COSTING AND PROJECT EVALUATION
253
“battery limits” is used to define a contractor’s responsibility. The main processing plant,
within the battery limits, would normally be built by one contractor. The utilities and other
ancillary equipment would often be the responsibility of other contractors and would be
said to be outside the battery limits. They are often also referred to as “off-sites”.
6.7. ESTIMATION OF PURCHASED EQUIPMENT COSTS
The cost of the purchased equipment is used as the basis of the factorial method of cost
estimation and must be determined as accurately as possible. It should preferably be based
on recent prices paid for similar equipment.
The relationship between size and cost given in equation 6.2 can also be used for
equipment, but the relationship is best represented by a log-log plot if the size range is
wide. A wealth of data has been published on equipment costs; see Guthrie (1969, 1974),
Hall et al. (1982), Page (1984), Ulrich (1984), Garrett (1989) and Peters et al. (2003).
Articles giving the cost of process equipment are frequently published in the journals
Chemical Engineering and Hydrocarbon Processing. Equipment prices can also be found
on various web sites, such as: MatchesMSN@msn.com.
The cost of specialised equipment, which cannot be found in the literature, can usually
be estimated from the cost of the components that make up the equipment. For example, a
reactor design is usually unique for a particular process but the design can be broken down
into standard components (vessels, heat-exchange surfaces, spargers, agitators) the cost of
which can be found in the literature and used to build up an estimate of the reactor cost.
Pikulik and Diaz (1977) give a method of costing major equipment items from cost
data on the basic components: shells, heads, nozzles, and internal fittings. Purohit (1983)
gives a detailed procedure for estimating the cost of heat exchangers.
Almost all the information on costs available in the open literature is in American
journals and refers to dollar prices in the US. Some UK equipment prices were published in
the journals British Chemical Engineering and Chemical and Process Engineering before
they ceased publication. The only comprehensive collection of UK prices available is
given in the Institution of Chemical Engineers booklet, IChemE (2000).
Up to 1970 US and UK prices for equipment could be taken as roughly equivalent,
converting from dollars to pounds using the rate of exchange ruling on the date the prices
were quoted. Since 1970 the rate of inflation in the US has been significantly lower than
in the UK, and rates of exchange have fluctuated since the pound was floated in 1972.
If it can be assumed that world market forces will level out the prices of equipment,
the UK price can be estimated from the US price by bringing the cost up to date using
a suitable US price index, converting to pounds sterling at the current rate of exchange,
and adding an allowance for freight and duty.
If an estimate is being made to compare two processes, the costing can be done in
dollars and any conclusion drawn from the comparison should still be valid for the United
Kingdom and other countries.
The cost data given in Figures 6.3 to 6.7, and Table 6.2 have been compiled from
various sources. They can be used to make preliminary estimates. The base date is
mid-2004, and the prices are thought to be accurate to within š25 per cent.
254
CHEMICAL ENGINEERING
Shell and tube heat exchangers
Time base mid 2004
Exchanger cost, £1000
1000.0
4
3
100.0
2
1
10.0
1.0
10.0
100.0
Heat transfer area, sq m
1000.0
(a) Pounds sterling
Shell and tube heat exchangers
Time base mid 2004
1000.0
Exchanger cost, $1000
4
3
2
100.0
1
10.0
1.0
10.0
100.0
Heat transfer area, sq m
1000.0
(b) US dollars
Materials
Shell
1
2
3
4
Pressure factors
Tubes
Carbon steel Carbon steel
C.S.
Brass
C.S.
Stainless steel
S.S.
S.S.
1
10
20
30
50
10 bar ð 1.0
20
ð 1.1
30
ð 1.25
50
ð 1.3
70
ð 1.5
Type factors
Floating head
Fixed tube sheet
U tube
Kettle
Figure 6.3a, b. Shell and tube heat exchangers. Time base mid-2004
Purchased cost D (bare cost from figure) ð Type factor ð Pressure factor
ð
ð
ð
ð
1.0
0.8
0.85
1.3
255
COSTING AND PROJECT EVALUATION
Time base mid 2004
Equipment cost, £
10,000.0
1
2
1000.0
1.0
10.0
100.0
1000.0
Heat transfer area
(a) Pounds sterling
Time base mid 2004
Equipment cost, $
100,000.0
10,000.0
1
2
1000.0
1.0
10.0
100.0
1000.0
Heat transfer area
(b) US dollars
Type
(1) Gasketed plate
(2) Double pipe
Figure 6.4a, b.
Area scale
m2
2
m × 10
Material
Stainless steel
Carbon steel
Gasketed plate and frame and double pipe heat exchangers, Time base mid-2004
256
CHEMICAL ENGINEERING
Time base mid 2004
Equipment cost, £1000
1000.0
100.0
10.0
4
3
2
1
1.0
1.0
100.0
10.0
Vessel height, m
(a) Pounds sterling
Time base mid 2004
Equipment cost, $1000
1000.0
100.0
4
3
2
1
10.0
1.0
1.0
10.0
Vessel height, m
100.0
(b) US dollars
Diameter, m
1
2
0.5
1.0
3
4
2.0
3.0
Material factors
Pressure factors
C.S.
S.S.
Monel
S.S. clad
Monel
clad
1
5
10
20
30
40
50
ð
ð
ð
ð
ð
1.0
2.0
3.4
1.5
2.1
5 bar
10
20
30
40
50
60
ð
ð
ð
ð
ð
ð
ð
1.0
1.1
1.2
1.4
1.6
1.8
2.2
Temperature up to 300° C
Figure 6.5a, b. Vertical pressure vessels. Time base mid-2004.
Purchased cost D (bare cost from figure) ð Material factor ð Pressure factor
257
COSTING AND PROJECT EVALUATION
Time base mid 2004
Equipment cost, £1000
100.0
10.0
4
3
2
1
1.0
1.0
Time base mid 2004
100.0
Equipment cost, $1000
100.0
10.0
Vessel length, m
(a) Pounds sterling
10.0
4
3
2
1
1.0
1.0
Diameter, m
1
2
0.5
1.0
100.0
10.0
Vessel length, m
(b) US dollars
3
4
2.0
3.0
Material factors
Pressure factors
C.S.
S.S.
Monel
S.S. clad
Monel
clad
1
5
10
20
30
40
50
ð
ð
ð
ð
ð
1.0
2.0
3.4
1.5
2.1
5 bar
10
20
30
40
50
60
ð
ð
ð
ð
ð
ð
ð
1.0
1.1
1.2
1.4
1.6
1.8
2.2
Temperature up to 300° C
Figure 6.6a, b. Horizontal pressure vessels. Time base mid-2004.
Purchase cost D (bare cost from figure) ð Material factor ð Pressure factor
258
CHEMICAL ENGINEERING
Time base mid 2004
Cost per plate, £
10000.0
1000.0
3
2
100.0
0.1
1
1.0
Plate diameter, m
(a) Pound sterling
Time base mid 2004
10000.0
Cost per plate, $
10.0
1000.0
3
2
1
100.0
0.1
1.0
Plate diameter, m
10.0
(b) US dollars
Type
1 Sieve
2 Valve
3 Bubble cap
Figure 6.7a, b.
Material factors
C.S. ð 1.0
S.S. ð 1.7
Column plates. Time base mid-2004 (for column costs see Figure 6.4)
Installed cost D (cost from figure) ð Material factor
259
COSTING AND PROJECT EVALUATION
Table 6.2.
Purchase cost of miscellaneous equipment, cost factors for use in equation 6.7. Cost basis mid 2004
Equipment
Agitators
Propeller
Turbine
Boilers
Packaged
up to 10 bar
10 to 60 bar
Centrifuges
Horizontal basket
Vertical basket
Compressors
Centrifugal
Reciprocating
Conveyors
Belt
0.5 m wide
1.0 m wide
Crushers
Cone
Pulverisers
Dryers
Rotary
Pan
Evaporators
Vertical tube
Falling film
Filters
Plate and frame
Vacuum drum
Furnaces
Process
Cylindrical
Box
Reactors
Jacketed,
agitated
Tanks
Process
vertical
horizontal
Storage
floating roof
cone roof
Size
unit, S
Size
range
driver
power, kW
5 75
kg/h steam
⊲5 50⊳ ð 103
dia., m
driver
power, kW
length, m
Constant
C,£
C,$
Index
n
Comment
1200
1800
1900
3000
0.5
0.5
70
60
120
100
0.8
0.8
0.5 1.0
35,000
35,000
58,000
58,000
1.3
1.0
carbon steel
ð1.7 for ss
20 500
1160
1920
0.8
1600
2700
0.8
electric,
max. press.
50 bar
1200
1800
1900
2900
0.75
0.75
2300
2000
3800
3400
0.85
0.35
oil or gas fired
2 40
t/h
kg/h
20 200
area, m2
5 30
2 10
21,000
4700
35,000
7700
0.45
0.35
direct
gas fired
area, m2
10 100
12,000
6500
20,000
10,000
0.53
0.52
carbon steel
area, m2
5 50
1 10
5400
21,000
8800
34,000
0.6
0.6
cast iron
carbon steel
heat abs, kW
103 104
103 105
330
340
540
560
0.77
0.77
carbon steel
ð2.0 ss
capacity, m3
3 30
9300
18,500
15,000
31,000
0.40
0.45
carbon steel
glass lined
1 50
10 100
1450
1750
2400
2900
0.6
0.6
atmos. press.
carbon steel
50 8000
50 8000
2500
1400
4350
2300
0.55
0.55
ð2 for
stainless
capacity, m3
Table 6.3.
Cost of column packing. Cost basis mid 2004
Cost
Size, mm
Saddles, stoneware
Pall rings, polypropylene
Pall rings, stainless steel
25
840 (1400)
650 (1080)
1500 (2500)
£/m3 ($/m3 )
38
620 (1020)
400 (650)
1500 (2500)
50
580 (960)
250 (400)
830 (1360)
260
CHEMICAL ENGINEERING
To use Table 6.2, substitute the values given for the particular type of equipment into
the equation:
Ce D CSn
⊲6.7⊳
where Ce
S
C
n
D
D
D
D
purchased equipment cost, £,
characteristic size parameter, in the units given in Table 6.2,
cost constant from Table 6.2,
index for that type of equipment.
6.8. SUMMARY OF THE FACTORIAL METHOD
Many variations on the factorial method are used. The method outlined below can be
used with the data given in this chapter to make a quick, approximate, estimate of the
investment need for a project.
Procedure
1. Prepare material and energy balances, draw up preliminary flow-sheets, size major
equipment items and select materials of construction.
2. Estimate the purchase cost of the major equipment items. Use Figures 6.3 to 6.6
and Tables 6.2 and 6.3, or the general literature.
3. Calculate the total physical plant cost (PPC), using the factors given in Table 6.1
PPC D PCE⊲1 C f1 C Ð Ð Ð C f9 ⊳
4.
5.
6.
7.
⊲6.8⊳
Calculate the indirect costs from the direct costs using the factors given in Table 6.1.
The direct plus indirect costs give the total fixed capital.
Estimate the working capital as a percentage of the fixed capital; 10 to 20 per cent.
Add the fixed and working capital to get the total investment required.
6.9. OPERATING COSTS
An estimate of the operating costs, the cost of producing the product, is needed to judge
the viability of a project, and to make choices between possible alternative processing
schemes. These costs can be estimated from the flow-sheet, which gives the raw material
and service requirements, and the capital cost estimate.
The cost of producing a chemical product will include the items listed below. They are
divided into two groups.
1. Fixed operating costs: costs that do not vary with production rate. These are the
bills that have to be paid whatever the quantity produced.
2. Variable operating costs: costs that are dependent on the amount of product produced.
Fixed costs
1.
2.
3.
4.
5.
Maintenance (labour and materials).
Operating labour.
Laboratory costs.
Supervision.
Plant overheads.
COSTING AND PROJECT EVALUATION
6.
7.
8.
9.
261
Capital charges.
Rates (and any other local taxes).
Insurance.
Licence fees and royalty payments.
Variable costs
1.
2.
3.
4.
Raw materials.
Miscellaneous operating materials.
Utilities (Services).
Shipping and packaging.
The division into fixed and variable costs is somewhat arbitrary. Certain items can
be classified without question, but the classification of other items will depend on the
accounting practice of the particular organisation.
The items may also be classified differently in cost sheets and cost standards prepared
to monitor the performance of the operating plant. For this purpose the fixed-cost items
should be those over which the plant supervision has no control, and the variable items
those for which they can be held accountable.
The costs listed above are the direct costs of producing the product at the plant site.
In addition to these costs the site will have to carry its share of the Company’s general
operating expenses. These will include:
1.
2.
3.
4.
General overheads.
Research and development costs.
Sales expense.
Reserves.
How these costs are apportioned will depend on the Company’s accounting methods.
They would add about 20 to 30 per cent to direct production costs at the site.
6.9.1. Estimation of operating costs
In this section the components of the fixed and variable costs are discussed and methods
given for their estimation.
It is usually convenient to do the costing on an annual basis.
Raw materials
These are the major (essential) materials required to manufacture the product. The
quantities can be obtained from the flow-sheet and multiplied by the operating hours
per year to get the annual requirements.
The price of each material is best obtained by getting quotations from potential suppliers,
but in the preliminary stages of a project prices can be taken from the literature.
The American journal Chemical Marketing Reporter, CMR (2004), publishes a weekly
review of prices for most chemicals. The prices for a limited number of chemicals in
Europe can be found in European Chemical News, ECN (2004). U.S. prices, converted to
the local currency at the current rate of exchange, can be used as a guide to the probable
price in other countries. An indication of the prices of a selected range of chemicals is
given in Table 6.4 (see p. 263).
262
CHEMICAL ENGINEERING
Miscellaneous materials (plant supplies)
Under this heading are included all the miscellaneous materials required to operate the
plant that are not covered under the headings raw materials or maintenance materials.
Miscellaneous materials will include:
1.
2.
3.
4.
Safety clothing: hard hats, safety glasses etc.
Instrument charts and accessories
Pipe gaskets
Cleaning materials
An accurate estimate can be made by detailing and costing all the items needed, based
on experience with similar plants. As a rough guide the cost of miscellaneous materials
can be taken as 10 per cent of the total maintenance cost.
Utilities (services)
This term includes, power, steam, compressed air, cooling and process water, and effluent
treatment; unless costed separately. The quantities required can be obtained from the
energy balances and the flow-sheets. The prices should be taken from Company records,
if available. They will depend on the primary energy sources and the plant location. The
figures given in Table 6.5 can be used to make preliminary estimates. The current cost
of utilities supplied by the utility companies: electricity, gas and water, can be obtained
from their local area offices.
Shipping and packaging
This cost will depend on the nature of the product. For liquids collected at the site in
the customer’s own tankers the cost to the product would be small; whereas the cost of
packaging and transporting synthetic fibres or polymers to a central distribution warehouse
would add significantly to the product cost.
Maintenance
This item will include the cost of maintenance labour, which can be as high as the
operating labour cost, and the materials (including equipment spares) needed for the
maintenance of the plant. The annual maintenance costs for chemical plants are high,
typically 5 to 15 per cent of the installed capital costs. They should be estimated from
a knowledge of the maintenance costs on similar plant. As a first estimate the annual
maintenance cost can be taken as 10 per cent of the fixed capital cost; the cost can be
considered to be divided evenly between labour and materials.
Operating labour
This is the manpower needed to operate the plant: that directly involved with running the
process.
The costs should be calculated from an estimate of the number of shift and day personnel
needed, based on experience with similar processes. It should be remembered that to
operate three shifts per day, at least five shift crews will be needed. The figures used for
263
COSTING AND PROJECT EVALUATION
Table 6.4.
Raw material and product costs
Typical prices for bulk purchases, mid-1998. All deliveries by rail or road tanker,
and all materials technical/industrial grade; unless otherwise stated
Chemical, and state
Cost unit
Acetaldehyde, 99%
Acetic acid
Acetic anhydride
Acetone
Acrylonitrile
Ally alcohol
Ammonia, anhydrous
Ammonium nitrate, bulk
Ammonium sulphate, bulk
Amyl alcohol, mixed isomers
Aniline
Benzaldehyde, drums
Benzene
Benzoic acid, drums
Butene-1
n-Butyl alcohol
n-Butyl ether, drums
Calcium carbide, bulk
Calcium carbonate, bulk, coarse
Calcium chloride, bulk
Calcium hydroxide (lime), bulk
Carbon disulphide
Carbon tetrachloride, drums
Chlorine
Chloroform
Cupric chloride, anhydrous
Dichlorobenzene
Diethanolamine
Ethanol, 90%
Ethyl ether
Ethylene, contract
Ethylene glycol
Ethylene oxide
Formaldehyde, 37% w/w
Formic acid, 94% w/w, drums
Glycerine, 99.7%
Heptane
Hexane
Hydrochloric acid, anhyd.
Hydrochloric acid, 30% w/w
Hydrogen fluoride, anhydrous
Hydrogen peroxide, 50% w/w
Isobutanol, alcohol
Isopropanol alcohol
Maleic anhydride, drums
Methanol
Methyl ethyl ketone
Monoethanolamine
Methylstyrene
Nitric acid, 50% w/w
98% w/w
Nitrobenzene
kg
kg
kg
kg
kg
kg
t
t
t
kg
kg
kg
kg
kg
kg
kg
kg
t
t
t
t
t
kg
t
kg
kg
kg
kg
kg
kg
kg
kg
kg
kg
kg
kg
kg
kg
kg
t
kg
kg
kg
kg
kg
kg
kg
kg
kg
t
t
kg
Cost £/unit
0.53
0.60
0.70
0.63
1.20
1.40
180
100
90
0.67
0.52
1.95
0.20
2.20
0.30
0.75
1.95
320
105
200
55
370
0.50
140
0.45
3.30
0.95
1.20
4.20
0.80
0.46
0.56
0.60
0.31
0.63
1.30
0.30
0.20
1.00
60
0.90
0.50
0.75
0.73
1.80
0.63
0.64
1.02
0.70
130
220
0.47
Cost $/unit
0.48
1.10
1.15
1.03
1.90
2.30
280
170
150
1.20
0.84
3.21
0.33
3.60
0.40
1.30
3.20
530
145
275
90
500
0.83
200
0.70
5.5
1.54
1.70
6.50
1.35
0.70
0.83
0.90
0.46
1.05
1.70
0.40
0.33
1.70
90
1.40
0.80
1.1
1.12
2.90
1.00
1.06
1.54
1.15
220
370
0.78
(continued overleaf)
264
CHEMICAL ENGINEERING
Table 6.4.
(continued)
Chemical, and state
Cost unit
Oxalic acid, sacks
Phenol
Phosgene, cyl.
Phosphoric acid 75% w/w
Potassium bicarbonate, sacks
Potassium carbonate, sacks
Potassium chloride
Potassium chromate, sacks
Potassium hydroxide
Potassium nitrate, bulk
Propylene
Propylene oxide
n-Propanol
Sodium carbonate, sacks
Sodium chloride, drums
Sodium hydroxide, drums
Sodium sulphate, bulk
Sodium thiosulphate
Sulphur, crude, 99.5%, sacks
Sulphuric acid, 98% w/w
Titanium dioxide, sacks
Toluene
Toluene diisocyanate
Trichloroethane
Trichloroethylene
Urea, 46% nitrogen, bulk
Vinyl acetate
Vinyl chloride
Xylenes
kg
kg
kg
kg
kg
kg
t
kg
kg
t
kg
kg
kg
kg
kg
kg
t
kg
t
t
kg
kg
kg
kg
kg
t
kg
kg
kg
Cost £/unit
0.58
0.90
1.09
0.47
0.45
0.56
70
0.80
2.00
350
0.43
1.00
0.93
0.35
0.40
1.60
72
0.38
85
40
1.50
0.32
2.20
0.56
0.84
120
0.65
0.44
0.29
Cost $/unit
0.96
1.53
1.62
0.78
0.75
0.92
110
1.30
3.70
570
0.64
1.60
1.438
0.58
0.65
2.60
120
0.57
140
65
2.50
0.47
3.20
0.94
1.40
160
1.08
0.66
0.43
Anhyd. = anhydrous, cyl. = cylinder, refin. = refined
Caution: Use these prices only as a rough guide to the probable price range.
Actual prices at a given time will vary considerably from these values, depending
on location, contract quantities, and the prevailing market forces.
Table 6.5.
Cost of utilities, typical figures mid-2004
Utility
UK
USA
Mains water (process water)
Natural gas
Electricity
Fuel oil
Cooling water (cooling towers)
Chilled water
Demineralised water
Steam (from direct fired boilers)
Compressed air (9 bar)
Instrument air (9 bar) (dry)
Refrigeration
Nitrogen
60 p/t
0.4 p/MJ
1.0 p/MJ
65 £/t
1.5 p/t
5 p/t
90 p/t
7 £/t
0.4 p/m3 (Stp)
0.6 p/m3 (Stp)
1.0 p/MJ
6 p/m3 (Stp)
50 c/t
0.7 c/MJ
1.5 c/MJ
100 $/t
1 c/t
8 c/t
90 c/t
12 $/t
0.6 c/m3
1 c/m3
1.5 c/MJ
8 c/m3
Note: £1 D 100p, 1$ D 100c, 1 t D 1000 kg D 2200 ib, stp D 1 atm, 0° C
These prices should be used only as a rough guide to the likely cost of
utilities. The cost of water will be very dependent on the plant location, and
the price of all utilities will be determined by the current cost of energy.
COSTING AND PROJECT EVALUATION
265
the cost of each man should include an allowance for holidays, shift allowances, national
insurance, pension contributions and any other overheads. The current wage rates per
hour in the UK chemical industry (mid-2004) are £15 20, to which must be added up to
50 per cent for the various allowances and overheads mentioned above.
Chemical plants do not normally employ many people and the cost of operating labour
would not normally exceed 15 per cent of the total operating cost. The direct overhead
charges would add 20 to 30 per cent to this figure.
Wessel (1952) gives a method of estimating the number of man-hours required based
on the plant capacity and the number of discrete operating steps.
Supervision
This heading covers the direct operating supervision: the management directly associated
with running the plant. The number required will depend on the size of the plant and
the nature of the process. The site would normally be broken down into a number of
manageable units. A typical management team for a unit would consist of four to five
shift foremen, a general foreman, and an area supervisor (manager) and his assistant. The
cost of supervision should be calculated from an estimate of the total number required and
the current salary levels, including the direct overhead costs. On average, one “supervisor”
would be needed for each four to five operators. Typical salaries, mid-2004, are £20,000
to £45,000, depending on seniority. An idea of current salaries can be obtained from the
salary reviews published periodically by the Institution of Chemical Engineers.
Laboratory costs
The annual cost of the laboratory analyses required for process monitoring and quality
control is a significant item in most modern chemical plants. The costs should be calculated
from an estimate of the number of analyses required and the standard charge for each
analysis, based on experience with similar processes.
As a rough estimate the cost can be taken as 20 to 30 per cent of the operating labour
cost, or 2 to 4 per cent of the total production cost.
Plant overheads
Included under this heading are all the general costs associated with operating the plant not
included under the other headings; such as, general management, plant security, medical,
canteen, general clerical staff and safety. It would also normally include the plant technical
personnel not directly associated with and charged to a particular operating area. This
group may be included in the cost of supervision, depending on the organisation’s practice.
The plant overhead cost is usually estimated from the total labour costs: operating,
maintenance and supervision. A typical range would be 50 to 100 per cent of the labour
costs; depending on the size of the plant and whether the plant was on a new site, or an
extension of an existing site.
Capital charges
The investment required for the project is recovered as a charge on the project. How
this charge is shown on an organisation’s books will depend on its accounting practices.
266
CHEMICAL ENGINEERING
Capital is often recovered as a depreciation charge, which sets aside a given sum each
year to repay the cost of the plant. If the plant is considered to “depreciate” at a fixed rate
over its predicted operating life, the annual sum to be included in the operating cost can
be easily calculated. The operating life of a chemical plant is usually taken as 10 years,
which gives a depreciation rate of 10 per cent per annum. The plant is not necessarily
replaced at the end of the depreciation period. The depreciation sum is really an internal
transfer to the organisation’s fund for future investment. If the money for the investment
is borrowed, the sum set aside would be used to repay the loan. Interest would also be
payable on the loan at the current market rates. Normally the capital to finance a particular
project is not taken as a direct loan from the market but comes from the company’s own
reserves. Any interest charged would, like depreciation, be an internal (book) transfer of
cash to reflect the cost of the capital used.
Rather than consider the cost of capital as depreciation or interest, or any other of
the accounting terms used, which will depend on the accounting practice of the particular
organisation and the current tax laws, it is easier to take the cost as a straight, unspecified,
capital charge on the operating cost. This would be typically around 10 per cent of the
fixed capital, annually, depending on the cost of money. As an approximate estimate the
“capital charge” can be taken as 2 per cent above the current minimum lending rate. For
a full discussion on the nature of depreciation and the cost of capital see Happle and
Jordan (1975), Holland et al. (1983), Valle-Riestra (1983).
Local taxes
This term covers local taxes, which are calculated on the value of the site. A typical figure
would be 1 to 2 per cent of the fixed capital.
Insurance
The cost of the site and plant insurance: the annual insurance premium paid to the insurers;
usually about 1 to 2 per cent of the fixed capital.
Royalties and licence fees
If the process used has not been developed exclusively by the operating company,
royalties and licence fees may be payable. These may be paid as a lump sum, included
in the fixed capital, or as an annual fee; or payments based on the amount of product
sold.
The cost would add about 1 per cent to 5 per cent to the sales price.
Summary of production costs
The various components of the operating costs are summarised in Table 6.6. The typical
values given in this table can be used to make an approximate estimate of production
costs.
COSTING AND PROJECT EVALUATION
Table 6.6.
267
Summary of production costs
Variable costs
1. Raw materials
2. Miscellaneous materials
3. Utilities
4. Shipping and packaging
Typical values
from flow-sheets
10 per cent of item (5)
from flow-sheet
usually negligible
Sub-total A
Fixed costs
5. Maintenance
6. Operating labour
7. Laboratory costs
8. Supervision
9. Plant overheads
10. Capital charges
11. Insurance
12. Local taxes
13. Royalties
......................
5 10 per cent of fixed capital
from manning estimates
20 23 per cent of 6
20 per cent of item (6)
50 per cent of item (6)
10 per cent of the fixed capital
1 per cent of the fixed capital
2 per cent of the fixed capital
1 per cent of the fixed capital
Sub-total B
......................
Direct production costs A + B
......................
13. Sales expense
20 30 per cent of the direct
14. General overheads
production cost
15. Research and development
Sub-total C
......................
Annual production cost D A C B C C D
......................
Annual production cost
Production cost £/kg D
Annual production rate
Example 6.4
Preliminary design work has been done on a process to recover a valuable product from
an effluent gas stream. The gas will be scrubbed with a solvent in a packed column;
the recovered product and solvent separated by distillation; and the solvent cooled and
recycled. The major items of equipment that will be required are detailed below.
1. Absorption column: diameter 1 m, vessel overall height 15 m, packed height 12 m,
packing 25 mm ceramic intalox saddles, vessel carbon steel, operating pressure 5 bar.
2. Recovery column: diameter 1 m, vessel overall height 20 m, 35 sieve plates, vessel
and plates stainless steel, operating pressure 1 bar.
3. Reboiler: forced convection type, fixed tube sheets, area 18.6 m2 , carbon steel shell,
stainless-steel tubes, operating pressure 1 bar.
4. Condenser: fixed tube sheets, area 25.3 m2 , carbon steel shell and tubes, operating
pressure 1 bar.
5. Recycle solvent cooler: U-tubes, area 10.1 m2 , carbon steel shell and tubes, operating
pressure 5 bar.
6. Solvent and product storage tanks: cone roof, capacity 35 m3 , carbon steel.
Estimated service requirements:
Steam
Cooling water
Electrical power
200 kg/h
5000 kg/h
100 kWh/d (360 MJ/d)
268
CHEMICAL ENGINEERING
Estimated solvent loss 10 kg/d; price £400/t. Plant attainment 95 per cent.
Estimate the capital investment required for this project, and the annual operating cost;
date mid-2004.
Solution
Purchased cost of major equipment items.
Absorption column
Bare vessel cost (Figure 6.5a) £21,000; material factor 1.0, pressure factor 1.1
Vessel cost D 21,000 ð 1.0 ð 1.1 D £23,000
Packing cost (Table 6.3) £840/m3
Volume of packing D ⊲/4⊳ ð 12 D 9.4 m3
Cost of column packing D 9.4 ð 840 D £7896
Total cost of column 21,000 C 7896 D 28,896, say £29,000
Recovery column
Bare vessel cost (Figure 6.5a) £26,000; material factor 2.0, pressure factor 1.0
Vessel cost 26,000 ð 2.0 ð 1.0 D £52,000
Cost of a plate (Figure 6.7a), material factor 1.7 D 200 ð 1.7 D £340
Total cost of plates D 35 ð 340 D £11,900
Total cost of column D 52,000 C 11,900 D 63,900, say £64,000
Reboiler
Bare cost (Figure 6.3a) £11,000; type factor 0.8, pressure factor 1.0
Purchased cost D 11,000 ð 0.8 ð 1.0 D £8800
Condenser
Bare cost (Figure 6.3a) £8500; type factor 0.8, pressure factor 1.0
Purchased cost D 8500 ð 0.8 ð 1.0 D £6800
Cooler
Bare cost (Figure 6.3a) £4300; type factor 0.85, pressure factor 1.0
Purchased cost D 4300 ð 0.85 ð 1.0 D £3700
Solvent tank
Purchase cost ⊲Table 6.2⊳ D 1400 ð ⊲35⊳0.55 D £9894, say £10,000
Product tank
Purchase cost same as solvent tank D £10,000
COSTING AND PROJECT EVALUATION
269
Total purchase cost of major equipment items (PCE)
Absorption column
Recovery column
Reboiler
Condenser
Cooler
Solvent tank
Product tank
Total
29,000
64,000
8000
6000
3000
10,000
10,000
£130,000
Estimation of fixed capital cost, reference Table 6.1, fluids processing plant:
PCE £130,000
f1
f2
f3
f4
f5
f6
f7
f8
f9
Equipment erection
Piping
Instrumentation
Electrical
Buildings
Utilities
Storages
Site development
Ancillary buildings
0.40
0.70
0.20
0.10
none required
not applicable
provided in PCE
not applicable
none required
Total physical plant cost ⊲PPC⊳ D 132,300⊲1 C 0.4 C 0.7 C 0.2 C 0.1⊳ D £317,520
f10 Design and Engineering
f11 Contractor’s Fee
f12 Contingencies
0.30
none (unlikely to be used for a small, plant project)
0.10
Fixed capital D 317,520⊲1 C 0.3 C 0.1⊳ D 44,528 round up to £445,000
Working capital, allow 5% of fixed capital to cover the cost of the initial solvent charge D
445,000 ð 0.05 D £22,250.
Total investment required for project D 445,000 C 22,250 D 467,250, say £468,000
Annual operating costs, reference Table 6.6:
Operating time, allowing for plant attainment D 365 ð 0.95 D 347 d/y, 347 ð 24 D
8328 h/y.
Variable costs:
1. Raw materials, solvent make-up D 10 ð 347 ð 400/1000 D
£ 1388
2. Miscellaneous materials, 10% of maintenance cost (item 5) D
£ 2200
3. Utilities, cost from Table 6.5:
Steam, at 7£/t D 7 ð 8328 ð 200/1000 D
£11,659
Cooling water, at 1.5 p/t D ⊲1.5/100⊳ ð 8328 ð 5000/1000 D
£ 625
Power, at 1.2 p/MJ D ⊲1.2/100⊳ ð 360 ð 347 D
£ 1499
4. Shipping and packaging
not applicable
Variable costs D £17,371
270
CHEMICAL ENGINEERING
Fixed costs:
5. Maintenance, take as 5% of fixed capital D 445,000 ð 0.05 D
6. Operating labour, allow one extra man on days. It is unlikely
that one extra man per shift would be needed to operate
this small plant, and one extra per shift would give
a disproportionately high labour cost.
Say, £30,000 per year, allowing for overheads D
7. Supervision, no additional supervision would be needed
8. Plant overheads, take as 50% of operating labour D
9. Laboratory, take as 30% of operating labour D
10. Capital charges, 6% of fixed capital (bank rate 4%)
11. Insurance, 1% of fixed capital
12. Local taxes
13. Royalties
Fixed cost D
Direct production costs D 17,396 C 107,400 D
14. Sales expense
15. General overheads
16. Research and development
£22,250
£30,000
£15,000
£ 9000
£26,700
£ 4450
neglect
not applicable
£107,400
£124,796
not applicable
not applicable
not applicable
Annual operating cost, rounded D £125,000
6.10. ECONOMIC EVALUATION OF PROJECTS
As the purpose of investing money in chemical plant is to earn money, some means of
comparing the economic performance of projects is needed.
For small projects, and for simple choices between alternative processing schemes and
equipment, the decisions can usually be made by comparing the capital and operating
costs. More sophisticated evaluation techniques and economic criteria are needed when
decisions have to be made between large, complex projects, particularly when the projects
differ widely in scope, time scale and type of product. Some of the more commonly used
techniques of economic evaluation and the criteria used to judge economic performance
are outlined in this section. For a full discussion of the subject one of the many specialist
texts that have been published should be consulted; Brennan (1998), Chauvel et al. (2003)
and Vale-Riestra (1983). The booklet published by the Institution of Chemical Engineers,
Allen (1991), is particularly recommended to students.
Making major investment decisions in the face of the uncertainties that will undoubtedly
exist about plant performance, costs, the market, government policy, and the world
economic situation, is a difficult and complex task (if not an impossible task) and in
a large design organisation the evaluation would be done by a specialist group.
6.10.1. Cash flow and cash-flow diagrams
The flow of cash is the life blood of any commercial organisation. The cash flows
in a manufacturing company can be likened to the material flows in a process plant.
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COSTING AND PROJECT EVALUATION
The inputs are the cash needed to pay for research and development; plant design and
construction; and plant operation. The outputs are goods for sale; and cash returns, are
recycled, to the organisation from the profits earned. The “net cash flow” at any time
is the difference between the earnings and expenditure. A cash-flow diagram, such as
that shown in Figure 6.8, shows the forecast cumulative net cash flow over the life of a
project. The cash flows are based on the best estimates of investment, operating costs,
sales volume and sales price, that can be made for the project. A cash-flow diagram gives
a clear picture of the resources required for a project and the timing of the earnings. The
diagram can be divided into the following characteristic regions:
F
Cumulative cash flow
Positive
E
Profit
Break - even
point
A
Negative
Debt
Working
capital
G
Maximum
investment
D
B
C
Pay - back time
Project life
Time
Figure 6.8.
Years
Project cash-flow diagram
A B The investment required to design the plant.
B C The heavy flow of capital to build the plant, and provide funds for start-up.
C D The cash-flow curve turns up at C, as the process comes on stream and income is
generated from sales. The net cash flow is now positive but the cumulative amount
remains negative until the investment is paid off, at point D.
Point D is known as the break-even point and the time to reach the break-even point
is called the pay-back time. In a different context, the term “break-even point” is
used for the percentage of plant capacity at which the income equals the cost for
production.
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CHEMICAL ENGINEERING
D E In this region the cumulative cash flow is positive. The project is earning a return
on the investment.
E F Toward the end of project life the rate of cash flow may tend to fall off, due to
increased operating costs and falling sale volume and price, and the slope of the
curve changes.
The point F gives the final cumulative net cash flow at the end of the project life.
Net cash flow is a relatively simple and easily understood concept, and forms the basis
for the calculation of other, more complex, measures of profitability.
6.10.2. Tax and depreciation
In calculating cash flows, as in Example 6.6, the project is usually considered as an
isolated system, and taxes on profits and the effect of depreciation of the investment are
not considered; tax rates are not constant and depend on government policy. In recent
years, corporation (profits) tax has been running at around 30 per cent and this figure
can be used to make an estimate of the cash flow after tax. Depreciation rates depend
on government policy, and on the accounting practices of the particular company. At
times, it has been government practice to allow higher depreciation rates for tax purposes
in development areas; or to pay capital grants to encourage investment in these areas.
The effect of government policy must clearly be taken into account at some stage when
evaluating projects, particularly when considering projects in different countries.
6.10.3. Discounted cash flow (time value of money)
In Figure 6.8 the net cash flow is shown at its value in the year in which it occurred. So
the figures on the ordinate show the “future worth” of the project: the cumulative “net
future worth” (NFW).
The money earned in any year can be put to work (reinvested) as soon as it is available
and start to earn a return. So money earned in the early years of the project is more
valuable than that earned in later years. This “time value of money” can be allowed for
by using a variation of the familiar compound interest formula. The net cash flow in
each year of the project is brought to its “present worth” at the start of the project by
discounting it at some chosen compound interest rate.
Estimated net cash flow in year n (NFW)
Net present worth (NPW)
D
⊲1 C r⊳n
of cash flow in year n
⊲6.9⊳
where r is the discount rate (interest rate) per cent/100 and
Total NPW of project D
nDt
NFW
⊲1 C r⊳n
nD1
⊲6.10⊳
t D life of project, years.
The discount rate is chosen to reflect the earning power of money. It would be roughly
equivalent to the current interest rate that the money could earn if invested.
The total NPW will be less than the total NFW, and reflects the time value of money
and the pattern of earnings over the life of the project; see Example 6.6.
COSTING AND PROJECT EVALUATION
273
Most proprietary spreadsheets have procedures for calculating the cumulative NPW
from a listing of the yearly net annual revenue (profit). Spreadsheets are useful tools for
economic analysis and project evaluation.
6.10.4. Rate of return calculations
Cash-flow figures do not show how well the capital invested is being used; two projects
with widely different capital costs may give similar cumulative cash-flow figures. Some
way of measuring the performance of the capital invested is needed. Rate of return (ROR),
which is the ratio of annual profit to investment, is a simple index of the performance
of the money invested. Though basically a simple concept, the calculation of the ROR is
complicated by the fact that the annual profit (net cash flow) will not be constant over
the life of the project. The simplest method is to base the ROR on the average income
over the life of the project and the original investment.
ROR D
Cumulative net cash flow at end of project
ð 100 per cent
Life of project ð original investment
⊲6.11⊳
From Figure 6.8.
Cumulative income D F C
Investment D C
Life of project D G
FC
then, ROR D
ð 100 per cent
CðG
The rate of return is often calculated for the anticipated best year of the project: the
year in which the net cash flow is greatest. It can also be based on the book value
of the investment, the investment after allowing for depreciation. Simple rate of return
calculations take no account of the time value of money.
6.10.5. Discounted cash-flow rate of return (DCFRR)
Discounted cash-flow analysis, used to calculate the present worth of future earnings
(Section 6.10.3), is sensitive to the interest rate assumed. By calculating the NPW for
various interest rates, it is possible to find an interest rate at which the cumulative net
present worth at the end of the project is zero. This particular rate is called the “discounted
cash-flow rate of return” (DCFRR) and is a measure of the maximum rate that the project
could pay and still break even by the end of the project life.
nDt
nD1
NFW
D0
⊲1 C r 0 ⊳n
where r 0 D the discounted cash-flow rate of return (per cent/100),
NFW D the future worth of the net cash flow in year n,
t D the life of the project, years.
⊲6.12⊳
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CHEMICAL ENGINEERING
The value of r 0 is found by trial-and-error calculations. Finding the discount rate that
just pays off the project investment over the project’s life is analogous to paying off a
mortgage. The more profitable the project, the higher the DCFRR that it can afford to pay.
DCFRR provides a useful way of comparing the performance of capital for different
projects; independent of the amount of capital used and the life of the plant, or the actual
interest rates prevailing at any time.
Other names for DCFRR are interest rate of return and internal rate of return.
6.10.6. Pay-back time
Pay-back time is the time required after the start of the project to pay off the initial
investment from income; point D on Figure 6.7. Pay-back time is a useful criterion for
judging projects that have a short life, or when the capital is only available for a short time.
It is often used to judge small improvement projects on operating plant. Typically, a
pay-back time of 2 to 5 years would be expected from such projects.
Pay-back time as a criterion of investment performance does not, by definition, consider
the performance of the project after the pay-back period.
6.10.7. Allowing for inflation
Inflation depreciates money in a manner similar to, but different from, the idea of
discounting to allow for the time value of money. The effect of inflation on the net
cash flow in future years can be allowed for in a similar manner to the net present worth
calculation given by equation 6.9, using an inflation rate in place of, or added to, the
discount rate r. However, the difficulty is to decide what the inflation rate is likely to be
in future years. Also, inflation may well affect the sales price, operating costs and raw
material prices differently. One approach is to argue that a decision between alternative
projects made without formally considering the effect of inflation on future earnings will
still be correct, as inflation is likely to affect the predictions made for both projects in a
similar way.
6.10.8. Sensitivity analysis
The economic analysis of a project can only be based on the best estimates that can be
made of the investment required and the cash flows. The actual cash flows achieved in
any year will be affected by any changes in raw-materials costs, and other operating costs;
and will be very dependent on the sales volume and price. A sensitivity analysis is a way
of examining the effects of uncertainties in the forecasts on the viability of a project. To
carry out the analysis the investment and cash flows are first calculated using what are
considered the most probable values for the various factors; this establishes the base case
for analysis. The cash flows, and whatever criteria of performance are to be used, are then
calculated assuming a range of error for each of the factors in turn; for example, an error
of, say, š10 per cent on the sales price might be assumed. This will show how sensitive
the cash flows and economic criteria are to errors in the forecast figures. It gives some
idea of the degree of risk involved in making judgements on the forecast performance of
the project.
275
COSTING AND PROJECT EVALUATION
6.10.9. Summary
The investment criteria discussed in this section are set out in Table 6.7, which shows the
main advantage and disadvantage of each criterion.
There is no one best criterion on which to judge an investment opportunity. A company
will develop its own methods of economic evaluation, using the techniques discussed in
this section, and will have a “target” figure of what to expect for the criterion used, based
on their experience with previous successful, and unsuccessful, projects.
Table 6.7.
Criterion
Abbreviation
Investment
Net future worth
Units
£, $
NFW
Pay-back time
£, $
years
Net present worth
NPW
£, $
Rate of return
ROR
%
DCFRR
%
Discounted
cash-flow rate
of return
Investment criteria
Main advantage
Main shortcoming
Shows financial resources
needed
Simple. When plotted as
cash-flow diagram, shows
timing of investment and
income
Shows how soon investment
will be recovered
As for NFW but accounts
for timing of cash flows
Measures performance of
capital
No indication of project
performance
Takes no account of the
time value of money
Measures performance of
capital allowing for
timing of cash flows
No information on later
years
Dependent on discount rate
used
Takes no account of timing
of cash flows
Dependent on definition of
income (profit) and
investment
No indication of the
resources needed
A figure of 20 to 30 per cent for the return on investment (ROR) can be used as a
rough guide for judging small projects, and when decisions have to be made on whether
to install additional equipment to reduce operating costs. This is equivalent to saying that
for a project to be viable the investment needed should not be greater than about 4 to 5
times the annual savings achieved.
As well as economic performance, many other factors have to be considered when
evaluating projects; such as those listed below:
1.
2.
3.
4.
5.
6.
7.
Safety.
Environmental problems (waste disposal).
Political considerations (government policies).
Location of customers.
Availability of labour.
Availability of supporting services.
Company experience in the particular technology.
Example 6.5
A plant is producing 10,000 t/y of a product. The overall yield is 70 per cent, on a mass
basis (kg of product per kg raw material). The raw material costs £10/t, and the product
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CHEMICAL ENGINEERING
sells for £35/t. A process modification has been devised that will increase the yield to
75 per cent. The additional investment required is £35,000, and the additional operating
costs are negligible. Is the modification worth making?
Solution
There are two ways of looking at the earnings to be gained from the modification:
1. If the additional production given by the yield increase can be sold at the current
price, the earnings on each additional ton of production will equal the sales price
less the raw material cost.
2. If the additional production cannot be readily sold, the modification results in a
reduction in raw material requirements, rather than increased sales, and the earnings
(savings) are from the reduction in annual raw material costs.
The second way gives the lowest figures and is the safest basis for making the evaluation.
At 10,000 t/y production
10,000
D 14,286
0.7
10,000
at 75 per cent yield D
D 13,333
0.75
savings 953 t/y
Raw material requirements at 70 per cent yield D
Cost savings, at £10/t, D 953 ð 10 D £9530 per year
9530
ROR D
ð 100 D 27 per cent
35,000
Pay-back time (as the annual savings are constant, the pay-back time will be the reciprocal
of the ROR)
100
D
D 3.7 years
27
On these figures the modification would be considered worthwhile.
Example 6.6
It is proposed to build a plant to produce a new product. The estimated investment required
is 12.5 million pounds and the timing of the investment will be:
year
year
year
year
1
2
3
4
1.0
5.0
5.0
1.5
million (design costs)
million (construction costs)
million
”
”
million (working capital)
The plant will start up in year 4.
The forecast sales price, sales volume, and raw material costs are shown in Table 6.8.
277
COSTING AND PROJECT EVALUATION
Table 6.8.
Summary of data and results for example 6.6
Discounted cash
flow at 15 per cent
106 £
Cumulative DCF
(Project NPW)
106 £
Project NPW
at 25 per cent
discount rate
Project NPW
at 35 per cent
discount rate
Project NPW
at 37 per cent
discount rate
At commencement of project
Cumulative cash
flow 106 £
(Project NFW)
90
90
90
90
90
90
85
85
85
85
80
75
75
70
70
70
0
0
0
4.6
4.85
5.10
5.60
6.10
6.50
7.00
6.93
7.60
8.05
8.05
7.62
7.19
5.06
3.93
2.15
At year
end
Net cash flow
106 £
150
150
150
150
150
150
145
140
140
140
135
130
120
115
110
100
Sale income
less operating
costs 106 £
0
0
0
100
105
110
120
130
140
150
165
180
190
200
190
180
170
160
150
Raw material costs
£/t product
Forecast sales
103 t
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Forecast selling
Price £/t
End of year
During year
1.0
5.0
5.0
3.10
4.85
5.10
5.60
6.10
6.50
7.00
6.93
7.60
8.05
8.05
7.62
7.19
5.06
3.93
2.15
1.00
6.00
11.00
7.90
3.05
2.05
7.65
13.75
20.25
27.25
34.18
41.78
49.83
57.88
65.50
72.69
77.75
81.68
83.83
0.87
3.78
3.29
1.77
2.41
2.20
2.11
1.99
1.85
1.73
1.49
1.42
1.31
1.14
0.94
0.77
0.47
0.32
0.15
0.87
4.65
7.94
6.17
4.03
1.83
0.28
2.27
4.12
5.85
7.34
8.76
10.07
11.21
12.15
12.92
13.39
13.71
13.86
0.80
4.00
6.56
5.29
3.70
2.36
1.19
0.17
0.70
1.45
2.05
2.57
3.01
3.36
3.63
3.83
3.95
4.02
4.05
0.74
3.48
5.52
4.58
3.50
2.66
1.97
1.42
0.98
0.64
0.38
0.17
0.01
0.11
0.19
0.25
0.28
0.30
0.31
0.73
3.39
5.34
4.46
3.45
2.68
2.06
1.57
1.19
0.89
0.67
0.50
0.36
0.27
0.20
0.15
0.13
0.12
0.11
The fixed operating costs are estimated to be:
£400,000 per year up to year 9
£500,000 per year from year 9 to 13
£550,000 per year from year 13
The variable operating costs are estimated to be:
£10 per ton of product up to year 13
£13 per ton of product from year 13
Calculate:
1.
2.
3.
4.
5.
The
The
The
The
The
net cash flow in each year.
future worth of the project, NFW.
present worth, NPW, at a discount rate of 15 per cent.
discounted cash-flow rate of return, DCFRR.
pay-back time.
No account needs to be taken of tax in this exercise; or the scrap value of the equipment
and value of the site at the end of the project life. For the discounting calculation, cash
flows can be assumed to occur at the end of the year in which they actually occur.
278
CHEMICAL ENGINEERING
Solution
The cash-flow calculations are summarised in Table 6.8. Sample calculations to illustrate
the methods used are given below.
For year 4
Investment (negative cash flow)
Sales income D 100 ð 103 ð 150
Raw material costs D 100 ð 103 ð 90
Fixed operating costs
Variable operating costs D 100 ð 103 ð 10
Net cash flow D sales income costs investment
D 15.0 10.4 1.5 D 3.1 million pounds
3.1
Discounted cash flow (at 15 per cent) D
⊲1 C 0.15⊳4
D
D
D
D
D
£1.5 ð 106
£15.0 ð 106
£9.0 ð 106
£0.4 ð 106
£1.0 ð 106
D £1.77 ð 106
For year 8
Investment
Sales income D 130 ð 103 ð 150
Raw material costs D 130 ð 103 ð 90
Fixed operating costs
Variable operating costs D 130 ð 103 ð 10
Net cash flow D 19.5 13.4 D 6.10 million pounds
6.1
DCF D
D 1.99
⊲1.15⊳8
D
D
D
D
nil
£19.5 ð 106
£11.7 ð 106
£0.4 ð 106
£1.3 ð 106
DCFRR
This is found by trial-and-error calculations. The present worth has been calculated at
discount rates of 25, 35 and 37 per cent. From the results shown in Table 6.8 it will
be seen that the rate to give zero present worth will be around 36 per cent. This is the
discounted cash-flow rate of return for the project.
6.11. COMPUTER METHODS FOR COSTING AND PROJECT
EVALUATION
Most large manufacturing and contracting organisations use computer programs to aid
in the preparation of cost estimates and in process evaluation. Many have developed
their own programs, using cost data available from company records to ensure that the
estimates are reliable. Of the packages available commercially, QUESTIMATE, marketed
by the Icarus Corporation, is probably the most widely used.
Costing and economic evaluation programs also form part of some of the commercial
process design packages; such as the ICARUS program which is available from Aspen
Tech, see Chapter 4, Table 4.1.
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COSTING AND PROJECT EVALUATION
6.12. REFERENCES
ALLEN, D. H. (1991) Economic Evaluation of Projects, 3rd edn (Institution of Chemical Engineers,
London).
ANON. (2004) Process Engineering (Mar) 85. UK and international cost indices.
BECHTEL, L. B. (1960) Chem. Eng., NY 67 (Feb. 22nd) 127. Estimate working capital needs.
BRENNAN, D. (1998) Process Industry Economics (Institution of Chemical Engineers, London).
CHAUVEL, A., FOURNIER, G. and RAIMBAULT, C. (2003) Process Economic Evaluation (Technip).
CMR (2004) Chemical Marketing Reporter (Reed business information).
ECN (2004) European Chemical News (Reed business information).
ESTRUP, C. (1972) Brit. Chem. Eng. Proc. Tech. 17, 213. The history of the six-tenths rule in capital cost
estimation.
GARRETT, D. E. (1989) Chemical Engineering Economics (Van Norstrand Reinhold).
GUTHRIE, K. M. (1969) Chem. Eng., NY 76 (March 24th) 114. Capital cost estimating.
GUTHRIE, K. M. (1970) Chem. Eng., NY 77 (June 15th) 140. Capital and operating costs for 54 processes.
(Note: correction Dec. 14th, 7).
GUTHRIE, K. M. (1974) Process Plant Estimating, Evaluation, and Control (Craftsman books).
HALL, R. S., MATLEY, J. and MCNAUGHTON, J. (1982) Chem. Eng., NY 89 (April 5th) 80. Current cost of process
equipment.
HAPPLE, J. and JORDAN, D. G. (1975) Chemical Process Economics, 2nd edn (Marcel Dekker).
HOLLAND, F. A., WATSON, F. A. and WILKINSON, J. K. (1983) Introduction to Process Economics 2nd edn
(Wiley).
ICHEME (2000) Guide to Capital Cost Estimation, 4th edn (Institution of Chemical Engineers, London).
LANG, H. J. (1948) Chem. Eng., NY 55 (June) 112. Simplified approach to preliminary cost estimates.
LYDA, T. B. (1972) Chem. Eng., NY 79 (Sept. 18th) 182. How much working capital will the new project need?
PAGE, J. S. (1984) Conceptual Cost Estimating (Gulf).
PETERS, M. S., TIMMERHAUS, K. D. and WEST, R. E. (2003) Plant Design and Economics, 5th edn (McGrawHill).
PIKULIK, A. and DIAZ, H. E. (1977) Chem. Eng., NY 84 (Oct. 10th) 106. Cost estimating for major process
equipment.
PUROHIT, G. P. (1983) Chem. Eng., NY 90 (Aug. 22nd) 56. Estimating the cost of heat exchangers.
SCOTT, R. (1978) Eng. and Proc. Econ., 3 105. Working capital and its estimation for project evaluation.
TAYLOR, J. H. (1977) Eng. and Proc. Econ. 2, 259. The process step scoring method for making quick capital
estimates.
ULRICH, G. D. (1984) A Guide to Chemical Engineering Process Design and Economics (Wiley).
VALLE-RIESTRA, J. F. (1983) Project Evaluation in the Chemical Process Industries (McGraw-Hill).
WESSEL, H. E. (1952) Chem. Eng., NY 59 (July) 209. New graph correlates operating labor data for chemical
processes.
WILSON, G. T. (1971) Brit. Chem. Eng. 16 931. Capital investment for chemical plant.
6.13. NOMENCLATURE
Dimensions
in MT £ or $
A
B
C
Ce
Cf
C1
C2
fL
f1 . . . f9
N
n
Q
S
Year in which cost is known (equation 6.1)
Year in which cost is to be estimated (equation 6.1)
Cost constant in equation 6.7
Purchased equipment cost
Fixed capital cost
Capital cost of plant 1
Capital cost of plant 2
Lang factors (equation 6.3)
Capital cost factors (Table 6.1)
Number of significant processing steps
Capital cost index in equation 6.4
Plant capacity
Equipment size unit in equation 6.4
T
T
Ł
£
£
£
£
or
or
or
or
$
$
$
$
MT1
Ł
280
S1
S2
s
CHEMICAL ENGINEERING
MT1
MT1
Capacity of plant 1
Capacity of plant 2
Reactor conversion
Asterisk (Ł ) indicates that these dimensions are dependent on the type of equipment.
6.14. PROBLEMS
6.1. The capital cost of a plant to produce 100 t per day of aniline was 8.5 million US
dollars in mid-1992. Estimate the cost in pounds sterling in January 2004. Take
the exchange rates as: £1 D $2.0 in mid-1992 and £1 D $1.8 in January 2004.
6.2. The process used in the manufacture of aniline from nitrobenzene is described
in Appendix G, design problem G.8. The process involves six significant stages:
Vaporisation of the nitrobenzene
Hydrogenation of the nitrobenzene
Separation of the reactor products by condensation
Recovery of crude aniline by distillation
Purification of the crude nitrobenzene
Recovery of aniline from waste water streams
Estimate the capital cost of a plant to produce 20,000 tonne per year.
6.3. A reactor vessel cost £365,000 in June 1998, estimate the cost in mid-2004.
6.4. The cost of a distillation column was $225,000 in early 1998, estimate the cost
in January 2004.
6.5. Using the data on equipment costs given in this chapter, estimate the cost of the
following equipment:
1. A shell and tube heat exchanger, heat transfer area 50 m2 , floating head type,
carbon steel shell, stainless steel tubes, operating pressure 25 bar.
2. A kettle reboiler: heat transfer area 25 m2 , carbon steel shell and tubes,
operating pressure 10 bar.
3. A horizontal, cylindrical, storage tank, 3 m diameter, 12 m long, used for
liquid chlorine at 10 bar, material carbon steel.
4. A plate column: diameter 2 m height 25 m, stainless clad vessel, 20 stainless
steel sieve plates, operating pressure 5 bar.
6.6. Compare the cost the following types of heat exchangers, to give a heat transfer
area of 10 m2 . Take the construction material as carbon steel.
1. Shell and tube, fixed head
2. Double-pipe
6.7. Estimate the cost of the following items of equipment:
1. A packaged boiler to produce 20,000 kg/h of steam at 10 bar.
2. A centrifugal compressor, driver power 75 kW
3. A plate and frame filter press, filtration area 10 m2
COSTING AND PROJECT EVALUATION
281
4. A floating roof storage tank, capacity 50,000 m3
5. A cone roof storage tank, capacity 35,000 m3
6.8. A storage tank is purged continuously with a stream of nitrogen. The purge
stream leaving the tank is saturated with the product stored in the tank. A major
part of the product lost in the purge could be recovered by installing a scrubbing
tower to absorb the product in a solvent. The solution from the tower could be
fed to a stage in the production process, and the product and solvent recovered
without significant additional cost. A preliminary design of the purge recovery
system has been made. It would consist of:
1. A small tower 0.5 m diameter, 4 m high, packed with 25 mm ceramic saddles,
packed height 3 m.
2. A small storage tank for the solution, 5 m3 capacity.
3. The necessary pipe work, pump, and instrumentation.
All materials of construction, carbon steel.
Using the following data, evaluate whether it would be economical to install the
recovery system:
1.
2.
3.
4.
5.
6.
cost of product £5 per kg,
cost of solvent 20 p/kg,
additional solvent make-up 10 kg/d,
current loss of product 0.7 kg/h,
anticipated recovery of product 80 per cent,
additional service(utility) costs, negligible.
Other operating costs will be insignificant.
6.9. Make a rough estimate of the cost of steam per ton, produced from a packaged
boiler. 10,000 kg per hour of steam are required at 15 bar. Natural gas will be
used as the fuel, calorific value 39 MJ/m3 . Take the boiler efficiency as 80 per
cent. No condensate will be returned to the boiler.
6.10. The production of methyl ethyl ketone (MEK) is described in Appendix G,
problem G.3. A preliminary design has been made for a plant to produce 10,000
tonne per year. The major equipment items required are listed below. The plant
attainment will be 8000 hours per year.
Estimate the capital required for this project, and the production cost.
The plant will be built on an existing site with adequate resources to provide the
ancillary requirements of the new plant.
Major equipment items
1. Butanol vaporiser: shell and tube heat exchanger, kettle type, heat transfer
area 15 m2 , design pressure 5 bar, materials carbon steel.
2. Reactor feed heaters, two off: shell and tube, fixed head, heat transfer area
25 m2 , design pressure 5 bar, materials stainless steel.
3. Reactor, three off: shell and tube construction, fixed tube sheets, heat transfer
area 50 m2 , design pressure 5 bar, materials stainless steel.
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CHEMICAL ENGINEERING
4. Condenser: shell and tube heat exchanger, fixed tube sheets, heat transfer area
25 m2 , design pressure 2 bar, materials stainless steel.
5. Absorption column: packed column, diameter 0.5 m, height 6.0 m, packing
height 4.5 m, packing 25 mm ceramic saddles, design pressure 2 bar, material
carbon steel.
6. Extraction column: packed column, diameter 0.5 m, height 4 m, packed height
3 m, packing 25 mm stainless steel pall rings, design pressure 2 bar, material
carbon steel.
7. Solvent recovery column: plate column, diameter 0.6 m, height 6 m, 10 stainless steel sieve plates, design pressure 2 bar, column material carbon steel.
8. Recover column reboiler: thermosyphon, shell and tube, fixed tube sheets,
heat transfer area 4 m2 , design pressure 2 bar, materials carbon steel.
9. Recovery column condenser: double-pipe, heat transfer area 1.5 m2 , design
pressure 2 bar, materials carbon steel.
10. Solvent cooler: double pipe exchanger, heat transfer area 2 m2 , materials
stainless steel.
11. Product purification column: plate column, diameter 1 m2 , height 20 m, 15
sieve plates, design pressure 2 bar, materials stainless steel.
12. Product column reboiler: kettle type, heat transfer area 4 m2 , design pressure
2 bar, materials stainless steel.
13. Product column condenser: shell and tube, floating head, heat transfer area
15 m2 , design pressure 2 bar, materials stainless steel.
14. Feed compressor: centrifugal, rating 750 kW.
15. Butanol storage tank: cone roof, capacity 400 m3 , material carbon steel.
16. Solvent storage tank: horizontal, diameter 1.5 m, length 5 m, material carbon
steel.
17. Product storage tank: cone roof, capacity 400 m3 , material carbon steel.
Raw materials
1. 2-butanol, 1.045 kg per kg of MEK, price £450/t ($750/t).
2. Solvent (trichloroethane) make-up 7000 kg per year, price 60p/kg. ($1.0/kg).
Utilities
Fuel oil, 3000 t per year
Cooling water, 120 t/hour
Steam, low pressure, 1.2 t/h
Electrical power, 1 MW
The fuel oil is burnt to provide flue gases for heating the reactor feed and the
reactor. The cost of the burner need not be included in this estimate. Some of
the fuel requirements could be provided by using the by-product hydrogen. Also,
the exhaust flue gases could be used to generate steam. The economics of these
possibilities need not be considered.
6.11. A plant is proposing to install a combined heat and power system to supply
electrical power and process steam. Power is currently taken from a utility
company and steam is generated using on-site boilers.
COSTING AND PROJECT EVALUATION
283
The capital cost of the CHP plant is estimated to be £3 million pounds (5 million
dollars). Combined heat and power is expected to give net savings of £700,000
($1,150,000) per year. The plant is expected to operate for 10 years after the
completion of construction.
Calculate the cumulative net present worth of the project, at a discount rate of 8
per cent. Also, calculate the discounted cash flow rate of return.
Construction will take two years, and the capital will be paid in two equal increments, at the end of the first and second year. The savings (income) can be
taken as paid at the end of each year. Production will start on the completion of
construction.
CHAPTER 7
Materials of Construction
7.1. INTRODUCTION
This chapter covers the selection of materials of construction for process equipment and
piping.
Many factors have to be considered when selecting engineering materials, but for
chemical process plant the overriding consideration is usually the ability to resist corrosion.
The process designer will be responsible for recommending materials that will be suitable
for the process conditions. He must also consider the requirements of the mechanical
design engineer; the material selected must have sufficient strength and be easily worked.
The most economical material that satisfies both process and mechanical requirements
should be selected; this will be the material that gives the lowest cost over the working
life of the plant, allowing for maintenance and replacement. Other factors, such as product
contamination and process safety, must also be considered. The mechanical properties that
are important in the selection of materials are discussed briefly in this chapter. Several
books have been published on the properties of materials, and the metal-working processes
used in equipment fabrication, and a selection suitable for further study is given in the
list of references at the end of this chapter. The mechanical design of process equipment
is discussed in Chapter 13.
A detailed discussion of the theoretical aspects of corrosion is not given in this chapter,
as this subject is covered comprehensively in several books: Revie (2002), Fontana (1986),
Dillon (1986) and Schweitzer (1989).
Corrosion and corrosion prevention are also the subject of one of the design guides
published by the Design Council, Ross (1977).
7.2. MATERIAL PROPERTIES
The most important characteristics to be considered when selecting a material of
construction are:
1. Mechanical properties
(a) Strength tensile strength
(b) Stiffness elastic modulus (Young’s modulus)
(c) Toughness fracture resistance
(d) Hardness wear resistance
(e) Fatigue resistance
(f) Creep resistance
2. The effect of high and low temperatures on the mechanical properties
284
285
MATERIALS OF CONSTRUCTION
3. Corrosion resistance
4. Any special properties required; such as, thermal conductivity, electrical resistance,
magnetic properties
5. Ease of fabrication forming, welding, casting (see Table 7.1)
6. Availability in standard sizes plates, sections, tubes
7. Cost
Mild steel
Low alloy steel
Cast iron
Stainless steel
(18Cr, 8Ni)
Nickel
Monel
Copper
(deoxidised)
Brass
Aluminium
Dural
Lead
Titanium
S
U
Annealing
temp.° C
Welding
Casting
Hot working
Cold working
Machining
Table 7.1. A guide to the fabrication properties of
common metals and alloys
S
S
S
S
D
U
S
S
U
D
D
S
S
750
S
750
D/U
S
S
S
S
S
S
S
S
S
D
S
S
S
S
S
1050
1150
1100
D
S
S
S
S
D
S
S
S
S
S
S
S
S
S
S
D
800
700
550
350
U
U
D
S
S
S
S
D
S
Satisfactory, D
Unsatisfactory.
Difficult, special techniques needed.
7.3. MECHANICAL PROPERTIES
Typical values of the mechanical properties of the more common materials used in the
construction of chemical process equipment are given in Table 7.2.
7.3.1. Tensile strength
The tensile strength (tensile stress) is a measure of the basic strength of a material. It is
the maximum stress that the material will withstand, measured by a standard tensile test.
The older name for this property, which is more descriptive of the property, was Ultimate
Tensile Strength (UTS).
The design stress for a material, the value used in any design calculations, is based on
the tensile strength, or on the yield or proof stress (see Chapter 13).
Proof stress is the stress to cause a specified permanent extension, usually 0.1 per cent.
7.3.2. Stiffness
Stiffness is the ability to resist bending and buckling. It is a function of the elastic modulus of
the material and the shape of the cross-section of the member (the second moment of area).
286
Table 7.2.
CHEMICAL ENGINEERING
Mechanical properties of common metals and alloys (typical values at room temperature)
Mild steel
Low alloy steel
Cast iron
Stainless steel
(18Cr, 8Ni)
Nickel
(>99 per cent Ni)
Monel
Copper
(deoxidised)
Brass
(Admiralty)
Aluminium
(>99 per cent)
Dural
Lead
Titanium
Tensile
strength
(N/mm2 )
0.1 per cent
proof stress
(N/mm2 )
Modulus of
elasticity
(kN/mm2 )
Hardness
Brinell
Specific
gravity
430
420 660
140 170
220
230 460
210
210
140
100 200
130 200
150 250
7.9
7.9
7.2
>540
200
210
160
8.0
500
650
130
170
210
170
80 150
120 250
8.9
8.8
200
60
110
30 100
8.9
400 600
130
115
100 200
8.6
70
70
15
110
30
100
5
150
2.7
2.7
11.3
4.5
80 150
400
30
500
150
350
7.3.3. Toughness
Toughness is associated with tensile strength, and is a measure of the material’s resistance
to crack propagation. The crystal structure of ductile materials, such as steel, aluminium
and copper, is such that they stop the propagation of a crack by local yielding at the crack
tip. In other materials, such as the cast irons and glass, the structure is such that local
yielding does not occur and the materials are brittle. Brittle materials are weak in tension
but strong in compression. Under compression any incipient cracks present are closed up.
Various techniques have been developed to allow the use of brittle materials in situations
where tensile stress would normally occur. For example, the use of prestressed concrete,
and glass-fibre-reinforced plastics in pressure vessels construction.
A detailed discussion of the factors that determine the fracture toughness of materials
can be found in the books by Institute of Metallurgists (1960) and Boyd (1970). Gordon
(1976) gives an elementary, but very readable, account of the strength of materials in
terms of their macroscopic and microscopic structure.
7.3.4. Hardness
The surface hardness, as measured in a standard test, is an indication of a material’s ability
to resist wear. This will be an important property if the equipment is being designed to
handle abrasive solids, or liquids containing suspended solids which are likely to cause
erosion.
7.3.5. Fatigue
Fatigue failure is likely to occur in equipment subject to cyclic loading; for example,
rotating equipment, such as pumps and compressors, and equipment subjected to pressure
cycling. A comprehensive treatment of this subject is given by Harris (1976).
MATERIALS OF CONSTRUCTION
287
7.3.6. Creep
Creep is the gradual extension of a material under a steady tensile stress, over a prolonged
period of time. It is usually only important at high temperatures; for instance, with steam
and gas turbine blades. For a few materials, notably lead, the rate of creep is significant
at moderate temperatures. Lead will creep under its own weight at room temperature and
lead linings must be supported at frequent intervals.
The creep strength of a material is usually reported as the stress to cause rupture in
100,000 hours, at the test temperature.
7.3.7. Effect of temperature on the mechanical properties
The tensile strength and elastic modulus of metals decrease with increasing temperature.
For example, the tensile strength of mild steel (low carbon steel, C < 0.25 per cent)
is 450 N/mm2 at 25Ž C falling to 210 at 500Ž C, and the value of Young’s modulus
200,000 N/mm2 at 25Ž C falling to 150,000 N/mm2 at 500Ž C. If equipment is being
designed to operate at high temperatures, materials that retain their strength must be
selected. The stainless steels are superior in this respect to plain carbon steels.
Creep resistance will be important if the material is subjected to high stresses at elevated
temperatures. Special alloys, such as Inconel (International Nickel Co.), are used for high
temperature equipment such as furnace tubes.
The selection of materials for high-temperature applications is discussed by Day (1979).
At low temperatures, less than 10Ž C, metals that are normally ductile can fail in a
brittle manner. Serious disasters have occurred through the failure of welded carbon steel
vessels at low temperatures. The phenomenon of brittle failure is associated with the
crystalline structure of metals. Metals with a body-centred-cubic (bcc) lattice are more
liable to brittle failure than those with a face-centred-cubic (fcc) or hexagonal lattice. For
low-temperature equipment, such as cryogenic plant and liquefied-gas storages, austenitic
stainless steel (fcc) or aluminium alloys (hex) should be specified; see Wigley (1978).
V-notch impact tests, such as the Charpy test, are used to test the susceptibility of
materials to brittle failure: see Wells (1968) and BS 131.
The brittle fracture of welded structures is a complex phenomenon and is dependent on
plate thickness and the residual stresses present after fabrication; as well as the operating
temperature. A comprehensive discussion of brittle fracture in steel structures is given by
Boyd (1970).
7.4. CORROSION RESISTANCE
The conditions that cause corrosion can arise in a variety of ways. For this brief discussion
on the selection of materials it is convenient to classify corrosion into the following
categories:
1.
2.
3.
4.
General wastage of material uniform corrosion.
Galvanic corrosion dissimilar metals in contact.
Pitting localised attack.
Intergranular corrosion.
288
5.
6.
7.
8.
9.
CHEMICAL ENGINEERING
Stress corrosion.
Erosion corrosion.
Corrosion fatigue.
High temperature oxidation.
Hydrogen embrittlement.
Metallic corrosion is essentially an electrochemical process. Four components are
necessary to set up an electrochemical cell:
1.
2.
3.
4.
Anode the corroding electrode.
Cathode the passive, non-corroding electrode.
The conducting medium the electrolyte the corroding fluid.
Completion of the electrical circuit through the material.
Cathodic areas can arise in many ways:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
Dissimilar metals.
Corrosion products.
Inclusions in the metal, such as slag.
Less well-aerated areas.
Areas of differential concentration.
Differentially strained areas.
7.4.1. Uniform corrosion
This term describes the more or less uniform wastage of material by corrosion, with no
pitting or other forms of local attack. If the corrosion of a material can be considered
to be uniform the life of the material in service can be predicted from experimentally
determined corrosion rates.
Corrosion rates are usually expressed as a penetration rate in inches per year, or mills
per year (mpy) (where a mill D 103 inches). They are also expressed as a weight loss
in milligrams per square decimetre per day (mdd). In corrosion testing, the corrosion rate
is measured by the reduction in weight of a specimen of known area over a fixed period
of time.
12w
ipy D
⊲7.1⊳
tA
where w
t
A
D
D
D
D
mass loss in time t, lb,
time, years,
surface area, ft2 ,
density of material, lb/ft3 ,
as most of the published data on corrosion rates are in imperial units.
In SI units 1 ipy D 25 mm per year.
When judging corrosion rates expressed in mdd it must be remembered that the
penetration rate depends on the density of the material. For ferrous metals 100 mdd
D 0.02 ipy.
What can be considered as an acceptable rate of attack will depend on the cost of the
material; the duty, particularly as regards to safety; and the economic life of the plant. For
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MATERIALS OF CONSTRUCTION
the more commonly used inexpensive materials, such as the carbon and low alloy steels,
a guide to what is considered acceptable is given in Table 7.3. For the more expensive
alloys, such as the high alloy steels, the brasses and aluminium, the figures given in
Table 7.3 should be divided by 2.
Table 7.3.
Acceptable corrosion rates
Corrosion rate
Completely satisfactory
Use with caution
Use only for short exposures
Completely unsatisfactory
ipy
mm/y
<0.01
<0.03
<0.06
>0.06
0.25
0.75
1.5
1.5
The corrosion rate will be dependent on the temperature and concentration of the
corrosive fluid. An increase in temperature usually results in an increased rate of corrosion;
though not always. The rate will depend on other factors that are affected by temperature,
such as oxygen solubility.
The effect of concentration can also be complex. For example, the corrosion of mild
steel in sulphuric acid, where the rate is unacceptably high in dilute acid and at concentrations above 70 per cent, but is acceptable at intermediate concentrations.
7.4.2. Galvanic corrosion
If dissimilar metals are placed in contact, in an electrolyte, the corrosion rate of the anodic
metal will be increased, as the metal lower in the electrochemical series will readily act as
a cathode. The galvanic series in sea water for some of the more commonly used metals is
shown in Table 7.4. Some metals under certain conditions form a natural protective film;
for example, stainless steel in oxidising environments. This state is denoted by “passive”
in the series shown in Table 7.4; active indicates the absence of the protective film. Minor
Table 7.4.
Noble end
(protected end)
Galvanic series in sea water
18/8 stainless steel (passive)
Monel
Inconel (passive)
Nickel (passive)
Copper
Aluminium bronze (Cu 92 per cent, Al 8 per cent)
Admiralty brass (Cu 71 per cent, Zn 28 per cent, Sn 1 per cent)
Nickel (active)
Inconel (active)
Lead
18/8 stainless steel (active)
Cast iron
Mild steel
Aluminium
Galvanised steel
Zinc
Magnesium
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CHEMICAL ENGINEERING
shifts in position in the series can be expected in other electrolytes, but the series for sea
water is a good indication of the combinations of metals to be avoided. If metals which are
widely separated in the galvanic series have to be used together, they should be insulated
from each other, breaking the conducting circuit. Alternatively, if sacrificial loss of the
anodic material can be accepted, the thickness of this material can be increased to allow
for the increased rate of corrosion. The corrosion rate will depend on the relative areas
of the anodic and cathodic metals. A high cathode to anode area should be avoided.
Sacrificial anodes are used to protect underground steel pipes.
7.4.3. Pitting
Pitting is the term given to very localised corrosion that forms pits in the metal surface.
If a material is liable to pitting penetration can occur prematurely and corrosion rate data
are not a reliable guide to the equipment life.
Pitting can be caused by a variety of circumstances; any situation that causes a localised
increase in corrosion rate may result in the formation of a pit. In an aerated medium the
oxygen concentration will be lower at the bottom of a pit, and the bottom will be anodic
to the surrounding metal, causing increased corrosion and deepening of the pit. A good
surface finish will reduce this type of attack. Pitting can also occur if the composition
of the metal is not uniform; for example, the presence of slag inclusions in welds. The
impingement of bubbles can also cause pitting, the effect of cavitation in pumps, which
is an example of erosion-corrosion.
7.4.4. Intergranular corrosion
Intergranular corrosion is the preferential corrosion of material at the grain (crystal) boundaries. Though the loss of material will be small, intergranular corrosion can cause the
catastrophic failure of equipment. Intergranular corrosion is a common form of attack
on alloys but occurs rarely with pure metals. The attack is usually caused by a differential couple being set up between impurities existing at the grain boundary. Impurities
will tend to accumulate at the grain boundaries after heat treatment. The classic example
of intergranular corrosion in chemical plant is the weld decay of unestablished stainless
steel. This is caused by the precipitation of chromium carbides at the grain boundaries in
a zone adjacent to the weld, where the temperature has been between 500 800Ž C during
welding. Weld decay can be avoided by annealing after welding, if practical; or by using
low carbon grades (<0.3 per cent C); or grades stabilised by the addition of titanium or
niobium.
7.4.5. Effect of stress
Corrosion rate and the form of attack can be changed if the material is under stress.
Generally, the rate of attack will not change significantly within normal design stress
values. However, for some combinations of metal, corrosive media and temperature, the
phenomenon called stress cracking can occur. This is the general name given to a form
MATERIALS OF CONSTRUCTION
291
of attack in which cracks are produced that grow rapidly, and can cause premature, brittle
failure, of the metal. The conditions necessary for stress corrosion cracking to occur are:
1. Simultaneous stress and corrosion.
2. A specific corrosive substance; in particular the presence of Cl , OH , NO
3 , or
ions.
NHC
4
Mild stress can cause cracking; the residual stresses from fabrication and welding are
sufficient.
For a general discussion of the mechanism of stress corrosion cracking see
Fontana (1986).
Some classic examples of stress corrosion cracking are:
The season cracking of brass cartridge cases.
Caustic embrittlement of steel boilers.
The stress corrosion cracking of stainless steels in the presence of chloride ions.
Stress corrosion cracking can be avoided by selecting materials that are not susceptible
in the specific corrosion environment; or, less certainly, by stress relieving by annealing
after fabrication and welding.
Comprehensive tables of materials susceptible to stress corrosion cracking in specific
chemicals are given by Moore (1979). Moore’s tables are taken from the corrosion data
survey published by NACE (1974).
The term corrosion fatigue is used to describe the premature failure of materials
in corrosive environments caused by cyclic stresses. Even mildly corrosive conditions
can markedly reduce the fatigue life of a component. Unlike stress corrosion cracking,
corrosion fatigue can occur in any corrosive environment and does not depend on a
specific combination of corrosive substance and metal. Materials with a high resistance
to corrosion must be specified for critical components subjected to cyclic stresses.
7.4.6. Erosion-corrosion
The term erosion-corrosion is used to describe the increased rate of attack caused by
a combination of erosion and corrosion. If a fluid stream contains suspended particles,
or where there is high velocity or turbulence, erosion will tend to remove the products
of corrosion and any protective film, and the rate of attack will be markedly increased.
If erosion is likely to occur, more resistant materials must be specified, or the material
surface protected in some way. For example, plastics inserts are used to prevent erosioncorrosion at the inlet to heat-exchanger tubes.
7.4.7. High-temperature oxidation
Corrosion is normally associated with aqueous solutions but oxidation can occur in dry
conditions. Carbon and low alloy steels will oxidise rapidly at high temperatures and their
use is limited to temperatures below 500Ž C.
Chromium is the most effective alloying element to give resistance to oxidation, forming
a tenacious oxide film. Chromium alloys should be specified for equipment subject to
temperatures above 500Ž C in oxidising atmospheres.
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CHEMICAL ENGINEERING
7.4.8. Hydrogen embrittlement
Hydrogen embrittlement is the name given to the loss of ductility caused by the absorption
(and reaction) of hydrogen in a metal. It is of particular importance when specifying steels
for use in hydrogen reforming plant. Alloy steels have a greater resistance to hydrogen
embrittlement than the plain carbon steels. A chart showing the suitability of various
alloy steels for use in hydrogen atmospheres, as a function of hydrogen partial pressure
and temperature, is given in the NACE (1974) corrosion data survey. Below 500Ž C plain
carbon steel can be used.
7.5. SELECTION FOR CORROSION RESISTANCE
In order to select the correct material of construction, the process environment to which
the material will be exposed must be clearly defined. Additional to the main corrosive
chemicals present, the following factors must be considered:
1.
2.
3.
4.
5.
6.
7.
Temperature affects corrosion rate and mechanical properties.
Pressure.
pH.
Presence of trace impurities stress corrosion.
The amount of aeration differential oxidation cells.
Stream velocity and agitation erosion-corrosion.
Heat-transfer rates differential temperatures.
The conditions that may arise during abnormal operation, such as at start-up and shutdown,
must be considered, in addition to normal, steady state, operation.
Corrosion charts
The resistance of some commonly used materials to a range of chemicals is shown in
Appendix C. More comprehensive corrosion data, covering most of the materials used
in the construction of process plant, in a wide range of corrosive media, are given by,
Rabald (1968), NACE (1974), Hamner (1974), Perry et al. (1997) and Schweitzer (1976)
(1989) (1998).
The twelve volume Dechema Corrosion Handbook is an extensive guide to the interaction of corrosive media with materials, Dechema (1987).
These corrosion guides can be used for the preliminary screening of materials that are
likely to be suitable, but the fact that published data indicate that a material is suitable
cannot be taken as a guarantee that it will be suitable for the process environment being
considered. Slight changes in the process conditions, or the presence of unsuspected
trace impurities, can markedly change the rate of attack or the nature of the corrosion.
The guides will, however, show clearly those materials that are manifestly unsuitable.
Judgement, based on experience with the materials in similar processes environments,
must be used when assessing published corrosion data.
Pilot plant tests, and laboratory corrosion tests under simulated plant conditions, will
help in the selection of suitable materials if actual plant experience is not available. Care
is needed in the interpretation of laboratory tests.
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MATERIALS OF CONSTRUCTION
The advice of the technical service department of the company supplying the materials
should also be sought.
7.6. MATERIAL COSTS
An indication of the cost of some commonly used metals is given in Table 7.5. The
actual cost of metals and alloys will fluctuate quite widely, depending on movements in
the world metal exchanges.
Table 7.5.
Basic cost of metals (mid-2004)
Metal
£/tonne
Carbon steel
Low alloy steel (Cr-Mo)
Austenitic stainless steel
304
316
Copper
Aluminium
Aluminium alloy
Nickel
Monel
Titanium
300
400 500
500
700 850
1400
1900
1500
900
850
6400
5000
20,000
2400
3200
2500
1500
1400
11,000
8500
34,000
US$/US ton
The quantity of a material used will depend on the material density and strength (design
stress) and these must be taken into account when comparing material costs. Moore (1970)
compares costs by calculating a cost rating factor defined by the equation:
Cost rating D
Cð
d
⊲7.2⊳
where C D cost per unit mass, £/kg,
D density, kg/m3 ,
d D design stress, N/mm2 .
His calculated cost ratings, relative to the rating for mild steel (low carbon), are shown in
Table 7.6. Materials with a relatively high design stress, such as stainless and low alloy
steels, can be used more efficiently than carbon steel.
The relative cost of equipment made from different materials will depend on the cost of
fabrication, as well as the basic cost of the material. Unless a particular material requires
special fabrication techniques, the relative cost of the finished equipment will be lower
than the relative bare material cost. For example; the purchased cost of a stainless-steel
storage tank will be 2 to 3 times the cost of the same tank in carbon steel, whereas the
relative cost of the metals is between 5 to 8.
If the corrosion rate is uniform, then the optimum material can be selected by calculating
the annual costs for the possible candidate materials. The annual cost will depend on the
predicted life, calculated from the corrosion rate, and the purchased cost of the equipment.
In a given situation, it may prove more economic to install a cheaper material with
a high corrosion rate and replace it frequently; rather than select a more resistant but
more expensive material. This strategy would only be considered for relatively simple
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CHEMICAL ENGINEERING
Table 7.6.
Relative cost ratings for metals
Design stress
(N/mm2 )
Carbon steel
Al-alloys (Mg)
Stainless steel 18/8 (Ti)
Inconel
Brass
Al-bronzes
Aluminium
Monel
Copper
Nickel
1
4
5
12
10 15
16
18
19
27
35
100
70
130
140
76
87
14
120
46
70
Note: the design stress figures are shown for the purposes
of illustration only and should not be used as design
values.
equipment with low fabrication costs, and where premature failure would not cause a
serious hazard. For example, carbon steel could be specified for an aqueous effluent
line in place of stainless steel, accepting the probable need for replacement. The pipe
wall thickness would be monitored in situ frequently to determine when replacement
was needed.
The more expensive, corrosion-resistant, alloys are frequently used as a cladding on
carbon steel. If a thick plate is needed for structural strength, as for pressure vessels, the
use of clad materials can substantially reduce the cost.
7.7. CONTAMINATION
With some processes, the prevention of the contamination of a process stream, or a
product, by certain metals, or the products of corrosion, overrides any other considerations
when selecting suitable materials. For instance, in textile processes, stainless steel or
aluminium is often used in preference to carbon steel, which would be quite suitable
except that any slight rusting will mark the textiles (iron staining).
With processes that use catalysts, care must be taken to select materials that will not
cause contamination and poisoning of the catalyst.
Some other examples that illustrate the need to consider the effect of contamination by
trace quantities of other materials are:
1. For equipment handling acetylene the pure metals, or alloys containing copper,
silver, mercury, gold, must be avoided to prevent the formation of explosive
acetylides.
2. The presence of trace quantities of mercury in a process stream can cause the catastrophic failure of brass heat-exchanger tubes, from the formation of a mercury-copper
amalgam. Incidents have occurred where the contamination has come from unsuspected sources, such as the failure of mercury-in-steel thermometers.
3. In the Flixborough disaster (see Chapter 9), there was evidence that the stress
corrosion cracking of a stainless-steel pipe had been caused by zinc contamination
from galvanised-wire supporting lagging.
MATERIALS OF CONSTRUCTION
295
7.7.1. Surface finish
In industries such as the food, pharmaceutical, biochemical, and textile industries, the
surface finish of the material is as important as the choice of material, to avoid contamination.
Stainless steel is widely used, and the surfaces, inside and out, are given a high finish by
abrasive blasting and mechanical polishing. This is done for the purposes of hygiene; to
prevent material adhering to the surface; and to aid cleaning and sterilisation. The surface
finishes required in food processing are discussed by Timperley (1984) and Jowitt (1980).
A good surface finish is important in textile fibre processing to prevent the fibres
snagging.
7.8. COMMONLY USED MATERIALS OF CONSTRUCTION
The general mechanical properties, corrosion resistance, and typical areas of use of some
of the materials commonly used in the construction of chemical plant are given in this
section. The values given are for a typical, representative, grade of the material or alloy.
The multitude of alloys used in chemical plant construction is known by a variety of
trade names, and code numbers designated in the various national standards. With the
exception of the stainless steels, no attempt has been made in this book to classify the
alloys discussed by using one or other of the national standards; the commonly used,
generic, names for the alloys have been used. For the full details of the properties and
compositions of the grades available in a particular class of alloy, and the designated
code numbers, reference should be made to the appropriate national code, to the various
handbooks, or to manufacturers’ literature. For the United Kingdom standards, the British
Standards Institute Catalogue should be consulted.
The US trade names and codes are given by Perry et al. (1997). A comprehensive
review of the engineering materials used for chemical and process plant can be found in
the book by Evans (1974).
7.8.1. Iron and steel
Low carbon steel (mild steel) is the most commonly used engineering material. It is cheap;
is available in a wide range of standard forms and sizes; and can be easily worked and
welded. It has good tensile strength and ductility.
The carbon steels and iron are not resistant to corrosion, except in certain specific
environments, such as concentrated sulphuric acid and the caustic alkalies. They are
suitable for use with most organic solvents, except chlorinated solvents; but traces of
corrosion products may cause discoloration.
Mild steel is susceptible to stress-corrosion cracking in certain environments.
The corrosion resistance of the low alloy steels (less than 5 per cent of alloying
elements), where the alloying elements are added to improve the mechanical strength
and not for corrosion resistance, is not significantly different from that of the plain
carbon steels.
A comprehensive reference covering the properties and application of steels, including
the stainless steels, is the book by Llewellyn (1992). The use of carbon steel in the
construction of chemical plant is discussed by Clark (1970).
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The high silicon irons (14 to 15 per cent Si) have a high resistance to mineral acids,
except hydrofluoric acid. They are particularly suitable for use with sulphuric acid at all
concentrations and temperatures. They are, however, very brittle.
7.8.2. Stainless steel
The stainless steels are the most frequently used corrosion resistant materials in the
chemical industry.
To impart corrosion resistance the chromium content must be above 12 per cent,
and the higher the chromium content, the more resistant is the alloy to corrosion in
oxidising conditions. Nickel is added to improve the corrosion resistance in non-oxidising
environments.
Types
A wide range of stainless steels is available, with compositions tailored to give the
properties required for specific applications. They can be divided into three broad classes
according to their microstructure:
1. Ferritic: 13 20 per cent Cr, < 0.1 per cent C, with no nickel
2. Austenitic: 18 20 per cent Cr, > 7 per cent Ni
3. Martensitic: 12 10 per cent Cr, 0.2 to 0.4 per cent C, up to 2 per cent Ni
The uniform structure of Austenite (fcc, with the carbides in solution) is the structure
desired for corrosion resistance, and it is these grades that are widely used in the chemical
industry. The composition of the main grades of austenitic steels, and the US, and equivalent UK designations are shown in Table 7.7. Their properties are discussed below.
Type 304 (the so-called 18/8 stainless steels): the most generally used stainless steel.
It contains the minimum Cr and Ni that give a stable austenitic structure. The carbon
content is low enough for heat treatment not to be normally needed with thin sections to
prevent weld decay (see Section 7.4.4).
Type 304L: low carbon version of type 304 ⊲< 0.03 per cent C) used for thicker welded
sections, where carbide precipitation would occur with type 304.
Type 321: a stabilised version of 304, stabilised with titanium to prevent carbide precipitation during welding. It has a slightly higher strength than 304L, and is more suitable
for high-temperature use.
Type 347: stabilised with niobium.
Type 316: in this alloy, molybdenum is added to improve the corrosion resistance
in reducing conditions, such as in dilute sulphuric acid, and, in particular, to solutions
containing chlorides.
Type 316L: a low carbon version of type 316, which should be specified if welding or
heat treatment is liable to cause carbide precipitation in type 316.
Types 309/310: alloys with a high chromium content, to give greater resistance to
oxidation at high temperatures. Alloys with greater than 25 per cent Cr are susceptible to
embrittlement due to sigma phase formation at temperatures above 500Ž C. Sigma phase is
an intermetallic compound, FeCr. The formation of the sigma phase in austenitic stainless
steels is discussed by Hills and Harries (1960).
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MATERIALS OF CONSTRUCTION
Table 7.7.
Commonly used grades of austenitic stainless steel
Specification no.
Composition per cent
BS 1501
AISI
C
max
801B
304
0.08
810 C
304 ELC
0.03
801 Ti
321
801 Nb
347
Mn
max
Cr
range
Ni
range
2.00
17.5
20.0
8.0
11.0
1.00
2.00
17.5
20.0
10 min
0.12
1.00
2.00
17.0
20.0
7.5 min
0.08
1.00
2.00
17.0
20.0
9 min
0.12
1.00
2.00
17.0
20.0
25 min
0.08
1.00
2.00
16.5
18.5
10 min
2.25
3.00
845 Ti
0.08
0.06
2.00
16.5
18.5
10 min
2.25
3.00
846
0.08
1.00
2.00
18.0
20.0
11.0
14.0
3.0
4.0
821 Ti
845 B
316
Si
max
Mo
range
Ti
Nb
4ðC
10 ð C
4ðC
4ðC
S and P 0.045 per cent all grades.
AISI American Iron and Steel Institute.
Table 7.8.
Comparative strength of stainless steel
Temperature ° C
Typical design
stress N/mm2
300
400
500
mild steel
77
62
31
stainless
18/8
108
100
92
600
62
Mechanical properties
The austenitic stainless steels have greater strength than the plain carbon steels, particularly at elevated temperatures (see Table 7.8).
As was mentioned in Section 7.3.7, the austenitic stainless steels, unlike the plain
carbon steels, do not become brittle at low temperatures. It should be noted that the
thermal conductivity of stainless steel is significantly lower than that of mild steel.
Typical at 100Ž C values are, type 304 (18/8) 16 W/mŽ C
mild steel
60 W/mŽ C
Austenitic stainless steels are non-magnetic in the annealed condition.
General corrosion resistance
The higher the alloying content, the better the corrosion resistance over a wide range of
conditions, strongly oxidising to reducing, but the higher the cost. A ranking in order of
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increasing corrosion resistance, taking type 304 as 1, is given below:
304
1.0
304L
1.1
321
1.1
316
1.25
316L
1.3
310
1.6
Intergranular corrosion (weld decay) and stress corrosion cracking are problems
associated with the use of stainless steels, and must be considered when selecting types
suitable for use in a particular environment. Stress corrosion cracking in stainless steels
can be caused by a few ppm of chloride ions (see Section 7.4.5).
In general, stainless steels are used for corrosion resistance when oxidising conditions
exist. Special types, or other high nickel alloys, should be specified if reducing conditions
are likely to occur. The properties, corrosion resistance, and uses of the various grades
of stainless steel are discussed fully by Peckner and Bernstein (1977). A comprehensive
discussion of the corrosion resistance of stainless steels is given in Sedriks (1979).
Stress corrosion cracking in stainless steels is discussed by Turner (1989).
High alloy content stainless steels
Super austenitic, high nickel, stainless steels, containing between 29 to 30 per cent
nickel and 20 per cent chromium, have a good resistance to acids and acid chlorides.
They are more expensive than the lower alloy content, 300 series, of austenitic stainless
steels.
Duplex, and super-duplex stainless steels, contain high percentages of chromium. They
are called duplex because their structure is a mixture of the austenitic and ferritic phases.
They have a better corrosion resistance than the austenitic stainless steels and are less
susceptible to stress corrosion cracking. The chromium content of duplex stainless steels is
around 20 per cent, and around 25 per cent in the super-duplex grades. The super-duplex
steels where developed for use in aggressive off-shore environments.
The duplex range of stainless steels can be readily cast, wrought and machined.
Problems can occur in welding, due to the need to keep the correct balance of ferrite and
austenite in the weld area, but this can be overcome using the correct welding materials
and procedures.
The cost of the duplex grades is comparable with the 316 steels. Super-duplex is around
fifty per cent higher than the cost of duplex.
The selection and properties of duplex stainless steels are discussed by Bendall and
Guha (1990), and Warde (1991).
7.8.3. Nickel
Nickel has good mechanical properties and is easily worked. The pure metal (>99 per
cent) is not generally used for chemical plant, its alloys being preferred for most applications. The main use is for equipment handling caustic alkalies at temperatures above
that at which carbon steel could be used; above 70Ž C. Nickel is not subject to corrosion
cracking like stainless steel.
MATERIALS OF CONSTRUCTION
299
7.8.4. Monel
Monel, the classic nickel-copper alloy with the metals in the ratio 2 : 1, is probably, after
the stainless steels, the most commonly used alloy for chemical plant. It is easily worked
and has good mechanical properties up to 500Ž C. It is more expensive than stainless
steel but is not susceptible to stress-corrosion cracking in chloride solutions. Monel has
good resistance to dilute mineral acids and can be used in reducing conditions, where
the stainless steels would be unsuitable. It may be used for equipment handling, alkalies,
organic acids and salts, and sea water.
7.8.5. Inconel
Inconel (typically 76 per cent Ni, 7 per cent Fe, 15 per cent Cr) is used primarily for
acid resistance at high temperatures. It maintains its strength at elevated temperature and
is resistant to furnace gases, if sulphur free.
7.8.6. The Hastelloys
The trade name Hastelloy covers a range of nickel, chromium, molybdenum, iron alloys
that were developed for corrosion resistance to strong mineral acids, particularly HCl.
The corrosion resistance, and use, of the two main grades, Hastelloy B (65 per cent Ni,
28 per cent Mo, 6 per cent Fe) and Hastelloy C (54 per cent Ni, 17 per cent Mo, 15 per
cent Cr, 5 per cent Fe), are discussed in papers by Weisert (1952a,b).
7.8.7. Copper and copper alloys
Pure copper is not widely used for chemical equipment. It has been used traditionally in
the food industry, particularly in brewing. Copper is a relatively soft, very easily worked
metal, and is used extensively for small-bore pipes and tubes.
The main alloys of copper are the brasses, alloyed with zinc, and the bronzes, alloyed
with tin. Other, so-called bronzes are the aluminium bronzes and the silicon bronzes.
Copper is attacked by mineral acids, except cold, dilute, unaerated sulphuric acid. It is
resistant to caustic alkalies, except ammonia, and to many organic acids and salts. The
brasses and bronzes have a similar corrosion resistance to the pure metal. Their main use
in the chemical industry is for valves and other small fittings, and for heat-exchanger tubes
and tube sheets. If brass is used, a grade must be selected that is resistant to dezincification.
The cupro-nickel alloys (70 per cent Cu) have a good resistance to corrosion-erosion
and are used for heat-exchanger tubes, particularly where sea water is used as a coolant.
7.8.8. Aluminium and its alloys
Pure aluminium lacks mechanical strength but has higher resistance to corrosion than its
alloys. The main structural alloys used are the Duralumin (Dural) range of aluminium-copper
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CHEMICAL ENGINEERING
alloys (typical composition 4 per cent Cu, with 0.5 per cent Mg) which have a tensile strength
equivalent to that of mild steel. The pure metal can be used as a cladding on Dural plates,
to combine the corrosion resistance of the pure metal with the strength of the alloy. The
corrosion resistance of aluminium is due to the formation of a thin oxide film (as with
the stainless steels). It is therefore most suitable for use in strong oxidising conditions. It
is attacked by mineral acids, and by alkalies; but is suitable for concentrated nitric acid,
greater than 80 per cent. It is widely used in the textile and food industries, where the use
of mild steel would cause contamination. It is also used for the storage and distribution of
demineralised water.
7.8.9. Lead
Lead was one of the traditional materials of construction for chemical plant but has now,
due to its price, been largely replaced by other materials, particularly plastics. It is a soft,
ductile material, and is mainly used in the form of sheets (as linings) or pipe. It has a
good resistance to acids, particularly sulphuric.
7.8.10. Titanium
Titanium is now used quite widely in the chemical industry, mainly for its resistance
to chloride solutions, including sea water and wet chlorine. It is rapidly attacked by
dry chlorine, but the presence of as low a concentration of moisture as 0.01 per cent
will prevent attack. Like the stainless steels, titanium depends for its resistance on the
formation of an oxide film.
Alloying with palladium (0.15 per cent) significantly improves the corrosion resistance,
particularly to HCl. Titanium is being increasingly used for heat exchangers, for both shell
and tube, and plate exchangers; replacing cupro-nickel for use with sea water.
The use of titanium for corrosion resistance is discussed by Deily (1997).
7.8.11. Tantalum
The corrosion resistance of tantalum is similar to that of glass, and it has been called
a metallic glass. It is expensive, about five times that of stainless steel, and is used for
special applications, where glass or a glass lining would not be suitable. Tantalum plugs
are used to repair glass-lined equipment.
The use of tantalum as a material of construction in the chemical industry is discussed
by Fensom and Clark (1984) and Rowe (1994) (1999).
7.8.12. Zirconium
Zirconium and zirconium alloys are used in the nuclear industry, because of their low
neutron absorption cross-section and resistance to hot water at high pressures.
In the chemical industry zirconium is finding use where resistance to hot and
boiling acids is required: nitric, sulphuric, and particularly hydrochloric. Its resistance
is equivalent to that of tantalum but zirconium is less expensive, similar in price to high
nickel steel. Rowe (1999) gives a brief review of the properties and use of zirconium for
chemical plant.
MATERIALS OF CONSTRUCTION
301
7.8.13. Silver
Silver linings are used for vessels and equipment handling hydrofluoric acid. It is also
used for special applications in the food and pharmaceutical industries where it is vital
to avoid contamination of the product.
7.8.14. Gold
Because of its high cost gold is rarely used as a material of construction. It is highly
resistant to attack by dilute nitric acid and hot concentrated sulphuric acid, but is dissolved
by aqua regia (a mixture of concentrated nitric and sulphuric acids). It is attacked by
chlorine and bromine, and forms an amalgam with mercury.
It has been used as thin plating on condenser tubes and other surfaces.
7.8.15. Platinum
Platinum has a high resistance to oxidation at high temperature. One of its main uses has
been, in the form of an alloy with copper, in the manufacture of the spinnerets used in
synthetic textile spinning processes.
7.9. PLASTICS AS MATERIALS OF CONSTRUCTION
FOR CHEMICAL PLANT
Plastics are being increasingly used as corrosion-resistant materials for chemical plant
construction. They can be divided into two broad classes:
1. Thermoplastic materials, which soften with increasing temperature; for example,
polyvinyl chloride (PVC) and polyethylene.
2. Thermosetting materials, which have a rigid, cross-linked structure; for example, the
polyester and epoxy resins.
Details of the chemical composition and properties of the wide range of plastics used as
engineering material can be found in the books by Butt and Wright (1980) and Evans (1974).
The biggest use of plastics is for piping; sheets are also used for lining vessels and for
fabricated ducting and fan casings. Mouldings are used for small items; such as, pump
impellers, valve parts and pipe fittings.
The mechanical strength and operating temperature of plastics are low compared with that
of metals. The mechanical strength, and other properties, can be modified by the addition of
fillers and plasticisers. When reinforced with glass or carbon fibres thermosetting plastics
can have a strength equivalent to mild steel, and are used for pressure vessels and pressure
piping. Unlike metals, plastics are flammable. Plastics can be considered to complement
metals as corrosion-resistant materials of construction. They generally have good resistance
to dilute acids and inorganic salts, but suffer degradation in organic solvents that would not
attack metals. Unlike metals, plastics can absorb solvents, causing swelling and softening.
The properties and typical areas of use of the main plastics used for chemical plant are
reviewed briefly in the following sections. A comprehensive discussion of the use of plastics
as corrosion-resistant materials is given in a book by Fontana (1986). The mechanical
properties and relative cost of plastics are given in Table 7.9.
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CHEMICAL ENGINEERING
Table 7.9.
Material
PVC
Polyethylene
(low density)
Polypropylene
PTFE
GRP polyester
GRP epoxy
Mechanical properties and relative cost of polymers
Tensile
strength
(N/mm2 )
Elastic
modulus
(kN/mm2 )
Density
(kg/m3 )
Relative
cost
55
3.5
1400
1.5
12
35
21
100
250
0.2
1.5
1.0
7.0
14.0
900
900
2100
1500
1800
1.0
1.5
30.0
3.0
5.0
Approximate cost relative to polyethylene, volumetric basis.
7.9.1. Poly-vinyl chloride (PVC)
PVC is probably the most commonly used thermoplastic material in the chemical industry.
Of the available grades, rigid (unplasticised) PVC is the most widely used. It is resistant to
most inorganic acids, except strong sulphuric and nitric, and inorganic salt solutions. It is
unsuitable, due to swelling, for use with most organic solvents. The maximum operating
temperature for PVC is low, 60 Ž C. The use of PVC as a material of construction in
chemical engineering is discussed in a series of articles by Mottram and Lever (1957).
7.9.2. Polyolefines
Low-density polyethylene (polythene) is a relatively cheap, tough, flexible plastic. It has
a low softening point and is not suitable for use above about 60Ž C. The higher density
polymer (950 kg/m3 ) is stiffer, and can be used at higher temperatures. Polypropylene is
a stronger material than the polyethylenes and can be used at temperatures up to 120Ž C.
The chemical resistance of the polyolefines is similar to that of PVC.
7.9.3. Polytetrafluroethylene (PTFE)
PTFE, known under the trade names Teflon and Fluon, is resistant to all chemicals, except
molten alkalies and fluorine, and can be used at temperatures up to 250Ž C. It is a relatively
weak material, but its mechanical strength can be improved by the addition of fillers (glass
and carbon fibres). It is expensive and difficult to fabricate. PTFE is used extensively for
gaskets and gland packings. As a coating, it is used to confer non-stick properties to
surfaces, such as filter plates. It can also be used as a liner for vessels.
7.9.4. Polyvinylidene fluoride (PVDF)
PVDF has properties similar to PTFE but is easier to fabricate. It has good resistance to
inorganic acids and alkalis, and organic solvents. It is limited to a maximum operating
temperature of 140Ž C.
7.9.5. Glass-fibre reinforced plastics (GRP)
The polyester resins, reinforced with glass fibre, are the most common thermosetting
plastics used for chemical plant. Complex shapes can be easily formed using the techniques
developed for working with reinforced plastics. Glass-reinforced plastics are relatively
MATERIALS OF CONSTRUCTION
303
strong and have a good resistance to a wide range of chemicals. The mechanical strength
depends on the resin used; the form of the reinforcement (chopped mat or cloth); and the
ratio of resin to glass.
By using special techniques, in which the reinforcing glass fibres are wound on in the
form of a continuous filament, high strength can be obtained, and this method is used to
produce pressure vessels.
The polyester resins are resistant to dilute mineral acids, inorganic salts and many
solvents. They are less resistant to alkalies.
Glass-fibre-reinforced epoxy resins are also used for chemical plant but are more
expensive than the polyester resins. In general they are resistant to the same range of
chemicals as the polyesters, but are more resistant to alkalies.
The chemical resistance of GRP is dependent on the amount of glass reinforcement
used. High ratios of glass to resin give higher mechanical strength but generally lower
resistance to some chemicals. The design of chemical plant equipment in GRP is the
subject of a book by Malleson (1969); see also Shaddock (1971) and Baines (1984).
7.9.6. Rubber
Rubber, particularly in the form of linings for tanks and pipes, has been extensively used
in the chemical industry for many years. Natural rubber is most commonly used, because
of its good resistance to acids (except concentrated nitric) and alkalies. It is unsuitable
for use with most organic solvents.
Synthetic rubbers are also used for particular applications. Hypalon (trademark, E. I. du
Pont de Nemours) has a good resistance to strongly oxidising chemicals and can be used
with nitric acid. It is unsuitable for use with chlorinated solvents. Viton (trademark,
E. I. du Pont de Nemours) has a better resistance to solvents, including chlorinated
solvents, than other rubbers. Both Hypalon and Viton are expensive, compared with other
synthetic, and natural, rubbers.
The use of natural rubber lining is discussed by Saxman (1965), and the chemical
resistance of synthetic rubbers by Evans (1963).
Butt and Wright (1984) give an authoritative account of the application and uses of
rubber and plastics linings and coatings.
7.10. CERAMIC MATERIALS (SILICATE MATERIALS)
Ceramics are compounds of non-metallic elements and include the following materials
used for chemical plant:
Glass, the borosilicate glasses (hard glass).
Stoneware.
Acid-resistant bricks and tiles.
Refractory materials.
Cements and concrete.
Ceramic materials have a cross-linked structure and are therefore brittle.
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CHEMICAL ENGINEERING
7.10.1. Glass
Borosilicate glass (known by several trade names, including Pyrex) is used for chemical
plant as it is stronger than the soda glass used for general purposes; it is more resistant
to thermal shock and chemical attack.
Glass equipment is available from several specialist manufacturers. Pipes and fittings
are produced in a range of sizes, up to 0.5 m. Special equipment, such as heat exchangers,
is available and, together with the larger sizes of pipe, is used to construct distillation and
absorption columns. Teflon gaskets are normally used for jointing glass equipment and pipe.
Where failure of the glass could cause injury, pipes and equipment should be protected
by external shielding or wrapping with plastic tape.
Glass linings, also known as glass enamel, have been used on steel and iron vessels
for many years. Borosilicate glass is used, and the thickness of the lining is about 1 mm.
The techniques used for glass lining, and the precautions to be taken in the design and
fabrication of vessels to ensure a satisfactory lining, are discussed by Landels and Stout
(1970). Borosilicate glass is resistant to acids, salts and organic chemicals. It is attacked
by the caustic alkalies and fluorine.
7.10.2. Stoneware
Chemical stoneware is similar to the domestic variety, but of higher quality; stronger and
with a better glaze. It is available in a variety of shapes for pipe runs and columns. As
for glass, it is resistant to most chemicals, except alkalies and fluorine. The composition
and properties of chemical stoneware are discussed by Holdridge (1961). Stoneware and
porcelain shapes are used for packing absorption and distillation columns (see Chapter 11).
7.10.3. Acid-resistant bricks and tiles
High-quality bricks and tiles are used for lining vessels, ditches and to cover floors. The
linings are usually backed with a corrosion-resistant membrane of rubber or plastic, placed
behind the titles, and special acid-resistant cements are used for the joints. Brick and tile
linings are covered in a book by Falcke and Lorentz (1985).
7.10.4. Refractory materials (refractories)
Refractory bricks and cements are needed for equipment operating at high temperatures;
such as, fired heaters, high-temperature reactors and boilers.
The refractory bricks in common use are composed of mixtures of silica (SiO2 ) and
alumina (Al2 O3 ). The quality of the bricks is largely determined by the relative amounts
of these materials and the firing temperature. Mixtures of silica and alumina form a
eutectic (94.5 per cent SiO2 , 1545Ž C) and for a high refractoriness under load (the ability
to resist distortion at high temperature) the composition must be well removed from
the eutectic composition. The highest quality refractory bricks, for use in load-bearing
structures at high temperatures, contain high proportions of silica or alumina. “Silica
bricks”, containing greater than 98 per cent SiO2 , are used for general furnace construction.
High alumina bricks, 60 per cent Al2 O3 , are used for special furnaces where resistance
to attack by alkalies is important; such as lime and cement kilns. Fire bricks, typical
MATERIALS OF CONSTRUCTION
305
composition 50 per cent SiO2 , 40 per cent Al2 O3 , balance CaO and Fe2 O3 , are used for
general furnace construction. Silica can exist in a variety of allotropic forms, and bricks
containing a high proportion of silica undergo reversible expansion when heated up to
working temperature. The higher the silica content the greater the expansion, and this
must be allowed for in furnace design and operation.
Ordinary fire bricks, fire bricks with a high porosity, and special bricks composed of
diatomaceous earths are used for insulating walls.
Full details of the refractory materials used for process and metallurgical furnaces can
be found in the books by Norton (1968) and Lyle (1947).
7.11. CARBON
Impervious carbon, impregnated with chemically resistant resins, is used for specialised
equipment; particularly heat exchangers. It has a high conductivity and a good resistance
to most chemicals, except oxidising acids, of concentrations greater than 30 per cent.
Carbon tubes can be used in conventional shell and tube exchanger arrangements; or
proprietary designs can be used, in which the fluid channels are formed in blocks of
carbon; see Hilland (1960) and Denyer (1991).
7.12. PROTECTIVE COATINGS
A wide range of paints and other organic coatings is used for the protection of mild steel
structures. Paints are used mainly for protection from atmospheric corrosion. Special
chemically resistant paints have been developed for use on chemical process equipment.
Chlorinated rubber paints and epoxy-based paints are used. In the application of paints
and other coatings, good surface preparation is essential to ensure good adhesion of the
paint film or coating.
Brief reviews of the paints used to protect chemical plant are given by Ruff (1984) and
Hullcoop (1984).
7.13. DESIGN FOR CORROSION RESISTANCE
The life of equipment subjected to corrosive environments can be increased by proper
attention to design details. Equipment should be designed to drain freely and completely.
The internal surfaces should be smooth and free from crevasses where corrosion products
and other solids can accumulate. Butt joints should be used in preference to lap joints.
The use of dissimilar metals in contact should be avoided, or care taken to ensure that
they are effectively insulated to avoid galvanic corrosion. Fluid velocities and turbulence
should be high enough to avoid the deposition of solids, but not so high as to cause
erosion-corrosion.
7.14. REFERENCES
BAINES, D. (1984) Chem. Engr., London No. 161 (July) 24. Glass reinforced plastics in the process industries.
BENDALL, K. and GUHA, P. (1990) Process Industry Journal (Mar.) 31. Balancing the cost of corrosion resistance.
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CHEMICAL ENGINEERING
BOYD, G. M. (1970) Brittle Fracture of Steel Structures (Butterworths).
BUTT, L. T. and WRIGHT, D. C. (1980) Use of Polymers in Chemical Plant Construction (Applied Science).
CHAMPION, F. A. (1967) Corrosion Testing Procedures 3rd edn (Chapman Hall).
CLARK, E. E. (1970) Chem. Engr. London No. 242 (Oct.) 312. Carbon Steels for the construction of chemical
and allied plant.
DAY, M. F. (1979) Materials for High Temperature Use, Engineering Design Guide No. 28 (Oxford U.P.).
DECHEMA (1987) Corrosion Handbook (VCH).
DEILY, J. E. (1997) Chem. Eng. Prog. 93 (June) 50. Use titanium to stand up to corrosives.
DENYER, M. (1991) Processing (July) 23. Graphite as a material for heat exchangers.
DILLON, C. P. (1986) Corrosion Control in the Chemical Industry (McGraw-Hill).
EVANS, L. S. (1963) Rubber and Plastics Age 44, 1349. The chemical resistance of rubber and plastics.
EVANS, L. S. (1974) Selecting Engineering Materials for Chemical and Process Plant (Business Books); see
also 2nd edn (Hutchinson, 1980).
EVANS, L. S. (1980) Chemical and Process Plant: a Guide to the Selection of Engineering Materials, 2nd edn
(Hutchinson).
FALCKE, F. K. and LORENTZ, G. (eds) (1985) Handbook of Acid Proof Construction (VCH).
FENSOM, D. H. and CLARK, B. (1984) Chem. Engr., London No. 162 (Aug.) 46. Tantalum: Its uses in the
chemical industry.
FONTANA, M. G. (1986) Corrosion Engineering, 3rd edn (McGraw-Hill).
GORDON, J. E. (1976) The New Science of Strong Materials, 2nd edn (Penguin Books).
HAMNER, N. E. (1974) Corrosion Data Survey, 5th edn (National Association of Corrosion Engineers).
HARRIS, W. J. (1976) The Significance of Fatigue (Oxford U.P.).
HILLAND, A. (1960) Chem. and Proc. Eng. 41, 416. Graphite for heat exchangers.
HILLS, R. F. and HARRIES, D. P. (1960) Chem. and Proc. Eng. 41, 391. Sigma phase in austenitic stainless
steel.
HOLDRIDGE, D. A. (1961) Chem. and Proc. Eng. 42, 405. Ceramics.
HULLCOOP, R. (1984) Processing (April) 13. The great cover up.
INSTITUTE OF METALLURGISTS (1960) Toughness and Brittleness of Metals (Iliffe).
JOWITT, R. (ed.) (1980) Hygienic design and operation of food plant (Ellis Horwood).
LANDELS, H. H. and STOUT, E. (1970) Brit. Chem. Eng. 15, 1289. Glassed steel equipment: a guide to current
technology.
LLEWELLYN, D. T. (1992) Steels: Metallurgy and Applications (Butterworth-Heinemann).
LYLE, O. (1947) Efficient Use of Steam (HMSO).
MALLESON, J. H. (1969) Chemical Plant Design with Reinforced Plastics (McGraw-Hill).
MOORE, D. C. (1970) Chem. Engr. London No. 242 (Oct.) 326. Copper.
MOORE, R. E. (1979) Chem. Eng., NY 86 (July 30th) 91. Selecting materials to resist corrosive conditions.
MOTTRAM, S. and LEVER, D. A. (1957) The Ind. Chem. 33, 62, 123, 177 (in three parts). Unplasticized P.V.C.
as a constructional material in chemical engineering.
NACE (1974) Standard TM-01-69 Laboratory Corrosion Testing of Metals for the Process Industries (National
Association of Corrosion Engineers).
NORTON, F. H. (1968) Refractories, 4th edn (McGraw-Hill).
PECKNER, D. and BERNSTEIN, I. M. (1977) Handbook of Stainless Steels (McGraw-Hill).
PERRY, R. H., GREEN, D. W. and MALONEY, J. O. (1997) Perry’s Chemical Engineers Handbook, 7th edn
(McGraw-Hill).
RABALD, E. (1968) Corrosion Guide, 2nd edn (Elsevier).
REVIE, R. W. (2000) Uhlig’s Corrosion Handbook, 2nd edn (Wiley).
ROSS, T. K. (1977) Metal Corrosion (Oxford U.P.).
ROWE, D. (1994) Process Industry Journal (March) 37. Tempted by tantalum.
ROWE, D. (1999) Chem. Engr., London No. 683 (June 24) 19. Tantalising Materials.
RUFF, C. (1984) Chem. Engr., London No. 409 (Dec.) 27. Paint for Plants.
SAXMAN, T. E. (1965) Materials Protection 4 (Oct.) 43. Natural rubber tank linings.
SCHWEITZER, P. A. (1976) Corrosion Resistance Tables (Dekker).
SCHWEITZER, P. A. (1989) (ed.) Corrosion and Corrosion Protection Handbook, 2nd edn (Marcell Dekker).
SCHWEITZER, P. A. (1998) Encyclopedia of Corrosion Protection (Marcel Dekker).
SEDRIKS, A. J. (1979) Corrosion Resistance of Stainless Steel (Wiley).
SHADDOCK, A. K. (1971) Chem. Eng., NY 78 (Aug. 9th) 116. Designing for reinforced plastics.
TIMPERLEY, D. A. (1984) Inst. Chem. Eng. Sym. Ser. No. 84, 31. Surface finish and spray cleaning of stainless
steel.
TURNER, M. (1989) Chem. Engr., London No. 460 (May) 52. What every chemical engineer should know about
stress corrosion cracking.
WARDE, E. (1991) Chem. Engr., London No. 502 (Aug. 15th) 35. Which super-duplex?
WEISERT, E. D. (1952a) Chem. Eng., NY 59 (June) 267. Hastelloy alloy C.
MATERIALS OF CONSTRUCTION
307
WEISERT, E. D. (1952b) Chem. Eng., NY 59 (July) 314. Hastelloy alloy B.
WELLS, A. A. (1968) British Welding Journal 15, 221. Fracture control of thick steels for pressure vessels.
WIGLEY, D. A. (1978) Materials for Low Temperatures, Engineering Design Guide No. 28 (Oxford U.P.).
Bibliography
Further reading on materials, materials selection and equipment fabrication.
CALLISTER, W. D. Materials Science and Engineering, an Introduction (Wiley, 1991).
CRANE, F. A. A. and CHARLES, J. A. Selection and Use of Engineering Materials, 2nd edn (Butterworths, 1989).
EWALDS, H. L. Fracture Mechanics (Arnold, 1984).
FLINN, R. A. and TROJAN, P. K. Engineering Materials and Their Applications, 4th edn (Houghton Mifflin,
1990).
RAY, M. S. The Technology and Application of Engineering Materials (Prentice Hall, 1987).
ROLFE, S. T. Fracture Mechanics and Fatigue Control in Structures, 2nd edn (Prentice Hall, 1987).
7.15. NOMENCLATURE
Dimensions
in MLT£
A
C
t
w
d
L2
£/M
T
M
ML3
ML1 T2
Area
Cost of material
Time
Mass loss
Density
Design stress
7.16. PROBLEMS
7.1. A pipeline constructed of carbon steel failed after 3 years operation. On examination it was found that the wall thickness had been reduced by corrosion to
about half the original value. The pipeline was constructed of nominal 100 mm
(4 in) schedule 40, pipe, inside diameter 102.3 mm (4.026 in), outside diameter
114.3 mm (4.5 in). Estimate the rate of corrosion in ipy and mm per year.
7.2. The pipeline described in question 7.1 was used to carry wastewater to a hold-up
tank. The effluent is not hazardous. A decision has to be made on what material
to use to replace the pipe. Three suggestion have been made:
1. Replace with the same schedule carbon steel pipe and accept renewal at 3-year
intervals.
2. Replace with a thicker pipe, schedule 80, outside diameter 114.3 mm (4.5 in),
inside diameter 97.2 mm (3.826 in).
3. Use stainless steel pipe, which will not corrode.
The estimated cost of the pipes, per unit length is: schedule 40 carbon steel £3 ($5),
schedule 80 carbon steel £5 ($8.3), stainless steel (304) schedule 40 £15 ($24.8).
Installation and fittings for all the materials adds £10 ($16.5) per unit length.
The downtime required to replace the pipe does not result in a loss of production.
If the expected future life of the plant is 7 years, recommend which pipe to use.
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CHEMICAL ENGINEERING
7.3. Choose a suitable material of construction for the following duties:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
98 per cent w/w sulphuric acid at 70 Ž C.
5 per cent w/w sulphuric acid at 30 Ž C.
30 per cent w/w hydrochloric acid at 50 Ž C.
5 per cent aqueous sodium hydroxide solution at 30 Ž C.
Concentrated aqueous sodium hydroxide solution at 50 Ž C.
5 per cent w/w nitric acid at 30 Ž C.
Boiling concentrated nitric acid.
10 per cent w/w sodium chloride solution.
A 5 per cent w/w solution of cuprous chloride in hydrochloric acid.
10 per cent w/w hydrofluoric acid.
In each case, select the material for a 50 mm pipe operating at approximately 2
bar pressure.
7.4. Suggest suitable materials of construction for the following applications:
A 10,000 m3 storage tank for toluene.
A 5.0 m3 tank for storing a 30% w/w aqueous solution of sodium chloride.
A 2m diameter, 20 m high distillation column, distilling acrylonitrile.
A 100 m3 storage tank for strong nitric acid.
A 500 m3 aqueous waste hold-up tank. The wastewater pH can vary from 1 to
12. The wastewater will also contain traces of organic material.
6. A packed absorption column 0.5 m diameter, 3 m high, absorbing gaseous
hydrochloric acid into water. The column will operate at essentially atmospheric
pressure.
1.
2.
3.
4.
5.
7.5. Aniline is manufactured by the hydrogenation of nitrobenzene in a fluidised bed
reactor. The reactor operates at 250 Ž C and 20 bar. The reactor vessel is approximately 3 m diameter and 9 m high. Suggest suitable materials of construction for
this reactor.
7.6. Methyl ethyl ketone (MEK) is manufactured by the dehydrogenation of 2-butanol
using a shell and tube type reactor. Flue gases are used for heating and pass though
the tubes. The flue gases will contain traces of sulphur dioxide. The reaction
products include hydrogen.
The reaction takes place in the shell at a pressure of 3 bar and temperature of
500 Ž C. Select suitable materials for the tubes and shell.
7.7. In the manufacture of aniline by the hydrogenation of nitrobenzene, the off-gases
from the reactor are cooled and the products and unreacted nitrobenzene condensed
in a shell and tube exchanger. A typical composition of the condensate is, kmol/h:
aniline 950, cyclo-hexylamine 10, water 1920, nitrobenzene 40. The gases enter
the condenser at 230 Ž C and leave at 50 Ž C. The cooling water enters the tubes at
20 Ž C and leaves at 50 Ž C. Suggest suitable materials of construction for the shell
and the tubes.
7.8. A slurry of acrylic polymer particles in water is held in storage tanks prior to
filtering and drying. Plain carbon steel would be a suitable material for the tanks,
but it is essential that the polymer does not become contaminated with iron in
storage. Suggest some alternative materials of construction for the tanks.
CHAPTER 8
Design Information and Data
8.1. INTRODUCTION
Information on manufacturing processes, equipment parameters, materials of construction,
costs and the physical properties of process materials are needed at all stages of design;
from the initial screening of possible processes, to the plant start-up and production.
Sources of data on costs were discussed in Chapter 6 and materials of construction in
Chapter 7. This chapter covers sources of information on manufacturing processes and
physical properties; and the estimation of physical property data. Information on the types
of equipment (unit operations) used in chemical process plants is given in Volume 2, and in
the Chapters concerned with equipment selection and design in this Volume, Chapters 10,
11 and 12.
When a project is largely a repeat of a previous project, the data and information
required for the design will be available in the Company’s process files, if proper detailed
records are kept. For a new project or process, the design data will have to be obtained
from the literature, or by experiment (research laboratory and pilot plant), or purchased
from other companies. The information on manufacturing processes available in the
general literature can be of use in the initial stages of process design, for screening
potential process; but is usually mainly descriptive, and too superficial to be of much use
for detailed design and evaluation.
The literature on the physical properties of elements and compounds is extensive, and
reliable values for common materials can usually be found. The principal sources of
physical property data are listed in the references at the end of this chapter.
Where values cannot be found, the data required will have to be measured experimentally or estimated. Methods of estimating (predicting) the more important physical
properties required for design are given in this chapter. A physical property data bank is
given in Appendix C.
Readers who are unfamiliar with the sources of information, and the techniques used for
searching the literature, should consult one of the many guides to the technical literature
that have been published; such as those by Lord (2000) and Maizell (1998).
8.2. SOURCES OF INFORMATION ON MANUFACTURING
PROCESSES
In this section the sources of information available in the open literature on commercial
processes for the production of chemicals and related products are reviewed.
309
310
CHEMICAL ENGINEERING
The chemical process industries are competitive, and the information that is published
on commercial processes is restricted. The articles on particular processes published in
the technical literature and in textbooks invariably give only a superficial account of the
chemistry and unit operations used. They lack the detailed information needed on reaction
kinetics, process conditions, equipment parameters, and physical properties needed for
process design. The information that can be found in the general literature is, however,
useful in the early stages of a project, when searching for possible process routes. It is
often sufficient for a flow-sheet of the process to be drawn up and a rough estimate of
the capital and production costs made.
The most comprehensive collection of information on manufacturing processes is
probably the Encyclopedia of Chemical Technology edited by Kirk and Othmer (2001)
(2003), which covers the whole range of chemical and associated products. Another
encyclopedia covering manufacturing processes is that edited by McKetta (2001). Several
books have also been published which give brief summaries of the production processes
used for the commercial chemicals and chemical products. The most well known of these
is probably Shreve’s book on the chemical process industries, now updated by Austin
and Basta (1998). Comyns (1993) lists named chemical manufacturing processes, with
references.
The extensive German reference work on industrial processes, Ullman’s Encyclopedia
of Industrial Technology, is now available in an English translation, Ullman (2002).
Specialised texts have been published on some of the more important bulk industrial
chemicals, such as that by Miller (1969) on ethylene and its derivatives; these are too
numerous to list but should be available in the larger reference libraries and can be found
by reference to the library catalogue.
Books quickly become outdated, and many of the processes described are obsolete,
or at best obsolescent. More up-to-date descriptions of the processes in current use can
be found in the technical journals. The journal Hydrocarbon Processing publishes an
annual review of petrochemical processes, which was entitled Petrochemical Developments and is now called Petrochemicals Notebook; this gives flow-diagrams and brief
process descriptions of new process developments. Patents are a useful source of information; but it should be remembered that the patentee will try to write the patent in
a way that protects his invention, whilst disclosing the least amount of useful information to his competitors. The examples given in a patent to support the claims often
give an indication of the process conditions used; though they are frequently examples
of laboratory preparations, rather than of the full-scale manufacturing processes. Several
guides have been written to help engineers understand the use of patents for the protection
of inventions, and as sources of information; such as those by Auger (1992) and Gordon
and Cookfair (2000).
World Wide Web
It is worthwhile searching the Internet for information on processes, equipment, products
and physical properties. Many manufacturers and government departments maintain web
sites. In particular, up-to-date information can be obtained on the health and environmental
effects of products.
DESIGN INFORMATION AND DATA
311
Internet sources
Many of the university libraries in the UK and USA provide information guides for the
students and these are available on the Internet. A search using the key words such as
“chemical engineering information” will usually find them. Some examples are:
Heriot-Watt University, Edinburgh, UK: www.hw.ac.uk/lib
Edinburgh, UK: www.eevl.ac.uk
University of Florida, USA: www.che.ufl.edu/
Karlsruhe, USA: www.ciw.uni-karlsruhe.de/chem-eng
Useful gateways
EEVL (Edinburgh Engineering Virtual Library) Internet Guide to Engineering,
Mathematics and Computing, www.eevl.ac.uk
Heriot-Watt University, Edinburgh, UK
World-Wide Web Virtual Library: www.che.ufl.edu/WWW-CHEindex.html
University of Florida, USA
International Directory of Chemical Engineering URLs: www.ciw.uni-karlsruhe.de/chemeng.html
Karlsburg University, Germany
Many of the important sources of engineering information are subscription services. In
the United Kingdom some of them can be accessed using the Athens service available to
universities.
Another important source is the Knovel organisation. This provides online access to most
standard reference books. It is a subscription service but can be accessed through many
libraries, including those of the professional engineering institutions and some universities.
8.3. GENERAL SOURCES OF PHYSICAL PROPERTIES
In this section those references that contain comprehensive compilations of physical
property data are reviewed. Sources of data on specific physical properties are given
in the remaining sections of the chapter.
International Critical Tables (1933) is still probably the most comprehensive compilation of physical properties, and is available in most reference libraries. Though it was
first published in 1933, physical properties do not change, except in as much as experimental techniques improve, and ICT is still a useful source of engineering data. ICT is
now available as an ebook and can be referenced on the Internet through Knovel (2003).
Tables and graphs of physical properties are given in many handbooks and textbooks
on Chemical Engineering and related subjects. Many of the data given are duplicated
from book to book, but the various handbooks do provide quick, easy access to data on
the more commonly used substances.
An extensive compilation of thermophysical data has been published by Plenum Press,
Touloukian (1970 77). This multiple-volume work covers conductivity, specific heat,
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CHEMICAL ENGINEERING
thermal expansion, viscosity and radiative properties (emittance, reflectance, absorptance
and transmittance).
Elsevier have published a series of volumes on physical property and thermodynamic
data. Those of use in design are included in the Bibliography at the end of this chapter.
The Engineering Sciences Data Unit (ESDU, www.ihsesdu.com) was set up to provide
validated data for engineering design, developed under the guidance and approval of
engineers from industry, the universities and research laboratories. ESDU data include
equipment design data and software and extensive high-quality physical property data
mostly for pure fluids that are in use in the oil and process industries and in university
chemical and mechanical engineering departments worldwide.
Caution should be exercised when taking data from the literature, as typographical
errors often occur. If a value looks doubtful it should be cross-checked in an independent
reference, or by estimation.
The values of some properties will be dependent on the method of measurement; for
example, surface tension and flash point, and the method used should be checked, by
reference to the original paper if necessary, if an accurate value is required.
The results of research work on physical properties are reported in the general
engineering and scientific literature. The Journal of Chemical Engineering Data
specialises in publishing physical property data for use in chemical engineering design. A
quick search of the literature for data can be made by using the abstracting journals; such
as Chemical Abstracts (American Chemical Society) and Engineering Index (Engineering
Index Inc., New York). Engineering Index is now called Engineering Information (Ei) and
is a web-based reference source owned by Elsevier information (www.ei.org).
Computerised physical property data banks have been set up by various organisations
to provide a service to the design engineer. They can be incorporated into computer-aided
design programs and are increasingly being used to provide reliable, authenticated, design
data. Examples of such programs are the PPDS and the DIPPR databases.
PPDS (Physical Property Data Service) was originally developed in the United Kingdom
by the Institution of Chemical Engineers and the National Physical Laboratory. It is now
available as a Microsoft Windows version from NEL, a division of the TUV Suddeuntschland Group (www.nel.uk). PPDS is made available to universities at a discount.
The DIPPR databases were developed in the United States by the Design Institute
for Physical Properties of the American Institute of Chemical Engineers. The DIPPR
projects are aimed at providing evaluated process design data for the design of chemical
processes and equipment (www.aiche.org/dippr/projects.htm). The Project 801 has been
made available to university departments; see Rowley et al. (2004) and http.//dippr.byu.
edu/description/htm.
8.4. ACCURACY REQUIRED OF ENGINEERING DATA
The accuracy needed depends on the use to which the data will be put. Before spending
time and money searching for the most accurate value, or arranging for special measurements to be made, the designer must decide what accuracy is required; this will depend
on several factors:
DESIGN INFORMATION AND DATA
313
1. The level of design; less accuracy is obviously needed for rough scouting calculations, made to sort out possible alternative designs, than in the final stages of design;
when money will be committed to purchase equipment, and for construction.
2. The reliability of the design methods; if there is some uncertainty in the techniques
to be used, it is clearly a waste of time to search out highly accurate physical
property data that will add little or nothing to the reliability of the final design.
3. The sensitivity to the particular property: how much will a small error in the property
affect the design calculation. For example, it was shown in Chapter 4 that the
estimation of the optimum pipe diameter is insensitive to viscosity. The sensitivity
of a design method to errors in physical properties, and other data, can be checked
by repeating the calculation using slightly altered values.
It is often sufficient to estimate a value for a property (sometimes even to make an
intelligent guess) if the value has little effect on the final outcome of the design calculation.
For example, in calculating the heat load for a reboiler or vaporiser an accurate value of
the liquid specific heat is seldom needed, as the latent heat load is usually many times
the sensible heat load and a small error in the sensible heat calculation will have little
effect on the design. The designer must, however, exercise caution when deciding to use
less reliable data, and to be sure that they are sufficiently accurate for his purpose. For
example, it would be correct to use an approximate value for density when calculating
the pressure drop in a pipe system where a small error could be tolerated, considering
the other probable uncertainties in the design; but it would be quite unacceptable in the
design of a decanter, where the operation depends on small differences in density.
Consider the accuracy of the equilibrium data required to calculate the number of
equilibrium stages needed for the separation of a mixture of acetone and water by distillation (see Chapter 11, Example 11.2). Several investigators have published vapour-liquid
equilibrium data for this system: Othmer et al. (1952), York and Holmes (1942), Kojima
et al. (1968), Reinders and De Minjer (1947).
If the purity of the acetone product required is less than 95 per cent, inaccuracies in the
v l e plot will have little effect on the estimate of the number of stages required, as the
relative volatility is very high. If a high purity is wanted, say >99 per cent, then reliable
data are needed in this region as the equilibrium line approaches the operating line (a
pinch point occurs). Of the references cited, none gives values in the region above 95 per
cent, and only two give values above 90 per cent; more experimental values are needed
to design with confidence. There is a possibility that the system forms an azeotrope in
this region. An azeotrope does form at higher pressure, Othmer et al. (1952).
8.5. PREDICTION OF PHYSICAL PROPERTIES
Whenever possible, experimentally determined values of physical properties should be
used. If reliable values cannot be found in the literature and if time, or facilities, are not
available for their determination, then in order to proceed with the design the designer must
resort to estimation. Techniques are available for the prediction of most physical properties
with sufficient accuracy for use in process and equipment design. A detailed review of
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CHEMICAL ENGINEERING
all the different methods available is beyond the scope of this book; selected methods
are given for the more commonly needed properties. The criterion used for selecting
a particular method for presentation in this chapter was to choose the most easily used,
simplest, method that had sufficient accuracy for general use. If highly accurate values are
required, then specialised texts on physical property estimation should be consulted; such
as those by: Reid et al. (1987), Poling et al. (2000), Bretsznajder (1971) and Sterbacek
et al. (1979), and AIChemE (1983) (1985).
A quick check on the probable accuracy of a particular method can be made by using
it to estimate the property for an analogous compound, for which experimental values are
available.
The techniques used for prediction are also useful for the correlation, and extrapolation
and interpolation, of experimental values.
Group contribution techniques are based on the concept that a particular physical
property of a compound can be considered to be made up of contributions from the
constituent atoms, groups, and bonds; the contributions being determined from experimental data. They provide the designer with simple, convenient, methods for physical
property estimation; requiring only a knowledge of the structural formula of the compound.
Also useful, and convenient to use, are prediction methods based on the use of reduced
properties (corresponding states); providing that values for the critical properties are
available, or can be estimated with sufficient accuracy; see Sterbacek et al. (1979).
8.6. DENSITY
8.6.1. Liquids
Values for the density of pure liquids can usually be found in the handbooks. It should be noted
that the density of most organic liquids, other than those containing a halogen or other “heavy
atom”, usually lies between 800 and 1000 kg/m3 . Liquid densities are given in Appendix C.
An approximate estimate of the density at the normal boiling point can be obtained
from the molar volume (see Table 8.6)
b D
M
Vm
⊲8.1⊳
where b D density, kg/m3 ,
M D molecular mass,
Vm D molar volume, m3 /kmol.
For mixtures, it is usually sufficient to take the specific volume of the components as
additive; even for non-ideal solutions, as is illustrated by Example 8.1.
The densities of many aqueous solutions are given by Perry et al. (1997).
Example 8.1
Calculate the density of a mixture of methanol and water at 20Ž C, composition 40 per cent
w/w methanol.
Density of water at 20Ž C
998.2 kg/m3
Ž
Density of methanol at 20 C
791.2 kg/m3
DESIGN INFORMATION AND DATA
315
Solution
Basis: 1000 kg
0.6 ð 1000
D 0.601 m3
998.2
0.4 ð 1000
Volume of methanol D
D 0.506 m3
791.2
Total 1.107 m3
Volume of water D
Density of mixture D
1000
D 903.3 kg/m3
1.107
Experimental value D 934.5 kg/m3
934.5 903.3
Error D
D 3 per cent, which would be acceptable for most
903.3
engineering purposes
If data on the variation of density with temperature cannot be found, they can be
approximated for non-polar liquids from Smith’s equation for thermal expansion (Smith
et al., 1954).
0.04314
⊲8.2⊳
ˇD
⊲Tc T⊳0.641
where ˇ D coefficient of thermal expansion, K1 ,
Tc D critical temperature, K,
T D temperature, K.
8.6.2. Gas and vapour density (specific volume)
For general engineering purposes it is often sufficient to consider that real gases, and
vapours, behave ideally, and to use the gas law:
where P
V
n
T
R
D
D
D
D
D
2
PV D nRT
⊲8.3⊳
absolute pressure N/m (Pa),
volume m3 ,
mols of gas
absolute temperature, K,
universal gas constant, 8.314 J K1 mol1 (or kJ K1 kmol1 ).
RT
(8.4)
P
These equations will be sufficiently accurate up to moderate pressures, in circumstances
where the value is not critical. If greater accuracy is needed, the simplest method is to
modify equation 8.3 by including the compressibility factor z:
Specific volume D
PV D znRT
⊲8.5⊳
The compressibility factor can be estimated from a generalised compressibility plot, which
gives z as a function of reduced pressure and temperature (Chapter 3, Figure 3.8).
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CHEMICAL ENGINEERING
For mixtures, the pseudocritical properties of the mixture should be used to obtain the
compressibility factor.
Pc,m D Pc,a ya C Pc,b yb C Ð Ð Ð
⊲8.6⊳
Tc,m D Tc,a ya C Tc,b yb C Ð Ð Ð
⊲8.7⊳
where Pc D critical pressure,
Tc D critical temperature,
y D mol fraction,
suffixes
m D mixture
a, b, etc. D components
8.7. VISCOSITY
Viscosity values will be needed for any design calculations involving the transport of fluids
or heat. Values for pure substances can usually be found in the literature; see Yaws (1993
1994). Liquid viscosities are given in Appendix C. Methods for the estimation of viscosity
are given below.
8.7.1. Liquids
A rough estimate of the viscosity of a pure liquid at its boiling point can be obtained
from the modified Arrhenius equation:
b D 0.01b0.5
⊲8.8⊳
where b D viscosity, mNs/m2 ,
b D density at boiling point, kg/m3 .
A more accurate value can be obtained if reliable values of density are available, or can
be estimated with sufficient accuracy, from Souders’ equation, Souders (1938):
I
log⊲log 10⊳ D ð 103 2.9
⊲8.9⊳
M
where D viscosity, mNs/m2 ,
M D molecular mass,
I D Souders’ index, estimated from the group contributions given in Table 8.1,
D density at the required temperature, kg/m3 .
Example 8.2
Estimate the viscosity of toluene at 20Ž C.
Solution
Toluene
CH 3
317
DESIGN INFORMATION AND DATA
Table 8.1.
Atom
Contribution
Contributions for calculating the viscosity constant I in Souders’ equation
H
O
C
N
Cl
Br
I
C2.7
C29.7
C50.2
C37.0
C60
C79
C110
Contributions of groups and bonds
Double bond
Five-member ring
Six-member ring
15.5
24
21
Side groups on a
six-member ring:
Molecular weight < 17
Molecular weight > 16
Ortho or para position
Meta position
R
9
17
C3
1
R
CH CH
R
C8
R
R
R
C
R
H
C
R
C10
O
CH
CH
CH
X
CH2
X†
C4
R
C6
R
OH
COO
COOH
NO2
C57.1
C90
C104.4
C80
C10
R
CH2
C55.6
† X is a negative group.
Contributions from Table 8.1:
7
8
3
1
1
carbon atoms
hydrogen atoms
double bonds
six-membered ring
side group
7 ð 50.2 D 351.4
8 ð 2.7 D 21.6
3⊲15.5⊳ D 46.5
21.1
9.0
Total, I
D 296.4
Density at 20Ž C D 866 kg/m3
Molecular weight 92
296.4 ð 866 ð 103
2.9 D 0.11
92
log 10 D 0.776
log⊲log 10⊳ D
D 0.597, rounded D 0.6 mNs/m2
experimental value, 0.6 cp D 0.6 mNs/m2
Author’s note: the fit obtained in this example is rather fortuitous, the usual accuracy
of the method for organic liquids is around š10 per cent.
Variation with temperature
If the viscosity is known at a particular temperature, the value at another temperature can
be estimated with reasonable accuracy (within š20 per cent) by using the generalised
318
CHEMICAL ENGINEERING
103
Viscosity mNs/m2
102
101
100
10−1
100
Figure 8.1.
100
100
100
Temperature °C
100
Generalised viscosity vs. temperature curve for liquids
plot of Lewis and Squires (1934), Figure 8.1. The scale of the temperature ordinate is
obtained by plotting the known value, as illustrated in Example 8.3.
Example 8.3
Estimate the viscosity of toluene at 80Ž C, using the value at 20Ž C given in Example 8.2.
DESIGN INFORMATION AND DATA
319
Solution
Temperature increment 80 20 D 60Ž C.
From Figure 8.1a, viscosity at 80Ž C D 0.26 mN s/m2 .
100
0.6
0.26
10−1
20°
80°
100°
60°
Figure 8.1a.
Effect of pressure
The viscosity of a liquid is dependent on pressure as well as temperature, but the effect
is not significant except at very high pressures. A rise in pressure of 300 bar is roughly
equivalent to a decrease in temperature of 1Ž C.
Mixtures
It is difficult to predict the viscosity of mixtures of liquids. Viscosities are rarely additive,
and the shape of the viscosity-concentration curve can be complex. The viscosity of the
mixture may be lower or, occasionally, higher than that of the pure components. A rough
check on the magnitude of the likely error in a design calculation, arising from uncertainty
in the viscosity of a mixture, can be made by using the smallest and largest values of the
pure components in the calculation, and noting the result.
As an approximation, the variation can be assumed to be linear, if the range of
viscosity is not very wide, and a weighted average viscosity calculated. For organic
liquid mixtures a modified form of Souders’ equation can be used; using a mol fraction
weighted average value for the viscosity constant for the mixture Im , and the average
molecular weight.
For a binary mixture equation 8.9 becomes:
x1 I1 C x2 I2
log⊲log 10 m ⊳ D m
ð 103 2.9
⊲8.10⊳
x1 M1 C x2 M2
320
CHEMICAL ENGINEERING
where m
m
x1 , x2
M1 , M2
D
D
D
D
viscosity of mixture,
density of mixture,
mol fraction of components,
molecular masses of components.
Bretsznajder (1971) gives a detailed review of the methods that have been developed
for estimating the viscosity of mixtures, including methods for aqueous solutions and
dispersions.
For heat-transfer calculations, Kern (1950) gives a rough rule of thumb for organic
liquid mixtures:
1
w1
w2
D
C
m
1
2
⊲8.11⊳
where w1 , w2 D mass fractions of the components 1 and 2,
1 , 2 D viscosities of components 1 and 2.
8.7.2 Gases
Reliable methods for the prediction of gas viscosities, and the effect of temperature and
pressure, are given by Bretsznajder (1971) and Reid et al. (1987).
Where an estimate of the viscosity is needed to calculate Prandtl numbers (see Volume 1,
Chapter 1) the methods developed for the direct estimation of Prandtl numbers should be
used.
For gases at low pressure Bromley (1952) has suggested the following values:
Monatomic gases (e.g. Ar, He)
Non-polar, linear molecules (e.g. O2 , Cl2 )
Non-polar, non-linear molecules (e.g. CH4 , C6 H6 )
Strongly polar molecules (e.g. CH3 OH, SO2 , HCl)
Prandtl
0.67 š
0.73 š
0.79 š
0.86 š
number
5 per cent
15 per cent
15 per cent
8 per cent
The Prandtl number for gases varies only slightly with temperature.
8.8 THERMAL CONDUCTIVITY
The experimental methods used for the determination of thermal conductivity are
described by Tsederberg (1965), who also lists values for many substances. The fourvolume handbook by Yaws (1995 1999) is a useful source of thermal conductivity data
for hydrocarbons and inorganic compounds.
8.8.1. Solids
The thermal conductivity of a solid is determined by its form and structure, as well as
composition. Values for the commonly used engineering materials are given in various
handbooks.
DESIGN INFORMATION AND DATA
321
8.8.2. Liquids
The data available in the literature up to 1973 have been reviewed by Jamieson et al.
(1975). The Weber equation (Weber, 1880) can be used to make a rough estimate of the
thermal conductivity of organic liquids, for use in heat-transfer calculations.
5
k D 3.56 ð 10 Cp
where k
M
Cp
D
D
D
D
4
M
1/3
⊲8.12⊳
thermal conductivity. W/mŽ C,
molecular mass,
specific heat capacity, kJ/kgŽ C,
density, kg/m3 .
Bretsznajder (1971) gives a group contribution method for estimating the thermal conductivity of liquids.
Example 8.4
Estimate the thermal conductivity of benzene at 30Ž C.
Solution
Density at 30Ž C D 875 kg/m3
Molecular mass D 78
Specific heat capacity D 1.75 kJ/kgŽ C
5
k D 3.56 ð 10
ð 1.75
8754
78
1/3
D 0.12 W/mŽ C
(8.12)
Experimental value, 0.16 W/mŽ C
8.8.3. Gases
Approximate values for the thermal conductivity of pure gases, up to moderate pressures,
can be estimated from values of the gas viscosity, using Eucken’s equation, Eucken (1911):
10.4
⊲8.13⊳
k D Cp C
M
where D viscosity, mNs/m2 ,
Cp D specific heat capacity, kJ/kgŽ C,
M D molecular mass.
Example 8.5
Estimate the thermal conductivity of ethane at 1 bar and 450Ž C.
322
CHEMICAL ENGINEERING
Solution
Viscosity D 0.0134 mNs/m2
Specific heat capacity D 2.47 kJ/kgŽ C
10.4
D 0.038 W/mŽ C
k D 0.0134 2.47 C
30
(8.13)
Experimental value, 0.043 W/mŽ C, error 12 per cent.
8.8.4. Mixtures
In general, the thermal conductivities of liquid mixtures, and gas mixtures, are not simple
functions of composition and the thermal conductivity of the components. Bretsznajder
(1971) discusses the methods that are available for estimating the thermal conductivities
of mixtures from a knowledge of the thermal conductivity of the components.
If the components are all non-polar a simple weighted average is usually sufficiently
accurate for design purposes.
km D k1 w1 C k2 w2 C Ð Ð Ð
⊲8.14⊳
where km D thermal conductivity of mixture,
k1 , k2 D thermal conductivity of components,
w1 , w2 D component mass fractions.
8.9. SPECIFIC HEAT CAPACITY
The specific heats of the most common organic and inorganic materials can usually be
found in the handbooks.
8.9.1. Solids and liquids
Approximate values can be calculated for solids, and liquids, by using a modified form of
Kopp’s law, which is given by Werner (1941). The heat capacity of a compound is taken
as the sum of the heat capacities of the individual elements of which it is composed. The
values attributed to each element, for liquids and solids, at room temperature, are given
in Table 8.2; the method illustrated in Example 8.6.
Table 8.2.
Heat capacities of the elements, J/mol° C
Element
Solids
Liquids
C
H
B
Si
O
F
P and S
all others
7.5
9.6
11.3
15.9
16.7
20.9
22.6
26.0
11.7
18.0
19.7
24.3
25.1
29.3
31.0
33.5
323
DESIGN INFORMATION AND DATA
Example 8.6
Estimate the specific heat capacity of urea, CH4 N2 O.
Solution
Element
C
H
N
O
mol. mass
12
4
28
16
60
Specific heat capacity D
Heat capacity
7.5
4 ð 9.6
2 ð 26.0
16.7
D
D
D
D
7.5
38.4
52.0
16.7
114.6 J/molŽ C
114.6
D 1.91 J/gŽ C ⊲kJ/kgŽ C⊳
60
Experimental value 1.34 kJ/kgŽ C.
Kopp’s rule does not take into account the arrangement of the atoms in the molecule,
and, at best, gives only very approximate, “ball-park” values.
For organic liquids, the group contribution method proposed by Chueh and Swanson
(1973a,b) will give accurate predictions. The contributions to be assigned to each
molecular group are given in Table 8.3 and the method illustrated in Examples 8.7 and 8.8.
Liquid specific heats do not vary much with temperature, at temperatures well below
the critical temperature (reduced temperature <0.7).
The specific heats of liquid mixtures can be estimated, with sufficient accuracy for most
technical calculations, by taking heat capacities of the components as additive.
For dilute aqueous solutions it is usually sufficient to take the specific heat of the
solution as that of water.
Example 8.7
Using Chueh and Swanson’s method, estimate the specific heat capacity of ethyl bromide
at 20Ž C.
Solution
Ethyl bromide CH3 CH2 Br
Group
CH3
CH2
Br
Contribution
36.84
30.40
37.68
No. of
1
D 36.84
1
D 30.40
1
D 37.68
Total
104.92 kJ/kmolŽ C
324
CHEMICAL ENGINEERING
Group contributions for liquid heat capacities at 20° C, kJ/kmol° C (Chueh and Swanson, 1973a, b)
Table 8.3.
Group
Value
Group
Value
O
Alkane
CH 3
36.84
CH2
30.40
CH
20.93
C
7.37
C
Olefin
CH2
H
C
CH2OH
73.27
CHOH
76.20
COH
111.37
OH
44.80
119.32
ONO2
21.77
C
21.35
Halogen
Cl (first or second on a carbon)
Cl (third or fourth on a carbon)
15.91
Br
36.01
25.12
37.68
F
16.75
Alkyne
C H
24.70
C
24.70
I
H
18.42
C
C
CH2
O
N
22.19
25.96
N
N
C
53.00
O
53.00
O
OH
43.96
31.40
(in a ring)
18.84
N
58.70
Sulphur
35.17
O
H
C
58.62
N
12.14
Oxygen
C
H
H
or
C
C
36.01
Nitrogen
In a ring
CH
60.71
O
SH
44.80
S
33.49
Hydrogen
(for formic acid, formates,
H
hydrogen cyanide, etc.)
14.65
79.97
Add 18.84 for any carbon group which fulfils the following criterion: a carbon group which is joined by a
single bond to a carbon group connected by a double or triple bond with a third carbon group. In some cases
a carbon group fulfils the above criterion in more ways than one; 18.84 should be added each time the group
fulfils the criterion.
Exceptions to the above 18.84 rule:
1. No such extra 18.84 additions for CH3 groups.
2. For a CH2 group fulfilling the 18.84 addition criterion add 10.47 instead of 18.84. However, when
the CH2 group fulfils the addition criterion in more ways than one, the addition should be 10.47 the
first time and 18.84 for each subsequent addition.
3. No such extra addition for any carbon group in a ring.
325
DESIGN INFORMATION AND DATA
mol. wt. D 109
Specific heat capacity D
104.92
D 0.96 kJ/kgŽ C
109
Experimental value 0.90 kJ/kgŽ C
Example 8.8
Estimate the specific heat capacity of chlorobutadiene at 20Ž C, using Chueh and Swanson’s
method.
Solution
Structural formula CH2
C
CH
CH2 , mol. wt. 88.5
Cl
Group
CH2
C
CH
Cl
Contribution
21.77
15.91
No. of
2
1
21.35
1
36.01
1
Specific heat capacity D
Addition rule
Total
D 43.54
18.84
D 34.75
18.84
D
D
40.19
36.01
154.49 kJ/kmolŽ C
154.49
D 1.75 kJ/kgŽ C
88.5
8.9.2. Gases
The dependence of gas specific heats on temperature was discussed in Chapter 3,
Section 3.5. For a gas in the ideal state the specific heat capacity at constant pressure
is given by:
CŽp D a C bT C cT2 C dT3
⊲equation 3.19⊳
Values for the constants in this equation for the more common gases can be found in the
handbooks, and in Appendix C.
Several group contribution methods have been developed for the estimation of the
constants, such as that by Rihani and Doraiswamy (1965) for organic compounds. Their
values for each molecular group are given in Table 8.4, and the method illustrated in
Example 8.9. The values should not be used for acetylenic compounds.
The correction of the ideal gas heat capacity to account for real conditions of temperature and pressure was discussed in Chapter 3, Section 3.7.
326
CHEMICAL ENGINEERING
Group contributions to ideal gas heat capacities, kJ/kmol° C (Rihani and Doraiswamy, 1965)
Table 8.4.
Group
a
b ð 102
c ð 104
d ð 106
Aliphatic hydrocarbon groups
CH3
2.5485
8.9740
0.3567
0.004752
CH2
1.6518
8.9447
0.5012
0.0187
CH2
2.2048
7.6857
0.3994
0.008264
14.7516
14.3020
1.1791
0.03356
24.4131
18.6493
1.7619
0.05288
1.1610
14.4786
0.8031
0.01792
1.7472
16.2694
1.1652
0.03083
13.0676
15.9356
0.9877
0.02305
3.9261
12.5208
0.7323
0.01641
14.1696
0.9927
0.02594
1.9829
14.7304
1.3188
0.03854
9.3784
17.9597
1.07433
0.02474
11.0146
17.4414
1.1912
0.03047
13.0833
20.8878
1.8018
0.05447
C
H
C
H
C
C
CH2
CH2
H
H
C
C
C
C
H
H
H
C
C
C
C
6.161
H
C
C
C
C
CH2
CH2
H
H
C
C
C
Aromatic hydrocarbon groups
HC
C
C
6.1010
8.0165
0.5162
0.01250
5.8125
6.3468
0.4476
0.01113
0.5104
5.0953
0.3580
0.00888
Contributions due to ring formation
Three-membered ring
Four-membered ring
Five-membered ring:
Pentane
Pentene
Six-membered ring:
Hexane
Hexene
14.7878
36.2368
0.1256
4.5134
0.3129
0.1779
0.02309
0.00105
51.4348
28.8106
7.7913
3.2732
0.4342
0.1445
0.00898
0.00247
56.0709
33.5941
8.9564
9.3110
0.1796
0.80118
0.00781
0.02291
327
DESIGN INFORMATION AND DATA
Table 8.4.
(continued)
Group
a
b ð 102
c ð 104
d ð 106
Oxygen-containing groups
OH
27.2691
0.5640
0.1733
O
0.00680
11.9161
0.04187
0.1901
0.01142
14.7308
3.9511
0.2571
0.02922
4.1935
8.6931
0.6850
0.01882
5.8846
14.4997
1.0706
0.02883
11.4509
4.5012
0.2793
0.03864
15.6352
5.7472
0.5296
0.01586
H
C
O
C
O
O
C
O
H
O
C
O
O
Nitrogen-containing groups
C
N
18.8841
2.2864
0.1126
N
C
0.01587
21.2941
1.4620
0.1084
0.01020
17.4937
3.0890
0.2843
0.03061
5.2461
9.1825
0.6716
0.01774
14.5186
12.3230
1.1191
0.03277
10.2401
1.4386
4.5638
11.0536
NH2
NH
N
N
NO2
0.07159
0.7834
0.01138
0.01989
Sulphur-containing groups
SH
10.7170
5.5881
0.4978
0.01599
S
17.6917
0.4719
0.0109
0.00030
17.0922
0.1260
0.3061
0.02546
28.9802
10.3561
0.7436
0.09397
S
SO3H
Halogen-containing groups
F
6.0215
1.4453
0.0444
0.00014
Cl
12.8373
0.8885
0.0536
0.00116
Br
11.5577
1.9808
0.0060
I
0.1905
13.6703
2.0520
0.2257
0.00746
328
CHEMICAL ENGINEERING
Example 8.9
Estimate the specific heat capacity of isopropyl alcohol at 500 K.
Solution
Structural formula
CH3
CH3
Group
CH3
CH
OH
No. of
a
CH
OH
b ð 102
c ð 104
d ð 106
2
5.0970
17.9480
0.7134
0.0095
1
14.7516
14.3020
1.1791
0.03356
1
27.2691
0.5640
0.1733
0.0068
17.6145
31.6860
1.7190
0.0363
Total
CŽp D 17.6145 C 31.6860 ð 102 T 1.7192 ð 104 T2 C 0.0363 ð 106 T3 .
At 500 K, substitution gives:
Cp D 137.6 kJ/kmolŽ C
Experimental value, 31.78 cal/molŽ C D 132.8 kJ/kmolŽ C, error 4 per cent.
8.10. ENTHALPY OF VAPORISATION (LATENT HEAT)
The latent heats of vaporisation of the more commonly used materials can be found in
the handbooks and in Appendix C.
A very rough estimate can be obtained from Trouton’s rule (Trouton, 1884), one of the
oldest prediction methods.
Lv
D constant
⊲8.15⊳
Tb
where Lv D latent heat of vaporisation, kJ/kmol,
Tb D normal boiling point, K.
For organic liquids the constant can be taken as 100.
More accurate estimates, suitable for most engineering purposes, can be made from
a knowledge of the vapour pressure-temperature relationship for the substance. Several
correlations have been proposed; see Reid et al. (1987).
The equation presented here, due to Haggenmacher (1946), is derived from the Antoine
vapour pressure equation (see Section 8.11).
Lv D
8.32 BT2 z
⊲T C C⊳2
⊲8.16⊳
DESIGN INFORMATION AND DATA
where Lv
T
B, C
z
D
D
D
D
latent heat at the required temperature, kJ/kmol,
temperature, K,
coefficients in the Antoine equation (equation 8.20),
zgas zliquid (where z is the compressibility constant), calculated
from the equation:
Pr 0.5
z D 1 3
Tr
329
(8.17)
Pr D reduced pressure,
Tr D reduced temperature.
If an experimental value of the latent heat at the boiling point is known, the Watson
equation (Watson, 1943), can be used to estimate the latent heat at other temperatures.
Tc T 0.38
Lv D Lv,b
⊲8.18⊳
Tc Tb
where Lv
Lv,b
Tb
Tc
T
D
D
D
D
D
latent heat at temperature T, kJ/kmol,
latent heat at the normal boiling point, kJ/kmol,
boiling point, K,
critical temperature, K,
temperature, K.
Over a limited range of temperature, up to 100Ž C, the variation of latent heat with temperature can usually be taken as linear.
8.10.1. Mixtures
For design purposes it is usually sufficiently accurate to take the latent heats of the
components of a mixture as additive:
Lv mixture D Lv1 x1 C Lv2 x2 C Ð Ð Ð
⊲8.19⊳
where Lv1 , Lv2 D latent heats of the components kJ/kmol,
x1 , x2 D mol fractions of components.
Example 8.10
Estimate the latent heat of vaporisation of acetic anhydride, C4 H6 O3 , at its boiling point,
139.6Ž C (412.7 K), and at 200Ž C (473 K).
Solution
For acetic anhydride Tc D 569.1 K, Pc D 46 bar,
Antoine constants A D 16.3982
B D 3287.56
C D 75.11
Experimental value at the boiling point 41,242 kJ/kmol.
330
CHEMICAL ENGINEERING
From Trouton’s rule:
Lv,b D 100 ð 412.7 D 41,270 kJ/kmol
Note: the close approximation to the experimental value is fortuitous, the rule normally
gives only a very approximate estimate.
From Haggenmacher’s equation:
1
D 0.02124
46
412.7
Tr D
D 0.7252
569.1
0.02124 0.5
D 0.972
z D 1
0.72523
at the b.p. Pr D
Lv,b D
8.32 ð 3287.6 ð ⊲412.7⊳2 ð 0.972
D 39,733 kJ/mol
⊲412.7 75.11⊳2
At 200Ž C, the vapour pressure must first be estimated, from the Antoine equation:
ln P D A
B
TCC
3287.56
D 8.14
473 75.11
P D 3421.35 mmHg D 4.5 bar
ln P D 16.3982
4.5
D 0.098
46
473
D 0.831
Tc D
569.1
0.098 0.5
D 0.911
z D 1
0.8313
Pc D
Lv D
8.32 ð 3287.6 ð ⊲473⊳2 ð 0.911
D 35,211 kJ/kmol
⊲473 75.11⊳2
Using Watson’s equation and the experimental value at the b.p.
569.1 473 0.38
D 34,260 kJ/kmol
Lv D 41,242
569.1 412.7
8.11. VAPOUR PRESSURE
If the normal boiling point (vapour pressure D 1 atm) and the critical temperature and
pressure are known, then a straight line drawn through these two points on a plot of logpressure versus reciprocal absolute temperature can be used to make a rough estimation
of the vapour pressure at intermediate temperatures.
DESIGN INFORMATION AND DATA
331
Several equations have been developed to express vapour pressure as a function of
temperature. One of the most commonly used is the three-term Antoine equation, Antoine
(1888):
B
ln P D A
⊲8.20⊳
TCC
where P D vapour pressure, mmHg,
A, B, C D the Antoine coefficients,
T D temperature, K.
Vapour pressure data, in the form of the constants in the Antoine equation, are given in
several references; the compilations by Ohe (1976), Dreisbach (1952), Hala et al. (1968) and
Hirata et al. (1975) give values for several thousand compounds. Antoine vapour pressure
coefficients for the elements are given by Nesmeyanov (1963). Care must be taken when
using Antoine coefficients taken from the literature in equation 8.20, as the equation is often
written in different and ambiguous forms; the logarithm of the pressure may be to the base 10,
instead of the natural logarithm, and the temperature may be degrees Celsius, not absolute
temperature. Also, occasionally, the minus sign shown in equation 8.20 is included in the
constant B and the equation written with a plus sign. The pressure may also be in units other
than mm Hg. Always check the actual form of the equation used in the particular reference.
Antoine constants for use in equation 8.20 are given in Appendix C. Vapour pressure data
for hydrocarbons can be found in the four-volume handbook by Yaws (1994 1995).
8.12. DIFFUSION COEFFICIENTS (DIFFUSIVITIES)
Diffusion coefficients are needed in the design of mass transfer processes; such as gas
absorption, distillation and liquid-liquid extraction.
Experimental values for the more common systems can be often found in the literature,
but for most design work the values will have to be estimated. Methods for the prediction
of gas and liquid diffusivities are given in Volume 1, Chapter 10; some experimental
values are also given.
8.12.1. Gases
The equation developed by Fuller et al. (1966) is easy to apply and gives reliable
estimates:
1 1/2
1
7 1.75
C
1.013 ð 10 T
Ma
Mb
⊲8.21⊳
Dv D
1/3
1/3 2
P
vi
vi
C
a
where Dv
T
Ma , Mb
P
D
D
D
D
b
diffusivity, m2 /s,
temperature, K,
molecular masses of components a and b,
total pressure, bar,
332
CHEMICAL ENGINEERING
vi , vi D the summation of the special diffusion volume coefficients for components
a
b
a and b, given in Table 8.5.
The method is illustrated in Example 8.11.
Table 8.5.
Special atomic diffusion volumes (Fuller et al., 1966)
Atomic and structural diffusion volume increments
C
H
O
N
16.5
1.98
5.48
5.69Ł
Cl
S
Aromatic or hetrocyclic rings
19.5Ł
17.0Ł
20.0
Diffusion volumes of simple molecules
H2
D2
He
N2
O2
Air
Ne
Ar
Kr
Xe
Ł Value
7.07
6.70
2.88
17.9
16.6
20.1
5.59
16.1
22.8
37.9Ł
CO
CO2
N2 O
NH3
H2
CCL2 F2
SF6
Cl2
Br2
SO2
18.9
26.9
35.9
14.9
12.7
114.8Ł
69.7Ł
37.7Ł
67.2Ł
41.1Ł
based on only a few data points
Example 8.11
Estimate the diffusivity of methanol in air at atmospheric pressure and 25Ž C.
Solution
Diffusion volumes from Table 8.5; methanol:
Element
C
H
O
vi
16.50
1.98
5.48
ð
ð
ð
No. of
1
4
1
vi
D 16.50
D 7.92
D 5.48
29.90
a
Diffusion volume for air D 20.1.
1 standard atmosphere D 1.013 bar.
molecular mass CH3 OH D 32, air D 29.
Dv D
1.013 ð 107 ð 2981.75 ⊲1/32 C 1/29⊳1/2
1.013[⊲29.90⊳1/3 C ⊲20.1⊳1/3 ]2
D 16.2 ð 106 m2 /s
Experimental value, 15.9 ð 106 m2 /s.
⊲8.21⊳
333
DESIGN INFORMATION AND DATA
8.12.2. Liquids
The equation developed by Wilke and Chang (1955), given below, can be used to predict
liquid diffusivity. This equation is discussed in Volume 1, Chapter 10.
DL D
1.173 ð 1013 ⊲M⊳0.5 T
V0.6
m
⊲8.22⊳
where DL D liquid diffusivity, m2 /s,
D an association factor for the solvent,
D 2.6 for water (some workers recommend 2.26),
D 1.9 for methanol,
D 1.5 for ethanol,
D 1.0 for unassociated solvents,
M D molecular mass of solvent,
D viscosity of solvent, mN s/m2 ,
T D temperature, K,
Vm D molar volume of the solute at its boiling point, m3 /kmol. This can be
estimated from the group contributions given in Table 8.6.
The method is illustrated in Example 8.12.
The Wilke-Chang correlation is shown graphically in Figure 8.2. This figure can be
used to determine the association constant for a solvent from experimental values for DL
in the solvent.
The Wilke-Chang equation gives satisfactory predictions for the diffusivity of organic
compounds in water but not for water in organic solvents.
Example 8.12
Estimate the diffusivity of phenol in ethanol at 20Ž C (293 K).
Solution
Viscosity of ethanol at 20Ž C, 1.2 mNs/m2 .
Molecular mass, 46.
OH from Table 8.6:
Molar volume of phenol
Atom
Vol.
C
0.0148
H
0.0037
O
0.0074
ring
0.015
DL D
ð
ð
ð
ð
No. of
6
6
1
1
D
0.0888
D
0.0222
D
0.0074
D 0.015
0.1034 m3 /k mol
1.173 ð 1013 ⊲1.5 ð 46⊳0.5 293
D 9.28 ð 1010 m2 /s
1.2 ð 0.10340.6
Experimental value, 8 ð 1010 m2 /s
(8.22)
334
CHEMICAL ENGINEERING
Table 8.6.
Structural contributions to molar volumes, m3 /kmol (Gambil, 1958)
Molecular volumes
Air
Br2
Cl2
CO
0.0299
0.0532
0.0484
0.0307
CO2
COS
H2
H2 O
0.0340
0.0515
0.0143
0.0189
H2 S
I2
N2
NH3
0.0329
0.0715
0.0312
0.0258
NO
N2 O
O2
SO2
0.0236
0.0364
0.0256
0.0448
0.0270
0.0480
0.0256
0.0342
0.0320
Sn
Ti
V
Zn
0.0423
0.0357
0.0320
0.0204
Atomic volumes
As
Bi
Br
C
Cr
0.0305
0.0480
0.0270
0.0148
0.0274
F
Ge
H
Hg
I
0.0087
0.0345
0.0037
0.0190
0.037
P
Pb
S
Sb
Si
Cl, terminal, as in RCl
medial, as in R CHCl R
Nitrogen, double-bonded
triply bonded, as in nitriles
in primary amines, RNH2
in secondary amines, R2 NH
in tertiary amines, R3 N
0.0216
0.0246
0.0156
0.0162
0.0105
0.012
0.0108
in higher esters, ethers
in acids
in union with S, P, N
three-membered ring
four-membered ring
five-membered ring
six-membered ring as in benzene,
cyclohexane, pyridine
0.0110
0.0120
0.0083
0.0060
0.0085
0.0115
Oxygen, except as noted below
in methyl esters
in methyl ethers
0.0074
0.0091
0.0099
Naphthalene ring
Anthracene ring
0.0300
0.0475
Figure 8.2.
The Wilke-Chang correlation
0.0150
335
DESIGN INFORMATION AND DATA
8.13. SURFACE TENSION
It is usually difficult to find experimental values for surface tension for any but the more
commonly used liquids. A useful compilation of experimental values is that by Jasper
(1972), which covers over 2000 pure liquids. Othmer et al. (1968) give a nomograph
covering about 100 compounds.
If reliable values of the liquid and vapour density are available, the surface tension can
be estimated from the Sugden parachor; which can be estimated by a group contribution
method, Sugden (1924).
Pch ⊲L v ⊳ 4
D
ð 1012
⊲8.23⊳
M
where D
Pch D
L D
v D
MD
, L , v
surface tension, mJ/m2 (dyne/cm),
Sugden’s parachor,
liquid density, kg/m3 ,
density of the saturated vapour, kg/m3 ,
molecular mass.
evaluated at the system temperature.
The vapour density can be neglected when it is small compared with the liquid density.
The parachor can be calculated using the group contributions given in Table 8.7. The
method is illustrated in Example 8.13.
Table 8.7.
Contribution to Sugdens’s parachor for organic compounds (Sugden, 1924)
Atom, group or bond
C
H
H in (OH)
O
O2 in esters, acids
N
S
P
F
Cl
Br
I
Se
Contribution
4.8
17.1
11.3
20.0
60.0
12.5
48.2
37.7
25.7
54.3
68.0
91.0
62.5
Atom, group or bond
Si
Al
Sn
As
Double bond: terminal
2,3-position
3,4-position
Triple bond
Rings
3-membered
4-membered
5-membered
6-membered
Contribution
25.0
38.6
57.9
50.1
23.2
46.6
16.7
11.6
8.5
6.1
8.13.1. Mixtures
The surface tension of a mixture is rarely a simple function of composition. However,
for hydrocarbons a rough value can be calculated by assuming a linear relationship.
m D 1 x 1 C 2 x 2 . . .
where m D surface tension of mixture,
1 , 2 D surface tension of components,
x1 , x2 D component mol fractions.
⊲8.24⊳
336
CHEMICAL ENGINEERING
Example 8.13
Estimate the surface tension of pure methanol at 20Ž C, density 791.7 kg/m3 , molecular
weight 32.04.
Solution
Calculation of parachor, CH3 OH, Table 8.7.
D
Group
Contribution
C
HO
HC
O
4.8
11.3
17.1
20.0
87.4 ð 791.7
32.04
4
No.
ð
ð
ð
ð
1
1
3
1
D 4.8
D 11.3
D 51.3
D 20.0
87.4
ð 1012 D 21.8 mJ/m2
(8.23)
Experimental value 22.5 mJ/m2 .
8.14. CRITICAL CONSTANTS
Values of the critical temperature and pressure will be needed for prediction methods that
correlate physical properties with the reduced conditions. Experimental values for many
substances can be found in various handbooks; and in Appendix C. Critical reviews of the
literature on critical constants, and summaries of selected values, have been published by
Kudchadker et al. (1968), for organic compounds, and by Mathews (1972), for inorganic
compounds. An earlier review was published by Kobe and Lynn (1953).
If reliable experimental values cannot be found, techniques are available for estimating
the critical constants with sufficient accuracy for most design purposes. For organic
compounds Lydersen’s method is normally used, Lydersen (1955):
Tb
[0.567 C T ⊲T⊳2 ]
M
Pc D
⊲0.34 C P⊳2
Vc D 0.04 C V
Tc D
where Tc
Pc
Vc
Tb
M
T
P
V
D
D
D
D
D
D
D
D
critical temperature, K,
critical pressure, atm (1.0133 bar),
molar volume at the critical conditions, m3 /kmol,
normal boiling point, K,
relative molecular mass,
critical temperature increments, Table 8.8,
critical pressure increments, Table 8.8,
molar volume increments, Table 8.8.
⊲8.25⊳
⊲8.26⊳
⊲8.27⊳
337
DESIGN INFORMATION AND DATA
Table 8.8.
Critical constant increments (Lydersen, 1955)
T
P
V
CH3
0.020
0.227
0.055
CH2
0.020
0.227
0.055
T
P
V
C
0.0
0.198
0.036
C
0.0
0.198
0.036
CH
0.005
0.153
0.036Ł
C
0.005
0.153
0.036Ł
H
0
0
0
CH
0.011
0.154
0.037
C
0.011
0.154
0.036
C
0.011
0.154
0.036
Non-ring increments
CH
0.012
C
0.210
0.051
0.00
0.210
0.041
CH2
0.018
0.198
0.045
CH
0.018
0.198
0.045
0.013
0.184
0.0445
0.012
0.192
0.046
0.007Ł
0.154Ł
0.031Ł
F
0.018
0.224
0.018
Br
0.010
0.50Ł
0.070Ł
Cl
0.017
0.320
0.049
I
0.012
0.83Ł
0.095Ł
0.082
0.06
0.018Ł
0.031
0.02Ł
0.030Ł
CO (ring)
0.033Ł
0.2Ł
0.050Ł
0.048
0.33
0.073
0.080
Ring increments
CH2
CH
C
Halogen increments
Oxygen increments
OH (alcohols)
OH (phenols)
O
(non-ring)
0.021
0.16
0.020
O
(ring)
0.014Ł
0.12Ł
0.080Ł
COOH (acid)
0.060
COO
C
O (non-ring)
0.040
0.29
O (aldehyde)
HC
0.085
0.4Ł
(ester)
0.047
0.47
0.080
O (except for
combinations
above)
0.02Ł
0.12Ł
0.011Ł
(ring)
0.007Ł
0.013Ł
0.032Ł
CN
0.060Ł
0.36Ł
0.080Ł
NO2
0.055Ł
0.42Ł
0.078Ł
Nitrogen increments
NH2
0.031
0.095
0.028
0.135
0.037Ł
N
NH (non-ring)
NH (ring)
N
(non-ring)
0.031
0.024Ł
0.09Ł
0.027Ł
0.014
0.17
0.042Ł
(continued overleaf)
338
CHEMICAL ENGINEERING
Table 8.8.
(continued)
T
P
V
0.015
0.27
0.055
T
P
V
0.008Ł
0.24Ł
0.045Ł
0.003Ł
0.24Ł
0.047Ł
Sulphur Increments
SH
S
(non-ring)
0.015
0.27
S
0.055
(ring)
S
Miscellaneous
Si
0.03Ł
B
0.54Ł
0.03
Dashes represent bonds with atoms other than hydrogen.
Values marked with an asterisk are based on too few experimental points to be reliable.
Fedons (1982) gives a simple method for the estimation of critical temperature, that
does not require a knowledge of the boiling point of the compound.
Example 8.14
Estimate the critical constants for diphenylmethane using Lydersen’s method; normal
boiling point 537.5 K, molecular mass 168.2, structural formula:
H
C
H
C
C
H
C
H
HC
H
C
C
H
H
C
H
C
C
H
C
H
CH
C
Solution
Total contribution
Group
H
C
No. of
(ring)
C (ring)
CH2
T
P
V
10
0.11
1.54
0.37
2
1
0.022
0.02
0.308
0.227
0.072
0.055
0.152
2.075
0.497
537.5
D 772 k
⊲0.567 C 0.152 0.1522 ⊳
experimental value 767 K,
168.2
Pc D
D 28.8 atm
⊲0.34 C 2.075⊳2
experimental value 28.2 atm,
Vc D 0.04 C 0.497 D 0.537 m3 /kmol
Tc D
DESIGN INFORMATION AND DATA
339
8.15. ENTHALPY OF REACTION AND ENTHALPY
OF FORMATION
Enthalpies of reaction (heats of reaction) for the reactions used in the production of
commercial chemicals can usually be found in the literature. Stephenson (1966) gives
values for most of the production processes he describes in his book.
Heats of reaction can be calculated from the heats of formation of the reactants
and products, as described in Chapter 3, Section 3.11. Values of the standard heats of
formation for the more common chemicals are given in various handbooks; see also
Appendix C. A useful source of data on heats of formation, and combustion, is the critical
review of the literature by Domalski (1972).
Benson has developed a detailed group contribution method for the estimation of heats
of formation; see Benson (1976) and Benson et al. (1968). He estimates the accuracy
of the method to be from š2.0 kJ/mol for simple compounds, to about š12 kJ/mol for
highly substituted compounds. Benson’s method, and other group contribution methods
for the estimation of heats of formation, are described by Reid et al. (1987).
8.16. PHASE EQUILIBRIUM DATA
Phase equilibrium data are needed for the design of all separation processes that depend
on differences in concentration between phases.
8.16.1. Experimental data
Experimental data have been published for several thousand binary and many multicomponent systems. Virtually all the published experimental data has been collected together in
the volumes comprising the DECHEMA vapour-liquid and liquid-liquid data collection,
DECHEMA (1977). The books by Chu et al. (1956), Hala et al. (1968, 1973), Hirata
et al. (1975) and Ohe (1989, 1990) are also useful sources.
8.16.2. Phase equilibria
The criterion for thermodynamic equilibrium between two phases of a multicomponent
mixture is that for every component, i:
fvi D fLi
⊲8.28⊳
where fi is the vapour-phase fugacity and fLi the liquid-phase fugacity of component i:
fi D i yi
⊲8.29⊳
fLi D fOL
i xi
i
⊲8.30⊳
and
where D total systems pressure
i D vapour fugacity coefficient
yi D concentration of component i in the vapour phase
340
CHEMICAL ENGINEERING
fOL
D standard state fugacity of the pure liquid
i
i D liquid-phase activity coefficient
xi D concentration of component i in the liquid phase
Substitution from equations 8.29 and 8.30 into equation 8.28, and rearranging gives:
Ki D
OL
yi
i fi
D
xi
i
⊲8.31⊳
where Ki is the distribution coefficient (the K value).
i can be calculated from an appropriate equation of state (see Section 8.16.3).
fOL
can be computed from the following
i
expression:
⊲ Pio ⊳ L
o s
(8.32)
exp
D
P
i
fOL
i
i i
RT
where Pio D the pure component vapour pressure (which can be calculated from the
Antoine equation, see Section 8.11), N/m2
s
i D the fugacity coefficient of the pure component i at saturation
iL D the liquid molar volume, m3 /mol
The exponential term in equation 8.32 is known as the Poynting correction, and corrects
for the effects of pressure on the liquid-phase fugacity.
is is calculated using the same equation of state used to calculate i .
For systems in which the vapour phase imperfections are not significant, equation 8.32
reduces to the familiar Raoult’s law equation (see Volume 2, Chapter 11):
Ki D
o
i Pi
⊲8.33⊳
Relative volatility
The relative volatility of two components can be expressed as the ratio of their K values:
Ki
Kj
⊲8.34⊳
Pio
P
⊲8.35⊳
Pio
Koi
o D o
Kj
Pj
⊲8.36⊳
˛ij D
For ideal mixtures (obeying Raoult’s law):
Ki D
and
˛ij D
where Koi and Koj are the ideal K values for components i and j.
DESIGN INFORMATION AND DATA
341
8.16.3. Equations of state
An equation of state is an algebraic expression which relates temperature, pressure and
molar volume, for a real fluid.
Many equations of state have been developed, of varying complexity. No one equation
is sufficiently accurate to represent all real gases, under all conditions. The equations of
state most frequently used in the design of multicomponent separation processes are given
below. The actual equation is only given for one of the correlations, the Redlich Kwong
equation, as an illustration. Equations of state would normally be incorporated in computer
aided design packages; see Chapter 11. For details of the other equations the reader should
consult the reference cited, or the books by Reid et al. (1987) and Walas (1989). To
selection the best equation to use for a particular process design refer to Table 8.11 and
Figure 8.4.
Redlich Kwong equation (R K)
This equation is an extension of the more familiar Van der Waal’s equation. The Redlich
Kwong equation is:
PT
a
PD
ð 1/2
⊲8.37⊳
V b T V⊲V C b⊳
where a
b
P
V
D
D
D
D
0.427 R2 T2.5
c /Pc
0.08664 RTc /Pc
pressure
volume
The R K equation is not suitable for use near the critical pressure (Pr > 0.8), or for
liquids; Redlich and Kwong (1949).
Redlich Kwong Soave equation (R K S)
Soave (1972) modified the Redlich Kwong equation to extend its usefulness to the critical
region, and for use with liquids.
Benedict Webb Rubin (B W R) equation
This equation has eight empirical constants and gives accurate predictions for vapour and
liquid phase hydrocarbons. It can also be used for mixtures of light hydrocarbons with
carbon dioxide and water; Benedict et al. (1951).
Lee Kesler Plocker (L K P) equation
Lee and Kesler (1975) extended the Benidict Webb Rubin equation to a wider variety of
substances, using the principle of corresponding states. The method was modified further
by Plocker et al. (1978).
342
CHEMICAL ENGINEERING
Chao Seader equation (C S)
The Chao Seader equation gives accurate predictions for light hydrocarbons and
hydrogen, but is limited to temperatures below 530 K; Chao and Seader (1961).
Grayson Stread equation (G S)
Grayson and Stread (1963) extended the Chao Seader equation for use with hydrogen
rich mixtures, and for high pressure and high temperature systems. It can be used up to
200 bar and 4700 K.
Peng Robinson equation (P R)
The Peng Robinson equation is related to the Redlich Kwong Soave equation of state
and was developed to overcome the instability in the Redlich Kwong Soave equation
near the critical point; Peng and Robinson (1970).
Brown K10 equation (B K10)
Brown, see Cajander et al. (1960), developed a method which relates the equilibrium
constant K to four parameters: component, pressure, temperature, and the convergence
pressure. The convergence pressure is the pressure at which all K values tend to 1. The
Brown K10 equation is limited to low pressure and its use is generally restricted to vacuum
systems.
8.16.4. Correlations for liquid phase activity coefficients
The liquid phase activity coefficient, i , is a function of pressure, temperature and liquid
composition. At conditions remote from the critical conditions it is virtually independent
of pressure and, in the range of temperature normally encountered in distillation, can be
taken as independent of temperature.
Several equations have been developed to represent the dependence of activity coefficients on liquid composition. Only those of most use in the design of separation processes
will be given. For a detailed discussion of the equations for activity coefficients and their
relative merits the reader is referred to the book by Reid et al. (1987), Walas (1984) and
Null (1970).
Wilson equation
The equation developed by Wilson (1964) is convenient to use in process design:
n
n
xi Aik
⊲xj Akj ⊳
⊲8.38⊳
ln k D 1.0 ln
n
iD1
jD1
⊲xj Aij ⊳
jD1
where k D activity coefficient for component k,
Aij , Aji D Wilson coefficients (A values) for the binary pair i, j,
n D number of components.
DESIGN INFORMATION AND DATA
343
The Wilson equation is superior to the familiar Van-Laar and Margules equations (see
Volume 2, Chapter 11) for systems that are severely non-ideal; but, like other three suffix
equations, it cannot be used to represent systems that form two phases in the concentration
range of interest.
A significant advantage of the Wilson equation is that it can be used to calculate
the equilibrium compositions for multicomponent systems using only the Wilson
coefficients obtained for the binary pairs that comprise the multicomponent mixture. The
Wilson coefficients for several hundred binary systems are given in the DECHEMA
vapour-liquid data collection, DECHEMA (1977), and by Hirata (1975). Hirata gives
methods for calculating the Wilson coefficients from vapour liquid equilibrium
experimental data.
The Wilson equation is best solved using a short computer program with the Wilson
coefficients in matrix form, or by using a spreadsheet. A suitable program is given in
Table 8.9 and its use illustrated in Example 8.9. The program language is GWBASIC and
it is intended for interactive use. It can be extended for use with any number of components
by changing the value of the constant N in the first data statement and including the
Table 8.9.
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360
370
380
390
400
410
420
430
440
450
460
Program for Wilson equation (Example 8.15)
REM WILSON EQUATION
REM CALCULATES ACTIVITY COEFFICIENTS FOR MULTICOMPONENT SYSTEMS
PRINT ‘‘DATA STATEMENTS LINES 410 TO 450’’
READ N
REM MAT READ A
FOR I = 1 TO N
FOR J = 1 TO N
READ A(I, J)
NEXT J
NEXT I
PRINT ‘‘TYPE IN LIQUID COMPOSITION, ONE COMPONENT AT A TIME’’
FOR P=1 TO N
PRINT ‘‘X’’;P;‘‘?’’
INPUT X(P)
NEXT P
FOR K=1 TO N
Q1=0
FOR J=1 TO N
Q1=Q1+X(J)*A(K,J)
NEXT J
Q2=0
FOR I=1 TO N
Q3=0
FOR J=1 TO N
Q3=Q3+X(J)*A(I,J)
NEXT J
Q2=Q2+(X(I)*A(I,K))/Q3
NEXT I
G(K) = EXP(1-LOG(Q1)-Q2)
PRINT ‘‘GAMMA’’;K;‘‘=’’;G(K)
NEXT K
DATA 4
DATA 1,2.3357,2.7385,0.4180
DATA 0.1924,1,1.6500,0.1108
DATA 0.2419,0.5343,1,0.0465
DATA 0.9699,0.9560,0.7795,1
END
344
CHEMICAL ENGINEERING
appropriate Wilson coefficients (Wilson A values) in the other data statements. The
program can easily be modified for use as a sub-routine for bubble-point and other vapour
composition programs.
The use of a spreadsheet to solve the Wilson equation is illustrated in Example 8.15b.
The spreadsheet used was Microsoft Excel. Copies of the spreadsheet example can be
downloaded from support material for this chapter given on the publisher’s web site at:
bh.com/companions/075641428.
Example 8.15a
Using the Wilson equation, calculate the activity coefficients for isopropyl alcohol (IPA)
and water in a mixture of IPA, methanol, water, and ethanol; composition, all mol fraction:
Methanol
0.05
Ethanol
0.05
IPA
0.18
Water
0.72
Solution
Use the binary Wilson A values given by Hirata (1975). The program “WILSON”,
Table 8.9, is used to solve this example.
The Wilson A-values for the binary pairs are Ai,j
j
i
Component 1
2
3
4
D
D
D
D
MeOH
EtOH
IPA
H2 O
1
2
1
1
2.3357
2
1
0.1924
3 0.2419 0.5343
4 0.9699 0.9560
3
4
2.7385 0.4180
1.6500 0.1108
1
0.0465
0.7795
1
The output from the program for the concentrations given was:
3
D 2.11,
4
D 1.25
4
D 1.3
Experimental values from Hirata (1975)
3
D 2.1,
Example 8.15b
Using the compositions and Wilson coefficients given in Example 8.15a, determine the
activity coefficient for methanol.
345
DESIGN INFORMATION AND DATA
Solution
Matrix of coefficients
j
1
2
3
4
i
k
1
2
3
4
1
0.1924
0.2419
0.9699
2.3357
1
0.5343
0.956
2.7385
1.6500
1
0.7795
0.4180
0.1108
0.0465
1
1
MeOH
comp
2
EtOH
0.05
3
IPA
0.05
4
H2O
0.18
0.72
Q1 D x⊲j⊳Ł A⊲k, j⊳
kD1
,j D 1
jD2
jD3
jD4
sumQ1
Q1 D
0.05
0.116785
0.4929
0.30096
0.960675
Q3 D x⊲j⊳Ł A⊲i, j⊳
jD1
jD2
jD3
jD4
sum
Q3 D
iD1
0.05
0.116785
0.49293
0.30096
0.960675
iD2
0.00962
0.05
0.297
0.079776
0.436396
iD3
0.012095
0.026715
0.18
0.03348
0.25229
iD4
0.048495
0.0478
0.14031
0.72
0.956605
Q2 D x⊲i⊳Ł A⊲i, k⊳/sumQ3
iD1
iD2
iD3
iD4
sum
Q2 D
kD1
0.052047
0.022044
0.172587
0.730007
0.976685
Gamma k D exp⊲1 Ln⊲sumQ1⊳ sumQ2⊳
gamma 1 D 1.06549
Non-random two liquid equation (NRTL) equation
The NRTL equation developed by Renon and Prausnitz overcomes the disadvantage of
the Wilson equation in that it is applicable to immiscible systems. If it can be used to
predict phase compositions for vapour-liquid and liquid-liquid systems.
346
CHEMICAL ENGINEERING
Universal quasi-chemical (UNIQUAC) equation
The UNIQUAC equation developed by Abrams and Prausnitz is usually preferred to the
NRTL equation in the computer aided design of separation processes. It is suitable for
miscible and immiscible systems, and so can be used for vapour-liquid and liquid-liquid
systems. As with the Wilson and NRTL equations, the equilibrium compositions for a
multicomponent mixture can be predicted from experimental data for the binary pairs that
comprise the mixture. Also, in the absence of experimental data for the binary pairs, the
coefficients for use in the UNIQUAC equation can be predicted by a group contribution
method: UNIFAC, described below.
The UNIQUAC equation is not given here as its algebraic complexity precludes its use
in manual calculations. It would normally be used as a sub-routine in a design or process
simulation program. For details of the equation consult the texts by Reid et al. (1987) or
Walas (1984).
The best source of data for the UNIQUAC constants for binary pairs is the DECHEMA
vapour-liquid and liquid-liquid data collection, DECHEMA (1977).
8.16.5. Prediction of vapour-liquid equilibria
The designer will often be confronted with the problem of how to proceed with the design
of a separation process without adequate experimentally determined equilibrium data.
Some techniques are available for the prediction of vapour liquid equilibria (v l e) data
and for the extrapolation of experimental values. Caution must be used in the application
of these techniques in design and the predictions should be supported with experimentally
determined values whenever practicable. The same confidence cannot be placed on the
prediction of equilibrium data as that for many of the prediction techniques for other
physical properties given in this chapter. Some of the techniques most useful in design
are given in the following paragraphs.
Estimation of activity coefficients from azeotropic data
If a binary system forms an azeotrope, the activity coefficients can be calculated from
a knowledge of the composition of the azeotrope and the azeotropic temperature. At
the azeotropic point the composition of the liquid and vapour are the same, so from
equation 8.31:
P
i D
P Ži
where P Ži is determined at the azeotropic temperature.
The values of the activity coefficients determined at the azeotropic composition can be
used to calculate the coefficients in the Wilson equation (or any other of the three-suffix
equations) and the equation used to estimate the activity coefficients at other compositions.
Horsley (1973) gives an extensive collection of data on azeotropes.
DESIGN INFORMATION AND DATA
347
Activity coefficients at infinite dilution
The constants in any of the activity coefficient equations can be readily calculated from
experimental values of the activity coefficients at infinite dilution. For the Wilson equation:
where
1
1
1 , 2
A12
A21
ln
1
1
ln
1
2
D ln A12 A21 C 1
⊲8.39a⊳
D ln A21 A12 C 1
⊲8.39b⊳
D the activity coefficients at infinite dilution for components 1 and 2,
respectively,
D the Wilson A-value for component 1 in component 2,
D the Wilson A-value for component 2 in component 1.
Relatively simple experimental techniques, using ebulliometry and chromatography, are
available for the determination of the activity coefficients at infinite dilution. The methods
used are described by Null (1970) and Conder and Young (1979).
Pieratti et al. (1955) have developed correlations for the prediction of the activity coefficients at infinite dilution for systems containing water, hydrocarbons and some other
organic compounds. Their method, and the data needed for predictions, is described by
Treybal (1963) and Reid et al. (1987).
Calculation of activity coefficients from mutual solubility data
For systems that are only partially miscible in the liquid state, the activity coefficient in the
homogeneous region can be calculated from experimental values of the mutual solubility
limits. The methods used are described by Reid et al. (1987), Treybal (1963), Brian (1965)
and Null (1970). Treybal (1963) has shown that the Van-Laar equation should be used
for predicting activity coefficients from mutual solubility limits.
Group contribution methods
Group contribution methods have been developed for the prediction of liquid-phase
activity coefficients. The objective has been to enable the prediction of phase equilibrium
data for the tens of thousands of possible mixtures of interest to the process designer to
be made from the contributions of the relatively few functional groups which made up the
compounds. The UNIFAC method, Fredenslund et al. (1977a), is probably the most useful
for process design. Its use is described in detail in a book by Fredenslund et al. (1977b),
which includes computer programs and data for the use of the UNIFAC method in the
design of distillation columns.
A method was also developed to predict the parameters required for the NRTL equation:
the ASOG method, Kojima and Tochigi (1979).
More extensive work has been done to develop the UNIFAC method, to include a wider
range of functional groups; see Gmeling et al. (1982) and Magnussen et al. (1981).
The UNIFAC equation is the preferred equation for use in design, and it is included as
a sub-routine in most simulation and design programs.
348
CHEMICAL ENGINEERING
Care must be exercised in applying the UNIFAC method. The specific limitations of
the method are:
1.
2.
3.
4.
Pressure not greater than a few bar (say, limit to 5 bar)
Temperature below 150Ž C
No non-condensable components or electrolytes
Components must not contain more than 10 functional groups.
8.16.6. K -values for hydrocarbons
A useful source of K-values for light hydrocarbons is the well-known “De Priester charts”,
Dabyburjor (1978), which are reproduced as Figure 8.3a and b. These charts give the Kvalues over a wide range of temperature and pressure.
8.16.7. Sour-water systems (Sour)
The term sour water is used for water containing carbon dioxide, hydrogen sulphide and
ammonia encountered in refinery operations.
Special correlations have been developed to handle the vapour-liquid equilibria of such
systems, and these are incorporated in most design and simulation programs.
Newman (1991) gives the equilibrium data required for the design of sour water
systems, as charts.
8.16.8. Vapour-liquid equilibria at high pressures
At pressures above a few atmospheres, the deviations from ideal behaviour in the gas phase
will be significant and must be taken into account in process design. The effect of pressure on
the liquid-phase activity coefficient must also be considered. A discussion of the methods used
to correlate and estimate vapour-liquid equilibrium data at high pressures is beyond the scope
of this book. The reader should refer to the texts by Null (1970) or Prausnitz and Chueh (1968).
Prausnitz and Chueh also discuss phase equilibria in systems containing components
above their critical temperature (super-critical components).
8.16.9. Liquid-liquid equilibria
Experimental data, or predictions, that give the distribution of components between the
two solvent phases, are needed for the design of liquid-liquid extraction processes; and
mutual solubility limits will be needed for the design of decanters, and other liquid-liquid
separators.
Perry et al. (1997) give a useful summary of solubility data. Liquid-liquid equilibrium
compositions can be predicted from vapour-liquid equilibrium data, but the predictions
are seldom accurate enough for use in the design of liquid-liquid extraction processes.
Null (1970) gives a computer program for the calculation of ternary diagrams from vle
data, using the Van-Laar equation.
The DECHEMA data collection includes liquid-liquid equilibrium data for several
hundred mixtures, DECHEMA (1977).
DESIGN INFORMATION AND DATA
Figure 8.3.
(a) De Priester chart
349
K-values for hydrocarbons, low temperature
The UNIQUAC equation can be used to estimate activity coefficients and liquid
compositions for multicomponent liquid-liquid systems. The UNIFAC method can be
used to estimate UNIQUAC parameters when experimental data are not available, see
Section 8.16.5.
It must be emphasised that extreme caution needs to be exercised when using predicted
values for liquid activity coefficients in design calculations.
350
CHEMICAL ENGINEERING
Figure 8.3.
(b) De Priester chart
K-values for hydrocarbons, high temperature
8.16.10. Choice of phase equilibria for design calculations
The choice of the best method for deducing vapour-liquid and liquid-liquid equilibria for
a given system will depend on three factors:
1. The composition of the mixture (the class of system)
2. The operating pressure (low, medium or high)
3. The experimental data available.
Classes of mixtures
For the purpose of deciding which phase equilibrium method to use, it is convenient to
classify components into the classes shown in Table 8.10.
351
DESIGN INFORMATION AND DATA
Table 8.10.
Classification of mixtures
Class
Principal interactions
Dispersion forces
Dispersion forces
H2 , N2 , CH4
CCl4 , iC5 H10
III.
IV.
Simple molecules
Complex non-polar
molecules
Polarisable
Polar molecules
Induction dipole
Dipole moment
V.
Hydrogen bonding
Hydrogen bonds
CO2 , C6 H6
dimethyl formamide,
chloroethane
alcohols, water
I.
II.
Table 8.11.
Examples
Selection of phase equilibrium method
Class of mixture
Pressure
Moderate
<15 bar
Low
<3 bar
High
>15 bar
fL
fV
fL
fV
fL
fV
I, II, III
(none supercritical)
ES
I
ES
ES
ES
ES and K
I, II, III
(supercritical)
ES
I
ES
ES
ES
ES and K
I, II, III, IV, V
(vapour-liquid)
ACT
I
ACT
ES
ES
ES and K
I, II, III, IV, V
(liquid-liquid)
ACT
I
ACT
ES
ES
ES
Hydrocarbons
and water
ES
ES and K
ES
ES and K
ES
ES and K
I
ES
K
ACT
D
D
D
D
Ideal, vapour fugacity D partial pressure.
appropriate equation of state.
equilibrium constant (K factor) derived from experimental data.
correlation for liquid-phase activity coefficient: such as, Wilson, NRTL, UNIQUAC, UNIFAC.
(See Section 8.16.4). Use UNIQUAC and UNIFAC v l e parameters for vapour-liquid systems
and l-l-e parameters for liquid-liquid systems.
Using the classification given in Table 8.10, Table 8.11 can be used to select the appropriate vapour-liquid and liquid-liquid phase equilibria method.
Flow chart for selection of phase equilibria method
The flow chart shown in Figure 8.4 has been adapted from a similar chart published by
Wilcon and White (1986). The abbreviations used in the chart for the equations of state
correspond to those given in Section 8.16.3.
8.16.11. Gas solubilities
At low pressures, most gases are only sparingly soluble in liquids, and at dilute
concentrations the systems obey Henry’s law (see Volume 2, Chapter 11). Markham and
Kobe (1941) and Battino and Clever (1966) give comprehensive reviews of the literature
on gas solubilities.
352
Start
N
Use G−S
Y
T < 250K
Use P−R
or R−K−S
Hydrocarbon
C5
or lighter
Y
Y
H2
present
N
Special
case
(polar)
Y
Sour water
Y
Use sour
water system
Y
Use tabular
data
Y
Use γi
correlations
Y
Use
UNIFAC
N
N
Use G−S
Use B−W−R
Y
Y
T < 250K
Experimental
data
H2
present
N
N
N
Use B−K10
Y
γi
Experimental
data
P < 1 bar
N
Use G−S
Y
P < 200 bar
Y
N
Figure 8.4.
P < 4 bar
T < 150 ° C
0 < T < 750K
N
Y
Use R−K−S
N
P < 350 bar
N
N
Further
experimental
work required
Flow chart for the selection of phase equilibria method
CHEMICAL ENGINEERING
N
DESIGN INFORMATION AND DATA
353
8.16.12. Use of equations of state to estimate specific enthalpy
and density
Computer aided packages for the design and simulation of separation processes will
contain sub-routines for the estimation of excess enthalpy and liquid and vapour density
from the appropriate equation of state.
Specific enthalpy
For the vapour phase, the deviation of the specific enthalpy from the ideal state can be
illustrated using the Redlich-Kwong equation, written in the form:
z3 C z2 C z⊲B2 C B A⊳ D 0
where z D the compressibility factor
aðP
AD 2
R ð T2.5
bðP
BD
RðT
The fugacity coefficient is given by:
B
A
ln 1
B
z
dP
P d
and the excess enthalpy ⊲H HŽ ⊳ D RT C
T
dT v
0
ln D z 1 ln⊲z b⊳
where H is enthalpy at the system temperature and pressure and HŽ enthalpy at the ideal
state.
Unless liquid phase activity coefficients have been used, it is best to use the same
equation of state for excess enthalpy that was selected for the vapour-liquid equilibria. If
liquid-phase activity coefficients have been specified, then a correlation appropriate for
the activity coefficient method should be used.
Density
For vapours, use the equation of state selected for predicting the vapour-liquid equilibria.
For liquids, use the same equation if it is suitable for estimating liquid density.
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ROWLEY, R. L., WILDING, W. V., OSCARSON, J. L., YANG, W. and ZUNDEL, N. A. (2004) DIPPR Data Compilation of Pure Chemical Properties (Design Institute for Physical Properties, AIChE).
SMITH, W. T., GREENBAUM, S. and RUTLEDGE, G. P. (1954) J. Phys. Chem. 58, 443. Correlation of critical
temperature with thermal expansion coefficients of organic liquids.
SOAVE, G. (1972) Chem. Eng. Sci. 27, 1197 Equilibrium constants from modified Redlich-Kwong equation of
state.
SOUDERS, M. (1938) J. Am. Chem. Soc. 60, 154. Viscosity and chemical constitution.
STERBACEK, Z., BISKUP, B. and TAUSK, P. (1979) Calculation of Properties using Corresponding-state Methods
(Elsevier).
356
CHEMICAL ENGINEERING
SUGDEN, S. (1924) J. Chem. Soc. 125, 1177. A relation between surface tension, density, and chemical composition.
TOULOUKIAN, Y. S. (ed.) (1970-77) Thermophysical Properties of Matter, TPRC Data Services (Plenum Press).
TREYBAL, R. E. (1963) Liquid Extraction, 2nd edn (McGraw-Hill).
TROUTON, F. T. (1884) Phil. Mag. 18, 54. On molecular latent heat.
TSEDERBERG, N. V. (1965) Thermal Conductivity of Gases and Liquids (Arnold).
ULLMAN (2002) Ullman’s Encyclopedia of Industrial Chemistry, 5th edn (VCH).
WALAS, S. M. (1985) Phase Equilibrium in Chemical Engineering (Butterworths).
WATSON, K. M. (1943) Ind. Eng. Chem. 35, 398. Thermodynamics of the liquid state: generalized prediction
of properties.
WEBER, H. F. (1980) Ann Phy. Chem. 10, 103. Untersuchungen über die wärmeleitung in flüssigkeiten.
WERNER, R. R. (1941) Thermochemical Calculations (McGraw-Hill).
WILKE, C. R. (1949) Chem. Eng. Prog. 45, 218. Estimation of liquid diffusion coefficients.
WILKE, C. R. and CHANG, P. (1955) A.I.Ch.E.Jl. 1, 264. Correlation of diffusion coefficients in dilute solutions.
WILCON, R. F. and WHITE, S. L. (1986) Chem. Eng., NY 93, (Oct. 27th) 142. Selecting the proper model to
stimulate vapour-liquid equilibrium.
WILSON, G. M. (1964) J. Am. Chem. Soc. 86, 127. A new expression for excess energy of mixing.
YAWS, C. L. (1993 1994) Handbook of Viscosity, 4 vols (Gulf Publishing).
YAWS, C. L. (1994 1995) Handbook of Vapor Pressure, 4 vols (Gulf Publishing).
YAWS, C. L. (1995 1997) Handbook of Thermal Conductivity, 4 vols (Gulf Publishing).
YORK, R. and HOLMES, R. C. (1942) Ind. Eng. Chem. 34, 345. Vapor-liquid equilibria of the system acetoneacetic acid-water.
Bibliography: general sources of physical properties
BOUBIK, T., FRIED, V. and HALA, E. (1984) The Vapour Pressures of Pure Substances, 2nd edn (Elsevier).
BOUL, M., NYVLT and SOHNEL (1981) Solubility of Inorganic Two-Component Systems (Elsevier).
CHRISTENSEN, J. J., HANKS, R. W. and IZATT (1982) Handbook of Heats of Mixing (Wiley).
DREISBACH, R. R. (1955-61) Physical Properties of Chemical Compounds, Vols. I, II, III (American Chemical
Society).
DREISBACH, R. R. (1952) Pressure-volume-temperature Relationships of Organic Compounds, 3rd edn
(Handbook Publishers).
FENSKE, M., BRAUN, W. G. and THOMPSON, W. H. (1966) Technical Data Book-Petroleum Refining (American
Petroleum Institute).
FLICK, E. W. (ed.) (1991) Industrial Solvent Handbook, 4th edn (Noyes).
GALLANT, R. W. (1968) (1970) Physical Properties of Hydrocarbons, Vols. 1 and 2 (Gulf).
LANGE, N. A. (ed.) (1961) Handbook of Chemistry, 10th edn (McGraw-Hill).
MAXWELL, J. B. (1950) Data Book on Hydrocarbons (Van Nostrand).
NATIONAL BUREAU OF STANDARDS (1951) Selected Values of Thermodynamic Properties, Circular C500 (US
Government Printing Office).
PERRY, R.H., GREEN, D. W. and MALONEY, J. O. (eds) (1997) Perry’s Chemical Engineers’ Handbook, 7th edn.
(McGraw-Hill).
RENON, H. (1986) Fluid Properties and Phase Equilibria for Chemical Engineers (Elsevier).
ROSS, T. K. and FRESHWATER, D. C. (1962) Chemical Engineers Data Book (Leonard Hill).
ROSSINI, F. D. (1953) Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related
Compounds (American Chemical Society).
SEIDELL, A. (1952) Solubilities of Inorganic and Organic Compounds, 3rd edn (Van Nostrand).
SOHNEL, O. and NOVOTNY (1985) Densities of Aqueous Solutions in Organic Substances (Elsevier).
SPIERS, H. M. (ed.) (1961) Technical Data on Fuel, 6th edn (British National Committee, Conference on World
Power).
STEPHEN, T. and STEPHEN, H. (1963) Solubilities of Inorganic and Organic Compounds, 2 vols. (Macmillan).
STEPHENSON, R. M. (1966) Introduction to Chemical Process Industries (Reinhold).
TAMIR, A., Tamir, E. and STEPHAN, K. (1983) Heats on Phase Change of Pure Components and Mixtures
(Elsevier).
TIMMERMANNS, J. (1950) Physico-chemical Constants of Pure Organic Compounds (Elsevier).
TIMMERMANNS, J. (1959) Physico-chemical Constants of Binary Systems, 4 vols. (Interscience).
VISWANATH, D. S. and NATARAJAN, G. (1989) Data Book on Viscosity (Hemisphere).
WEAST, R. C. (ed.) (1972) Handbook of Chemistry and Physics, 53rd edn (the Chemical Rubber Co.).
WASHBURN, E. W. (ed.) (1933) International Critical Tables of Numerical Data, Physics, Chemistry, and
Technology, 8 vols. (McGraw-Hill).
357
DESIGN INFORMATION AND DATA
WISNIAK, J. and TAMIR, A. (1980) Liquid-liquid Equilibria and Extraction: A Literature Source Book, Parts A
and B.
WISNIAK, J. and HERSKOWITZ, M. (1984) Solubility of Gases and Solids, 2 vols. (Elsevier).
YAWS, C. L. (1977) Physical Properties (McGraw-Hill).
YAWS, C. L. (ed) (1999) Chemical Properties Handbook (McGraw-Hill).
Yaw’s Handbook of Thermodynamic and Physical Properties of Chemical Compounds (2003) Knovel.
8.18. NOMENCLATURE
Dimensions
in MLTq
A
A1,2
a
B
Bi
b
C
Cp
DL
Dv
fi
fOL
i
H
H0
I
K
K0
k
km
Lv
Lv,b
M
n
P
Pc
Pch
Pi0
Pk
Pr
Pc
R
T
Tb
Tc
Tr
Tc
t
Vc
Vm
Vc
vi
v0i
w
x
y
z
Coefficient in the Antoine equation
Coefficients in the Wilson equation for the binary pair 1, 2
Coefficient in the Redlich Kwong equation of state
Coefficient in the Antoine equation
Second viral coefficient for component i
Coefficient in the Redlich Kwong equation of state
Coefficient in the Antoine equation
Specific heat capacity at constant pressure
Liquid diffusivity
Gas diffusivity
Fugacity coefficient for component i
Standard state fugacity coefficient of pure liquid
Specific enthalpy
Excess specific enthalpy
Souders’ index (equation 8.9)
Equilibrium constant (ratio)
Equilibrium constant for an ideal mixture
Thermal conductivity
Thermal conductivity of a mixture
Latent heat of vaporisation
Latent heat at normal boiling point
Molecular mass (weight)
Number of components
Pressure
Critical pressure
Sugden’s parachor (equation 8.23)
Vapour pressure of component i
Vapour pressure of component k
Reduced pressure
Critical constant increment in Lydersen equation (equation 8.26)
Universal gas constant
Temperature, absolute scale
Normal boiling point, absolute scale
Critical temperature
Reduced temperature
Critical constant increment in Lydersen equation (Equation 8.25)
Temperature, relative scale
Critical volume
Molar volume at normal boiling point
Critical constant increment in Lydersen equation (Equation 8.27)
Special diffusion volume coefficient for component i (Table 8.5)
Liquid molar volume
Mass fraction (weight fraction)
Mol fraction, liquid phase
Mol fraction, vapour phase
Compressibility factor
q
M1 L3
q
L2 T2 q1
L2 T1
L2 T1
L2 T2
L2 T2
M1 L3
MLT3 q1
MLT3 q1
L2 T2
L2 T2
M
ML1 T2 or L
ML1 T2
ML1 T2 or L
ML1 T2 or L
M1/2 L1/2 T
L2 T2 q1
q
q
q
q
M1 L3
M1 L3
M1 L3
L3
M1 L3
358
˛
ˇ
1
b
m
L
v
b
m
s
L
V
CHEMICAL ENGINEERING
Relative volatility
Coefficient of thermal expansion
Liquid activity coefficient
Activity coefficient at infinite dilution
Dynamic viscosity
Viscosity at boiling point
Viscosity of a mixture
Density
Liquid density
Vapour (gas) density
Density at normal boiling point
Surface tension
Surface tension of a mixture
Fugacity coefficient
Fugacity coefficient of pure component
Fugacity coefficient of pure liquid
Fugacity coefficient of pure vapour
q1
ML1 T1
ML1 T1
ML1 T1
ML3
ML3
ML3
ML3
MT2
MT2
Suffixes
a, b
i, j, k
1, 2
L
V
Components
Liquid
Vapour
8.19. PROBLEMS
8.1. Estimate the liquid density at their boiling points for the following:
1.
2.
3.
4.
5.
2-butanol,
Methyl chloride,
Methyl ethyl ketone,
Aniline,
Nitrobenzene.
8.2. Estimate the density of the following gases at the conditions given:
1.
2.
3.
4.
5.
6.
Hydrogen at 20 bara and 230 Ž C,
Ammonia at 1 bara and 50 Ž C and at 100 bara and 300 Ž C,
Nitrobenzene at 20 bara and 230 Ž C,
Water at 100 bara and 500 Ž C. Check your answer using steam tables,
Benzene at 2 barg and 250 Ž C,
Synthesis gas (N2 C 3H2 ) at 5 barg and 25 Ž C.
8.3. Make a rough estimate of the viscosity of 2-butanol and aniline at their boiling
points, using the modified Arrhenius equation. Compare your values with those
given using the equation for viscosity in Appendix C.
8.4. Make a rough estimate of the thermal conductivity of n-butane both as a liquid
at 20 Ž C and as a gas at 5 bara and 200 Ž C. Take the viscosity of the gaseous
n-butane as 0.012 mN m2 s.
8.5. Estimate the specific heat capacity of liquid 1,4 pentadiene and aniline at 20 Ž C.
359
DESIGN INFORMATION AND DATA
8.6. For the compounds listed below, estimate the constants in the equation for ideal
gas heat capacity, equation 3.19, using the method given in Section 8.9.2.
1.
2.
3.
4.
3-methyl thiophene.
Nitrobenzene.
2-methyl-2-butanethiol.
Methyl-t-butyl ether.
8.7. Estimate the heat of vaporisation of methyl-t-butyl ether, at 100 Ž C.
8.8. Estimate the gaseous phase diffusion coefficient for the following systems, at 1
atmosphere and the temperatures given:
1.
2.
3.
4.
5.
Carbon dioxide in air at 20 Ž C,
Ethane in hydrogen at 0 Ž C,
Oxygen in hydrogen at 0 Ž C,
Water vapour in air at 450 Ž C,
Phosgene in air at 0 Ž C.
8.9. Estimate the liquid phase diffusion coefficient for the following systems at 25 Ž C:
1.
2.
3.
4.
5.
Toluene in n-heptane,
Nitrobenzene in carbon tetrachloride,
Chloroform in benzene,
Hydrogen chloride in water,
Sulphur dioxide in water.
8.10. Estimate the surface tension of pure acetone and ethanol at 20 Ž C, and benzene at
16 Ž C, all at 1 atmosphere pressure.
8.11. Using Lydersen’s method, estimate the critical constants for isobutanol.
Compare your values with those given in Appendix C.
8.12. The composition of the feed to a debutaniser is given below. The column will
operate at 14 bar and below 750 K. The process is to be modelled using a
commercial simulation program. Suggest a suitable phase equilibrium method to
use in the simulation.
Feed composition:
propane
isobutane
n-butane
isopentane
normal pentane
normal hexane
C3
i C4
n C4
i C5
n C5
n C6
kg/h
910
180
270
70
90
20
8.13. In the manufacture of methyl ethyl ketone from butanol, the product is separated
from unreacted butanol by distillation. The feed to the column consists of a mixture
of methyl ethyl ketone, 2-butanol and trichloroethane. What would be a suitable
phase equilibrium correlation to use in modelling this process?
CHAPTER 9
Safety and Loss Prevention
9.1. INTRODUCTION
Any organisation has a legal and moral obligation to safeguard the health and welfare of
its employees and the general public. Safety is also good business; the good management
practices needed to ensure safe operation will also ensure efficient operation.
The term “loss prevention” is an insurance term, the loss being the financial loss caused
by an accident. This loss will not only be the cost of replacing damaged plant and third
party claims, but also the loss of earnings from lost production and lost sales opportunity.
All manufacturing processes are to some extent hazardous, but in chemical processes
there are additional, special, hazards associated with the chemicals used and the process
conditions. The designer must be aware of these hazards, and ensure, through the application of sound engineering practice, that the risks are reduced to acceptable levels.
In this book only the particular hazards associated with chemical and allied processes
will be considered. The more general, normal, hazards present in all manufacturing process
such as, the dangers from rotating machinery, falls, falling objects, use of machine tools,
and of electrocution will not be considered. General industrial safety and hygiene are
covered in several books, King and Hirst (1998), Ashafi (2003) and Ridley (2003).
Safety and loss prevention in process design can be considered under the following
broad headings:
1. Identification and assessment of the hazards.
2. Control of the hazards: for example, by containment of flammable and toxic
materials.
3. Control of the process. Prevention of hazardous deviations in process variables
(pressure, temperature, flow), by provision of automatic control systems, interlocks,
alarms, trips; together with good operating practices and management.
4. Limitation of the loss. The damage and injury caused if an incident occurs: pressure
relief, plant layout, provision of fire-fighting equipment.
In this chapter the discussion of safety in process design will of necessity be limited. A
more complete treatment of the subject can be found in the books by Wells (1980) (1997),
Lees (1996), Fawcett and Wood (1984), Green (1982) and Carson and Mumford (1988)
(2002); and in the general literature, particularly the publications by the American Institute
of Chemical Engineers and the Institution of Chemical Engineers. The proceedings of the
symposia on safety and loss prevention organised by these bodies, and the European
Federation of Chemical Engineering, also contain many articles of interest on general
safety philosophy, techniques and organisation, and the hazards associated with specific
360
SAFETY AND LOSS PREVENTION
361
processes and equipment. The Institution of Chemical Engineers has published a book on
safety of particular interest to students of Chemical Engineering, Marshall and Ruhemann
(2000).
9.2. INTRINSIC AND EXTRINSIC SAFETY
Processes can be divided into those that are intrinsically safe, and those for which the
safety has to be engineered in. An intrinsically safe process is one in which safe operation
is inherent in the nature of the process; a process which causes no danger, or negligible danger, under all foreseeable circumstances (all possible deviations from the design
operating conditions). The term inherently safe is often preferred to intrinsically safe, to
avoid confusion with the narrower use of the term intrinsically safe as applied to electrical
equipment (see Section 9.3.4).
Clearly, the designer should always select a process that is inherently safe whenever
it is practical, and economic, to do so. However, most chemical manufacturing processes
are, to a greater or lesser extent, inherently unsafe, and dangerous situations can develop
if the process conditions deviate from the design values.
The safe operation of such processes depends on the design and provision of engineered
safety devices, and on good operating practices, to prevent a dangerous situation developing, and to minimise the consequences of any incident that arises from the failure of
these safeguards.
The term “engineered safety” covers the provision in the design of control systems,
alarms, trips, pressure-relief devices, automatic shut-down systems, duplication of key
equipment services; and fire-fighting equipment, sprinkler systems and blast walls, to
contain any fire or explosion.
The design of inherently safe process plant is discussed by Kletz in a booklet published
by the Institution of Chemical Engineers, Kletz (1984) and Keltz and Cheaper (1998). He
makes the telling point that what you do not have cannot leak out: so cannot catch fire,
explode or poison anyone. Which is a plea to keep the inventory of dangerous material
to the absolute minimum required for the operation of the process.
9.3. THE HAZARDS
In this section the special hazards of chemicals are reviewed (toxicity, flammability and
corrosivity); together with the other hazards of chemical plant operation.
9.3.1. Toxicity
Most of the materials used in the manufacture of chemicals are poisonous, to some extent.
The potential hazard will depend on the inherent toxicity of the material and the frequency
and duration of any exposure. It is usual to distinguish between the short-term effects
(acute) and the long-term effects (chronic). A highly toxic material that causes immediate
injury, such as phosgene or chlorine, would be classified as a safety hazard. Whereas a
material whose effect was only apparent after long exposure at low concentrations, for
instance, carcinogenic materials, such as vinyl chloride, would be classified as industrial
362
CHEMICAL ENGINEERING
health and hygiene hazards. The permissible limits and the precautions to be taken to
ensure the limits are met will be very different for these two classes of toxic materials.
Industrial hygiene is as much a matter of good operating practice and control as of good
design.
The inherent toxicity of a material is measured by tests on animals. It is usually
expressed as the lethal dose at which 50 per cent of the test animals are killed, the
LD50 (lethal dose fifty) value. The dose is expressed as the quantity in milligrams of the
toxic substance per kilogram of body weight of the test animal.
Some values for tests on rats are given in Table 9.1. Estimates of the LD50 for man
are based on tests on animals. The LD50 measures the acute effects; it gives only a crude
indication of the possible chronic effects.
Table 9.1.
Some LD50 values
Compound
mg/kg
Potassium cyanide
Tetraethyl lead
Lead
DDT
Aspirin
Table salt
10
35
100
150
1500
3000
Source: Lowrance (1976).
There is no generally accepted definition of what can be considered toxic and non-toxic.
A system of classification is given in the Classification, Packaging and Labelling of
Dangerous Substances, Regulations, 1984 (United Kingdom), which is based on European
Union (EU) guidelines; for example:
LD50 , absorbed orally in rats, mg/kg
25
very toxic
25 to 200
toxic
200 to 2000
harmful
These definitions apply only to the short-term (acute) effects. In fixing permissible limits
on concentration for the long-term exposure of workers to toxic materials, the exposure
time must be considered together with the inherent toxicity of the material. The “Threshold
Limit Value” (TLV) is a commonly used guide for controlling the long-term exposure of
workers to contaminated air. The TLV is defined as the concentration to which it is
believed the average worker could be exposed to, day by day, for 8 hours a day, 5 days
a week, without suffering harm. It is expressed in ppm for vapours and gases, and in
mg/m3 (or grains/ft3 ) for dusts and liquid mists. A comprehensive source of data on the
toxicity of industrial materials is Sax’s handbook, Lewis (2004); which also gives guidance
on the interpretation and use of the data. Recommended TLV values are published in
bulletins by the United States Occupational Safety and Health Administration. Since
1980 the United Kingdom Health and Safety Executive (HSE) has published values for
the Occupational Exposure Limits (OEL), for both long and short term exposure, in place
of TLV values.
SAFETY AND LOSS PREVENTION
363
Fuller details of the methods used for toxicity testing, the interpretation of the result
and their use in setting standards for industrial hygiene are given in the more specialised
texts on the subject; see Carson and Mumford (1988) and Lees (1996).
Control of substances hazardous to health
In the United Kingdom the use of substances likely to be harmful to employees is covered
by regulations issued by the Health and Safety Executive (HSE), under the Health and
Safety at Work Act, 1974 (HSAWA). The principal set of regulations in force is the
Control of Substances Hazardous to Health regulations, 2002; known under the acronym:
the COSHH regulations. The COSHH regulations apply to any hazardous substance in
use in any place of work.
The employer is required to carry out an assessment to evaluate the risk to health,
and establish what precautions are needed to protect employees. A written record of the
assessment would be kept, and details made available to employees.
A thorough explanation of the regulations is not within the scope of this book, as they
will apply more to plant operation and maintenance than to process design. The HSE
has published a series of booklets giving details of the regulations and their application
(see www.hse.gov.uk/pubns). A comprehensive guide to the COSHH regulations has also
been published by the Royal Society of Chemistry, Simpson and Simpson (1991).
The designer will be concerned more with the preventative aspects of the use of
hazardous substances. Points to consider are:
1. Substitution: of the processing route with one using less hazardous material. Or,
substitution of toxic process materials with non-toxic, or less toxic materials.
2. Containment: sound design of equipment and piping, to avoid leaks. For example,
specifying welded joints in preference to gasketed flanged joints (liable to leak).
3. Ventilation: use open structures, or provide adequate ventilation systems.
4. Disposal: provision of effective vent stacks to disperse material vented from pressure
relief devices; or use vent scrubbers.
5. Emergency equipment: escape routes, rescue equipment, respirators, safety showers,
eye baths.
In addition, good plant operating practice would include:
1.
2.
3.
4.
5.
Written instruction in the use of the hazardous substances and the risks involved.
Adequate training of personnel.
Provision of protective clothing.
Good housekeeping and personal hygiene.
Monitoring of the environment to check exposure levels. Consider the installation
of permanent instruments fitted with alarms.
6. Regular medical check-ups on employees, to check for the chronic effects of toxic
materials.
9.3.2. Flammability
The term “flammable” is now more commonly used in the technical literature than
“inflammable” to describe materials that will burn, and will be used in this book. The
hazard caused by a flammable material depends on a number of factors:
364
1.
2.
3.
4.
CHEMICAL ENGINEERING
The
The
The
The
flash-point of the material.
autoignition temperature of the material.
flammability limits of the material.
energy released in combustion.
Flash-point
The flash-point is a measure of the ease of ignition of the liquid. It is the lowest temperature at which the material will ignite from an open flame. The flash-point is a function of
the vapour pressure and the flammability limits of the material. It is measured in standard
apparatus, following standard procedures (BS 2000). Both open- and closed-cup apparatus
is used. Closed-cup flash-points are lower than open cup, and the type of apparatus used
should be stated clearly when reporting measurements. Flash-points are given in Sax’s
handbook, Lewis (2004). The flash-points of many volatile materials are below normal
ambient temperature; for example, ether 45Ž C, petrol (gasoline) 43Ž C (open cup).
Autoignition temperature
The autoignition temperature of a substance is the temperature at which it will ignite
spontaneously in air, without any external source of ignition. It is an indication of the
maximum temperature to which a material can be heated in air; for example, in drying
operations.
Flammability limits
The flammability limits of a material are the lowest and highest concentrations in air, at
normal pressure and temperature, at which a flame will propagate through the mixture.
They show the range of concentration over which the material will burn in air, if ignited.
Flammability limits are characteristic of the particular material, and differ widely for
different materials. For example, hydrogen has a lower limit of 4.1 and an upper limit of
74.2 per cent by volume, whereas for petrol (gasoline) the range is only from 1.3 to 7.0
per cent.
The Flammability limits for a number of materials are given in Table 9.2.
The limits for a wider range of materials are given in Sax’s handbook, Lewis (2004).
A flammable mixture may exist in the space above the liquid surface in a storage
tank. The vapour space above highly flammable liquids is usually purged with inert gas
(nitrogen) or floating-head tanks are used. In a floating-head tank a “piston” floats on top
of the liquid, eliminating the vapour space.
Flame traps
Flame arresters are fitted in the vent lines of equipment that contains flammable material
to prevent the propagation of flame through the vents. Various types of proprietary flame
arresters are used. In general, they work on the principle of providing a heat sink,
usually expanded metal grids or plates, to dissipate the heat of the flame. Flame arrestors
and their applications are discussed by Rogowski (1980), Howard (1992) and Mendoza
et al. (1988).
Traps should also be installed in plant ditches to prevent the spread of flame. These
are normally liquid U-legs, which block the spread of flammable liquid along ditches.
365
SAFETY AND LOSS PREVENTION
Table 9.2.
Material
Hydrogen
Ammonia
Hydrocyanic acid
Hydrogen sulphide
Carbon disulphide
Carbon monoxide
Methane
Ethane
Propane
Butane
Isobutane
Ethylene
Propylene
n-Butene
Isobutene
Butadiene
Benzene
Toluene
Cyclohexane
Methanol
Ethanol
Isopropanol
Formaldehyde
Acetaldehyde
Aetone
Methylethyl ketone
Dimethylamine (DEA)
Trimethylamine (TEA)
Petrol (gasoline)
Paraffin (kerosene)
Gas oil (diesel)
Flammability ranges
Lower limit
Upper limit
4.1
15.0
5.6
4.3
1.3
12.5
5.3
3.0
2.3
1.9
1.8
3.1
2.4
1.6
1.8
2.0
1.4
1.4
1.3
7.3
4.3
2.2
7.0
4.1
3.0
1.8
2.8
2.0
1.3
0.7
6.0
74.2
28.0
40.0
45.0
44.0
74.2
14.0
12.5
9.5
8.5
8.4
32.0
10.3
9.3
9.7
11.5
7.1
6.7
8.0
36.0
19.0
12.0
73.0
57.0
12.8
10.0
184
11.6
7.0
5.6
13.5
Volume percentage in air at ambient conditions
Fire precautions
Recommendations on the fire precautions to be taken in the design of chemical plant are
given in the British Standard, BS 5908.
9.3.3. Explosions
An explosion is the sudden, catastrophic, release of energy, causing a pressure wave (blast
wave). An explosion can occur without fire, such as the failure through over-pressure of
a steam boiler or an air receiver.
When discussing the explosion of a flammable mixture it is necessary to distinguish
between detonation and deflagration. If a mixture detonates the reaction zone propagates
at supersonic velocity (approximately 300 m/s) and the principal heating mechanism in
the mixture is shock compression. In a deflagration the combustion process is the same
as in the normal burning of a gas mixture; the combustion zone propagates at subsonic
366
CHEMICAL ENGINEERING
velocity, and the pressure build-up is slow. Whether detonation or deflagration occurs
in a gas-air mixture depends on a number of factors; including the concentration of the
mixture and the source of ignition. Unless confined or ignited by a high-intensity source
(a detonator) most materials will not detonate. However, the pressure wave (blast wave)
caused by a deflagration can still cause considerable damage.
Certain materials, for example, acetylene, can decompose explosively in the absence
of oxygen; such materials are particularly hazardous.
Confined vapour cloud explosion (CVCE)
A relatively small amount of flammable material, a few kilograms, can lead to an explosion
when released into the confined space of a building.
Unconfined vapour cloud explosions (UCVCE)
This type of explosion results from the release of a considerable quantity of flammable
gas, or vapour, into the atmosphere, and its subsequent ignition. Such an explosion can
cause extensive damage, such as occurred at Flixborough, HMSO (1975). Unconfined
vapour explosions are discussed by Munday (1976) and Gugan (1979).
Boiling liquid expanding vapour explosions (BLEVE)
Boiling liquid expanding vapour explosions occur when there is a sudden release of
vapour, containing liquid droplets, due to the failure of a storage vessel exposed to fire. A
serious incident involving the failure of a LPG (Liquified Petroleum Gas) storage sphere
occurred at Feyzin, France, in 1966, when the tank was heated by an external fire fuelled
by a leak from the tank; see Lees (1996) and Marshall (1987).
Dust explosions
Finely divided combustible solids, if intimately mixed with air, can explode. Several
disastrous explosions have occurred in grain silos.
Dust explosions usually occur in two stages: a primary explosion which disturbs
deposited dust; followed by the second, severe, explosion of the dust thrown into
the atmosphere. Any finely divided combustible solid is a potential explosion hazard.
Particular care must be taken in the design of dryers, conveyors, cyclones, and storage
hoppers for polymers and other combustible products or intermediates. The extensive
literature on the hazard and control of dust explosions should be consulted before
designing powder handling systems: Field (1982), Cross and Farrer (1982), Barton (2001),
and Eckhoff (2003).
9.3.4. Sources of ignition
Though precautions are normally taken to eliminate sources of ignition on chemical plants,
it is best to work on the principle that a leak of flammable material will ultimately find
an ignition source.
SAFETY AND LOSS PREVENTION
367
Electrical equipment
The sparking of electrical equipment, such as motors, is a major potential source of ignition,
and flame proof equipment is normally specified. Electrically operated instruments, controllers and computer systems are also potential sources of ignition of flammable mixtures.
The use of electrical equipment in hazardous areas is covered by British Standards BS
5345 and BS 5501. The code of practice, BS 5345, Part 1, defines hazardous areas as
those where explosive gas-air mixtures are present, or may be expected to be present,
in quantities such as to require special precautions for the construction and use of
electrical apparatus. Non-hazardous areas are those where explosive gas-air mixtures are
not expected to be present.
Three classifications are defined for hazardous areas:
Zone 0:
Specify:
Zone 1:
Specify:
explosive gas-air mixtures are present continuously or present for long periods.
intrinsically safe equipment.
explosive gas-air mixtures likely to occur in normal operation.
intrinsically safe equipment, or flame-proof enclosures: enclosures with pressurizing and purging.
Zone 3: explosive gas-air mixtures not likely to occur during normal operation, but could
occur for short periods.
Specify: intrinsically safe equipment, or total enclosure, or non-sparking apparatus.
Consult the standards for the full specification before selecting equipment for use in
the designated zones.
The design and specification of intrinsically safe control equipment and systems is
discussed by MacMillan (1998) and Cooper and Jones (1993).
Static electricity
The movement of any non-conducting material, powder, liquid or gas, can generate static
electricity, producing sparks. Precautions must be taken to ensure that all piping is properly
earthed (grounded) and that electrical continuity is maintained around flanges. Escaping
steam, or other vapours and gases, can generate a static charge. Gases escaping from a
ruptured vessel can self-ignite from a static spark. For a review of the dangers of static
electricity in the process industries, see the article by Napier and Russell (1974); and the
books by Pratt (1999) and Britton (1999). A code of practice for the control of static
electricity is given in BS 5938 (1991).
Process flames
Open flames from process furnaces and incinerators are obvious sources of ignition and
must be sited well away from plant containing flammable materials.
Miscellaneous sources
It is the usual practice on plants handling flammable materials to control the entry on to the
site of obvious sources of ignition; such as matches, cigarette lighters and battery-operated
368
CHEMICAL ENGINEERING
equipment. The use of portable electrical equipment, welding, spark-producing tools and
the movement of petrol-driven vehicles would also be subject to strict control.
Exhaust gases from diesel engines are also a potential source of ignition.
9.3.5. Ionising radiation
The radiation emitted by radioactive materials is harmful to living matter. Small quantities
of radioactive isotopes are used in the process industry for various purposes; for example, in
level and density-measuring instruments, and for the non-destructive testing of equipment.
The use of radioactive isotopes in industry is covered by government legislation, see
hse.gov.uk/pubns.
A discussion of the particular hazards that arise in the chemical processing of nuclear
fuels is outside the scope of this book.
9.3.6. Pressure
Over-pressure, a pressure exceeding the system design pressure, is one of the most serious
hazards in chemical plant operation. Failure of a vessel, or the associated piping, can
precipitate a sequence of events that culminate in a disaster.
Pressure vessels are invariably fitted with some form of pressure-relief device, set at
the design pressure, so that (in theory) potential over-pressure is relieved in a controlled
manner.
Three basically different types of relief device are commonly used:
Directly actuated valves: weight or spring-loaded valves that open at a predetermined
pressure, and which normally close after the pressure has been relieved. The system
pressure provides the motive power to operate the valve.
Indirectly actuated valves: pneumatically or electrically operated valves, which are
activated by pressure-sensing instruments.
Bursting discs: thin discs of material that are designed and manufactured to fail at a
predetermined pressure, giving a full bore opening for flow.
Relief valves are normally used to regulate minor excursions of pressure; and bursting
discs as safety devices to relieve major over-pressure. Bursting discs are often used in
conjunction with relief valves to protect the valve from corrosive process fluids during
normal operation. The design and selection of relief valves is discussed by Morley
(1989a,b), and is also covered by the pressure vessel standards, see Chapter 13. Bursting
discs are discussed by Mathews (1984), Askquith and Lavery (1990) and Murphy (1993).
In the United Kingdom the use of bursting discs is covered by BS 2915. The discs are
manufactured in a variety of materials for use in corrosive conditions; such as, impervious carbon, gold and silver; and suitable discs can be found for use with all process
fluids.
Bursting discs and relief valves are proprietary items and the vendors should be
consulted when selecting suitable types and sizes.
The factors to be considered in the design of relief systems are set out in a comprehensive paper by Parkinson (1979) and by Moore (1984); and in a book published by the
Institution of Chemical Engineers, Parry (1992).
SAFETY AND LOSS PREVENTION
369
Vent piping
When designing relief venting systems it is important to ensure that flammable or toxic
gases are vented to a safe location. This will normally mean venting at a sufficient
height to ensure that the gases are dispersed without creating a hazard. For highly toxic
materials it may be necessary to provide a scrubber to absorb and “kill” the material;
for instance, the provision of caustic scrubbers for chlorine and hydrochloric acid gases.
If flammable materials have to be vented at frequent intervals; as, for example, in some
refinery operations, flare stacks are used.
The rate at which material can be vented will be determined by the design of the
complete venting system: the relief device and the associated piping. The maximum
venting rate will be limited by the critical (sonic) velocity, whatever the pressure drop
(see Volume 1, Chapter 4). The design of venting systems to give adequate protection
against over-pressure is a complex and difficult subject, particularly if two-phase flow is
likely to occur. For complete protection the venting system must be capable of venting
at the same rate as the vapour is being generated. For reactors, the maximum rate of
vapour generation resulting from a loss of control can usually be estimated. Vessels must
also be protected against over-pressure caused by external fires. In these circumstances the
maximum rate of vapour generation will depend on the rate of heating. Standard formulae
are available for the estimation of the maximum rates of heat input and relief rates, see
ROSPA (1971) and NFPA (1987a,b).
For some vessels, particularly where complex vent piping systems are needed, it may be
impractical for the size of the vent to give complete protection against the worst possible
situation.
For a comprehensive discussion of the problem of vent system design, and the design
methods available, see the papers by Duxbury (1976, 1979).
The design of relief systems has been studied by the Design Institute for Emergency
Relief Systems (DIERS), established by the American Institute of Chemical Engineers;
Fisher (1985). DIERS has published recommended design methods; see Poole (1985) and
AIChemE (1992a,b). Computer programs based on the work by DIERS are also available.
Under-pressure (vacuum)
Unless designed to withstand external pressure (see Chapter 13) a vessel must be protected
against the hazard of under-pressure, as well as over-pressure. Under-pressure will normally
mean vacuum on the inside with atmospheric pressure on the outside. It requires only a slight
drop in pressure below atmospheric pressure to collapse a storage tank. Though the pressure
differential may be small, the force on the tank roof will be considerable. For example, if the
pressure in a 10-m diameter tank falls to 10 millibars below the external pressure, the total
load on the tank roof will be around 80,000 N (8 tonne). It is not an uncommon occurrence
for a storage tank to be sucked in (collapsed) by the suction pulled by the discharge pump,
due to the tank vents having become blocked. Where practical, vacuum breakers (valves that
open to atmosphere when the internal pressure drops below atmospheric) should be fitted.
9.3.7. Temperature deviations
Excessively high temperature, over and above that for which the equipment was designed,
can cause structural failure and initiate a disaster. High temperatures can arise from loss
370
CHEMICAL ENGINEERING
of control of reactors and heaters; and, externally, from open fires. In the design of
processes where high temperatures are a hazard, protection against high temperatures is
provided by:
1. Provision of high-temperature alarms and interlocks to shut down reactor feeds, or
heating systems, if the temperature exceeds critical limits.
2. Provision of emergency cooling systems for reactors, where heat continues to be
generated after shut-down; for instance, in some polymerisation systems.
3. Structural design of equipment to withstand the worst possible temperature excursion.
4. The selection of intrinsically safe heating systems for hazardous materials.
Steam, and other vapour heating systems, are intrinsically safe; as the temperature
cannot exceed the saturation temperature at the supply pressure. Other heating systems
rely on control of the heating rate to limit the maximum process temperature. Electrical
heating systems can be particularly hazardous.
Fire protection
To protect against structural failure, water-deluge systems are usually installed to keep
vessels and structural steelwork cool in a fire.
The lower section of structural steel columns are also often lagged with concrete or
other suitable materials.
9.3.8. Noise
Excessive noise is a hazard to health and safety. Long exposure to high noise levels
can cause permanent damage to hearing. At lower levels, noise is a distraction and
causes fatigue.
The unit of sound measurement is the decibel, defined by the expression:
RMS sound pressure (Pa)
, dB
⊲9.1⊳
Sound level D 20 log10
2 ð 105
The subjective effect of sound depends on frequency as well as intensity.
Industrial sound meters include a filter network to give the meter a response that
corresponds roughly to that of the human ear. This is termed the “A” weighting network
and the readings are reported as dB(A).
Permanent damage to hearing can be caused at sound levels above about 90 dB(A), and
it is normal practice to provide ear protection in areas where the level is above 80 dB(A).
Excessive plant noise can lead to complaints from neighbouring factories and local
residents. Due attention should be given to noise levels when specifying, and when laying
out, equipment that is likely to be excessively noisy; such as, compressors, fans, burners
and steam relief valves.
Several books are available on the general subject of industrial noise control, Bias
and Hansen (2003), and on noise control in the process industries, Cheremisnoff (1996),
ASME (1993).
SAFETY AND LOSS PREVENTION
371
9.4. DOW FIRE AND EXPLOSION INDEX
The hazard classification guide developed by the Dow Chemical Company and published
by the American Institute of Chemical Engineering, Dow (1994) (www.aiche.org), gives
a method of evaluating the potential risk from a process, and assessing the potential loss.
A numerical “Fire and explosion index” (F & EI) is calculated, based on the nature
of the process and the properties of the process materials. The larger the value of the
F & EI, the more hazardous the process, see Table 9.3.
Table 9.3.
Assessment of hazard
Fire and explosion index range
1 60
61 96
97 127
128 158
>159
Degree of hazard
Light
Moderate
Intermediate
Heavy
Severe
Adapted from the Dow F & EI guide (1994).
To assess the potential hazard of a new plant, the index can be calculated after the
Piping and Instrumentation and equipment layout diagrams have been prepared. In earlier
versions of the guide the index was then used to determine what preventative and
protection measures were needed, see Dow (1973). In the current version the preventative and protection measures, that have been incorporated in the plant design to reduce
the hazard are taken into account when assessing the potential loss; in the form of loss
control credit factors.
It is worthwhile estimating the F & EI index at an early stage in the process design, as
it will indicate whether alternative, less hazardous, process routes should be considered.
Only a brief outline of the method used to calculate the Dow F & EI will be given in
this section. The full guide should be studied before applying the technique to a particular
process. Judgement, based on experience with similar processes, is needed to decide the
magnitude of the various factors used in the calculation of the index, and the loss control
credit factors.
9.4.1. Calculation of the Dow F & EI
The procedure for calculating the index and the potential loss is set out in Figure 9.1.
The first step is to identify the units that would have the greatest impact on the
magnitude of any fire or explosion. The index is calculated for each of these units.
The basis of the F & EI is a Material Factor (MF). The MF is then multiplied by a Unit
Hazard Factor, F3 , to determine the F & EI for the process unit. The Unit Hazard factor
is the product of two factors which take account of the hazards inherent in the operation
of the particular process unit: the general and special process hazards, see Figure 9.2.
Material factor
The material factor is a measure of the intrinsic rate of energy release from the burning,
explosion, or other chemical reaction of the material. Values for the MF for over 300 of
372
CHEMICAL ENGINEERING
Select Pertinent
Process Unit
Determine
Material Factor
Calculate F1
General Process Hazards Factor
Calculate F2
Special Process Hazards Factor
Determine Process Unit Hazards
Factor F3 = F1 x F2
Calculate Loss Control
Credit Factor = C1 x C2 x C3
Determine F&EI
F&EI = F3 x Material Factor
Determine Area of Exposure
Determine Replacement
Value in Exposure Area
Determine Base MPPD
Determine Damage Factor
Determine Actual MPPD
Determine MPDO
Determine BI
Figure 9.1. Procedure for calculating the fire and explosion index and other risk analysis information. From
Dow (1994) reproduced by permission of the American Institute of Chemical Engineers. 1994 AIChE. All
rights reserved.
the most commonly used substances are given in the guide. The guide also includes a
procedure for calculating the MF for substances not listed: from a knowledge of the flash
points, (for dusts, dust explosion tests) and a reactivity value, Nr . The reactivity value is
a qualitative description of the reactivity of the substance, and ranges from 0 for stable
substances, to 4 for substances that are capable of unconfined detonation.
Some typical material factors are given in Table 9.4.
In calculating the F & EI for a unit the value for the material with the highest MF,
which is present in significant quantities, is used.
General process hazards
The general process hazards are factors that play a primary role in determining the
magnitude of the loss following an incident.
Six factors are listed on the calculation form, Figure 9.2.
373
SAFETY AND LOSS PREVENTION
Table 9.4.
Acetaldehyde
Acetone
Acetylene
Ammonia
Benzene
Butane
Chlorine
Cyclohexane
Ethyl alcohol
Hydrogen
Nitroglycerine
Sulphur
Toluene
Vinyl Chloride
Some typical material factors
MF
Flash
point° C
Heat of combustion
MJ/kg
24
16
40
4
16
21
1
16
16
21
40
4
16
21
39
20
gas
gas
11
gas
24.4
28.6
48.2
18.6
40.2
45.8
0.0
43.5
26.8
120.0
18.2
9.3
31.3
18.6
20
13
gas
40
gas
A. Exothermic chemical reactions: the penalty varies from 0.3 for a mild exotherm, such
as hydrogenation, to 1.25 for a particularly sensitive exotherm, such as nitration.
B. Endothermic processes: a penalty of 0.2 is applied to reactors, only. It is increased
to 0.4 if the reactor is heated by the combustion of a fuel.
C. Materials handling and transfer: this penalty takes account of the hazard involved
in the handling, transfer and warehousing of the material.
D. Enclosed or indoor process units: accounts for the additional hazard where ventilation is restricted.
E. Access of emergency equipment: areas not having adequate access are penalised.
Minimum requirement is access from two sides.
F. Drainage and spill control: penalises design conditions that would cause large spills
of flammable material adjacent to process equipment; such as inadequate design of
drainage.
Special process hazards
The special process hazards are factors that are known from experience to contribute to
the probability of an incident involving loss.
Twelve factors are listed on the calculation form, Figure 9.2.
A. Toxic materials: the presence of toxic substances after an incident will make the
task of the emergency personnel more difficult. The factor applied ranges from
0 for non-toxic materials, to 0.8 for substances that can cause death after short
exposure.
B. Sub-atmospheric pressure: allows for the hazard of air leakage into equipment. It is
only applied for pressure less than 500 mmHg (9.5 bara).
C. Operation in or near flammable range: covers for the possibility of air mixing with
material in equipment or storage tanks, under conditions where the mixture will be
within the explosive range.
374
CHEMICAL ENGINEERING
Figure 9.2. Dow Fire and Explosion Index calculation form.
From Dow (1994) reproduced by permission of the American Institute of Chemical Engineers. 1994 AIChE.
All rights reserved. Note: the figure numbers refer to the Dow guide. Gallons are US gallons.
Note: 1 m3 D 264.2 US gal; 1 kN/m2 D 0.145 psi;
1 kg D 2.2 lbs; 1 kJ/Kg D 0.43 BTU/lb.
SAFETY AND LOSS PREVENTION
375
D. Dust explosion: covers for the possibility of a dust explosion. The degree of risk
is largely determined by the particle size. The penalty factor varies from 0.25 for
particles above 175 m, to 2.0 for particles below 75 m.
E. Relief pressure: this penalty accounts for the effect of pressure on the rate of leakage,
should a leak occur. Equipment design and operation becomes more critical as the
operating pressure is increased. The factor to apply depends on the relief device
setting and the physical nature of the process material. It is determined from Figure 2
in the Dow Guide.
F. Low temperature: this factor allows for the possibility of brittle fracture occurring
in carbon steel, or other metals, at low temperatures (see Chapter 7 of this book).
G. Quantity of flammable material: the potential loss will be greater the greater the
quantity of hazardous material in the process or in storage. The factor to apply
depends on the physical state and hazardous nature of the process material, and the
quantity of material. It varies from 0.1 to 3.0, and is determined from Figures 3, 4
and 5 in the Dow Guide.
H. Corrosion and erosion: despite good design and materials selection, some corrosion
problems may arise, both internally and externally. The factor to be applied depends
on the anticipated corrosion rate. The severest factor is applied if stress corrosion
cracking is likely to occur (see Chapter 7 of this book).
I. Leakage joints and packing: this factor accounts for the possibility of leakage from
gaskets, pump and other shaft seals, and packed glands. The factor varies from 0.1
where there is the possibility of minor leaks, to 1.5 for processes that have sight
glasses, bellows or other expansion joints.
J. Use of fired heaters: the presence of boilers or furnaces, heated by the combustion of
fuels, increases the probability of ignition should a leak of flammable material occur
from a process unit. The risk involved will depend on the siting of the fired equipment
and the flash point of the process material. The factor to apply is determined with
reference to Figure 6 in the Dow Guide.
K. Hot oil heat exchange system: most special heat exchange fluids are flammable and
are often used above their flash points; so their use in a unit increases the risk of
fire or explosion. The factor to apply depends on the quantity and whether the fluid
is above or below its flash point; see Table 5 in the Guide.
L. Rotating equipment: this factor accounts for the hazard arising from the use of large
pieces of rotating equipment: compressors, centrifuges, and some mixers.
9.4.2 Potential loss
The procedure for estimating the potential loss that would follow an incident is set out in
Table 9.5: the Unit analysis summary.
The first step is to calculate the Damage factor for the unit. The Damage factor depends
on the value of the Material factor and the Process unit hazards factor (F3 in Figure 2).
It is determined using Figure 8 in the Dow Guide.
An estimate is then made of the area (radius) of exposure. This represents the area
containing equipment that could be damaged following a fire or explosion in the unit
being considered. It is evaluated from Figure 7 in the Guide and is a linear function of
the Fire and Explosion Index.
376
CHEMICAL ENGINEERING
Table 9.5.
Loss control credit factors
1. Process Control Credit Factor (C1 )
Credit
Credit
Factor
Factor
Feature
Range
Used(2)
a. Emergency Power
0.98
f. Inert Gas
b. Cooling
0.97 to 0.99
g. Operating Instructions/Procedures
c. Explosion Control
0.84 to 0.98
h. Reactive Chemical Review
d. Emergency Shutdown 0.96 to 0.99
i. Other Process Hazard Analysis
e. Computer Control
0.93 to 0.99
Feature
Credit
Credit
Factor
Factor
Range
Used(2)
0.94 to 0.96
0.91 to 0.99
0.91 to 0.98
0.91 to 0.98
C1 Value(3)
2. Material lsolation Credit Factor (C2 )
Feature
a. Remote Control Valves
b. Dump/Blowdown
Credit
Factor
Range
0.96 to 0.98
0.96 to 0.98
Credit
Factor
Used(2)
Feature
c. Drainage
d. Interlock
Credit
Factor
Range
0.91 to 0.97
0.98
Credit
Factor
Used(2)
C2 Value(3)
3. Fire Protection Credit Factor (C3 )
Feature
a. Leak Detection
b. Structural Steel
c. Fire Water Supply
d. Special Systems
e. Sprinkler Systems
Credit
Factor
Range
0.94 to 0.98
0.95 to 0.98
0.94 to 0.97
0.91
0.74 to 0.97
Credit
Factor
Used(2)
Feature
f. Water Curtains
g. Foam
h. Hand Extinguishers/Monitors
i. Cable Protection
Credit
Factor
Range
0.97 to 0.98
0.92 to 0.97
0.93 to 0.98
0.94 to 0.98
Credit
Factor
Used(2)
C3 Value(3)
Loss Control Credit Factor D C1 ð C2 ð C3 ⊲3⊳ D
(enter on line 7 Table 9.6)
From Dow (1994) reproduced by permission of the American Institute of Chemical Engineers. 1994 AIChE.
All rights reserved.
An estimate of the replacement value of the equipment within the exposed area is then
made, and combined with by the damage factor to estimate the Base maximum probable
property damage (Base MPPD).
The Maximum probable property damage (MPPD) is then calculated by multiplying
the Base MPPD by a Credit control factor. The Loss control credit control factors, see
Table 9.6, allow for the reduction in the potential loss given by the preventative and
protective measures incorporated in the design.
The MPPD is used to predict the maximum number of days which the plant will be down
for repair, the Maximum probable days outage (MPDO). The MPDO is used to estimate
377
SAFETY AND LOSS PREVENTION
Table 9.6.
Process unit risk analysis Summary
1. Fire & Explosion Index (F& El) . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Radius of Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (Figure 7)Ł
ft or m
ft2 or m2
3. Area of Exposure . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Value of Area of Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Damage Factor . . . . . . . . . . . . . . . . . . . . . . . . . . (Figure
6. Base Maximum Probable Property Damage
$MM
8)Ł
(Base MPPD) [4 ð 5] . . . . . . . . . . . . .
$MM
7. Loss Control Credit Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . (See Above)
8. Actual Maximum Probable Property Damage
9. Maximum Probable Days Outage
10. Business Interruption
(Actual MPPD) [6 ð 7] . . . . . . . . . . . . .
(MPDO) . . . . . . . . . . . . . . . (Figure 9)Ł
(Bl) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(2) For no credit factor enter 1.00.
$MM
days
$MM
(3) Product of all factors used.
Ł Refer
to Fire & Explosion Index Hazard Classification Guide for details.
From Dow (1994) reproduced by permission of the American Institute of Chemical
Engineers. 1994 AIChE. All rights reserved.
the financial loss due to the lost production: the Business interruption (BI). The financial
loss due to lost business opportunity can often exceed the loss from property damage.
9.4.3. Basic preventative and protective measures
The basic safety and fire protective measures that should be included in all chemical
process designs are listed below. This list is based on that given in the Dow Guide, with
some minor amendments.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
Adequate, and secure, water supplies for fire fighting.
Correct structural design of vessels, piping, steel work.
Pressure-relief devices.
Corrosion-resistant materials, and/or adequate corrosion allowances.
Segregation of reactive materials.
Earthing of electrical equipment.
Safe location of auxiliary electrical equipment, transformers, switch gear.
Provision of back-up utility supplies and services.
Compliance with national codes and standards.
Fail-safe instrumentation.
Provision for access of emergency vehicles and the evacuation of personnel.
Adequate drainage for spills and fire-fighting water.
Insulation of hot surfaces.
No glass equipment used for flammable or hazardous materials, unless no suitable
alternative is available.
Adequate separation of hazardous equipment.
Protection of pipe racks and cable trays from fire.
Provision of block valves on lines to main processing areas.
Protection of fired equipment (heaters, furnaces) against accidental explosion and fire.
Safe design and location of control rooms.
378
CHEMICAL ENGINEERING
Note: the design and location of control rooms, particularly as regards protection against
an unconfined vapour explosion, is covered in a publication of the Chemical Industries
Association, CIA (1979a).
9.4.4. Mond fire, explosion, and toxicity index
The Mond index was developed from the Dow F and E index by personnel at the ICI
Mond division. The third edition of the Dow index, Dow (1973), was extended to cover
a wider range of process and storage installations; the processing of chemicals with
explosive properties; and the evaluation of a toxicity hazards index. Also included was
a procedure to allow for the off-setting effects of good design, and of control and safety
instrumentation. Their revised, Mond fire, explosion and toxicity index was discussed in
a series of papers by Lewis (1979a, 1979b); which included a technical manual setting
out the calculation procedure. An extended version of the manual was issued in 1985,
and an amended version published in 1993, ICI (1993).
Procedure
The basic procedures for calculating the Mond indices are similar to those used for the
Dow index.
The process is first divided into a number of units which are assessed individually.
The dominant material for each unit is then selected and its material factor determined.
The material factor in the Mond index is a function of the energy content per unit weight
(the heat of combustion).
The material factor is then modified to allow for the effect of general and special
process and material hazards; the physical quantity of the material in the process step;
the plant layout; and the toxicity of process materials.
Separate fire and explosion indices are calculated. An aerial explosion index can also
be estimated, to assess the potential hazard of aerial explosions. An equivalent Dow index
can also be determined.
The individual fire and explosion indexes are combined to give an overall index for the
process unit. The overall index is the most important in assessing the potential hazard.
The magnitude of the potential hazard is determined by reference to rating tables,
similar to that shown for the Dow index in Table 9.2.
After the initial calculation of the indices (the initial indices), the process is reviewed
to see what measures can be taken to reduce the rating (the potential hazard).
The appropriate off-setting factors to allow for the preventative features included in the
design are then applied, and final hazard indices calculated.
Preventative measures
Preventative measures fall into two categories:
1. Those that reduce the number of incidents. Such as: sound mechanical design of
equipment and piping; operating and maintenance procedures, and operator training.
2. Those that reduce the scale of a potential incident; such as: measures for fire
protection, and fixed fire fighting equipment.
Many measures will not fit neatly into individual categories but will apply to both.
SAFETY AND LOSS PREVENTION
379
Implementation
The Mond technique of hazard evaluation is fully explained in the ICI technical manual,
ICI (1993)⊲1⊳ , to which reference should be made to implement the method. The calculations are made using a standard form, similar to that used for the Dow index. A computer
program is available for use with IBM compatible personal computers.
9.4.5. Summary
The Dow and Mond indexes are useful techniques, which can be used in the early stages
of a project design to evaluate the hazards and risks of the proposed process.
Calculation of the indexes for the various sections of the process will highlight any
particularly hazardous sections and indicate where a detailed study is needed to reduce
the hazards.
Example 9.1
Evaluate the Dow F & EI for the nitric acid plant described in Chapter 4, Example 4.4.
Solution
The calculation is set out on the special form shown in Figure 9.2a. Notes on the decisions
taken and the factors used are given below.
Unit: consider the total plant, no separate areas, but exclude the main storages.
Material factor: for ammonia, from Dow Guide, and Table 9.3.
MF D 4.0
Note: Hydrogen is present, and has a larger material factor (21) but the concentration is
too small for it to be considered the dominant material.
General process hazards:
A.
B.
C.
D.
E.
F.
Oxidising reaction, factor D 0.5
Not applicable.
Not applicable.
Not applicable.
Adequate access would be provided, factor D 0.0.
Adequate drainage would be provided, factor D 0.0.
Special process hazards:
A. Ammonia is highly toxic, likely to cause serious injury, factor D 0.6.
B. Not applicable.
⊲1⊳ Published under licence from Imperial Chemical Industries plc by Dr P. Doran and T. R. Greig, 40 Mors
Lane, Northwich, Cheshire, CW8 2PX, United Kingdom.
380
CHEMICAL ENGINEERING
Figure 9.2a. Fire and explosion index calculation form, Example 9.1.
From Dow (1994) reproduced by permission of the American Institute of Chemical Engineers. 1994 AIChE.
All rights reserved.
SAFETY AND LOSS PREVENTION
381
C. Operation always is within the flammable limits, factor D 0.8.
D. Not applicable.
E. Operation pressure 8 atm D 8 ð 14.7 14.7 D 103 psig. Set relief valve at 20%
above the operating pressure (see Chapter 13 of this book) D 125 psig.
From Figure 2 in the guide, factor D 0.35.
Note: psig D pounds force per square inch, gauge.
F. Not applicable.
G. The largest quantity of ammonia in the process will be the liquid in the vaporiser,
say around 500 kg.
Heat of combustion, Table 9.3 D 18.6 MJ/kg
Potential energy release D 500 ð 18.6 D 9300 MJ
D 9300 ð 106 /⊲1.05506 ð 103 ⊳ D 8.81 ð 106 Btu
which is too small to register on Figure 3 in the Guide, factor D 0.0.
H. Corrosion resistant materials of construction would be specified, but external
corrosion is possible due to nitric oxide fumes, allow minimum factor D 0.1.
I. Welded joints would be used on ammonia service and mechanical seals on pumps.
Use minimum factor as full equipment details are not known at the flow-sheet stage,
factor D 0.1.
J. Not applicable.
K. Not applicable.
L. Large turbines and compressors used, factor D 0.5.
The index works out at 21: classified as “Light”. Ammonia would not normally be
considered a dangerously flammable material; the danger of an internal explosion in the
reactor is the main process hazard. The toxicity of ammonia and the corrosiveness of
nitric acid would also need to be considered in a full hazard evaluation.
9.5. HAZARD AND OPERABILITY STUDIES
A hazard and operability study is a procedure for the systematic, critical, examination
of the operability of a process. When applied to a process design or an operating plant,
it indicates potential hazards that may arise from deviations from the intended design
conditions.
The technique was developed by the Petrochemicals Division of Imperial Chemical
Industries, see Lawley (1974), and is now in general use in the chemical and process
industries.
The term “operability study” should more properly be used for this type of study, though
it is usually referred to as a hazard and operability study, or HAZOP study. This can
cause confusion with the term “hazard analysis”, which is a technique for the quantitative
assessment of a hazard, after it has been identified by an operability study, or similar
technique. Numerous books have been written illustrating the use of HAZOP. Those by
Hyatt (2003), AIChemE (2000), Taylor (2000) and Kletz (1999a) give comprehensive
descriptions of the technique, with examples.
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CHEMICAL ENGINEERING
A brief outline of the technique is given in this section to illustrate its use in process
design. It can be used to make a preliminary examination of the design at the flow-sheet
stage; and for a detailed study at a later stage, when a full process description, final
flow-sheets, P and I diagrams, and equipment details are available.
9.5.1. Basic principles
A formal operability study is the systematic study of the design, vessel by vessel, and
line by line, using “guide words” to help generate thought about the way deviations from
the intended operating conditions can cause hazardous situations.
The seven guide words recommended in the CIA booklet are given in Table 9.7. In
addition to these words, the following words are also used in a special way, and have the
precise meanings given below:
Intention: the intention defines how the particular part of the process was intended to
operate; the intention of the designer.
Deviations: these are departures from the designer’s intention which are detected by
the systematic application of the guide words.
Causes: reasons why, and how, the deviations could occur. Only if a deviation can be
shown to have a realistic cause is it treated as meaningful.
Consequences: the results that follow from the occurrence of a meaningful deviation.
Hazards: consequences that can cause damage (loss) or injury.
The use of the guide words can be illustrated by considering a simple example. Figure 9.3
shows a chlorine vaporiser, which supplies chlorine at 2 bar to a chlorination reactor. The
vaporiser is heated by condensing steam.
PC
H
LA
Vapour
reactor
S/D
LC
FC
Steam
Chlorine
feed
Trap
Figure 9.3.
Chlorine vaporiser instrumentation
Consider the steam supply line and associated control instrumentation. The designer’s
intention is that steam shall be supplied at a pressure and flow rate to match the required
chlorine demand.
Apply the guide word No:
Possible deviation
no steam flow.
SAFETY AND LOSS PREVENTION
383
Possible causes blockage, valve failure (mechanical or power), failure of steam supply
(fracture of main, boiler shut-down).
Clearly this is a meaningful deviation, with several plausible causes.
Consequences the main consequence is loss of chlorine flow to the chlorination reactor.
The effect of this on the reactor operation would have to be considered. This would be
brought out in the operability study on the reactor; it would be a possible cause of no
chlorine flow.
Apply the guide word MORE:
Possible deviation more steam flow.
Possible cause valve stuck open.
Consequences low level in vaporiser (this should activate the low level alarm), higher
rate of flow to the reactor.
Note: to some extent the level will be self-regulating, as the level falls the heating
surface is uncovered.
Hazard depends on the possible effect of high flow on the reactor.
Possible deviation more steam pressure (increase in mains pressure).
Possible causes failure of pressure-regulating valves.
Consequences increase in vaporisation rate. Need to consider the consequences of the
heating coil reaching the maximum possible steam system pressure.
Hazard rupture of lines (unlikely), effect of sudden increase in chlorine flow on reactor.
9.5.2. Explanation of guide words
The basic meaning of the guide words in Table 9.7. The meaning of the words No/Not,
MORE and LESS are easily understood; the NO/NOT, MORE and LESS could, for example,
refer to flow, pressure, temperature, level and viscosity. All circumstances leading to No
flow should be considered, including reverse flow.
The other words need some further explanation:
AS WELL AS: something in addition to the design intention; such as, impurities, sidereactions, ingress of air, extra phases present.
PART OF: something missing, only part of the intention realized; such as, the change in
composition of a stream, a missing component.
REVERSE: the reverse of, or opposite to, the design intention. This could mean reverse
flow if the intention was to transfer material. For a reaction, it could mean the reverse
reaction. In heat transfer, it could mean the transfer of heat in the opposite direction to
what was intended.
OTHER THAN: an important and far-reaching guide word, but consequently more vague
in its application. It covers all conceivable situations other than that intended; such
as, start-up, shut-down, maintenance, catalyst regeneration and charging, failure of
plant services.
When referring to time, the guide words SOONER THAN and LATER THAN can also be
used.
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CHEMICAL ENGINEERING
Table 9.7.
Guide words
NO or NOT
MORE
A list of guide words
Meanings
Comments
The complete negation of these
intentions
Quantitative increases or decreases
No part of the intentions is achieved but
nothing else happens
These refer to quantities and properties
such as flow rates and temperatures,
as well as activities like “HEAT” and
“REACT”
All the design and operating intentions are
achieved together with some additional
activity
Only some of the intentions are achieved;
some are not
This is mostly applicable to activities,
for example reverse flow or chemical
reaction. It can also be applied to
substances, e.g. “POISON instead of
“ANTIDOTE” or “D” instead of “L”
optical isomers
No part of the original intention is
achieved. Something quite different
happens
LESS
AS WELL AS
A qualitative increase
PART OF
A qualitative decrease
REVERSE
The logical opposite of the intention
OTHER THAN
Complete substitution
9.5.3. Procedure
An operability study would normally be carried out by a team of experienced people,
who have complementary skills and knowledge; led by a team leader who is experienced
in the technique.
The team examines the process vessel by vessel, and line by line, using the guide words
to detect any hazards.
The information required for the study will depend on the extent of the investigation.
A preliminary study can be made from a description of the process and the process flowsheets. For a detailed, final, study of the design, the flow-sheets, piping and instrument
diagrams, equipment specifications and layout drawings would be needed. For a batch
process information on the sequence of operation will also be required, such as that given
in operating instructions, logic diagrams and flow charts.
A typical sequence of events is shown in Figure 9.4. After each line has been studied
it is marked on the flow-sheet as checked.
A written record is not normally made of each step in the study, only those deviations
that lead to a potential hazard are recorded. If possible, the action needed to remove the
hazard is decided by the team and recorded. If more information, or time, is needed to
decide the best action, the matter is referred to the design group for action, or taken up
at another meeting of the study team.
When using the operability study technique to vet a process design, the action to be
taken to deal with a potential hazard will often be modifications to the control systems and
instrumentation: the inclusion of additional alarms, trips, or interlocks. If major hazards
SAFETY AND LOSS PREVENTION
385
Beginning
1
Select a vessel
2
3
Explain the general intention of the vessel and
its lines
Select a line
4
Explain the intention of the line
5
Apply guide word
6
Develop a meaningful deviation
7
Examine possible causes
8
Examine consequences
9
Detect hazards or operating problems
10
Make suitable record
11
12
Repeat 6-10 for all meaningful deviations derived
from the guide word
Repeat 5-11 for all the guide words
13
Mark line as having been examined
14
Repeat 3-13 for each line
15
Select an auxiliary (e.g., heating system)
16
Explain the intention of the auxiliary
17
Repeat 5-12 for the auxiliary
18
Mark auxiliary as having been examined
19
Repeat 15-18 for all auxiliaries
20
Explain intention of the vessel
21
Repeat 5-12 for the vessel
22
Mark vessel as completed
23
Repeat 1-22 for all vessels on flowsheet
24
Mark flowsheet as completed
25
Repeat 1-24 for all flowsheets
End
Figure 9.4.
Detailed sequence of an operability study
are identified, major design changes may be necessary; alternative processes, materials or
equipment.
Example 9.2
This example illustrates how the techniques used in an operability study can be used
to decide the instrumentation required for safe operation. Figure 9.5a shows the basic
instrumentation and control systems required for the steady-state operation of the reactor
section of the nitric acid process considered in Example 4.4. Figure 9.5b shows the
386
CHEMICAL ENGINEERING
P5
FRC
1
CV4
CV - Control valve
NRV - Non-return
P4
P3
Air
Ratio
Compressor
Filter
Key to valve
symbols
Secondary air
to absorber
FR
2
FrC
1
Manual operated
block valves
are not shown
FR
1
TIC
1
CV 3
P2
P6
PIC
1
C
LC
1
Multi-point
Steam
CV 1
NH from
3
storage
TRI
2
CRV 2
Reactor
S1
P1
P7
Evaporator
To
W.H.B.
Line numbers
P5
(a)
FRC
Pd
1
CV4
NRV 1
FR
1
LA
1
L1
TIC
1
SV 1
CV 3
H
L
FrC
1
FR
2
LA
2
PA
1
NRV 3
NRV 4
4
PIC
1
SV 3
QA
1
H
QA
2
H
SV 2
LC
1
CV 1 NRV 2
CRV 2
L/H
TA
1
NH3 from
storage
TRI
2
To scrubber
(b)
Figure 9.5.
Nitric acid plant, reactor section (a) basic instrumentation (b) full instrumentation
additional instrumentation and safety trips added after making the operability study set
out below. The instrument symbols used are explained in Chapter 5.
The most significant hazard of this process is the probability of an explosion if the
concentration of ammonia in the reactor is inadvertently allowed to reach the explosive
range, >14 per cent.
387
SAFETY AND LOSS PREVENTION
Operability study
The sequence of steps shown in Figure 9.4 is followed. Only deviations leading to action,
and those having consequences of interest, are recorded.
Vessel Air Filter
Intention to remove particles that would foul the reactor catalyst
Guide
word
Deviation
Cause
Consequences and action
Line No. P3
Intention transfers clear air at atmospheric pressure and ambient
temperature to compressor
LESS OF
Flow
Partially blocked filter Possible dangerous increase in
NH3 concentration: measure
and log pressure differential
AS WELL
Composition
Filter damaged,
Impurities, possible poisoning
incorrectly installed
of catalyst: proper
AS
maintenance
Vessel Compressor
Intention to supply air at 8 bar, 12,000 kg/h, 250Ž C, to the mixing tee
Line No. P4
Intention transfers air to reactor (mixing tee)
NO/NONE
Flow
Compressor failure
MORE
Flow
Failure of compressor
controls
REVERSE
Flow
Fall in line press.
(compressor fails)
high pressure at
reactor
Line No. P5
Intention transfer secondary air to absorber
NO
Flow
Compressor failure
CV4 failure
LESS
Flow
CV4 pluggage FRC1
failure
Possible dangerous NH3 conc.:
low flow pressure alarm
(PA1) interlocked to
shut-down NH3 flow
High rate of reaction, high
reactor temperature:
high-temperature alarms
(TA1)
NH3 in compressor explosion
hazard: fit non-return valve
(NRV1); hot wet acid
gas-corrosion; fit second
valve (NRV4)
Incomplete oxidation, air
pollution from absorber
vent: operating procedures
As no flow
388
CHEMICAL ENGINEERING
Vessel Ammonia vaporiser
Intention evaporate liquid ammonia at 8 bar, 25Ž C, 731 kg/h
Guide
word
Deviation
Cause
Line No. P1
Intention transfer liquid NH3 from storage
NO
Flow
Pump failure CV1
fails
LESS
Flow
Partial failure
pump/valve
MORE
Flow
CV1 sticking, LC1
fails
AS WELL
Water brine
Leakage into storages
from refrigeration
Flow
Pump fails, vaporiser
press. higher than
delivery
AS
REVERSE
Line No. P2
Intention transfers vapour to mixing tee
Flow
Failure of steam flow,
NO
CV3 fails closed
LESS
Flow
MORE
Level
Flow
REVERSE
Level
Flow
Line S1 (auxiliary)
Partial failure or
blockage CV3
LC1 fails
FR2/ratio control
mis-operation
LC1 fails
Steam failure
CRV2 fails, trap
frozen
Consequences and action
Level falls in vaporiser: fit
low-level alarm (LA1)
(LA1) alarms
Vaporiser floods, liquid to
reactor: fit high-level alarm
(LA2) with automatic pump
shut-down
Concentration of NH4 OH in
vaporiser: routine analysis,
maintenance
Flow of vapour into storages:
(LA1) alarms; fit non-return
valve (NRV2)
(LA1) alarms, reaction ceases:
considered low flow alarm,
rejected needs resetting at
each rate
As no flow
LA2 alarms
Danger of high ammonia
concentration: fit alarm, fit
analysers (duplicate) with
high alarm 12 per cent NH3
(QA1, QA2)
LA2 alarms
Hot, acid gases from
reactor corrosion: fit
non-return valve (NRV3)
High level in vaporiser: LA2
actuated
389
SAFETY AND LOSS PREVENTION
Guide
word
Deviation
Cause
Consequences and action
Vessel Reactor
Intention oxidises NH3 with air, 8 bar, 900Ž C
Line No. P6
Intention transfers mixture to reactor, 250Ž C
NO
Flow
NRV4 stuck closed
LESS
Flow
NH3 conc.
NRV4 partially closed
Failure of ratio control
MORE
NH3 conc.
Failure of ratio
control, air flow
restricted
Flow
Control systems
failure
Fall in reaction rate: fit low
temp. alarm (TA1)
A S NO
Temperatures fall: TA1 alarms
(consider low conc. alarm
on QA1, 2)
High reactor temp.: TA1
alarms 14 per cent explosive
mixture enters
reactor disaster: include
automatic shut-down by-pass
actuated by QA1, 2, SV2,
SV3
High reactor temp.: TA1
alarms
Line No. P7
Intention transfers reactor products to waste-heat boiler
AS WELL
Composition
Refractory particles
Possible pluggage of boiler
from reactor
tubes: install filter up-stream
AS
of boiler
9.6. HAZARD ANALYSIS
An operability study will identify potential hazards, but gives no guidance on the likelihood
of an incident occurring, or the loss suffered; this is left to the intuition of the team
members. Incidents usually occur through the coincident failure of two or more items;
failure of equipment, control systems and instruments, and mis-operation. The sequence
of events that leads to a hazardous incident can be shown as a fault tree (logic tree), such
as that shown in Figure 9.6. This figure shows the set of circumstances that would result
in the flooding of the chloride vaporiser shown in Figure 9.3. The AND symbol is used
where coincident inputs are necessary before the system fails, and the OR symbol where
failure of any input, by itself, would cause failure of the system. A fault tree is analogous
to the type of logic diagram used to represent computer operations, and the symbols are
analogous to logic AND and OR gates.
The fault trees for even a simple process unit will be complex, with many branches.
Fault trees are used to make a quantitive assessment of the likelihood of failure of a
system, using data on the reliability of the individual components of the system. For
example, if the following figures represent an estimate of the probability of the events
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CHEMICAL ENGINEERING
Failure of
steam trap
Failure of
flow valve
or
Failure of
level control
Failure of
high-level
S / D system
Figure 9.6.
and
Flooding of vaporiser
Liquid chlorine
to reactor
Simple fault chart (logic diagram)
shown in Figure 9.6 happening, the probability of failure of the total system by this route
can be calculated.
Steam trap
Flow control valve
Level control, sub-system
High level shut-down, sub-system
Probability of failure ð103
1
0.1
0.5
0.04
The probabilities are added for OR gates, and multiplied for AND gates; so the probability
of flooding the vaporiser is given by:
⊲1 C 0.1 C 0.5⊳103 ð 0.04 ð 103 D 0.06 ð 106
The data on probabilities given in this example are for illustration only, and do not
represent actual data for these components. Some quantitive data on the reliability of
instruments and control systems is given by Lees (1976). Examples of the application of
quantitive hazard analysis techniques in chemical plant design are given by Wells (1996)
and Prugh (1980). Much of the work on the development of hazard analysis techniques,
and the reliability of equipment, has been done in connection with the development of
the nuclear energy programmes in the USA (USAEC, 1975) and the UK.
The Centre for Chemical Process Safety of the American Institute of Chemical
Engineers has published a comprehensive and authoritative guide to quantitative risk
analysis, AIChemE (2001).
Several other texts are available on the application of risk analysis techniques in the
chemical process industries; see AIChemE (2000), Frank and Whittle (2001) and Kletz
(1999b).
9.7. ACCEPTABLE RISK AND SAFETY PRIORITIES
If the consequences of an incident can be predicted quantitatively (property loss and the
possible number of fatalities), then a quantitive assessment can be made of the risk.
loss per
Frequency of
Quantitive assessment
ð
D
incident
incident
of risk
391
SAFETY AND LOSS PREVENTION
If the loss can be measured in money, the cash value of the risk can be compared with
the cost of safety equipment or design changes to reduce the risk. In this way, decisions
on safety can be made in the same way as other design decisions: to give the best return
of the money invested.
Hazards invariably endanger life as well as property, and any attempt to make cost
comparisons will be difficult and controversial. It can be argued that no risk to life should
be accepted. However, resources are always limited and some way of establishing safety
priorities is needed.
One approach is to compare the risks, calculated from a hazard analysis, with risks that
are generally considered acceptable; such as, the average risks in the particular industry,
and the kind of risks that people accept voluntarily. One measure of the risk to life is
the “Fatal Accident Frequency Rate” (FAFR), defined as the number of deaths per 108
working hours. This is equivalent to the number of deaths in a group of 1000 men over
their working lives. The FAFR can be calculated from statistical data for various industries
and activities; some of the published values are shown in Tables 9.8 and 9.9. Table 9.8
shows the relative position of the chemical industry compared with other industries;
Table 9.9 gives values for some of the risks that people accept voluntarily.
Table 9.8. FAFR for some industries for
the period 1978 90
Industry
Chemical industry
UK manufacturing
Deep sea fishing
Table 9.9.
FAFR
1.2
1.2
4.2
FAFR for some non-industrial activities
Activity
FAFR
Staying at home
Travelling by rail
Travelling by bus
Travelling by car
Travelling by air
Travelling by motor cycle
Rock climbing
3
5
3
57
240
660
4000
Source: Brown (2004).
In the chemical process industries it is generally accepted that risks with an FAFR
greater than 0.4 (one-tenth of the average for the industry) should be eliminated as a
matter of priority, the elimination of lesser risks depending on the resources available;
see Kletz (1977a). This criterion is for risks to employees; for risks to the general public
(undertaken involuntarily) a lower criterion must be used. The level of risk to which the
public outside the factory gate should be exposed by the operations will always be a
matter of debate and controversy. Kletz (1977b) suggests that a hazard can be considered
acceptable if the average risk is less than one in 10 million, per person, per year. This
is equivalent to a FAFR of 0.001; about the same as deaths from the bites of venomous
creatures in the UK, or the chance of being struck by lightning.
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CHEMICAL ENGINEERING
For further reading on the subject of acceptable risk and risk management, see Cox
and Tait (1998).
9.8. SAFETY CHECK LISTS
Check lists are useful aids to memory. A check list that has been drawn up by experienced
engineers can be a useful guide for the less experienced. However, too great a reliance
should never be put on the use of check lists, to the exclusion of all other considerations
and techniques. No check list can be completely comprehensive, covering all the factors
to be considered for any particular process or operation.
A short safety check list, covering the main items which should be considered in process
design, is given below.
More detailed check lists are given by Carson and Mumford (1988) and Wells (1980).
Balemans (1974) gives a comprehensive list of guidelines for the safe design of chemical
plant, drawn up in the form of a check list. A loss prevention check list is included in
the Dow Fire and Explosion Index Hazard Classification Guide, Dow (1987).
Design safety check list
Materials
(a) flash-point
(b) flammability range
(c) autoignition temperature
(d) composition
(e) stability (shock sensitive?)
(f) toxicity, TLV
(g) corrosion
(h) physical properties (unusual?)
(i) heat of combustion/reaction
Process
1. Reactors
(a) exothermic heat of reaction
(b) temperature control emergency systems
(c) side reactions dangerous?
(d) effect of contamination
(e) effect of unusual concentrations (including catalyst)
(f) corrosion
2. Pressure systems
(a) need?
(b) design to current codes (BS 5500)
(c) materials of construction adequate?
(d) pressure relief adequate?
(e) safe venting systems
(f) flame arresters
SAFETY AND LOSS PREVENTION
Control systems
(a) fail safe
(b) back-up power supplies
(c) high/low alarms and trips on critical variables
(i) temperature
(ii) pressure
(iii) flow
(iv) level
(v) composition
(d) back-up/duplicate systems on critical variables
(e) remote operation of valves
(f) block valves on critical lines
(g) excess-flow valves
(h) interlock systems to prevent mis-operation
(i) automatic shut-down systems
Storages
(a) limit quantity
(b) inert purging/blanketing
(c) floating roof tanks
(d) dykeing
(e) loading/unloading facilities
(f) earthing
(g) ignition sources vehicles
safety
General
(a) inert purging systems needed
(b) compliance with electrical codes
(c) adequate lighting
(d) lightning protection
(e) sewers and drains adequate, flame traps
(f) dust-explosion hazards
(g) build-up of dangerous impurities purges
(h) plant layout
(i) separation of units
(ii) access
(iii) siting of control rooms and offices
(iv) services
(i) safety showers, eye baths
Fire protection
(a) emergency water supplies
(b) fire mains and hydrants
(c) foam systems
(d) sprinklers and deluge systems
(e) insulation and protection of structures
(f) access to buildings
(g) fire-fighting equipment
393
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CHEMICAL ENGINEERING
The check list is intended to promote thought; to raise questions such as: is it needed,
what are the alternatives, has provision been made for, check for, has it been provided?
9.9. MAJOR HAZARDS
A series of major accidents at manufacturing sites and storage installation has focused
the attention of national governments on the need to control the planning and operation
of sites where there is the potential for a major accident. That is, those sites posing a
substantial threat to the employees, the public and the environment.
In the United Kingdom this is covered by the Control of Major Accident Hazards
Regulations 1999 (COMAH), set up by the HSE (Health and Safety Executive) to
implement the Seveso II directive of the EC (European Union): see www.hse.gov.uk. The
COMAH regulations supersede the previous CIMAH (1984) regulations, set up under
Seveso I.
Other countries have set up similar regulations for the control of major hazards.
The aim of the COMAH regulations is to prevent major accidents involving dangerous
materials from occurring and to mitigate the effects on people and the environment.
The COMAH regulations apply to both the manufacture and storage of dangerous
substances. They will, in effect, apply to any chemical manufacturing process involving
flammable or toxic materials that are likely to constitute a hazard. The degree of the hazard
with material storage depends on the nature of the material and the quantity stored. The
regulations define the minimum storage quantities for hazardous substances above which
the regulations will apply.
The regulations require industrial companies to report on the operation of dangerous
installations, and on the storage of dangerous materials.
It is the duty of the company to prepare a Major Accident Prevention Policy (MAPP).
This will set out the policies for ensuring the safe operation of the plant and the protection
of employees and the environment. It will include details of the safety management
organisation that will implement the policy.
The report should include:
i. Identification of the hazards.
ii. The steps taken to ensure the proper design, testing and operation of the plant.
iii. The steps taken to prevent or minimise the consequences that would follow a
major incident.
iv. The programme for training employees and providing them with safety equipment.
v. The preparation and procedures for updating an emergency plan covering procedures to deal with a major incident.
vi. The procedures for informing the public living outside the site, who may be affected
by a major accident, of the nature of the hazard, and what to do in the event of
an accident.
vii. Policies for liaising with the local authorities in the preparation of an off-site
emergency plan.
In preparing the report for the HSE the company would usually prepare a safety case
assessing the nature and degree of the hazard and the consequences of an incident. This
395
SAFETY AND LOSS PREVENTION
would include details of the measures taken to alleviate the hazard and the consequences
of an accident.
The preparation of safety cases under the CIMAH regulations is covered by Lees and
Ang (1989). The company is required to report any major incident to the Health and
Safety Executive (HSE).
The regulations covering the control of major industrial accident hazards in the United
States are discussed by Brooks et al. in Lees and Ang (1989). Major hazards and their
management are covered by Wells (1997).
9.9.1. Computer software for quantitative risk analysis
The assessment of the risks and consequences involved in the planning and operation of
a major plant site is a daunting task.
The methodology of the classical method of quantitative risk analysis is shown in
Figure 9.7. First, the likely frequency of failure of equipment, pipe-lines, and storage
vessels must be predicted; using the techniques mentioned in Section 9.6. The probable
magnitude of any discharges must then be estimated, and the consequences of failure
evaluated: fire, explosion or toxic fume release. Other factors, such as, site geography,
weather conditions, site layout, and safety management practices, must be taken into
consideration. The dispersion of gas clouds can be predicted using suitable models. This
methodology enables the severity of the risks to be assessed. Limits have to be agreed on
the acceptable risks; such as the permitted concentrations of toxic gases. Decisions can
then be made on the siting of plant equipment (see Chapter 14), on the suitability of a
site location, and on emergency planning procedures.
Plant data
Management
factors
Failure rate
data
Generate failure
cases
Calculate
consequences
Meteorological
data
Calculate
risks
Population
data
Ignition
sources
Assess risks
Figure 9.7.
Quantitative risk assessment procedure
396
CHEMICAL ENGINEERING
The comprehensive and detailed assessment of the risks required for a “safety-case”
can only be satisfactorily carried out for major installations with the aid of computer
software. Suites of programmes for quantitative risk analysis have been developed over
the past decade by consulting firms specializing in safety and environmental protection.
Typical of the software available is the SAFETI (Suite for Assessment of Flammability
Explosion and Toxic Impact) suite of programs developed by DNV Technica Ltd. These
programs were initially developed for the authorities in the Netherlands, as a response
to the Seveso Directives of the EU (which requires the development of safety cases and
hazard reviews). The programs have subsequently been developed further and extended,
and are widely used in the preparation of safety cases; see Pitblado et al. (1990).
Computer programs can be used to investigate a range of possible scenarios for a
site. But, as with all computer software used in design, they should not be used without
caution and judgement. They would normally be used with the assistance and guidance
of the consulting firm supplying the software. With intelligent use, guided by experience,
such programs can indicate the magnitude of the likely risks at a site, and allow sound
decisions to be made when licensing a process operation or granting planning permission
for a new installation.
9.10 REFERENCES
Anon. (1988) Extremely Hazardous Substances: superfund chemical profiles, U.S. Environmental Protection
Agency, 2 vols. (Noyes).
ASKQUITH, W. and LAVERY, K. (1990) Proc. Ind. Jl. (Sept.) 15. Bursting discs the vital element in relief.
AIChemE (1987) Guidelines for Hazard Evaluation Procedures (Center for Chemical Process Safety, American
Institute of Chemical Engineers, New York).
AIChemE (1992a) Emergency Relief Systems for Runaway Chemical Reactions and Storage Vessels (American
Institute of Chemical Engineers, New York).
AIChemE (1992b) Emergency Relief Design using DIERS Technology. (American Institute of Chemical
Engineers).
AIChemE (2000) Guidelines for Hazard Evaluation Procedures with worked examples, 2nd edn (Center for
Chemical Process Safety, American Institute of Chemical Engineers, New York).
AIChemE (2001) Guidelines for Chemical Processes Qualitative Risk Analysis, 2nd edn (Center for Chemical
Process Safety, American Institute of Chemical Engineers, New York).
ASME (1993) Noise Control in the Process Industries (ASME).
ASHAFI, C. R. (2003) Industrial Safety and Health Management, 5th edn (Prentice Hall).
BALEMANS, A. W. M. (1974) Check-lists: guide lines for safe design of process plants. Loss Prevention and
Safety Promotion in the Process Industries, C. H. Bushmann (ed.) (Elsevier).
BARTON, J. (2001) Dust Explosion, Prevention and Protection A Practical Guide (Institution of Chemical
Engineers, London).
BIAS, D. and HANSEN, C. (2003) Engineering Noise: Theory and Practice (Spon Press).
BRITTON L. G. (1999) Avoiding Static Ignition Hazards in Chemical Processes (AIChE).
BROWN, D. (2004) Chem. Engr. London No. 758 (August) 42. It’s a risky business.
CARSON, P. A. and MUMFORD, C. J. (1988) Safe Handling of Chemicals in Industry, 2 vols. (Longmans).
CARSON, P. A. and MUMFORD, C. J. (2002) Hazardous Chemicals Handbook, 2nd edn (Newnes).
CHEREMISNOFF, N. P. (1996) Noise Control in Industry: A Practical Guide (Noyes).
COOPER, W. F. and JONES, D. A. (1993) Electrical Safety Engineering, 3rd edn (Butterworth-Heinemann).
COX, S. and TAIT, R. (1998) Safety, Reliability and Risk Management An Integrated Approach (Elsevier).
CROSS, J. and FARRER, D. (1982) Dust Explosions (Plenum Press).
DOW (1973) Fire and Explosion Index Hazard Classification Guide, 3rd edn Dow Chemical Company.
DOW (1994) Dow’s Fire and Explosion Index Hazard Classification Guide (American Institute of Chemical
Engineers, New York).
DOW CHEMICAL CO. (1973) The Dow Safety Guide, a reprint from Chemical Engineering Progress (AIChE).
DUXBURY, H. A. (1976) Loss Prevention No. 10 (AIChE) 147. Gas vent sizing methods.
DUXBURY, H. A. (1979) Chem. Engr. London No. 350 (Nov.) 783. Relief line sizing for gases.
ECKHOFF, R. K. (2003) Dust Explosions (Butterworth-Heinemann).
SAFETY AND LOSS PREVENTION
397
FAWCETT, H. H. and WOOD, W. S. (1982) Safety and Accident Prevention in Chemical Operations (Wiley).
FIELD, P. (1982) Dust Explosions (Elsevier).
FISHER, H. G. (1985) Chem. Eng. Prog. 81 (August) 33 DIERS research program on emergency relief systems.
FRANK, W. I. and WHITTLE, D. K. (2001) I Revalidating Process Hazard Analysis (AIChE).
GREEN, A. E. (ed.) (1982) High Risk Technology (Wiley).
GREEN, A. E. (ed.) (1983) Safety System Reliability (Wiley).
GUGAN, K. (1979) Unconfined Vapour Cloud Explosions (Gulf Publishing).
HMSO (1975) The Flixborough Disaster, Report of the Court of Enquiry (Stationery Office).
HMSO (1989a) Control of Substances Hazardous to Health Regulations 1988 (COSHH) Introducing COSHH
(HMSO).
HMSO (1989b) Control of Substances Hazardous to Health Regulations 1988 (COSHH) Introductory
Assessment COSHH (HMSO).
HOWARD, W. B. (1992) Chem. Eng. Prog. 88 (April) 69. Use precautions in selection, installation and operation
of flame arresters.
HSC (1977) The Advisory Commission on Major Hazards, First Report, Health and Safety Commission
(HMSO).
HSC (1979) The Advisory Commission on Major Hazards, Second Report, Health and Safety Commission
(HMSO).
HYATT, N. (2003) Guidelines for Process Hazard Analysis (PHA, Hazop), Hazard Identification and Risk Analysis
(CRC Press).
ICI (1993) Mond Index: How to Identify, Assess and Minimise Potential Hazards on Chemical Plant Units for
New and Existing Processes. 2nd edn, ICI, Northwich.
KING, R. and HIRST, R. (1998) King’s Safety in the Process Industries, 2nd edn (Elsevier).
KLETZ, T. A. (1977a) New Scientist (May 12th) 320. What risks should we run.
KLETZ, T. A. (1977b) Hyd. Proc. 56 (May) 207. Evaluate risk in plant design.
KLETZ, T. A. (1984) Cheaper, Safer Plants or Wealth and Safety at Work (Institution of Chemical Engineers,
London).
KLETZ, T. A. (1991) Plant Design for Safety: A User Friendly Approach (Hemisphere Books).
KLETZ, T. A. (1999a) Hazop and Hazan, 4th edn (Taylor and Francis).
KLETZ, T. A. (1999b) Hazop and Hazan: Identifying Process Industry Hazards (Institution of Chemical
Engineers, London).
KLETZ, T. A. and CHEAPER, T. A. (1998) A Handbook for Inherently Safer Design, 2nd edn (Taylor and Francis).
LAWLEY, H. G. (1974) Loss Prevention No. 8 (AIChE) 105. Operability Studies and hazard analysis.
LEES, F. P. (1976) Inst. Chem. Eng. Sym. Ser. No. 47, 73. A review of instrument failure data.
LEES, F. P. (1996) Loss Prevention in the Process Industries, 2nd edn, 2 vols. (Butterworths).
LEES, F. P. and ANG, M. L. (eds) (1989) Safety Cases Within the Control of Industrial Major Accident Hazards
(CIMAH) Regulations 1984 (Butterworths).
LEWIS, D. J. (1979a) AIChE Loss Prevention Symposium, Houston, April. The Mond fire, explosion and toxicity
index: a development of the Dow index.
LEWIS, D. J. (1979b) Loss Prevention No. 13 (AIChE) 20. The Mond fire, explosion and toxicity index applied
to plant layout and spacing.
LEWIS, J. R. (2004) Sax’s Dangerous Properties of Hazardous Materials, 11th edn (Van Nostrand Reinhold).
LOWRANCE, W. W. (1976) Of Acceptable Risk (W. Kaufmann, USA).
MACMILLAN, A. (1998) Electrical Installations in Hazardous Areas (Butterworth-Heinemann)
MARSHALL, V. C. (1987) Major Chemical Hazards (Ellis Horwood).
MARSHALL, V. C. and RUHEMANN, S. (2000) Fundamentals of Process Safety (Institution of Chemical Engineers,
London).
MATHEWS, T. (1984) Chem. Engr., London No. 406 (Aug.-Sept.) 21. Bursting discs for over-pressure protection.
MENDOZA, V. A., SMOLENSKY, J. F. and STRAITZ, J. F. (1998) Hyd. Proc. 77 (Oct.) 63. Do your flame arrestors
provide adequate protection.
MOORE, A. (1984) Chem. Engr., London No. 407 (Oct.) 13. Pressure relieving systems.
MORLEY, P. G. (1989a) Chem. Engr., London No. 463 (Aug.) 21. Sizing pressure safety valves for gas duty.
MORLEY, P. G. (1989b) Chem. Engr., London No. 465 (Oct.) 47. Sizing pressure safety valves for flashing
liquid duty.
MUNDAY, G. (1976) Chem. Engr. London No. 308 (April) 278. Unconfined vapour explosions.
MURPHY, G. (1993) Processing (Nov.) 6. Quiet life ends in burst of activity.
NAPIER, D. H. and RUSSELL, D. A. (1974) Proc. First Int. Sym. on Loss Prevention (Elsevier). Hazard assessment
and critical parameters relating to static electrification in the process industries.
NFPA (1987a) Flammable and Combustible Liquids Code, NFPA 30 (National Fire Protection Association,
USA).
NFPA (1987b) Flammable and Combustible Liquids Code Handbook (National Fire Protection Association,
USA).
398
CHEMICAL ENGINEERING
PARKINSON, J. S. (1979) Inst. Chem. Eng. Sym. Design 79, K1. Assessment of plant pressure relief systems.
PARRY, C. F. (1992) Relief Systems Handbook (Institution of Chemical Engineers, London).
PITBLADO, R. M., SHAW, S. J. and SEVENS, G. (1990) Inst. Chem. Eng. Sym. Ser. No. 120, 51. The SAFETI
risk assessment package and case study application.
POOLE, G. (1985) Proc. Eng. (May) 67. Improving the design of emergency relief systems.
PRATT, T. H. (1999) Electrostatic Ignitions of Fires and Explosions (AIChE).
PRUGH, R. N. (1980) Chem. Eng. Prog. 76 (July) 59. Applications of fault tree analysis.
RIDLEY, J. (ed.) (2003) Safety at Work (Elsevier).
ROGOWSKI, Z. W. (1980) Inst. Chem. Eng. Sym. Ser. No. 58, 53. Flame arresters in industry.
ROSPA (1971) Liquid Flammable Gases: Storage and Handling (Royal Society for the Prevention of Accidents,
London).
RSC (1991ff) Dictionary of Substances and Their Effects, 5 vols (Royal Society of Chemistry).
SIMPSON, D. AND SIMPSON, W. G. (1991) The COSHH Regulations: a practical guide (Royal Society of
Chemistry).
TAYLOR, B. T. et al. (2000) HAZOP: A Guide to Best Practice (Institution of Chemical Engineers, London).
USAEC (1975) Reactor Safety Study, WASH-1400 (United States Atomic Energy Commission).
WELLS, G. L. (1996) Hazard Identification and Risk Assessment (Institution of Chemical Engineers, London).
WELLS, G. L. (1997) Major Hazards and their Management (Institution of Chemical Engineers, London).
Bibliography
Further reading on process safety
Croner’s Dangerous Goods Safety Advisor (Croner).
Dictionary of Substances and Chemical Effects (RCS).
FINGAS, M. (2002) (ed.) Handbook of Hazardous Materials Spills and Technology (McGraw-Hill).
GHAIVAL, S. (2004) (ed.) Tolley’s Health and Safety at Work Handbook (Tolley Publishing).
JOHNSON, R. W., RUDY, S. W. and UNWIN, S. D. (2003) Essential Practices for Managing Chemical Reactivity
Harards (CCPS, American Institute of Chemical Engineers).
MARTEL, B. (2000) Chemical Risk Analysis (English translation) (Penton Press).
REDMILLA, F., CHUDLEIGH, M. and CATMUR, J. (1999) Systems Safety: HAZOP and Software HAZOP (Wiley).
SMITH, D. J. (2001) Reliability, Maintainability and Risk Practical Methods for Engineers, 6th edn (Elsevier).
British Standards
BS 2915:
BS 5345:
1990
Specification for bursting discs and bursting disc devices.
1977 90 Code of practice for the installation and maintenance of
electrical apparatus for use in potentially explosive atmospheres (other than mining
applications or explosives processing and manufacture), 8 parts.
BS 5501:
1977 82 Electrical apparatus for potentially explosive atmospheres, 9 parts.
BS 5908:
1990
Code of practice for fire precautions in the chemical and allied industries.
BS 5958:
1991
Code of practice for the control of undesirable static electricity.
Part 1:
General considerations.
Part 2:
Recommendations for particular industries.
BS 2000-34 2002
Methods of test for petroleum and its products. Determination of flash point. PenskyMartens closed cup method.
BS 2000-35 1993
Methods of test for petroleum and its products. Determination of open, flash and fire
point. Pensky-Martens method.
9.11. PROBLEMS
9.1. In the storage of flammable liquids, if the composition of the vapour air mixture
above the liquid surface falls within the flammability limits, a floating roof tank
would be used or the tank blanketed with inert gas. Check if the vapour composition
for liquids listed below will fall within their flammability range, at atmospheric
pressure and 25Ž C.
SAFETY AND LOSS PREVENTION
1.
2.
3.
4.
399
Toluene
Acrylonitrile
Nitrobenzene
Acetone
9.2. Estimate the Dow Fire and Explosion Index, and determine the hazard rating, for
the processes listed below.
Use the process descriptions given in Appendix G and develop the designs, as
needed, to estimate the index.
1.
2.
3.
4.
5.
Ethylhexanol from propylene and synthesis gas, G.1.
Chlorobenzenes from benzene and chlorine, G.2.
Methyl ethyl ketone from 2-butanol, G.3.
Acrylonitrile from propylene and ammonia, G.4.
Aniline from nitrobenzene and hydrogen. G.8.
9.3. Devise a preliminary control scheme for the sections of the nitric acid plant
described in Chapter 4, flow-sheet Figure 4.2, which are listed below. Make a
practice HAZOP study of each section and revise your preliminary control scheme.
1. Waste heat boiler (WHB)
2. Condenser
3. Absorption column
CHAPTER 10
Equipment Selection, Specification
and Design
10.1. INTRODUCTION
The first chapters of this book covered process design: the synthesis of the complete
process as an assembly of units; each carrying out a specific process operation. In this and
the following chapters, the selection, specification and design of the equipment required to
carry out the function of these process units (unit operations) is considered in more detail.
The equipment used in the chemical processes industries can be divided into two classes:
proprietary and non-proprietary. Proprietary equipment, such as pumps, compressors,
filters, centrifuges and dryers, is designed and manufactured by specialist firms. Nonproprietary equipment is designed as special, one-off, items for particular processes; for
example, reactors, distillation columns and heat exchangers.
Unless employed by one of the specialist equipment manufacturers, the chemical
engineer is not normally involved in the detailed design of proprietary equipment. His
job will be to select and specify the equipment needed for a particular duty; consulting
with the vendors to ensure that the equipment supplied is suitable. He may be involved
with the vendor’s designers in modifying standard equipment for particular applications;
for example, a standard tunnel dryer designed to handle particulate solids may be adapted
to dry synthetic fibres.
As was pointed out in Chapter 1, the use of standard equipment, whenever possible,
will reduce costs.
Reactors, columns and other vessels are usually designed as special items for a given
project. In particular, reactor designs are usually unique, except where more or less
standard equipment is used; such as an agitated, jacketed, vessel.
Distillation columns, vessels and tubular heat exchangers, though non-proprietary items,
will be designed to conform to recognised standards and codes; this reduces the amount
of design work involved.
The chemical engineer’s part in the design of “non-proprietary” equipment is usually
limited to selecting and “sizing” the equipment. For example, in the design of a distillation
column his work will typically be to determine the number of plates; the type and design of
plate; diameter of the column; and the position of the inlet, outlet and instrument nozzles.
This information would then be transmitted, in the form of sketches and specification
sheets, to the specialist mechanical design group, or the fabricator’s design team, for
detailed design.
In this chapter the emphasis is put on equipment selection, rather than equipment
design; as most of the equipment described is proprietary equipment. Design methods
400
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
401
are given for some miscellaneous non-proprietary items. A brief discussion of reactor
design is included. The design of two important classes of equipment, columns and heat
exchangers, is covered separately in Chapters 11 and 12. A great variety of equipment
is used in the process industries, and it is only possible to give very brief descriptions
of the main types in this volume. Further details are given in Volume 2; and descriptions
and illustrations of most of the equipment used can be found in various handbooks: Perry
et al. (1997), Schweitzer (1988) and Walas (1990). Equipment manufacturers’ advertisements in the technical press should also be studied. It is worthwhile building up a personal
file of vendors’ catalogues to supplement those that may be held in a firm’s library. In
the United Kingdom, a commercial organisation, Technical Indexes Ltd., publishes the
Process Engineering Index; which contains on microfilm information from over 3000
manufacturers and suppliers of process equipment.
The scientific principles and theory that underlie the design of and operation of processing equipment is covered in Volume 2.
10.2. SEPARATION PROCESSES
As was discussed in Chapter 1, chemical processes consist essentially of reaction stages
followed by separation stages in which the products are separated and purified.
The main techniques used to separate phases, and the components within phases, are
listed in Table 10.1 and discussed in Sections 10.3 to 10.9.
10.3. SOLID-SOLID SEPARATIONS
Processes and equipment are required to separate valuable solids from unwanted material,
and for size grading (classifying) solid raw materials and products.
The equipment used for solid-solid separation processes was developed primarily for the
minerals processing and metallurgical industries for the benefication (up-grading) of ores.
The techniques used depend on differences in physical, rather than chemical, properties,
though chemical additives may be used to enhance separation. The principal techniques
used are shown in Figure 10.1; which can be used to select the type of processes likely
to be suitable for a particular material and size range.
Sorting material by appearance, by hand, is now rarely used due to the high cost of
labour.
10.3.1. Screening (sieving)
The methods used for laboratory particle size analysis are discussed in detail in Volume 2,
Chapter 1.
Screens separate particles on the basis of size. Their main application is in grading raw
materials and products into size ranges, but they are also used for the removal of trash
(over-and under-sized contaminants) and for dewatering. Industrial screening equipment
is used over a wide range of particle sizes, from fine powders to large rocks. For small
particles woven cloth or wire screens are used, and for larger sizes, perforated metal plates
or grids.
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CHEMICAL ENGINEERING
Table 10.1. Separation processes
Numbers refer to the sections in this chapter. Processes in brackets are used for separating dissolved components
(solutions). The terms major and minor component only apply where different phases are to be separated; i.e. not
to those on the diagonal
MINOR COMPONENT
Sorting
Screening
Hydrocyclones
Classifiers
Jigs
Tables
Centrifuges
Dense media
Flotation
Magnetic
Electrostatic
10.3
10.3.1
10.3.2
10.3.3
10.3.4
10.3.5
10.3.6
10.3.7
10.3.8
10.3.9
10.3.10
Pressing
Drying
10.4.5
10.4.6.
Crushing
Heating
10.10
SOLID
GAS/VAPOUR
Thickeners
Clarifiers
Hydrocyclones
Filtration
Centrifuges
(Crystallisers)
(Evaporators)
10.4.1
10.4.1
10.4.4
10.4.2
10.4.3
10.5.2
10.5.1
Decanters
Coalescers
(Solvent
extraction)
(Distillation)
(Adsorption)
(Ion exchange)
10.6.1
10.6.3
(Stripping)
Volume 2
LIQUID
LIQUID
GAS/VAPOUR
MAJOR COMPONENT
SOLID
Gravity
settlers
Impingement
settlers
Cyclones
Filters
Wet scrubbers
Electrostatic
precipitators
(Adsorption)
(Absorption)
Volume 2
Volume 2
10.8.1
10.8.2
10.8.3
10.8.4
10.8.5
Separating
vessels
Demisting pads
Cyclones
Wet scrubbers
Electrostatic
precipitators
10.7.1
Chapter 11
Volume 2
Volume 2
10.9
10.9
10.8.3
10.8.5
10.8.6
10.8.6
Screen sizes are defined in two ways: by a mesh size number for small sizes and by
the actual size of opening in the screen for the larger sizes. There are several different
standards in use for mesh size, and it is important to quote the particular standard used
when specifying particle size ranges by mesh size. In the UK the appropriate British
Standards should be used; BS 410 and BS 1796. A comparison of the various international
standard sieve mesh sizes is given in Volume 2, Chapter 1.
The simplest industrial screening equipment are stationary screens, over which the
material to be screened flows. Typical of this type are “Grizzly” screens, which consist of
rows of equally spaced parallel bars, and which are used to “scalp” off over-sized rocks
in the feed to crushers.
Dynamic screening equipment can be categorised according to the type of motion used
to shake-up and transport the material on the screen. The principal types used in the
chemical process industries are described briefly below.
403
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Hand sorting
Colour, appearance
Size alone
Screening
Liquid cyclones
Hydroseparators - classifiers
Centrifuges
Sizers
Density alone, heavy media
In cyclones In cones In drums
Size and density
Jigs
Wet tables, spirals
(Ores) Dry tables (Coal)
Magnetic permeability
Magnetic separators, dry
Magnetic separators, wet
Electrical conductivity
Electrostatic separators
Surface wetability
Froth flotation
0.001
0.01
0.1
1
10
100
Particle size, mm
Figure 10.1.
A particle size selection guide to solid-solid separation techniques and equipment (after Roberts
et al. 1971)
Vibrating screens: horizontal and inclined screening surfaces vibrated at high
frequencies (1000 to 7000 Hz). High capacity units, with good separating efficiency,
which are used for a wide range of particle sizes.
Oscillating screens: operated at lower frequencies than vibrating screens (100 400 Hz)
with a longer, more linear, stroke.
Reciprocating screens: operated with a shaking motion, a long stroke at low frequency
(20 200 Hz). Used for conveying with size separation.
Shifting screens: operated with a circular motion in the plane of the screening surface.
The actual motion may be circular, gyratory, or circularly vibrated. Used for the wet and
dry screening of fine powders.
Revolving screens: inclined, cylindrical screens, rotated at low speeds (10 20 rpm).
Used for the wet screening of relatively coarse material, but have now been largely
replaced by vibrating screens.
Figure 10.2, which is based on a similar chart given by Matthews (1971), can be
used to select the type of screening equipment likely to be suitable for a particular size
range. Equipment selection will normally be based on laboratory and pilot scale screening
tests, conducted with the co-operation of the equipment vendors. The main factors to be
considered, and the information that would be required by the firms supplying proprietary
screening equipment, are listed below:
1.
2.
3.
4.
5.
Rate, throughput required.
Size range (test screen analysis).
Characteristics of the material: free-flowing or sticky, bulk density, abrasiveness.
Hazards: flammability, toxicity, dust explosion.
Wet or dry screening to be used.
404
CHEMICAL ENGINEERING
Vibrating screens
inclined
Vibrating screens
inclined and horizontal
Grizzly
Rod
grizzly
Rod - deck screen
High speed vibrating screens
Oscillating screens
Sifter screens
circular, gyratory, circular vibrated
Centrifugal screen
Static sieves
Revolving screens
trommels, scrubbers
Revolving filter screens
50 µ
102 µ
103 µ
104 µ
105 µ
1mm
10 mm
100 mm
300 mm
Particle size
Figure 10.2.
Screen selection by particle size range
10.3.2. Liquid-solid cyclones
Cyclones can be used for the classification of solids, as well as for liquid-solid, and
liquid-liquid separations. The design and application of liquid cyclones (hydrocyclones)
is discussed in Section 10.4.4. A typical unit is shown in Figure 10.3.
Figure 10.3.
Liquid-solid cyclone (hydrocyclone)
Liquid cyclones can be used for the classification of solid particles over a size range
from 5 to 100 m. Commercial units are available in a wide range of materials of
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
405
construction and sizes; from as small as 10 mm to up to 30 m diameter. The separating
efficiency of liquid cyclones depends on the particle size and density, and the density and
viscosity of the liquid medium.
10.3.3. Hydroseparators and sizers (classifiers)
Classifiers that depend on the difference in the settling rates of different size particles in
water are frequently used for separating fine particles, in the 50 to 300 m range. Various
designs are used. The principal ones used in the chemical process industries are described
below.
Thickeners: thickeners are primarily used for liquid-solid separation (see Section 10.4).
When used for classification, the feed rate is such that the overflow rate is greater than
the settling rate of the slurry, and the finer particles remain in the overflow stream.
Rake classifiers: are inclined, shallow, rectangular troughs, fitted with mechanical rakes
at the bottom to rake the deposited solids to the top of the incline (Figure 10.4). Several
rake classifiers can be used in series to separate the feed into different size ranges.
Bowl classifiers: are shallow bowls with concave bottoms, fitted with rakes. Their
operation is similar to that of thickeners.
Figure 10.4.
Rake classifier
10.3.4. Hydraulic jigs
Jigs separate solids by difference in density and size. The material is immersed in water,
supported on a screen (Figure 10.5). Pulses of water are forced through the bed of material,
either by moving the screen or by pulsating the water level. The flow of water fluidises
the bed and causes the solids to stratify with the lighter material at the top and the heavier
at the bottom.
10.3.5. Tables
Tables are used wet and dry. The separating action of a wet table resembles that of
the traditional miner’s pan. Riffled tables (Figure 10.6) are basically rectangular decks,
inclined at a shallow angle to the horizontal (2 to 5Ž ), with shallow slats (riffles) fitted to
406
CHEMICAL ENGINEERING
Figure 10.5.
Feed
A hydraulic jig
Water
Motion
Large Middilings Fines
Figure 10.6.
Wilfley riffled table
the surface. The table is mechanically shaken, with a slow stroke in the forward direction
and a faster backward stroke. The particles are separated into different size ranges under
the combined action of the vibration, water flow, and the resistance to flow over the riffles.
10.3.6. Classifying centrifuges
Centrifuges are used for the classification of particles in size ranges below 10 m. Two
types are used: solid bowl centrifuges, usually with a cylindrical, conical bowl, rotated
about a horizontal axis; and “nozzle” bowl machines, fitted with discs.
These types are described in Section 10.4.3.
10.3.7. Dense-medium separators (sink and float processes)
Solids of different densities can be separated by immersing them in a fluid of intermediate
density. The heavier solids sink to the bottom and the lighter float to the surface. Water
suspensions of fine particles are often used as the dense liquid (heavy-medium). The
technique is used extensively for the benefication (concentration) of mineral ores.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
407
10.3.8. Flotation separators (froth-flotation)
Froth-flotation processes are used extensively for the separation of finely divided solids.
Separation depends on differences in the surface properties of the materials. The particles
are suspended in an aerated liquid (usually water), and air bubbles adhere preferentially
to the particles of one component and bring them to the surface. Frothing agents are used
so that the separated material is held on the surface as a froth and can be removed.
Froth-flotation is an extensively used separation technique, having a wide range of
applications in the minerals processing industries and other industries. It can be used for
particles in the size range from 50 to 400 m.
10.3.9. Magnetic separators
Magnetic separators can be used for materials that are affected by magnetic fields; the
principle is illustrated in Figure 10.7. Rotating-drum magnetic separators are used for a
wide range of materials in the minerals processing industries. They can be designed to
handle relatively high throughputs, up to 3000 kg/h per metre length of drum.
Simple magnetic separators are often used for the removal of iron from the feed to
a crusher.
The various types of magnetic separators used and their applications are described by
Bronkala (1988).
Magnetic pulley
Magnetic
material
Figure 10.7.
Magnetic separator
Active electrode
Earthed
rotor
−
+
Figure 10.8.
Electrostatic separator
408
CHEMICAL ENGINEERING
10.3.10. Electrostatic separators
Electrostatic separation depends on differences in the electrical properties (conductivity)
of the materials to be treated. In a typical process the material particles pass through a
high-voltage electric field as it is fed on to a revolving drum, which is at earth potential
(Figure 10.8). Those particles that acquire a charge adhere to the drum surface and are
carried further around the drum before being discharged.
10.4. LIQUID-SOLID (SOLID-LIQUID) SEPARATORS
The need to separate solid and liquid phases is probably the most common phase separation
requirement in the process industries, and a variety of techniques is used (Figure 10.9).
Separation is effected by either the difference in density between the liquid and solids,
using either gravity or centrifugal force, or, for filtration, depends on the particle size and
shape. The most suitable technique to use will depend on the solids concentration and
feed rate, as well as the size and nature of the solid particles. The range of application of
various techniques and equipment, as a function of slurry concentration and particle size,
is shown in Figure 10.10.
Solid - liquid seperations
Settling (sedimentation)
Gravity
Thickeners
(Screening)
Filtration
Centrifugal
Pressing (expression)
Drying
Gravity
Hydrocyclones
Pressure
Vacuum
Clarifiers
Centrifugal
Centrifuges
Solid product
Increasing feed solids concentration
Figure 10.9.
Solid-liquid separation techniques
The choice of equipment will also depend on whether the prime objective is to obtain
a clear liquid or a solid product, and on the degree of dryness of the solid required.
The design, construction and application of thickeners, centrifuges and filters is a
specialised subject, and firms who have expertise in these fields should be consulted
when selecting and specifying equipment for new applications. Several specialist texts
on the subject are available: Svarovsky (2001), Ward (2000) and Wakeman and Tarleton
(1998). The theory of sedimentation processes is covered in Volume 2, Chapter 5 and
filtration in Chapter 7.
10.4.1. Thickeners and clarifiers
Thickening and clarification are sedimentation processes, and the equipment used for
the two techniques are similar. The primary purpose of thickening is to increase the
concentration of a relatively large quantity of suspended solids; whereas that of clarifying,
409
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
100,000
Screens
Particle size range, microns
10,000
1,000
100
er
en
ick
Th
Classifier
Filters and
centrifuges
10
Cyclones
Dryers
1
1
Figure 10.10.
10
Feed, % solids
100
Solid-liquid separation techniques (after Dahlstrom and Cornell, 1971)
as the name implies, is to remove a small quantity of fine solids to produce a clear liquid
effluent. Thickening and clarification are relatively cheap processes when used for the
treatment of large volumes of liquid.
A thickener, or clarifier, consists essentially of a large circular tank with a rotating
rake at the base. Rectangular tanks are also used, but the circular design is preferred.
They can be classified according to the way the rake is supported and driven. The three
basic designs are shown in Figure 10.11 (see p. 410). Various designs of rake are used,
depending on the nature of the solids.
The design and construction of thickeners and clarifiers is described by Dahlstrom and
Cornell (1971).
Flocculating agents are often added to promote the separating performance of thickeners.
10.4.2. Filtration
In filtration processes the solids are separated from the liquid by passing (filtering) the
slurry through some form of porous filter medium. Filtration is a widely used separation
410
CHEMICAL ENGINEERING
Feed
Overflow
Underflow
(a)
Feed
Overflow
Underflow
(b)
Feed
Overflow
Underflow
(c)
Figure 10.11.
Types of thickener and clarifier (a) Bridge supported (up to <40 m dia.) (b) Centre column
supported (<30 m dia.) (c) Traction driven (<60 m dia.)
process in the chemical and other process industries. Many types of equipment and filter
media are used; designed to meet the needs of particular applications. Descriptions of the
filtration equipment used in the process industries and their fields of application can be
found in various handbooks: Perry et al. (1997), Dickenson (1997), Schweitzer (1997),
and in several specialist texts on the subject: Cheremisnoff (1998), Orr (1977). A short
discussion of filtration theory and descriptions of the principal types of equipment is given
in Volume 2, Chapter 7.
The most commonly used filter medium is woven cloth, but a great variety of other
media is also used. The main types are listed in Table 10.2. A comprehensive discussion
of the factors to be considered when selecting filter media is given by Purchas (1971)
and Mais (1971); see also Purchas and Sutherland (2001). Filter aids are often used to
increase the rate of filtration of difficult slurries. They are either applied as a precoat
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
411
to the filter cloth or added to the slurry, and deposited with the solids, assisting in the
formation of a porous cake.
Table 10.2.
Type
1. Solid fabrications
2. Rigid porous
media
3. Metal
4. Porous plastics
5. Woven fabrics
6. Non-woven sheets
7. Cartridges
8. Loose solids
Filter media
Examples
Scalloped washers
Wire-wound tubes
Ceramics, stoneware
Sintered metal
Perforated sheets
Woven wire
Pads, sheets
Membranes
Natural and synthetic
fibre cloths
Felts, lap
Paper, cellulose
Yarn-wound spools,
graded fibres
Fibres, asbestos,
cellulose
Minimum size particle
trapped (m)
5
1
3
100
5
3
0.005
10
10
5
2
sub-micron
Industrial filters use vacuum, pressure, or centrifugal force to drive the liquid (filtrate)
through the deposited cake of solids. Filtration is essentially a discontinuous process.
With batch filters, such as plate and frame presses, the equipment has to be shut down to
discharge the cake; and even with those filters designed for continuous operation, such as
rotating-drum filters, periodic stoppages are necessary to change the filter cloths. Batch
filters can be coupled to continuous plant by using several units in parallel, or by providing
buffer storage capacity for the feed and product.
The principal factors to be considered when selecting filtration equipment are:
1.
2.
3.
4.
5.
6.
7.
8.
The nature of the slurry and the cake formed.
The solids concentration in the feed.
The throughput required.
The nature and physical properties of the liquid: viscosity, flammability, toxicity,
corrosiveness.
Whether cake washing is required.
The cake dryness required.
Whether contamination of the solid by a filter aid is acceptable.
Whether the valuable product is the solid or the liquid, or both.
The overriding factor will be the filtration characteristics of the slurry; whether it is
fast filtering (low specific cake resistance) or slow filtering (high specific cake resistance).
The filtration characteristics can be determined by laboratory or pilot plant tests. A guide
to filter selection by the slurry characteristics is given in Table 10.3; which is based on a
similar selection chart given by Porter et al. (1971).
412
CHEMICAL ENGINEERING
Table 10.3.
Guide to filter selection
Slurry characteristics
Fast
filtering
Medium
filtering
Slow
filtering
Dilute
Cake formation rate
Normal concentration
Settling rate
Leaf test rate, kg/h m2
Filtrate rate, m3 /h m2
cm/s
>20%
Very fast
>2500
>10
mm/s
10 20%
Fast
250 2500
5 10
0.02 0.12 mm/s
1 10%
Slow
25 250
0.02 0.05
0.02 mm/s
<5%
Slow
<25
0.02 5
Very
dilute
No cake
<0.1%
0.02 5
Filter application
Continuous vacuum filters
Multicompartment drum
Single compartment drum
Top feed drum
Scroll discharge drum
Tilting pan
Belt
Disc
Batch vacuum leaf
Batch nutsche
Batch pressure filters
Plate and frame
Vertical leaf
Horizontal plate
Cartridge edge
The principal types of industrial scale filter used are described briefly below.
Nutsche (gravity and vacuum operation)
This is the simplest type of batch filter. It consists of a tank with a perforated base, which
supports the filter medium.
Plate and frame press (pressure operation) (Figure 10.12)
The oldest and most commonly used batch filter. Versatile equipment, made in a variety of
materials, and capable of handling viscous liquids and cakes with a high specific resistance.
Plates
and frame
Figure 10.12.
Plate and frame filter press
Leaf filters (pressure and vacuum operation)
Various types of leaf filter are used, with the leaves arranged in horizontal or vertical
rows. The leaves consist of metal frames over which filter cloths are draped. The cake is
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
413
removed either mechanically or by sluicing it off with jets of water. Leaf filters are used for
similar applications as plate and frame presses, but generally have lower operating costs.
Rotary drum filters (usually vacuum operation) (Figure 10.13)
A drum filter consists essentially of a large hollow drum round which the filter medium is
fitted. The drum is partially submerged in a trough of slurry, and the filtrate sucked through
the filter medium by vacuum inside the drum. Wash water can be sprayed on to the drum
surface and multicompartment drums are used so that the wash water can be kept separate
from the filtrate. A variety of methods is used to remove the cake from the drum: knives,
strings, air jets and wires. Rotating drum filters are essentially continuous in operation.
They can handle large throughputs, and are widely used for free filtering slurries.
Wash
distributors
Dewatering
on
tati
Ro
Initial
dewatering
Cake washing
(max allowable)
Final
dewatering
Discharge
Slurry level
Filtering
Figure 10.13.
Discharged
filter cake
Drum filter
Disc filters (pressure and vacuum operation)
Disc filters are similar in principle to rotary filters, but consist of several thin discs
mounted on a shaft, in place of the drum. This gives a larger effective filtering area on a
given floor area, and vacuum disc filters are used in preference to drum filters where space
is restricted. At sizes above approximately 25 m2 filtration area, disc filters are cheaper;
but their applications are more restricted, as they are not as suitable for the application
of wash water, or precoating.
Belt filters (vacuum operation) (Figure 10.14)
A belt filter consists of an endless reinforced rubber belt, with drainage hole along its
centre, which supports the filter medium. The belt passes over a stationary suction box,
into which the filtrate is sucked. Slurry and wash water are sprayed on to the top of
the belt.
414
CHEMICAL ENGINEERING
Feed
Wash
+
+
+
Mother
liquor
+
Wash
liquor
Filter belt
Figure 10.14.
Filter
media
Cake
Support belt
Belt filter
Horizontal pan filters (vacuum operation) (Figure 10.15)
This type is similar in operation to a vacuum Nutsche filter. It consists of shallow pans
with perforated bases, which support the filter medium. By arranging a series of pans
around the circumference of a rotating wheel, the operation of filtering, washing, drying
and discharging can be made automatic.
Figure 10.15.
Pan filters
Centrifugal filters
Centrifugal filters use centrifugal force to drive the filtrate through the filter cake. The
equipment used is described in the next section.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
415
10.4.3. Centrifuges
Centrifuges are classified according to the mechanism used for solids separation:
(a) Sedimentation centrifuges: in which the separation is dependent on a difference in
density between the solid and liquid phases (solid heavier).
(b) Filtration centrifuges: which separate the phases by filtration. The walls of the
centrifuge basket are porous, and the liquid filters through the deposited cake of
solids and is removed.
The choice between a sedimentation or filtration centrifuge for a particular application
will depend on the nature of the feed and the product requirements.
The main factors to be considered are summarised in Table 10.4. As a general rule,
sedimentation centrifuges are used when it is required to produce a clarified liquid, and
filtration centrifuges to produce a pure, dry, solid.
Table 10.4.
Selection of sedimentation or filter centrifuge
Factor
Solids size, fine
Solids size, >150 m
Compressible cakes
Open cakes
Dry cake required
High filtrate clarity
Crystal breakage problems
Pressure operation
High-temperature
operation
Sedimentation
Filtration
x
x
x
x
x
x
x
will depend on the type of
centrifuge used
A variety of centrifugal filter and sedimenter designs is used. The main types are
listed in Table 10.5. They can be classified by a number of design and operating features,
such as:
1.
2.
3.
4.
5.
6.
Mode of operation batch or continuous.
Orientation of the bowl/basket horizontal or vertical.
Position of the suspension and drive overhung or underhung.
Type of bowl solid, perforated basket, disc bowl.
Method of solids cake removal.
Method of liquid removal.
Descriptions of the various types of centrifuges and their fields of application can be
found in various handbooks, in a book by Leung (1998) and articles by Ambler (1971)
and Linley (1984).
The fields of application of each type, classified by the size range of the solid
particles separated, are given in Figure 10.16. A similar selection chart is given by
Schroeder (1998).
Sedimentation centrifuges
There are four main types of sedimentation centrifuge:
416
CHEMICAL ENGINEERING
Table 10.5.
Centrifuge types (after Sutherland, 1970)
Sedimentation
Laboratory
Bottle
Ultra
Filtration-fixed bed
Vertical basket
Manual discharge
Bag discharge
Knife discharge
Horizontal basket
Inclined basket
Tubular bowl
Disc
Batch bowl
Nozzle discharge
Valve discharge
Opening bowl
Filtration-moving bed
Imperforate basket
Manual discharge
Skimmer discharge
Conical bowl
Wide angle
Vibrating
Torsional
Tumbling
Scroll discharge
Scroll discharge
Horizontal
Cantilevered
Vertical
Screen bowl
0.01
0.1
Cylindrical bowl
Scroll discharge
Pusher
Particle diameter - microns
1
10
100
1000
10,000
Ultra
Bottle
Tubular bowl
Batch disc
Nozzle disc
Valve disc
Opening bowl
Imperf basket
Decanter
Screen bowl
Vertical basket
Knife discharge
Peeler
Wide angle
Vibrating
Tumbling
Scroll discharge
Pusher
Figure 10.16.
Classification of centrifuges by particle size (after Sutherland, 1970)
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
417
1. Tubular bowl (Figure 10.17)
High-speed, vertical axis, tubular bowl centrifuges are used for the separation of immiscible liquids, such as water and oil, and for the separation of fine solids. The bowl
is driven at speeds of around 15,000 rpm (250 Hz) and the centrifugal force generated
exceeds 130,000 N.
Figure 10.17.
Tubular Bowl centrifuge
2. Disc bowl (Figure 10.18)
The conical discs in a disc bowl centrifuge split the liquid flow into a number of very
thin layers, which greatly increases the separating efficiency. Disc bowl centrifuges are
used for separating liquids and fine solids, and for solids classification.
3. Scroll discharge
In this type of machine the solids deposited on the wall of the bowl are removed by a
scroll (a helical screw conveyer) which revolves at a slightly different speed from the
418
CHEMICAL ENGINEERING
Feed
Overflow
Figure 10.18.
Disc bowl centrifuge
bowl. Scroll discharge centrifuges can be designed so that solids can be washed and
relatively dry solids be discharged.
4. Solid bowl batch centrifuge
The simplest type; similar to the tubular bowl machine type but with a smaller bowl
length to diameter ratio (less than 0.75). The tubular bowl type is rarely used for solids
concentrations above 1 per cent by volume. For concentrations between 1 to 15 per cent,
any of the other three types can be used. Above 15 per cent, either the scroll discharge
type or the batch type may be used, depending on whether continuous or intermittent
operation is required.
Sigma theory for sedimentation centrifuges
The basic equations describing sedimentation in a centrifugal field have been developed
in Volume 2, Chapter 9. In that discussion the term sigma () is introduced, which can
be used to define the performance of a centrifuge independently of the physical properties
of the solid-fluid system. The sigma value of a centrifuge, normally expressed in cm2 ,
is equal to the cross-sectional area of a gravity settling tank having the same clarifying
capacity.
This approach to describing centrifuge performance has become known as the “sigma
theory”. It provides a means for comparing the performance of sedimentation centrifuges
and for scaling up from laboratory and pilot scale tests; see Ambler (1952) and
Trowbridge (1962).
In the general case, it can be shown that:
and (where Stokes’ law applies)
Q D 2ug
d2s g
ug D
18
(10.1)
(10.2)
Note: The factor of 2 is included in equation 10.1 as ds is the cut-off size, 50 per cent
of particles of this size will be removed in passage through the centrifuge.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
419
where Q D volumetric flow of liquid through the centrifuge, m3 /s,
ug D terminal velocity of the solid particle settling under gravity through the
liquid, m/s,
D sigma value of the centrifuge, m2 ,
D density difference between solid and liquid, kg/m3
ds D the diameter of the solid particle, the cut-off size, m (m ð 106 ),
D viscosity of the liquid, Nm2 s.
g D gravitational acceleration, 9.81 m/s2 ,
Morris (1966) gives a method for the selection of the appropriate type of sedimentation
centrifuge for a particular application based on the ratio of the liquid overflow to sigma
value (Q/). His values for the operating range of each type, and their approximate
efficiency rating, are given in Table 10.6. The efficiency term is used to account for the
different amounts by which the various designs differ from the theoretical sigma values
given by equation 10.1. Sigma values depend solely on the geometrical configuration and
speed of the centrifuge. Details of the calculation for various types are given by Ambler
(1952). To use Table 10.6, it is necessary to know the feed rate of slurry (and hence
the liquid overflow Q), the density of the liquid and solid, the liquid viscosity; and the
diameter of the particle for, say, a 98 per cent size removal. The use of Table 10.6 is
illustrated in Example 10.1.
Table 10.6.
Selection of sedimentation centrifuges
Approximate
efficiency (%)
Type
Tubular bowl
Disc
Solid bowl (scroll discharge)
Solid bowl (basket)
90
45
60
75
Normal operating range
Q, m3 /h at Q/ m/s
0.4
0.1
0.7
0.4
at
at
at
at
5 ð 108 to 4 at 3.5 ð 107
7 ð 108 to 110 at 4.5 ð 107
1.5 ð 106 to 15 at 1.5 ð 105
5 ð 106 to 4 at 1.5 ð 104
A selection guide for sedimentation centrifuges by Lavanchy et al. (1964), which includes
other types of solid-liquid separators, is shown in Figure 10.19, adapted to SI units.
Example 10.1
A precipitate is to be continuously separated from a slurry. The solids concentration is 5
per cent and the slurry feed rate 5.5 m3 /h. The relevant physical properties at the system
operating temperature are:
liquid density 1050 kg/m3 , viscosity 4 cp (mNm2 s),
solid density 2300 kg/m3 , “cut-off” particle size 10 m D 10 ð 106 m.
Solution
Overflow rate, Q D 0.95 ð 5.5 D 5.23 m3 /h
5.13
D 1.45 ð 103 m3 /s
D
3600
D 2300 1050 D 1250 kg/m3
420
CHEMICAL ENGINEERING
100
Scroll
type
Basket
type
10
Disc
1
3
Q, m h
−1
Tubular
Laboratory disc
Gravity tank
0.1m
0.1
Laboratory
tubular
0.01
Hydrocyclones
0.001
10
−10
10
−9
−8
10
−7
10
10
−6
10
−5
Q/Σ = 2 x settling velocity under gravity,
Figure 10.19.
−4
10
10
−3
10
−2
ms−1
Performance of sedimentation equipment (after Lavanchy et al., 1964)
From equations 10.1 and 10.2
1250⊲10 ð 106 ⊳2
Q
D2ð
ð 9.81 D 3.4 ð 105
18 ð 4 ð 103
From Table 10.6 for a Q of 5.23 m3 /h at a Q/ of 3.4 ð 105 a solid bowl basket
type should be used.
To obtain an idea of the size of the machine needed the sigma value can be calculated
using the efficiency value from Table 10.6.
From equation 10.1:
D
Q
1.45 ð 103
D
eff . ð 2ug
0.75 ð 3.4 ð 105
D 56.9 m2
The sigma value is the equivalent area of a gravity settler that would perform the same
separation as the centrifuge.
Filtration centrifuges (centrifugal filters)
It is convenient to classify centrifugal filters into two broad classes, depending on how
the solids are removed: fixed bed or moving bed.
In the fixed-bed type, the cake of solids remains on the walls of the bowl until removed
manually, or automatically by means of a knife mechanism. It is essentially cyclic in
operation. In the moving-bed type, the mass of solids is moved along the bowl by the
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
421
action of a scroll (similar to the solid-bowl sedimentation type); or by a ram (pusher
type); or by a vibration mechanism; or by the bowl angle. Washing and drying zones can
be incorporated into the moving bed type.
Bradley (1965) has grouped the various types into the family tree shown in
Figure 10.20.
Fixed
bed
Batch
manual
Cyclic
automatic
Vertical
axis
multi speed
Top drive
Top
discharge
Bag
Figure 10.20.
Moving
bed
Scroll
discharge
Horizontal
axis
single speed
Rising
knife
Vibratory
discharge
Inclined
bowl
discharge
Bottom
drive
Bottom
discharge
manual
Manual
Reciprocating push
discharge
Constant
angle
Rotary
knife
Variable
angle
tumbler
Traversing
knife
Filtration centrifuge family tree (after Bradley, 1965a)
Schematic diagrams of the various types are shown in Figure 10.21. The simplest
machines are the basket types (Figures 10.21a, b, c), and these form the basic design
from which the other types have been developed (Figures 10.21d to o).
The various arrangements of knife mechanisms used for automatic removal of
the cake are shown in Figures 10.21d to h. The bottom discharge-type machines
(Figures 10.21d, e) can be designed for variable speed, automatic discharge; and are
suitable for use with fragile, or plate or needle-shaped crystals, where it is desirable
to avoid breakage or compaction of the bed. They can be loaded and discharged at
low speeds, which reduces breakage and compaction of the cake. The single-speed
machines (Figures 10.21f, g, h) are used where cakes are thin, and short cycle times
are required. They can be designed for high-temperature and pressure operation. When
continuous operation is required, the scroll, pusher, or other self-discharge types are used
(Figures 10.21i to o). The scroll discharge centrifuge is a low-cost, flexible machine,
capable of a wide range of applications; but is not suitable for handling fragile materials.
422
CHEMICAL ENGINEERING
Figure 10.21. Schematic diagrams of filtration centrifuge types (Bradley, 1965) (a) Bottom drive batch
basket with bag (b) Top drive bottom discharge batch basket (c) Bottom drive bottom discharge batch basket
(d) Bottom drive automatic basket, rising knife (e) Bottom drive automatic basket, rotary knife (f) Singlereversing knife rising knife (g) Single-speed automatic rotary knife (h) Single-speed automatic traversing
knife (i) Inclined wall self-discharge (j) Inclined vibrating wall self-discharge (k) Inclined “tumbling” wall
self-discharge (l) Inclined wall scroll discharge (m) Traditional single-stage pusher (n) Traditional multi-stage
pusher (o) Conical pusher with de-watering cone
It is normally used for coarse particles, where some contamination of the filtrate with
fines can be tolerated.
The capacity of filtration centrifuges is very dependent on the solids concentration in
the feed. For example, at 10 per cent feed slurry concentration 9 kg of liquid will be
centrifuged for every 1 kg of solids separated; whereas with a 50 per cent solids concentration the quantity will be less than 1 kg. For dilute slurries it is well worth considering
using some form of pre-concentration; such as gravity sedimentation or a hydrocyclone.
10.4.4. Hydrocyclones (liquid-cyclones)
Hydrocyclones are used for solid-liquid separations; as well as for solids classification, and
liquid-liquid separation. It is a centrifugal device with a stationary wall, the centrifugal force
being generated by the liquid motion. The operating principle is basically the same as that
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
423
of the gas cyclone described in Section 10.8.3, and in Volume 2, Chapter 8. Hydrocyclones
are simple, robust, separating devices, which can be used over the particle size range from
4 to 500 m. They are often used in groups, as illustrated in Figure 10.24b. The design
and application of hydrocyclones is discussed fully in books by Abulnaga (2002) and
Svarovsky and Thew (1992). Design methods and charts are also given by Zanker (1977),
Day et al. (1997) and Moir (1985).
The nomographs by Zanker can be used to make a preliminary estimate of the size
of cyclone needed. The specialist manufacturers of hydrocyclone equipment should be
consulted to determine the best arrangements and design for a particular application.
Zanker’s method is outlined below and illustrated in Example 10.2. Figure 10.23 is
based on an empirical equation by Bradley (1960):
Dc3
d50 D 4.5 1.2
⊲10.3⊳
L ⊲s L ⊳
where d50 D the particle diameter for which the cyclone is 50 per cent efficient, m,
Dc D diameter of the cyclone chamber, cm,
Figure 10.22.
Determination of d50 from the desired particle separation (Equation 10.3, Zanker, 1977)
(Example 10.2)
424
Figure 10.23.
CHEMICAL ENGINEERING
Chamber dia. Dc from flow-rate, physical properties, and d50 particle size (Equation 10.4,
Zanker, 1977) (Example 10.2)
(a)
Figure 10.24.
(a) Hydrocyclone-typical proportions
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
425
(b)
Figure 10.24.
L
L
s
(b) A “Clog” assembly of 16 ð 2 in (50 mm) diameter hydrocyclone. (Courtesy of Richard
Mozley Ltd.)
D
D
D
D
liquid viscosity, centipoise (mN s/m2 ),
feed flow rate, l/min,
density of the liquid, g/cm3 ,
density of the solid, g/cm3 .
The equation gives the chamber diameter required to separate the so-called d50 particle
diameter, as a function of the slurry flow rate and the liquid and solid physical properties.
The d50 particle diameter is the diameter of the particle, 50 per cent of which will appear in
the overflow, and 50 per cent in the underflow. The separating efficiency for other particles is
related to the d50 diameter by Figure 10.22, which is based on a formula by Bennett (1936).
426
CHEMICAL ENGINEERING
3
D 100 1 e⊲d/d50 0.115⊳
⊲10.4⊳
where D the efficiency of the cyclone in separating any particle of diameter d,
per cent,
d D the selected particle diameter, m.
The method applies to hydrocyclones with the proportions shown in Figure 10.24.
Example 10.2
Estimate the size of hydrocyclone needed to separate 90 per cent of particles with a
diameter greater than 20 m, from 10 m3 /h of a dilute slurry.
Physical properties: solid density 2000 kg/m3 , liquid density 1000 kg/m3 , viscosity
1 mN s/m2
Solution
10 ð 103
D 166.71/min
60
⊲s L ⊳ D 2.0 1.0 D 1.0 g/cm3
Flow-rate D
From Figure 10.22, for 90 per cent removal of particles above 20 m
d50 D 14 m
From Figure 10.23, for D 1 mN s/m2 , (s L ) = 1.0 g/cm3 , L = 167/min
Dc D 16 cm
10.4.5. Pressing (expression)
Pressing, in which the liquid is squeezed (expressed) from a mass of solids by
compression, is used for certain specialised applications. Pressing consumes a great deal of
energy, and should not be used unless no other separating technique is suitable. However,
in some applications dewatering by pressing can be competitive with drying.
Presses are of two basic types: hydraulic batch presses and screw presses. Hydraulic
presses are used for extracting fruit juices, and screw presses for dewatering materials;
such as paper pulp, rubbish and manure. The equipment used is described in the
handbooks; Perry et al. (1997).
10.4.6. Solids drying
Drying is the removal of water, or other volatile liquids, by evaporation. Most solid materials
require drying at some stage in their production. The choice of suitable drying equipment
cannot be separated from the selection of the upstream equipment feeding the drying stage.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
427
428
CHEMICAL ENGINEERING
The overriding consideration in the selection of drying equipment is the nature and concentration of the feed. Drying is an energy-intensive process, and the removal of liquid by
thermal drying will be more costly than by mechanical separation techniques.
Drying equipment can be classified according to the following design and operating
features:
1.
2.
3.
4.
Batch or continuous.
Physical state of the feed: liquid, slurry, wet solid.
Method of conveyance of the solid: belt, rotary, fluidised.
Heating system: conduction, convection, radiation.
Except for a few specialised applications, hot air is used as the heating and mass transfer
medium in industrial dryers. The air may be directly heated by the products of combustion
of the fuel used (oil, gas or coal) or indirectly heated, usually by banks of steamheated finned tubes. The heated air is usually propelled through the dryer by electrically
driven fans.
Table 10.7, adapted from a similar selection guide by Parker (1963a), shows the basic
features of the various types of solids dryer used in the process industries; and Table 10.8,
by Williams-Gardner (1965), shows typical applications.
Batch dryers are normally used for small-scale production and where the drying cycle
is likely to be long. Continuous dryers require less labour, less floor space; and produce
a more uniform quality product.
When the feed is solids, it is important to present the material to the dryer in a form
that will produce a bed of solids with an open, porous, structure.
For pastes and slurries, some form of pretreatment equipment will normally be needed,
such as extrusion or granulation.
The main factors to be considered when selecting a dryer are:
1.
2.
3.
4.
5.
6.
7.
Feed condition: solid, liquid, paste, powder, crystals.
Feed concentration, the initial liquid content.
Product specification: dryness required, physical form.
Throughput required.
Heat sensitivity of the product.
Nature of the vapour: toxicity, flammability.
Nature of the solid: flammability (dust explosion hazard), toxicity.
The drying characteristics of the material can be investigated by laboratory and pilot plant
tests; which are best carried out in consultation with the equipment vendors.
The theory of drying processes is discussed in Volume 2, Chapter 16. Full descriptions
of the various types of dryer and their applications are given in that chapter and in Perry
et al. (1997) and Walas (1990). Only brief descriptions of the principal types will be given
in this section.
The basic types used in the chemical process industries are: tray, band, rotary, fluidised,
pneumatic, drum and spray dryers.
Tray dryers (Figure 10.25)
Batch tray dryers are used for drying small quantities of solids, and are used for a wide
range of materials.
429
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Table 10.8.
Dryer type
System
Dryer applications
Feed form
Typical products
Paste, granules,
extrude cake
Batch ovens
Forced convection
Vacuum
Extrude cake
Pigment dyestuffs,
pharmaceuticals,
fibres
Pharmaceuticals
” pan (agitated)
Atmospheric and
vacuum
Crystals, granules,
powders
Fine chemicals,
food products
” rotary
Vacuum
Crystals, granules
solvent recovery
Pharmaceuticals
” fluid bed
Forced convection
Granular, crystals
Fine chemicals,
pharmaceuticals,
plastics
” infra-red
Radiant
Components sheets
Metal products,
plastics
Continuous rotary
Convection
Direct/indirect
Direct
Indirect
Conduction
Crystals, coarse
powders, extrudes,
preformed cake
lumps, granular
paste and fillers,
cakes back-mixed
with dry product
Chemical ores,
food products,
clays, pigments,
chemicals
Liquids,
suspensions
Carbon black
” film drum
Conduction
Foodstuffs,
pigment
” trough
” spray
Conduction
Convection
Liquids, suspensions
Foodstuffs,
pharmaceuticals,
ceramics, fine
chemicals, detergents, organic
extracts
” band
Convection
Preformed solids
Foodstuffs, pigments, chemicals,
rubber, clays, ores,
textiles
” fluid bed
Convection
Preformed solids
granules, crystals
Ores, coal, clays,
chemicals
” pneumatic
Convection
Preformed pastes,
granules, crystals,
coarse products
Chemicals, starch,
flour, resins, woodproducts, food
products
” infra-red
Radiant
Components sheets
Metal products,
moulded fibre
articles, painted
surfaces
Ceramics, adhesives
The material to be dried is placed in solid bottomed trays over which hot air is blown;
or perforated bottom trays through which the air passes.
Batch dryers have high labour requirements, but close control can be maintained over
the drying conditions and the product inventory, and they are suitable for drying valuable
products.
430
CHEMICAL ENGINEERING
Figure 10.25.
Tray dryer
Conveyor dryers (continuous circulation band dryers) (Figure 10.26)
In this type, the solids are fed on to an endless, perforated, conveyor belt, through which
hot air is forced. The belt is housed in a long rectangular cabinet, which is divided up
into zones, so that the flow pattern and temperature of the drying air can be controlled.
The relative movement through the dryer of the solids and drying air can be parallel or,
more usually, counter-current.
Zone 1
Zone 2
Zone 1
air up
Zone 2
air down
Zone 3
cooler
Zone 3
Figure 10.26.
Conveyor dryer
This type of dryer is clearly only suitable for materials that form a bed with an open
structure. High drying rates can be achieved, with good product-quality control. Thermal
efficiencies are high and, with steam heating, steam usage can be as low as 1.5 kg per
kg of water evaporated. The disadvantages of this type of dryer are high initial cost and,
due to the mechanical belt, high maintenance costs.
Rotary dryer (Figure 10.27)
In rotary dryers the solids are conveyed along the inside of a rotating, inclined, cylinder
and are heated and dried by direct contact with hot air gases flowing through the cylinder.
In some, the cylinders are indirectly heated.
431
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Figure 10.27.
Rotary dryer
Rotating dryers are suitable for drying free-flowing granular materials. They are suitable
for continuous operation at high throughputs; have a high thermal efficiency and relatively
low capital cost and labour costs. Some disadvantages of this type are: a non-uniform
residence time, dust generation and high noise levels.
Fluidised bed dryers (Figure 10.28)
In this type of dryer, the drying gas is passed through the bed of solids at a velocity
sufficient to keep the bed in a fluidised state; which promotes high heat transfer and
drying rates.
Fan
Product feed
Weir plate
Cooling zone
Air
Heater
Dust rotor
Fluidised product
Discharge
valves
Gas
distributor plate
Figure 10.28.
Belt
Fluidised bed dryer
Fluidised bed dryers are suitable for granular and crystalline materials within the particle
size range 1 to 3 mm. They are designed for continuous and batch operation.
The main advantages of fluidised dryers are: rapid and uniform heat transfer; short
drying times, with good control of the drying conditions; and low floor area requirements.
The power requirements are high compared with other types.
432
CHEMICAL ENGINEERING
Stack
Induced-draught
fan
Cyclone
Dryer duct
Rotary valve
Feeder
screw
Air heater
Forced-draught fan
Figure 10.29.
Pneumatic dryer
Pneumatic dryers (Figure 10.29)
Pneumatic dryers, also called flash dryers, are similar in their operating principle to spray
dryers. The product to be dried is dispersed into an upward-flowing stream of hot gas by a
suitable feeder. The equipment acts as a pneumatic conveyor and dryer. Contact times are
short, and this limits the size of particle that can be dried. Pneumatic dryers are suitable
for materials that are too fine to be dried in a fluidised bed dryer but which are heat
sensitive and must be dried rapidly. The thermal efficiency of this type is generally low.
Spray dryers (Figure 10.30)
Spray dryers are normally used for liquid and dilute slurry feeds, but can be designed to
handle any material that can be pumped. The material to be dried is atomised in a nozzle,
or by a disc-type atomiser, positioned at the top of a vertical cylindrical vessel. Hot air
flows up the vessel (in some designs downward) and conveys and dries the droplets. The
liquid vaporises rapidly from the droplet surface and open, porous particles are formed.
The dried particles are removed in a cyclone separator or bag filter.
The main advantages of spray drying are the short contact time, making it suitable for
drying heat-sensitive materials, and good control of the product particle size, bulk density,
and form. Because the solids concentration in the feed is low the heating requirements
will be high. Spray drying is discussed in a book by Masters (1991).
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
433
Furnace
Cyclone
Exhaust to
atmosphere
Fan
Feed
Pump
Product
collection
Figure 10.30.
Spray dryer
Rotary drum dryers (Figure 10.31)
Drum dryers are used for liquid and dilute slurry feeds. They are an alternative choice to
spray dryers when the material to be dried will form a film on a heated surface, and is
not heat sensitive.
Figure 10.31.
Rotary drum dryers
434
CHEMICAL ENGINEERING
They consist essentially of a revolving, internally heated, drum, on which a film of the
solids is deposited and dried. The film is formed either by immersing part of the drum in
a trough of the liquid or by spraying, or splashing, the feed on to the drum surface; double
drums are also used in which the feed is fed into the “nip” formed between the drums.
The drums are usually heated with steam, and steam economies of 1.3 kg steam per
kg of water evaporated are typically achieved.
10.5. SEPARATION OF DISSOLVED SOLIDS
On an industrial scale, evaporation and crystallisation are the main processes used for the
recovery of dissolved solids from solutions.
Membrane filtration processes, such as reverse osmosis, and micro and ultra filtration,
are used to “filter out” dissolved solids in certain applications; see Table 10.9. These
specialised processes will not be discussed in this book. A comprehensive description of
the techniques used and their applications is given in Volume 2, Chapter 8; see also: Scott
and Hughes (1995), Cheryan (1986), McGregor (1986) and Porter (1997).
Table 10.9.
Process
Microfiltration
Ultrafiltration
Nanofiltration
Reverse osmosis
Dialysis
Electrodialysis
Pervaporation
Gas permeation
Membrane filtration process
Approximate size
range (m)
108 to 104
109 to 108
5 ð 109 to 15 ð 109
1010 to 109
109 to molecules
109 to molecules
109 to molecules
109 to molecules
Applications
pollen, bacteria, blood cells
proteins and virus
water softening
desalination
blood purification
separation of electrolytes
dehydration of ethanol
hydrogen recovery, dehydration
10.5.1. Evaporators
Evaporation is the removal of a solvent by vaporisation, from solids that are not volatile.
It is normally used to produce a concentrated liquid, often prior to crystallisation, but a
dry solid product can be obtained with some specialised designs. The general subject of
evaporation is covered in Volume 2, Chapter 14. That chapter includes a discussion of
heat transfer in evaporators, multiple-effect evaporators, and a description of the principal
types of equipment. The selection of the appropriate type of evaporator is discussed by
Cole (1984). Evaporation is the subject of a book by Billet (1989).
A great variety of evaporator designs have been developed for specialised applications
in particular industries. The designs can be grouped into the following basic types.
Direct-heated evaporators
This type includes solar pans and submerged combustion units. Submerged combustion
evaporators can be used for applications where contamination of the solution by the
products of combustion is acceptable.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Figure 10.32.
435
Long-tube evaporators (a) Rising film (b) Falling film
Long-tube evaporators (Figure 10.32)
In this type the liquid flows as a thin film on the walls of a long, vertical, heated, tube.
Both falling film and rising film types are used. They are high capacity units; suitable for
low viscosity solutions.
Forced-circulation evaporators (Figure 10.33)
In forced circulation evaporators the liquid is pumped through the tubes. They are suitable
for use with materials which tend to foul the heat transfer surfaces, and where crystallisation can occur in the evaporator.
Agitated thin-film evaporators (Figure 10.34)
In this design a thin layer of solution is spread on the heating surface by mechanical
means. Wiped-film evaporators are used for very viscous materials and for producing
solid products. The design and applications of this type of evaporator are discussed by
Mutzenburg (1965), Parker (1965) and Fischer (1965).
Short-tube evaporators
Short-tube evaporators, also called callandria evaporators, are used in the sugar industry;
see Volume 2.
436
CHEMICAL ENGINEERING
Vapour
Vapour
Steam
Steam
Vent
Condensate
Product
Feed
Vent
Condensate
Product
Feed
Lumps
(a)
Figure 10.33.
(b)
Forced-circulation evaporators (a) Submerged tube (b) Boiling tube
Steam
Feed
Blade
Drive
Rotor
Heating jacket
Condensate
Figure 10.34.
Product
Horizontal wiped-film evaporator
Evaporator selection
The selection of the most suitable evaporator type for a particular application will depend
on the following factors:
1. The throughput required.
2. The viscosity of the feed and the increase in viscosity during evaporation.
437
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
3.
4.
5.
6.
7.
The nature of the product required; solid, slurry, or concentrated solution.
The heat sensitivity of the product.
Whether the materials are fouling or non-fouling.
Whether the solution is likely to foam.
Whether direct heating can be used.
A selection guide based on these factors is given in Figure 10.35; see also Parker (1963b).
Feed conditions
Viscosity, mN s/m
Evaporator
type
2
Very
Low
Medium
viscous viscosity
viscosity
> 1000 < 1000 max < 100
Scaling
Foaming or
fouling
Solids
Crystals in
produced suspension
Recirculating
Calandria
(short vertical
tube)
Forced
circulation
Falling film
Natural
circulation
Suitable
for
heatsensitive
materials
No
Yes
No
No
Single pass
wiped film
Yes
Tubular
(long tube)
Falling film
Yes
Rising film
Yes
Figure 10.35.
Evaporator selection guide
Auxilliary equipment
Condensers and vacuum pumps will be needed for evaporators operated under vacuum.
For aqueous solutions, steam ejectors and jet condensers are normally used. Jet condensers
are direct-contact condensers, where the vapour is condensed by contact with jets of
cooling water. Indirect, surface condensers, are used where it is necessary to keep the
condensed vapour and cooling water effluent separate.
10.5.2. Crystallisation
Crystallisation is used for the production, purification and recovery of solids. Crystalline
products have an attractive appearance, are free flowing, and easily handled and packaged.
The process is used in a wide range of industries: from the small-scale production of
specialised chemicals, such as pharmaceutical products, to the tonnage production of
products such as sugar, common salt and fertilisers.
Crystallisation theory is covered in Volume 2, Chapter 15 and in other texts: Mullin
(2001) and Jones (2002). Descriptions of the various crystallisers used commercially can
be found in these texts and in handbooks: Mersmann (2001), Perry et al. (1997) and
438
CHEMICAL ENGINEERING
Schweitzer (1997). Procedures for the scale-up and design of crystallisers are given by
Mersmann (2001), and Mersham (1988), (1984).
Precipitation, which can be considered as a branch of crystallisation, is covered by
Sohnel and Garside (1992).
Crystallisation equipment can be classified by the method used to obtain supersaturation
of the liquor, and also by the method used to suspend the growing crystals. Supersaturation
is obtained by cooling or evaporation. There are four basic types of crystalliser; these are
described briefly below.
Tank crystallisers
This is the simplest type of industrial crystallising equipment. Crystallisation is induced
by cooling the mother liquor in tanks; which may be agitated and equipped with cooling
coils or jackets. Tank crystallisers are operated batchwise, and are generally used for
small-scale production.
Scraped-surface crystallisers
This type is similar in principle to the tank type, but the cooling surfaces are continually
scraped or agitated to prevent the fouling by deposited crystals and to promote
heat transfer. They are suitable for processing high-viscosity liquors. Scraped-surface
Non-condensable
gas outlet
Cooling
water inlet
Barometric
condenser
Recirculation
pipe
Body
Steam
jet
Swirl breaker
Heat
exchanger
Condensate
outlet
Circulation
pump
Figure 10.36.
Circulating pipe
Expansion
joint
Feed
inlet
Product
discharge
Circulating magma crystalliser (evaporative type)
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
439
crystallisers can be operated batchwise, with recirculation of the mother liquor, or
continuously. A disadvantage of this type is that they tend to produce very small crystals.
Circulating magma crystallisers (Figure 10.36)
In this type both the liquor and growing crystals are circulated through the zone in
which supersaturation occurs. Circulating magma crystallisers are probably the most
important type of large-scale crystallisers used in the chemical process industry. Designs
are available in which supersaturation is achieved by direct cooling, evaporation or
evaporative cooling under vacuum.
Circulating liquor crystallisers (Figure 10.37)
In this type only the liquor is circulated through the heating or cooling equipment; the
crystals are retained in suspension in the crystallising zone by the up-flow of liquor.
Circulating liquor crystallisers produce crystals of regular size. The basic design consists
of three components: a vessel in which the crystals are suspended and grow and are
removed; a means of producing supersaturation, by cooling or evaporation; and a means of
circulating the liquor. The Oslo crystalliser (Figure 10.37) is the archetypical design for
this type of crystallising equipment.
Circulating liquor crystallisers and circulating magma crystallisers are used for the
large-scale production of a wide range of crystal products.
Typical applications of the main types of crystalliser are summarised in Table 10.10
(see page 440); see also Larson (1978).
Water
Steam
To hot well
Heater
Crystal discharge
Feed
Overflow
Live steam
Vapour recompressor
Condensate
Pump
Crystal
suspension
Figure 10.37.
Oslo evaporative crystalliser
440
CHEMICAL ENGINEERING
Table 10.10.
Crystalliser type
Tank
Scraped surface
Circulating magma
Circulating liquor
Selection of crystallisers
Applications
Batch operation, small-scale
production
Organic compounds, where
fouling is a problem, viscous
materials
Production of large-sized
crystals. High throughputs
Production of uniform crystals
(smaller size than circulating
magma). High throughputs.
Typical uses
Fatty acids, vegetable oils, sugars
Chlorobenzenes, organic acids,
paraffin waxes, naphthalene, urea
Ammonium and other inorganic salts,
sodium and potassium chlorides
Gypsum, inorganic salts, sodium
and potassium nitrates, silver
nitrates
10.6. LIQUID-LIQUID SEPARATION
Separation of two liquid phases, immiscible or partially miscible liquids, is a common
requirement in the process industries. For example, in the unit operation of liquid-liquid
extraction the liquid contacting step must be followed by a separation stage (Chapter 11,
Section 11.16). It is also frequently necessary to separate small quantities of entrained
water from process streams. The simplest form of equipment used to separate liquid phases
is the gravity settling tank, the decanter. Various proprietary equipment is also used to
promote coalescence and improve separation in difficult systems, or where emulsions are
likely to form. Centrifugal separators are also used.
10.6.1. Decanters (settlers)
Decanters are used to separate liquids where there is a sufficient difference in density
between the liquids for the droplets to settle readily. Decanters are essentially tanks
which give sufficient residence time for the droplets of the dispersed phase to rise (or
settle) to the interface between the phases and coalesce. In an operating decanter there
will be three distinct zones or bands: clear heavy liquid; separating dispersed liquid (the
dispersion zone); and clear light liquid.
Decanters are normally designed for continuous operation, but the same design
principles will apply to batch operated units. A great variety of vessel shapes is used
for decanters, but for most applications a cylindrical vessel will be suitable, and will be
the cheapest shape. Typical designs are shown in Figures 10.38 and 10.39. The position
of the interface can be controlled, with or without the use of instruments, by use of a
syphon take-off for the heavy liquid, Figure 10.38.
The height of the take-off can be determined by making a pressure balance. Neglecting
friction loss in the pipes, the pressure exerted by the combined height of the heavy and
light liquid in the vessel must be balanced by the height of the heavy liquid in the take-off
leg, Figure 10.38.
⊲z1 z3 ⊳1 g C z3 2 g D z2 2 g
hence
z2 D
⊲z1 z3 ⊳1
C z3
2
(10.5)
441
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Figure 10.38.
Vertical decanter
Level
Feed
Drain
Heavy
liquid
off-take
Dispersion
band
Figure 10.39.
where 1
2
z1
z2
z3
D
D
D
D
D
Horizontal decanter
density of the light liquid, kg/m3 ,
density of the heavy liquid, kg/m3 ,
height from datum to light liquid overflow, m,
height from datum to heavy liquid overflow, m,
height from datum to the interface, m.
The height of the liquid interface should be measured accurately when the liquid
densities are close, when one component is present only in small quantities, or when the
throughput is very small. A typical scheme for the automatic control of the interface, using
a level instrument that can detect the position of the interface, is shown in Figure 10.40.
Where one phase is present only in small amounts it is often recycled to the decanter feed
to give more stable operation.
Decanter design
A rough estimate of the decanter volume required can be made by taking a hold-up time of
5 to 10 min, which is usually sufficient where emulsions are not likely to form. Methods
442
CHEMICAL ENGINEERING
Light
liquid
Feed
LC
Heavy
liquid
Figure 10.40.
Automatic control, level controller detecting interface
for the design of decanters are given by Hooper (1997) and Signales (1975). The general
approach taken is outlined below and illustrated by Example 10.3.
The decanter vessel is sized on the basis that the velocity of the continuous phase
must be less than settling velocity of the droplets of the dispersed phase. Plug flow
is assumed, and the velocity of the continuous phase calculated using the area of the
interface:
Lc
< ud
⊲10.6⊳
uc D
Ai
where ud
uc
Lc
Ai
D
D
D
D
settling velocity of the dispersed phase droplets, m/s,
velocity of the continuous phase, m/s,
continuous phase volumetric flow rate, m3 /s,
area of the interface, m2 .
Stokes’ law (see Volume 2, Chapter 3) is used to determine the settling velocity of the
droplets:
d2 g⊲d c ⊳
⊲10.7⊳
ud D d
18c
where dd D droplet diameter, m,
ud D settling (terminal) velocity of the dispersed phase droplets with
diameter d, m/s,
c D density of the continuous phase, kg/m3 ,
d D density of the dispersed phase, kg/m3 ,
c D viscosity of the continuous phase, N s/m2 ,
g D gravitational acceleration, 9.81 m/s2 .
Equation 10.7 is used to calculate the settling velocity with an assumed droplet size of
150 m, which is well below the droplet sizes normally found in decanter feeds. If the
calculated settling velocity is greater than 4 ð 103 m/s, then a figure of 4 ð 103 m/s
is used.
For a horizontal, cylindrical, decanter vessel, the interfacial area will depend on the
position of the interface.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
443
w
Interface
z
2r
Ai = wl
and
where w
z
l
r
D
D
D
D
w D 2⊲2rz z2 ⊳1/2
width of the interface, m,
height of the interface from the base of the vessel, m,
length of the cylinder, m,
radius of the cylinder, m.
For a vertical, cylindrical decanter:
Ai D r 2
The position of the interface should be such that the band of droplets that collect at
the interface waiting to coalesce and cross the interface does not extend to the bottom (or
top) of the vessel. Ryon et al. (1959) and Mizrahi and Barnea (1973) have shown that the
depth of the dispersion band is a function of the liquid flow rate and the interfacial area.
A value of 10 per cent of the decanter height is usually taken for design purposes. If the
performance of the decanter is likely to be critical the design can be investigated using
scale models. The model should be scaled to operate at the same Reynolds number as the
proposed design, so that the effect of turbulence can be investigated; see Hooper (1975).
Example 10.3
Design a decanter to separate a light oil from water.
The oil is the dispersed phase.
Oil, flow rate 1000 kg/h, density 900 kg/m3 , viscosity 3 mN s/m2 .
Water, flow rate 5000 kg/h, density 1000 kg/m3 , viscosity 1 mN s/m2 .
Solution
Take dd D 150 m
⊲150 ð 106 ⊳2 9.81⊲900 1000⊳
18 ð 1 ð 103
D 0.0012 m/s, 1.2 mm/s (rising)
ud D
As the flow rate is small, use a vertical, cylindrical vessel.
5000
1
Lc D
ð
D 1.39 ð 103 m3 /s
1000 3600
Lc
uc 6> ud , and uc D
Ai
⊲10.7⊳
444
CHEMICAL ENGINEERING
1.39 ð 103
D 1.16 m2
0.0012
1.16
rD
D 0.61 m
diameter D 1.2 m
Ai D
hence
Take the height as twice the diameter, a reasonable value for a cylinder:
height D 2.4 m
Take the dispersion band as 10 per cent of the height D 0.24 m
Check the residence time of the droplets in the dispersion band
D
0.24
0.24
D
D 200 s ⊲¾3 min⊳
ud
0.0012
This is satisfactory, a time of 2 to 5 min is normally recommended. Check the size of
the water (continuous, heavy phase) droplets that could be entrained with the oil (light
phase).
Velocity of oil phase D
1
1
1000
ð
ð
900
3600 1.16
D 2.7 ð 104 m/s ⊲0.27 mm/s⊳
From equation 10.7
ud 18c
dd D
g⊲d c ⊳
1/2
so the entrained droplet size will
1/2
2.7 ð 104 ð 18 ð 3 ð 103
D
9.81⊲1000 900⊳
D 1.2 ð 104 m D 120 m
which is satisfactory; below 150 m.
Piping arrangement
To minimise entrainment by the jet of liquid entering the vessel, the inlet velocity for a
decanter should keep below 1 m/s.
1000 5000
1
C
D 1.7 ð 103 m3 /s
Flow-rate D
900
1000 3600
1.7 ð 103
D 1.7 ð 103 m2
1
1.7 ð 103 ð 4
Pipe diameter D
D 0.047 m, say 50 mm
Area of pipe D
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
445
Take the position of the interface as half-way up the vessel and the light liquid off-take
as at 90 per cent of the vessel height, then
z1 D 0.9 ð 2.4 D 2.16 m
z3 D 0.5 ð 2.4 D 1.2 m
⊲2.16 1.2⊳
ð 900 C 1.2 D 2.06 m
1000
say 2.0 m
z2 D
⊲10.5⊳
Proposed design
2.0 m
1.2 m
2.16 m
1.2 m
Drain valves should be fitted at the interface so that any tendency for an emulsion to form
can be checked; and the emulsion accumulating at the interface drained off periodically
as necessary.
10.6.2. Plate separators
Stacks of horizontal, parallel, plates are used in some proprietary decanter designs to
increase the interfacial area per unit volume and to reduce turbulence. They, in effect,
convert the decanter volume into several smaller separators connected in parallel.
10.6.3. Coalescers
Proprietary equipment, in which the dispersion is forced through some form of coalescing
medium, is often used for the coalescence and separation of finely dispersed droplets. A
medium is chosen that is preferentially wetted by the dispersed phase; knitted wire or
plastic mesh, beds of fibrous material, or special membranes are used. The coalescing
medium works by holding up the dispersed droplets long enough for them to form globlets
of sufficient size to settle. A typical unit is shown in Figure 10.41; see Redmon (1963).
Coalescing filters are suitable for separating small quantities of dispersed liquids from
large throughputs.
Electrical coalescers, in which a high voltage field is used to break down the stabilising
film surrounding the suspended droplets, are used for desalting crude oils and for similar
applications; see Waterman (1965).
446
CHEMICAL ENGINEERING
Inlet
Swing bolts
Outlet
;yy;y;
Air vent
;yy;y;y;y;y;y;
Cover seal
Drain
Flow legend
Contaminated product
Water
Clean dry product
Water
drain
Figure 10.41.
Typical coalescer design
10.6.4. Centrifugal separators
Sedimentation centrifuges
For difficult separations, where simple gravity settling is not satisfactory, sedimentation
centrifuges should be considered. Centrifuging will give a cleaner separation than that
obtainable by gravity settling. Centrifuges can be used where the difference in gravity
between the liquids is very small, as low as 100 kg/m3 , and they can handle high
throughputs, up to around 100 m3 /h. Also, centrifuging will usually break any emulsion
that may form. Bowl or disc centrifuges are normally used (see Section 10.4.3).
Hydrocyclones
Hydrocyclones are used for some liquid-liquid separations, but are not so effective in this
application as in separating solids from liquids.
10.7. SEPARATION OF DISSOLVED LIQUIDS
The most commonly used techniques for the separation and purification of miscible liquids
are distillation and solvent extraction. In recent years, adsorption, ion exchange and
chromatography have become practical alternatives to distillation or solvent extraction
in many special applications.
Distillation is probably the most widely used separation technique in the chemical
process industries, and is covered in Chapter 11 of this volume, and Chapter 11
of Volume 2. Solvent extraction and the associated technique, leaching (solid-liquid
extraction) are covered in Volume 2, Chapters 13 and 10. Adsorption, which can be
used for the separation of liquid and gases mixtures, is covered in Chapter 17 of
Volume 2. Adsorption is also covered in the books by Suziki (1990) and Crittenden
and Thomas (1998).
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
447
Ion exchange, the separation of dissolved solids, is covered in Chapter 18 of Volume 2.
Through ion exchange is usually associated with water purification the technique has
applications in other industries.
Chromatography, which is finding increasing applications in the downstream processing
of biochemical products, is covered in Chapter 19 of Volume 2.
In this section, the discussion is restricted to a brief review of solvent-extraction
processes.
10.7.1. Solvent extraction and leaching
Solvent extraction (liquid liquid extraction)
Solvent extraction, also called liquid liquid extraction, can be used to separate a substance
from a solution by extraction into another solvent. It can be used ether to recover a valuable
substance from the original solution, or to purify the original solvent by removing an
unwanted component. Examples of solvent extraction are: the extraction of uranium and
plutonium salts from solution in nitric acid, in the nuclear industry; and the purification
of water.
The process depends on the substance being extracted, the solute, having a greater
solubility in the solvent used for the extraction than in the original feed solvent. The two
solvents must be essentially immiscible.
The solvents are mixed in a contactor, to effect the transfer of solute, and then the
phases separated. The depleted feed solvent leaving the extractor is called the raffinate,
and the solute rich extraction solvent, the extract. The solute is normally recovered from
the extraction solvent, by distillation, and the extraction solvent recycled.
The simplest form of extractor is a mixer-settler, which consist of an agitated tank and
a decanter.
The design of extraction columns is discussed in Chapter 11, Section 11.16. See also,
Volume 2, Chapter 13, Walas (1990) and Perry et al. (1997).
Leaching
Liquids can be extracted from solids by leaching. As the name implies, the soluble liquid
contained in a solid is leached out by contacting the solid with a suitable solvent. A
principal application of leaching is in the extraction of valuable oils from nuts and seeds;
such as, palm oil and rape seed oil.
The equipment used to contact the solids with the solvent is usually a special designs
to suit the type of solid being processed, and is to an extent unique to the particular
industry. General details of leaching equipment are given in Volume 2, Chapter 10 and
in Perry et al. (1997).
The leaching is normally done using a number of stages. In this respect, the process
is similar to liquid liquid extraction, and the methods used to determine the number of
stages required are similar.
For a detailed discussion of the procedures used to determine the number of stages
required for a particular process, see Volume 2, Chapter 10 or Prabhudesai (1997).
448
CHEMICAL ENGINEERING
10.8. GAS-SOLIDS SEPARATIONS (GAS CLEANING)
The primary need for gas-solid separation processes is for gas cleaning: the removal
of dispersed finely divided solids (dust) and liquid mists from gas streams. Process gas
streams must often be cleaned up to prevent contamination of catalysts or products, and
to avoid damage to equipment, such as compressors. Also, effluent gas streams must be
cleaned to comply with air-pollution regulations and for reasons of hygiene, to remove
toxic and other hazardous materials; see IChemE (1992).
There is also often a need for clean, filtered, air for process using air as a raw material,
and where clean working atmospheres are needed: for instance, in the pharmaceutical and
electronics industries.
The particles to be removed may range in size from large molecules, measuring a few
hundredths of a micrometre, to the coarse dusts arising from the attrition of catalysts or
the fly ash from the combustion of pulverised fuels.
A variety of equipment has been developed for gas cleaning. The principal types used
in the process industries are listed in Table 10.11, which is adapted from a selection
guide given by Sargent (1971). Table 10.11 shows the general field of application of
each type in terms of the particle size separated, the expected separation efficiency,
and the throughput. It can be used to make a preliminary selection of the type of
equipment likely to be suitable for a particular application. Descriptions of the equipment
shown in Table 10.11 can be found in various handbooks: Perry et al. (1997), Schweitzer
(1997); and in specialist texts: Strauss (1975). Gas cleaning is also covered in Volume 2,
Chapter 1.
Gas-cleaning equipment can be classified according to the mechanism employed to
separate the particles: gravity settling, impingement, centrifugal force, filtering, washing
and electrostatic precipitation.
10.8.1. Gravity settlers (settling chambers)
Settling chambers are the simplest form of industrial gas-cleaning equipment, but have
only a limited use; they are suitable for coarse dusts, particles larger than 50 m. They
are essentially long, horizontal, rectangular chambers; through which the gas flows. The
solids settle under gravity and are removed from the bottom of the chamber. Horizontal
plates or vertical baffles are used in some designs to improve the separation. Settling
chambers offer little resistance to the gas flow, and can be designed for operation at high
temperature and high pressure, and for use in corrosive atmospheres.
The length of chamber required to settle a given particle size can be estimated from the
settling velocity (calculated using Stokes’ law) and the gas velocity. A design procedure
is given by Jacob and Dhodapkar (1997).
10.8.2. Impingement separators
Impingement separators employ baffles to achieve the separation. The gas stream flows
easily round the baffles, whereas the solid particles, due to their higher momentum, tend
to continue in their line of flight, strike the baffles and are collected. A variety of baffle
Type of
equipment
Minimum particle
size
(m)
Dry collectors
Settling chamber
50
Baffle chamber
50
Louver
20
Cyclone
10
Multiple cyclone
5
Impingement
10
Wet scrubbers
Gravity spray
10
Centrifugal
5
Impingement
5
Packed
5
Jet
0.5 to 5 (range)
Venturi
0.5
Others
Fabric filters
0.2
Electrostatic
precipitators
2
Gas-cleaning equipment
Minimum
loading
(mg/m3 )
Approx.
efficiency
(%)
Typical gas
velocity
(m/s)
Maximum
capacity
(m3 /s)
12,000
12,000
2500
2500
2500
2500
50
50
80
85
95
90
1.5
5
10
10
10
15
3
10
20
20
20
30
2500
2500
2500
250
250
250
70
90
95
90
90
99
0.5
10
15
0.5
10
50
1
20
30
1
100
200
50
50
50
25
50
50
25
50 150
50 200
25 250
none
250 750
250
99
0.01 0.1
100
50 150
Large
250
99
5 30
1000
5 25
Large
none
none
15
25
100
none
Gas pressure
drop
(mm H2 O)
Liquid
rate
(m3 /103 m3 gas)
5
3
10
10
50
25
Space
required
(relative)
Large
Medium
Small
Medium
Small
Small
12
50
70
150
50
0.05
0.1
0.1
0.7
7
0.4
0.3
1.0
0.7
2.0
14
1.4
Medium
Medium
Medium
Medium
Small
Small
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Table 10.11.
449
450
CHEMICAL ENGINEERING
Figure 10.42.
Impingement separator (section showing gas flow)
designs is used in commercial equipment; a typical example is shown in Figure 10.42.
Impingement separators cause a higher pressure drop than settling chambers, but are
capable of separating smaller particle sizes, 10 20 m.
10.8.3. Centrifugal separators (cyclones)
Cyclones are the principal type of gas-solids separator employing centrifugal force, and
are widely used. They are basically simple constructions; can be made from a wide range
of materials; and can be designed for high temperature and pressure operation.
Cyclones are suitable for separating particles above about 5 m diameter; smaller
particles, down to about 0.5 m, can be separated where agglomeration occurs.
The most commonly used design is the reverse-flow cyclone, Figure 10.43; other configurations are used for special purposes. In a reverse-flow cyclone the gas enters the top
chamber tangentially and spirals down to the apex of the conical section; it then moves
upward in a second, smaller diameter, spiral, and exits at the top through a central vertical
pipe. The solids move radially to the walls, slide down the walls, and are collected at
the bottom. Design procedures for cyclones are given by Constantinescu (1984). Strauss
(1975), Koch and Licht (1977) and Stairmand (1951). The theoretical concepts and experimental work on which the design methods are based on discussed in Volume 2, Chapter 8.
Stairmand’s method is outlined below and illustrated in Example 10.4.
Cyclone design
Stairmand developed two standard designs for gas-solid cyclones: a high-efficiency
cyclone, Figure 10.44a, and a high throughput design, Figure 10.44b. The performance
curves for these designs, obtained experimentally under standard test conditions, are shown
in Figures 10.45a and 10.45b. These curves can be transformed to other cyclone sizes
and operating conditions by use of the following scaling equation, for a given separating
efficiency:
1/2
1
2
Dc2 3 Q1
d2 D d1
ð
ð
ð
⊲10.8⊳
Dc1
Q2
2
1
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
451
where d1 D mean diameter of particle separated at the standard conditions, at the
chosen separating efficiency, Figures 10.45a or 10.45b,
d2 D mean diameter of the particle separated in the proposed design, at the
same separating efficiency,
Dc1 D diameter of the standard cyclone D 8 inches (203 mm),
Dc2 D diameter of proposed cyclone, mm,
Q1 D standard flow rate:
for high efficiency design D 223 m3 /h,
for high throughput design D 669 m3 /h,
Q2 D proposed flow rate, m3 /h,
1 D solid-fluid density difference in standard conditions D 2000 kg/m3 ,
2 D density difference, proposed design,
1 D test fluid viscosity (air at 1 atm, 20Ž C)
D 0.018 mN s/m2 ,
2 D viscosity, proposed fluid.
A performance curve for the proposed design can be drawn up from Figures 10.45a or
10.45b by multiplying the grade diameter at, say, each 10 per cent increment of efficiency,
by the scaling factor given by equation 10.8; as shown in Figure 10.46 (p. 453).
Gas
out
Feed
Solids
out
Figure 10.43.
Reverse-flow cyclone
452
CHEMICAL ENGINEERING
0.5DC
0.75DC
0.5DC x 0.2DC
0.5DC
1.5DC
DC
0.75 DC X 0.375 DC
360˚ wrap-round
inlet
0.125DC
2.5DC
Collecting
hopper
diameter DC
0.875DC
1.5DC
DC
2.5DC
Collecting
hopper
diameter DC
0.375 DC
(a)
Figure 10.44.
0.375 DC
(b)
Standard cyclone dimension (a) High efficiency cyclone (b) High gas rate cyclone
Figure 10.45.
Performance curves, standard conditions (a) High efficiency cyclone
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Figure 10.45 (continued).
453
Performance curves, standard conditions (b) High gas rate cyclone
Figure 10.46.
Scaled performance curve
An alternative method of using the scaling factor, that does not require redrawing the
performance curve, is used in Example 10.4. The cyclone should be designed to give an
inlet velocity of between 9 and 27 m/s (30 to 90 ft/s); the optimum inlet velocity has
been found to be 15 m/s (50 ft/s).
Pressure drop
The pressure drop in a cyclone will be due to the entry and exit losses, and friction and
kinetic energy losses in the cyclone. The empirical equation given by Stairmand (1949)
can be used to estimate the pressure drop:
f
2 2rt
2
u1 1 C 2
⊲10.9⊳
1 C 2u22
P D
203
re
where P D cyclone pressure drop, millibars,
f D gas density, kg/m3 ,
454
CHEMICAL ENGINEERING
10
9
8
10
9
8
7
7
6
6
5
5
4
4
.0
=0
Ψ
3
3
0.05
Ψ=
Ψ = 0.1
2
2
Ψ = 0.2
φ
Ψ= 0.5
1.0
.9
.8
.7
1.0
.9
.8
.7
Ψ= 1.0
Ψ= 1.8
Ψ= 2.0
.6
.5
.5
Ψ= 5.0
.4
0.3
1.0
2
3
4
Radius ratio
Figure 10.47.
u1
u2
rt
re
.6
5
.4
0.3
6 7 8 9 10
rt
re
Cyclone pressure drop factor
D inlet duct velocity, m/s,
D exit duct velocity, m/s,
D radius of circle to which the centre line of the inlet is tangential, m,
D radius of exit pipe, m,
D factor from Figure 10.47,
D parameter in Figure 10.47, given by:
D fc
As
A1
fc D friction factor, taken as 0.005 for gases,
As D surface area of cyclone exposed to the spinning fluid, m2 .
For design purposes this can be taken as equal to the surface area of a
cylinder with the same diameter as the cylone and length equal to the total
height of the cyclone (barrel plus cone).
A1 D area of inlet duct, m2 .
455
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Stairmand’s equation is for the gas flowing alone, containing no solids. The presence of
solids will normally increase the pressure drop over that calculated using equation 10.9,
depending on the solids loading. Alternative design methods for cyclones, which include
procedures for estimating the true pressure drop, are given by Perry et al. (1997) and
Yang (1999); see also Zenz (2001).
General design procedure
1. Select either the high-efficiency or high-throughput design, depending on the performance required.
2. Obtain an estimate of the particle size distribution of the solids in the stream to be
treated.
3. Estimate the number of cyclones needed in parallel.
4. Calculate the cyclone diameter for an inlet velocity of 15 m/s (50 ft/s). Scale the
other cyclone dimensions from Figures 10.44a or 10.44b.
5. Calculate the scale-up factor for the transposition of Figures 10.45a or 10.45b.
6. Calculate the cyclone performance and overall efficiency (recovery of solids). If
unsatisfactory try a smaller diameter.
7. Calculate the cyclone pressure drop and, if required, select a suitable blower.
8. Cost the system and optimise to make the best use of the pressure drop available,
or, if a blower is required, to give the lowest operating cost.
Example 10.4
Design a cyclone to recover solids from a process gas stream. The anticipated particle size
distribution in the inlet gas is given below. The density of the particles is 2500 kg/m3 , and
the gas is essentially nitrogen at 150Ž C. The stream volumetric flow-rate is 4000 m3 /h, and
the operation is at atmospheric pressure. An 80 per cent recovery of the solids is required.
Particle size
(m)
50
40
30
20
10
5
2
Percentage by
weight less than
90
75
65
55
30
10
4
Solution
As 30 per cent of the particles are below 10 m the high-efficiency design will be required
to give the specified recovery.
4000
D 1.11 m3 /s
Flow-rate D
3600
1.11
Area of inlet duct, at 15 m/s D
D 0.07 m2
15
From Figure 10.44a, duct area D 0.5 Dc ð 0.2 Dc
so, Dc D 0.84
This is clearly too large compared with the standard design diameter of 0.203 m.
456
CHEMICAL ENGINEERING
Try four cyclones in parallel, Dc D 0.42 m.
Flow-rate per cyclone D 1000 m3 /h
Density of gas at 150Ž C D
273
28
ð
D 0.81 kg/m2 ,
22.4 423
negligible compared with the solids density
From equation 10.8,
Viscosity of N2 at 150Ž C D 0.023 cp⊲mN s/m2 ⊳
scaling factor D
0.42
0.203
3
223
2000 0.023
ð
ð
ð
1000 2500 0.018
1/2
D 1.42
6
7
Per cent in
range
>50
50 40
40 30
30 20
20 10
10 5
5 2
2 0
10
15
10
10
25
20
6
4
Per cent
at exit
5
Grading at
exit
(2) (5)
4
Collected
⊲2⊳ ð ⊲4⊳
100
3
Efficiency at
scaled size %
(Figure 10.46a)
2
Mean particle
size ł scaling
factor
1
Particle size
(m)
The performance calculations, using this scaling factor and Figure 10.45a, are set out in
the table below:
Calculated performance of cyclone design, Example 10.4
35
32
25
18
11
5
3
1
98
97
96
95
93
86
72
10
9.8
14.6
9.6
9.5
23.3
17.2
4.3
0.4
0.2
0.4
0.4
0.5
1.7
2.8
1.7
3.6
1.8
3.5
3.5
4.4
15.1
24.8
15.1
31.8
Overall
collection
efficiency
88.7
11.3
100.0
100
The collection efficiencies shown in column 4 of the table were read from Figure 10.45a
at the scaled particle size, column 3. The overall collection efficiency satisfies the
specified solids recovery. The proposed design with dimension in the proportions given
in Figure 10.44a is shown in Figure 10.48.
Pressure-drop calculation
Area of inlet duct, A1 , D 210 ð 80 D 16,800 mm2
Cyclone surface area, As D 420 ð ⊲630 C 1050⊳
D 2.218 ð 106 mm2
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
80
630
210
210
1050
420
160
Figure 10.48.
Proposed cyclone design, all dimensions mm (Example 10.4)
fc taken as 0.005
D
0.005 ð 2.218 ð 106
f c , As
D 0.66
D
A1
16,800
⊲420 ⊲80/2⊳⊳
rt
D 1.81
D
re
210
From Figure 10.47, = 0.9.
u1 D
Area of exit pipe D
1000
106
ð
D 16.5 m/s
3600 16,800
ð 2102
D 34,636 mm2
4
1000
106
u2 D
ð
D 8.0 m/s
3600 34,636
From equation 10.6
0.81
[16.52 [1 C 2 ð 0.92 ⊲2 ð 1.81 1⊳] C 2 ð 8.02 ]
203
D 6.4 millibar ⊲67 mm H2 O⊳
P D
This pressure drop looks reasonable.
457
458
CHEMICAL ENGINEERING
10.8.4. Filters
The filters used for gas cleaning separate the solid particles by a combination of
impingement and filtration; the pore sizes in the filter media used are too large simply to
filter out the particles. The separating action relies on the precoating of the filter medium
by the first particles separated; which are separated by impingement on the filter medium
fibres. Woven or felted cloths of cotton and various synthetic fibres are commonly used
as the filter media. Glass-fibre mats and paper filter elements are also used.
A typical example of this type of separator is the bag filter, which consists of a number
of bags supported on a frame and housed in a large rectangular chamber, Figure 10.49.
The deposited solids are removed by mechanically vibrating the bag, or by periodically
reversing the gas flow. Bag filters can be used to separate small particles, down to around
1 m, with a high separating efficiency. Commercial units are available to suit most
applications and should be selected in consultation with the vendors.
The design and specification of bag filters (baghouses) is covered by Kraus (1979).
Figure 10.49.
Multi-compartment vibro bag filter
Air filters
Dust-free air is required for many process applications. The requirements of air filtration
differ from those of process gas filtration mainly in that the quantity of dust to be removed
will be lower, typically less than 10 mg/m3 (¾5 grains per 1000 ft3 ); and also in that
there is no requirement to recover the material collected.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
459
Three basic types of air filter are used: viscous, dry and continuous. Viscous and dry
units are similar in construction, but the filter medium of the viscous type is coated with
a viscous material, such as a mineral oil, to retain the dust. The filters are made up from
standard, preformed, sections, supported on a frame in a filter housing. The sections are
removed periodically for cleaning or replacement. Various designs of continuous filtration
equipment are also available, employing either viscous or dry filter elements, but in which
the filter is cleaned continuously. A comprehensive description of air-filtration equipment
is given by Strauss (1975).
10.8.5. Wet scrubbers (washing)
In wet scrubbing the dust is removed by counter-current washing with a liquid, usually
water, and the solids are removed as a slurry. The principal mechanism involved is the
impact (impingement) of the dust particles and the water droplets. Particle sizes down to
0.5 m can be removed in suitably designed scrubbers. In addition to removing solids,
wet scrubbers can be used to simultaneously cool the gas and neutralise any corrosive
constituents.
Spray towers, and plate and packed columns are used, as well as a variety of proprietary
designs. Spray towers have a low pressure drop but are not suitable for removing very
fine particles, below 10 m. The collecting efficiency can be improved by the use of
plates or packing but at the expense of a higher pressure drop.
Venturi and orifice scrubbers are simple forms of wet scrubbers. The turbulence created
by the venturi or orifice is used to atomise water sprays and promote contact between the
liquid droplets and dust particles. The agglomerated particles of dust and liquid are then
collected in a centrifugal separator, usually a cyclone.
10.8.6. Electrostatic precipitators
Electrostatic precipitators are capable of collecting very fine particles, <2 m, at high
efficiencies. However, their capital and operating costs are high, and electrostatic precipitation should only be considered in place of alternative processes, such as filtration,
where the gases are hot or corrosive. Electrostatic precipitators are used extensively
in the metallurgical, cement and electrical power industries. Their main application is
probably in the removal of the fine fly ash formed in the combustion of pulverised coal
in powerstation boilers. The basic principle of operation is simple. The gas is ionised
in passing between a high-voltage electrode and an earthed (grounded) electrode; the
dust particles become charged and are attracted to the earthed electrode. The precipitated
dust is removed from the electrodes mechanically, usually by vibration, or by washing.
Wires are normally used for the high-voltage electrode, and plates or tubes for the earthed
electrode. A typical design is shown in Figure 10.50. A full description of the construction,
design and application of electrostatic precipitators is given by Schneider et al. (1975)
and Parker (2002).
460
CHEMICAL ENGINEERING
Discharge system
support insulator
High voltage cable
Precipitator plate cover
D.C. output
Collecting
(positive)
plates
Clean gas
outlet
Discharge
(negative)
electrodes
Direction
of gas flow
Transformer
rectifier set
A.C. Input
Collecting
(positive) plates
Figure 10.50.
Electrostatic precipitator
10.9. GAS LIQUID SEPARATORS
The separation of liquid droplets and mists from gas or vapour streams is analogous to
the separation of solid particles and, with the possible exception of filtration, the same
techniques and equipment can be used.
Where the carryover of some fine droplets can be tolerated it is often sufficient to rely
on gravity settling in a vertical or horizontal separating vessel (knockout pot).
Knitted mesh demisting pads are frequently used to improve the performance of
separating vessels where the droplets are likely to be small, down to 1 m, and where
high separating efficiencies are required. Proprietary demister pads are available in a
wide range of materials, metals and plastics; thickness and pad densities. For liquid
separators, stainless steel pads around 100 mm thick and with a nominal density of
150 kg/m3 would generally be used. Use of a mister pad allows a smaller vessel to
be used. Separating efficiencies above 99% can be obtained with low pressure drop. The
design and specification of demister pads for gas liquid separators is discussed by Pryce
Bailey and Davies (1973).
The design methods for horizontal separators given below are based on a procedure
given by Gerunda (1981).
Cyclone separators are also frequently used for gas liquid separation. They can be
designed using the same methods for gas solids cyclones. The inlet velocity should be
kept below 30 m/s to avoid pick-up of liquid form the cyclone surfaces.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
461
10.9.1. Settling velocity
Equation 10.10 can be used to estimate the settling velocity of the liquid droplets, for the
design of separating vessels.
ut D 0.07[⊲L v ⊳/v ⊳]1/2
⊲10.10⊳
where ut D settling velocity, m/s,
L D liquid density, kg/m3 ,
v D vapour density, kg/m3 .
If a demister pad is not used, the value of ut obtained from equation 10.10 should be
multiplied by a factor of 0.15 to provide a margin of safety and to allow for flow surges.
10.9.2. Vertical separators
The layout and typical proportions of a vertical liquid gas separator are shown in
Figure 10.51a.
The diameter of the vessel must be large enough to slow the gas down to below the
velocity at which the particles will settle out. So the minimum allowable diameter will
Vapour
outlet
Demister
pad
0.4 m
min.
Dv
Dv
1.0 m
min.
Inlet
Dv
2
0.6 m
min.
Liquid level
Liquid
outlet
Figure 10.51a.
Vertical liquid-vapour separator
462
CHEMICAL ENGINEERING
be given by:
Dv D
4Vv
us
⊲10.11⊳
where Dv D minimum vessel diameter, m,
Vv D gas, or vapour volumetric flow-rate, m3 /s,
us D ut , if a demister pad is used, and 0.15 ut for a separator without a
demister pad; ut from equation (10.10), m/s.
The height of the vessel outlet above the gas inlet should be sufficient to allow for
disengagement of the liquid drops. A height equal to the diameter of the vessel or 1 m,
which ever is the greatest, should be used, see Figure 10.51a.
The liquid level will depend on the hold-up time necessary for smooth operation and
control; typically 10 minutes would be allowed.
Example 10.5
Make a preliminary design for a separator to separate a mixture of steam and water;
flow-rates: steam 2000 kg/h, water 1000 kg/h; operating pressure 4 bar.
Solution
From steam tables, at 4 bar: saturation temperature 143.6Ž C, liquid density 926.4 kg/m3 ,
vapour density 2.16 kg/m3 .
1
ut D 0.07[⊲926.4 2.16⊳/2.16] 2 D 1.45 m/s
⊲10.10⊳
As the separation of condensate from steam is unlikely to be critical, a demister pad will
not be specified.
So, ut D 0.15 ð 1.45 D 0.218 m/s
2000
D 0.257 m3 /s
Vapour volumetric flow-rate D
3600 ð 2.16
Dv D
[⊲4 ð 0.257⊳/⊲ ð 0.218⊳] D 1.23 m, round to 1.25 m ⊲4 ft⊳.
1000
D 3.0 ð 104 m3 /s
3600 ð 926.14
Allow a minimum of 10 minutes hold-up.
Liquid volumetric flow-rate D
Volume held in vessel D 3.0 ð 104 ð ⊲10 ð 60⊳ D 0.18 m3
volume held-up
vessel cross-sectional area
0.18
D
D 0.15 m
⊲ ð 1.252 /4⊳
Liquid depth required, hv D
Increase to 0.3 m to allow space for positioning the level controller.
⊲10.11⊳
463
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
10.9.3. Horizontal separators
The layout of a typical horizontal separator is shown in Figure 10.51b.
A horizontal separator would be selected when a long liquid hold-up time is required.
Demister paos
Vapour
outlet
Inlet
Vapour
outlet
Liquid level
Weir
Liquid outlet
Figure 10.51b.
Horizontal liquid vapour separator
In the design of a horizontal separator the vessel diameter cannot be determined
independently of its length, unlike for a vertical separator. The diameter and length,
and the liquid level, must be chosen to give sufficient vapour residence time for the liquid
droplets to settle out, and for the required liquid hold-up time to be met.
The most economical length to diameter ratio will depend on the operating pressure
(see Chapter 13). As a general guide the following values can be used:
Operating pressure, bar
0 20
20 35
>35
Length: diameter, Lv /Dv
3
4
5
The relationship between the area for vapour flow, Av , and the height above the liquid
level, hv , can been found from tables giving the dimensions of the segments of circles;
see Perry and Green (1984), or from Figure 11.32 and 11.33 in Chapter 11.
For preliminary designs, set the liquid height at half the vessel diameter,
hv D Dv /2 and fv D 0.5,
where fv is the fraction of the total cross-sectional area occupied by the vapour.
The design procedure for horizontal separators is illustrated in the following example,
example 10.6.
Example 10.6
Design a horizontal separator to separate 10,000 kg/h of liquid, density 962.0 kg/m3 , from
12,500 kg/h of vapour, density 23.6 kg/m3 . The vessel operating pressure will be 21 bar.
464
CHEMICAL ENGINEERING
Solution
ut D 0.07[⊲962.0 23.6⊳/23.6]1/2 D 0.44 m/s
Try a separator without a demister pad.
ua D 0.15 ð 0.44 D 0.066 m/s
Vapour volumetric flow-rate D
Take hv D 0.5Dv and Lv /Dv D 4
12,500
D 0.147 m3 /s
3600 ð 23.6
Dv2
Cross-sectional area for vapour flow D
ð 0.5 D 0.393Dv2
4
0.147
D 0.374Dv2
Vapour velocity, uv D
0.393Dv2
Vapour residence time required for the droplets to settle to liquid surface
D hv /ua D 0.5Dv /0.66 D 7.58Dv
Actual residence time D vessel length/vapour velocity
D Lv /uv D
4Dv
D 10.70Dv3
0.374 Dv2
For satisfactory separation required residence time D actual.
So, 7.58Dv D 10.70Dv3
Dv D 0.84 m, say 0.92 m (3 ft, standard pipe size)
Liquid hold-up time,
liquid volumetric flow-rate D
liquid cross-sectional area D
10,000
D 0.00289 m3 /s
3600 ð 962.0
ð 0.922
ð 0.5 D 0.332 m2
4
Length, Lv D 4 ð 0.92 D 3.7 m
Hold-up volume D 0.332 ð 3.7 D 1.23 m3
Hold-up time D liquid volume/liquid flow-rate
D 1.23/0.00289 D 426 s D 7 minutes.
This is unsatisfactory, 10 minutes minimum required.
Need to increase the liquid volume. This is best done by increasing the vessel diameter.
If the liquid height is kept at half the vessel diameter, the diameter must be increased by
a factor of roughly ⊲10/7⊳0.5 D 1.2.
New Dv D 0.92 ð 1.2 D 1.1 m
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
465
Check liquid residence time,
new liquid volume D
ð 1.12
ð 0.5 ð ⊲4 ð 1.1⊳ D 2.09 m3
4
new residence time D 2.09/0.00289 D 723 s D 12 minutes, satisfactory
Increasing the vessel diameter will have also changed the vapour velocity and the height
above the liquid surface. The liquid separation will still be satisfactory as the velocity,
and hence the residence time, is inversely proportional to the diameter squared, whereas
the distance the droplets have to fall is directly proportional to the diameter.
In practice, the distance travelled by the vapour will be less than the vessel length, Lv ,
as the vapour inlet and outlet nozzles will be set in from the ends. This could be allowed
for in the design but will make little difference.
10.10. CRUSHING AND GRINDING (COMMINUTION) EQUIPMENT
Crushing is the first step in the process of size reduction; reducing large lumps to
manageable sized pieces. For some processes crushing is sufficient, but for chemical
processes it is usually followed by grinding to produce a fine-sized powder. Though
many articles have been published on comminution, and Marshall (1974) mentions over
4000, the subject remains essentially empirical. The designer must rely on experience,
and the advice of the equipment manufacturers, when selecting and sizing crushing and
grinding equipment; and to estimate the power requirements. Several models have been
proposed for the calculation of the energy consumed in size reduction; some of which are
discussed in Volume 2, Chapter 2. For a fuller treatment of the subject the reader should
refer to the book by Lowrison (1974) and Prasher (1987).
Table 10.12.
Range of
feed to
product
size
Typical
size reduction
ratio
Selection of comminution equipment (after Lowrison, 1974)
Moh's hardness of material handled
9
8
10
Diamond Sapphire Topaz
7
6
5
4
3
2
1
Quartz Feldspar Apatite Fluorspar Calcite Gypsum Talc
104 µm
103 µm
(1mm)
102 µm
5
Roll crushers
50
10 µm
500
Very fine
Stamp mills
Pan mill (dry)
Fine
105 µm
(1 m)
Intermediate Coarse
Jaw crushers
Gyratory crushers
Rotary impactors
Autogeneous mills (dry)
Disc mills
Hammer mill
Rod − loaded Tumbling mill (dry)
Ultra − rotor
Ring roll and ball mills
Ball - loaded tumbling mill (dry)
Vibration mill (dry)
Pin mills
Sand mills
Fluid − energy mills
Colloid mills
Sticky
materials
Material
class
no
Selection of comminution equipment for various materials (after Marshall, 1974) Note: Moh’s scale of hardness is given in Table 10.12
Material
classification
Typical
materials
in class
Suitable equipment for product size classes
Down to 5 mesh
Between 5 and
300 mesh
Hard and tough
Mica
Scrap and
powdered metals
Jaw crushers
Gyratory crushers
Cone crushers
Autogeneous mills
Ball, pebble,
rod and cone
mills
Tube mills
Vibration mills
2
Hard, abrasive
and brittle
Coke, quartz,
granite
Jaw crushers
Gyratory and cone crushers
Roll crushers
Ball, pebble,
rod and cone
mills
Vibration mills
Roller mills
3
Intermediate
hard, and
friable
Barytes, fluorspar, limestone
Jaw crushers
Gyratory crushers
Roll crushers
Edge runner mills
Impact breakers
Autogeneous mills
Cone crushers
Ball, pebble,
rod and cone
mills
Tube mills
Ring roll mills
Ring ball mills
Roller mills
Peg and disc mills
Cage mills
Impact breakers
Vibration mills
Less than 300
mesh
Ball, pebble and
cone mills
Tube mills
Vibration and
vibro-energy
mills
Fluid-energy mills
Ball, pebble and
cone mills
Tube mills
Vibration and
vibro-energy mills
Fluid-energy mills
Ball, pebble and
cone mills
Tube mills
Perl mills
Vibration and
vibro-energy mills
Fluid-energy mills
Moh’s hardness
5 10, but
includes other
tough materials
of lower
hardness
Moh’s hardness
5 10
High wear rate/
contamination in
high-speed
machinery
Use machines with
abrasion resistant
linings
Moh’s hardness
3 5
CHEMICAL ENGINEERING
1
Remarks
466
Table 10.13.
Fibrous, low
abrasion and
possibly tough
Wood, asbestos
Cone crushers
Roll crushers
Edge runner mills
Autogeneous mills
Impact breakers
5
Soft and friable
Sulphur, gypsum
rock salt
Cone crushers
Roll crushers
Edge runner mills
Impact breakers
Autogeneous mills
6
Sticky
Clays, certain
organic pigments
Roll crushers
Impact breakers
Edge runner mills
Ball, pebble,
rod and cone
mills
Tube mills
Roller mills
Peg and disc mills
Cage mills
Impact breakers
Vibration mills
Rotary cutters
and dicers
Ball, pebble and
cone mills
Tube mills
Ring roll mills
Ring ball mills
Roller mills
Peg and disc mills
Cage mills
Impact breakers
Vibration mills
Ball, pebble,
rod and cone
millsŁ
Tube millsŁ
Peg and disc mills
Cage mills
Ring roll mills
Ball, pebble and
cone mills
Tube mills
Sand mills
Perl mills
Vibration and
vibro-energy mills
Colloid mills
Wide range of
hardness
Low-temperature,
liquid nitrogen,
useful to
embrittle soft but
tough materials
Ball, pebble and
cone mills
Tube mills
Sand mills
Perl mills
Vibration and
vibro-energy mills
Colloid mills
Fluid-energy mills
Peg and disc mills
Ball, pebble and
cone millsŁ
Tube millsŁ
Sand mills
Perl mills
Vibration and
vibro-energy mills
Colloid mills
Moh’s hardness
1 3
Wide range of
Moh’s hardness
although mainly
less than 3
Tends to clog
Ł Wet grinding employed except for
certain exceptional
cases
ball, pebble, rod and cone mills, edge runner mills, tube mills, vibration mills and some ring ball mills may be used wet or dry except where stated. The perl
mills, sand mills and colloid mills may be used for wet milling only.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Ł All
4
467
468
CHEMICAL ENGINEERING
The main factors to be considered when selecting equipment for crushing and grinding
are:
1.
2.
3.
4.
5.
The size of the feed.
The size reduction ratio.
The required particle size distribution of the product.
The throughput.
The properties of the material: hardness, abrasiveness, stickiness, density, toxicity,
flammability.
6. Whether wet grinding is permissible.
The selection guides given by Lowrison (1974) and Marshall (1974), which are reproduced in Tables 10.12 (see p. 465) and 10.13, can be used to make a preliminary selection
based on particle size and material hardness. Descriptions of most of the equipment listed
in these tables are given in Volume 2, Chapter 2; or can be found in the literature; Perry
et al. (1997), Hiorns (1970), Lowrison (1974). The most commonly used equipment for
coarse size reduction are jaw crushers and rotary crushers; and for grinding, ball mills or
their variants: pebble, roll and tube mills.
10.11. MIXING EQUIPMENT
The preparation of mixtures of solids, liquids and gases is an essential part of most
production processes in the chemical and allied industries; covering all processing stages,
from the preparation of reagents through to the final blending of products. The equipment
used depends on the nature of the materials and the degree of mixing required. Mixing
is often associated with other operations, such as reaction and heat transfer. Liquid and
solids mixing operations are frequently carried out as batch processes.
In this section, mixing processes will be considered under three separate headings:
gases, liquids and solids.
10.11.1. Gas mixing
Specialised equipment is seldom needed for mixing gases, which because of their low
viscosities mix easily. The mixing given by turbulent flow in a length of pipe is usually
sufficient for most purposes. Turbulence promoters, such as orifices or baffles, can be
used to increase the rate of mixing. The piping arrangements used for inline mixing are
discussed in the section on liquid mixing.
10.11.2. Liquid mixing
The following factors must be taken into account when choosing equipment for mixing
liquids:
1. Batch of continuous operation.
2. Nature of the process: miscible liquids, preparation of solutions, or dispersion of
immiscible liquids.
3. Degree of mixing required.
4. Physical properties of the liquids, particularly the viscosity.
5. Whether the mixing is associated with other operations: reaction, heat transfer.
469
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
For the continuous mixing of low viscosity fluids inline mixers can be used. For other
mixing operations stirred vessels or proprietary mixing equipment will be required.
Inline mixing
Static devices which promote turbulent mixing in pipelines provide an inexpensive way
of continuously mixing fluids. Some typical designs are shown in Figures 10.52a, b, c.
A simple mixing tee, Figure 10.52a, followed by a length of pipe equal to 10 to 20 pipe
diameters, is suitable for mixing low viscosity fluids (50 mN s/m2 ) providing the flow
is turbulent, and the densities and flow-rates of the fluids are similar.
Mixing length
10-20 Pipe diameter
(b)
(a)
D
O.63 D
(c)
Figure 10.52.
Inline mixers (a) Tee (b) Injection (c) Annular
With injection mixers (Figures 10.52b,c), in which the one fluid is introduced into the
flowing stream of the other through a concentric pipe or an annular array of jets, mixing will
take place by entrainment and turbulent diffusion. Such devices should be used where one
flow is much lower than the other, and will give a satisfactory blend in about 80 pipe diameters.
The inclusion of baffles or other flow restrictions will reduce the mixing length required.
The static inline mixer shown in Figure 10.53 is effective in both laminar and turbulent
flow, and can be used to mix viscous mixtures. The division and rotation of the fluid at
each element causes rapid radical mixing; see Rosenzweig (1977) and Baker (1991). The
Figure 10.53.
Static mixer (Kenics Corporation)
470
CHEMICAL ENGINEERING
dispersion and mixing of liquids in pipes is discussed by Zughi et al. (2003) and Lee and
Brodkey (1964).
Centrifugal pumps are effective inline mixers for blending and dispersing liquids.
Various proprietary motor-driven inline mixers are also used for special applications;
see Perry et al. (1997).
Stirred tanks
Mixing vessels fitted with some form of agitator are the most commonly used type of
equipment for blending liquids and preparing solutions.
Liquid mixing in stirred tanks is covered in Volume 1, Chapter 7, and in several
textbooks; Uhl and Gray (1967), Harnby et al. (1997) and Tatterson (1991), (1993).
A typical arrangement of the agitator and baffles in a stirred tank, and the flow pattern
generated, is shown in Figure 10.54. Mixing occurs through the bulk flow of the liquid
and, on a microscopic scale, by the motion of the turbulent eddies created by the agitator.
Bulk flow is the predominant mixing mechanism required for the blending of miscible
liquids and for solids suspension. Turbulent mixing is important in operations involving
mass and heat transfer; which can be considered as shear controlled processes.
Figure 10.54.
Agitator arrangements and flow patterns
The most suitable agitator for a particular application will depend on the type of mixing
required, the capacity of the vessel, and the fluid properties, mainly the viscosity.
The three basic types of impeller which are used at high Reynolds numbers (low
viscosity) are shown in Figures 10.55a, b, c. They can be classified according to the
predominant direction of flow leaving the impeller. The flat-bladed (Rushton) turbines
are essentially radial-flow devices, suitable for processes controlled by turbulent mixing
(shear controlled processes). The propeller and pitched-bladed turbines are essentially
axial-flow devices, suitable for bulk fluid mixing.
Paddle, anchor and helical ribbon agitators (Figures 10.56a, b, c), and other special
shapes, are used for more viscous fluids.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Hub-mounted
flate-blade
turbine
Disc-mounted flatblade turbine
471
Shrouded turbine
impeller
Hub-mounted
curved-blade
turbine
(a)
(c)
(b)
Figure 10.55.
Basic impeller types (a) Turbine impeller (b) Pitched bladed turbine (c) Marine propeller
(b)
(a)
(c)
Figure 10.56.
Low-speed agitators (a) Paddle (b) Anchor (c) Helical ribbon
472
CHEMICAL ENGINEERING
The selection chart given in Figure 10.57, which has been adapted from a similar chart
given by Penney (1970), can be used to make a preliminary selection of the agitator type,
based on the liquid viscosity and tank volume.
For turbine agitators, impeller to tank diameter ratios of up to about 0.6 are used, with
the depth of liquid equal to the tank diameter. Baffles are normally used, to improve
the mixing and reduce problems from vortex formation. Anchor agitators are used with
close clearance between the blades and vessel wall, anchor to tank diameter ratios of
103
Anchor, helical ribbon
102
Liquid viscosity, Ns/m2
Paddle
101
Turbine
100
ell
op
Pr
er
Propeller (420 rpm)
or turbine
0
15
(1
m)
rp
Turbine or
propeller
(1750 rpm)
or
b
tur
10-1
ine
10-2
10-1
100
101
Tank volume, m3
Figure 10.57.
Agitator selection guide
102
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
473
0.95 or higher. The selection of agitators for dispersing gases in liquids is discussed by
Hicks (1976).
Agitator power consumption
The shaft power required to drive an agitator can be estimated using the following
generalised dimensionless equation, the derivation of which is given in Volume 2,
Chapter 13.
Np D KReb Fr c
⊲10.11⊳
where Np D power number D
P
D5 N3
Re D Reynolds number D
Fr D Froude number D
,
D2 N
,
DN2
,
g
P D shaft power, W,
K D a constant, dependent on the agitator type, size, and the agitator-tank
geometry,
D fluid density, kg/m3 ,
D fluid viscosity, Ns/m2 ,
N D agitator speed, s1 (revolutions per second) (rps),
D D agitator diameter, m,
g D gravitational acceleration, 9.81 m/s2 .
Values for the constant K and the indices b and c for various types of agitator, tank-agitator
geometries, and dimensions, can be found in the literature; Rushton et al. (1950). A useful
review of the published correlations for agitator power consumption and heat transfer in
agitated vessels is given by Wilkinson and Edwards (1972); they include correlations for
non-Newtonian fluids. Typical power curves for propeller and turbine agitators are given
in Figures 10.58 and 10.59. In the laminar flow region the index “b” D 1; and at high
Reynolds number the power number is independent of the Froude number; index “c” D 0.
An estimate of the power requirements for various applications can be obtained from
Table 10.14.
Table 10.14.
Power requirements
baffled agitated tanks
Agitation
Applications
Power, kW/m3
Mild
Blending, mixing
Homogeneous reactions
Heat transfer
Liquid-liquid mixing
Slurry suspension
Gas absorption,
Emulsions
Fine slurry suspension
0.04 0.10
0.01 0.03
0.03 1.0
1.0 1.5
1.5 2.0
1.5 2.0
1.5 2.0
>2.0
Medium
Severe
Violent
474
CHEMICAL ENGINEERING
Figure 10.58.
Power correlation for single three-bladed propellers baffled, (from Uhl and Gray (1967) with permission). p D blade pitch, D D impeller diameter,
DT D tank diameter
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Power correlations for baffled turbine impellers, for tank with 4 baffles (From Uhl and Gray (1967) with permission). w D impeller width,
D D impeller diameter
475
Figure 10.59.
476
CHEMICAL ENGINEERING
Side-entering agitators
Side-entering agitators are used for blending low viscosity liquids in large tanks, where
it is impractical to use conventional agitators supported from the top of the tank; see
Oldshue et al. (1956).
Where they are used with flammable liquids, particular care must be taken in the design
and maintenance of the shaft seals, as any leakage may cause a fire.
For blending flammable liquids, the use of liquid jets should be considered as an
“intrinsically” safer option; see Fossett and Prosser (1949).
10.11.3. Solids and pastes
A great variety of specialised equipment has been developed for mixing dry solids and
pastes (wet solids). The principal types of equipment and their fields of application are
given in Table 10.15. Descriptions of the equipment can be found in the literature; Perry
et al. (1997), Reid (1979). Cone blenders are used for free-flowing solids. Ribbon blenders
can be used for dry solids and for blending liquids with solids. Z-blade mixers and pan
mixers are used for kneading heavy pastes and doughs. Most solid and paste mixers are
designed for batch operation.
A selection chart for solids mixing equipment is given by Jones (1985).
Table 10.15.
Type of equipment
Solids and paste mixers
Mixing action
Applications
Rotating: cone,
double cone, drum
Tumbling action
Air blast fluidisation
Air blast lifts and mixes
particles
Horizontal trough
mixer, with ribbon
blades, paddles or
beaters
Z-blade mixers
Rotating element
produces contra-flow
movement of materials
Dry and moist powders
Shearing and kneading by
the specially shaped
blades
Vertical, rotating paddles,
often with planetary
motion
Mixing heavy pastes,
creams and doughs
Pan mixers
Cylinder mixers,
single and double
Shearing and kneading
action
Blending dry, freeflowing powders,
granules, crystals
Dry powders and
granules
Mixing, whipping and
kneading of materials
ranging from low
viscosity pastes to stiff
doughs
Compounding of rubbers
and plastics
Examples
Pharmaceuticals, food,
chemicals
Milk powder;
detergents,
chemicals
Chemicals, food,
pigments, tablet
granulation
Bakery industry,
rubber doughs,
plastic dispersions
Food, pharmaceuticals
and chemicals,
printing inks and
ceramics
Rubbers, plastics, and
pigment dispersion
10.12. TRANSPORT AND STORAGE OF MATERIALS
In this section the principal means used for the transport and storage of process materials:
gases, liquids and solids are discussed briefly. Further details and full descriptions of the
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EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
equipment used can be found in various handbooks. Pumps and compressors are also
discussed in Chapters 3 and 5 of this volume, and in Volume 1, Chapter 8.
10.12.1. Gases
Discharge pressure, bar
The type of equipment best suited for the pumping of gases in pipelines depends on the
flow-rate, the differential pressure required, and the operating pressure.
In general, fans are used where the pressure drop is small, <35 cm H2 O (0.03 bar);
axial flow compressors for high flow-rates and moderate differential pressures; centrifugal
compressors for high flow-rates and, by staging, high differential pressures. Reciprocating
compressors can be used over a wide range of pressures and capacities, but are normally
only specified in preference to centrifugal compressors where high pressures are required
at relatively low flow-rates.
Reciprocating, centrifugal and axial flow compressors are the principal types used in
the chemical process industries, and the range of application of each type is shown in
Figure 10.60 which has been adapted from a similar diagram by Dimoplon (1978). A
more comprehensive selection guide is given in Table 10.16. Diagrammatic sketches of
the compressors listed are given in Figure 10.61.
10
5
10
4
10
3
2
10
Reciprocating
Centrifugal
1
10
Axial
flow
0
10
10
1
2
3
10
10
4
10
Flow rate, m3/h at inlet conditions
Figure 10.60.
Compressor operating ranges
5
10
6
10
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CHEMICAL ENGINEERING
Table 10.16.
Type of compressor
Displacement
1. Reciprocating
2. Sliding vane
3. Liquid ring
4. Rootes
5. Screw
Dynamic
6. Centrifugal fan
7. Turbo blower
8. Turbo compressor
9. Axial flow fan
10. Axial flow blower
Operating range of compressors and blowers (after Begg, 1966)
Normal maximum
speed
(rpm)
Normal maximum
capacity
(m3 /h)
Single stage
Multiple stage
300
300
200
250
10,000
85,000
3400
2550
4250
12,750
3.5
3.5
0.7
0.35
3.5
5000
8
1.7
1.7
17
1000
3000
10,000
1000
3000
170,000
8500
136,000
170,000
170,000
0.35
3.5
0.35
3.5
0.2
1.7
100
2.0
10
Figure 10.61.
Normal maximum pressure
(differential) (bar)
Type of compressor (Begg, 1966)
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
479
Several textbooks are available on compressor design, selection and operation: Bloch
et al. (1982), Brown (1990) and Aungier (1999), (2003).
Vacuum production
The production of vacuum (sub-atmospheric pressure) is required for many chemical
engineering processes; for example, vacuum distillation, drying and filtration. The type
of vacuum pump needed will depend on the degree of vacuum required, the capacity of
the system and the rate of air inleakage.
Reciprocating and rotary positive displacement pumps are commonly used where
moderately low vacuum is required, about 10 mmHg (0.013 bar), at moderate to high
flow rates; such as in vacuum filtration.
Steam-jet ejectors are versatile and economic vacuum pumps and are frequently used,
particularly in vacuum distillation. They can handle high vapour flow rates and, by
using several ejectors in series, can produce low pressures, down to about 0.1 mmHg
(0.13 mbar).
The operating principle of steam-jet ejectors is explained in Volume 1, Chapter 8. Their
specification, sizing and operation are covered in a comprehensive series of papers by
Power (1964). Diffusion pumps are used where very low pressures are required (hard
vacuum) for processes such as molecular distillation.
For a general reference on the design and application of vacuum system see Ryan and
Roper (1986).
Storage
Gases are stored at low pressure in gas holders similar to those used for town gas, which
are a familiar sight in any town. The liquid sealed type are most commonly used. These
consist of a number of telescopic sections (lifts) which rise and fall as gas is added to or
withdrawn from the holder. The dry sealed type is used where the gas must be kept dry.
In this type the gas is contained by a piston moving in a large vertical cylindrical vessel.
Water seal holders are intrinsically safer for use with flammable gases than the dry seal
type; as any leakage through the piston seal may form an explosive mixture in the closed
space between the piston and the vessel roof. Details of the construction of gas holders
can be found in text books on Gas Engineering; Meade (1921), Smith (1945).
Gases are stored at high pressures where this is a process requirement and to reduce
the storage volume. For some gases the volume can be further reduced by liquefying the
gas by pressure or refrigeration. Cylindrical and spherical vessels (Horton spheres) are
used. The design of pressure vessels is discussed in Chapter 13.
10.12.2. Liquids
The selection of pumps for liquids is discussed in Chapter 5. Descriptions of most of the
types of pumps used in the chemical process industries are given in Volume 1, Chapter 8.
Several textbooks and handbooks have also been published on this subject: Garay (1997),
Karassik (2001) and Parmley (2000).
The principal types used and their operating pressures and capacity ranges are
summarised in Table 10.17 and Figure 10.63. Centrifugal pumps will normally be the first
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CHEMICAL ENGINEERING
Table 10.17.
Normal operating range of pumps
Type
Capacity range
(m3 /h)
Typical head
(m of water)
Centrifugal
0.25 103
Reciprocating
Diaphragm
Rotary
gear and similar
Rotary
sliding vane
or similar
0.5 500
0.05 50
10 50
300 (multistage)
50 200
5 60
0.05 500
60 200
0.25 500
7 70
choice for pumping process fluids, the other types only being used for special applications;
such as the use of reciprocating and gear pumps for metering.
Pump shaft power
The power required for pumping an incompressible fluid is given by:
Power D
PQp
ð 100
p
⊲10.12⊳
where P D pressure differential across the pump, N/m2 ,
Qp D flow rate, m3 /s,
p D pump efficiency, per cent.
See also, Chapter 5, Section 5.4.3.
The efficiency of centrifugal pumps depends on their size. The values given in
Figure 10.62 can be used to estimate the power and energy requirements for preliminary
design purpose. The efficiency of reciprocating pumps is usually around 90 per cent.
100
Pump efficiency, %
80
60
40
20
0
0
1
10
10
10
2
3
Capacity, m /h
Figure 10.62.
Efficiencies of centrifugal pumps
10
3
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
Figure 10.63.
481
Selection of positive displacement pumps (adapted from Marshall (1985)). Descriptions of the
types mentioned are given in Volume 1, Chapter 8
Storage
Liquids are usually stored in bulk in vertical cylindrical steel tanks. Fixed and floating-roof
tanks are used. In a floating-roof tank a movable piston floats on the surface of the liquid and
is sealed to the tank walls. Floating-roof tanks are used to eliminate evaporation losses and,
for flammable liquids, to obviate the need for inert gas blanketing to prevent an explosive
mixture forming above the liquid, as would be the situation with a fixed-roof tank.
Horizontal cylindrical tanks and rectangular tanks are also used for storing liquids,
usually for relatively small quantities.
The design of fixed roof, vertical tanks is discussed in Chapter 13, Section 13.16.
10.12.3. Solids
The movement and storage of solids is usually more expensive than the movement of
liquids and gases, which can be easily pumped down a pipeline. The best equipment to
use will depend on a number of factors:
1.
2.
3.
4.
The throughput.
Length of travel.
Change in elevation.
Nature of the solids: size, bulk density, angle of repose, abrasiveness, corrosiveness,
wet or dry.
Belt conveyors are the most commonly used type of equipment for the continuous
transport of solids. They can carry a wide range of materials economically over long and
short distances; both horizontally or at an appreciable angle, depending on the angle of
repose of the solids. A belt conveyor consists of an endless belt of a flexible material,
supported on rollers (idlers), and passing over larger rollers at each end, one of which is
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CHEMICAL ENGINEERING
driven. The belt material is usually fabric-reinforced rubber or plastics; segmental metal
belts are also used. Belts can be specified to withstand abrasive and corrosive materials;
see BS 490.
Screw conveyors, also called worm conveyors, are used for materials that are free
flowing. The basic principle of the screw conveyor has been known since the time of
Archimedes. The modern conveyor consists of a helical screw rotating in a U-shaped
trough. They can be used horizontally or, with some loss of capacity, at an incline to
lift materials. Screw conveyors are less efficient than belt conveyors, due to the friction
between the solids and the flights of the screw and the trough, but are cheaper and easier
to maintain. They are used to convey solids over short distances, and when some elevation
(lift) is required. They can also be used for delivering a metered flow of solids.
The most widely used equipment where a vertical lift is required is the bucket elevator.
This consists of buckets fitted to an endless chain or belt, which passes over a driven
roller or sprocket at the top end. Bucket elevators can handle a wide range of solids, from
heavy lumps to fine powders, and are suitable for use with wet solids and slurries.
The mechanical conveying of solids is the subject of a book by Colijn (1985).
Pneumatic and hydraulic conveying, in which the solid particles are transported along
a pipeline in suspension in a fluid, are discussed in Volume 1, Chapter 5, and in a book
by Mills (2003); see also Mills et al. (2004).
Storage
The simplest way to store solids is to pile them on the ground in the open air. This is
satisfactory for the long-term storage of materials that do not deteriorate on exposure
to the elements; for example, the seasonal stock piling of coal at collieries and power
stations. For large stockpiles, permanent facilities are usually installed for distributing
and reclaiming the material; travelling gantry cranes, grabs and drag scrapers feeding belt
conveyors are used. For small, temporary, storages mechanical shovels and trunks can be
used. Where the cost of recovery from the stockpile is large compared with the value of
the stock held, storage in silos or bunkers should be considered.
Overhead bunkers, also called bins or hoppers, are normally used for the short-term
storage of materials that must be readily available for the process. They are arranged so
that the material can be withdrawn at a steady rate from the base of the bunker on to a
suitable conveyor. Bunkers must be carefully designed to ensure the free flow of material
within the bunker, to avoid packing and bridging. Jenike (1967) and Jenike and Johnson
(1970), has studied the flow of solids in containers and developed design methods. All
aspects of the design of bins and hoppers, including feeding and discharge systems, are
covered in a book by Reisner (1971).
See also the British Material Handling Board’s code of practice on the design of silos
and bunkers, BMHB (1992).
The storage and transport of wet solids are covered by Heywood (1991).
10.13. REACTORS
The reactor is the heart of a chemical process. It is the only place in the process where
raw materials are converted into products, and reactor design is a vital step in the overall
design of the process.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
483
Numerous texts have been published on reactor design, and a selection is given in the
bibliography at the end of this chapter. The volumes by Rase (1977), (1990) cover the
practical aspects of reactor design and include case studies of industrial reactors. The design
of electrochemical reactors is covered by Rousar et al. (1985) and Scott (1991).
The treatment of reactor design in this section will be restricted to a discussion of the
selection of the appropriate reactor type for a particular process, and an outline of the
steps to be followed in the design of a reactor.
The design of an industrial chemical reactor must satisfy the following requirements:
1. The chemical factors: the kinetics of the reaction. The design must provide sufficient residence time for the desired reaction to proceed to the required degree of
conversion.
2. The mass transfer factors: with heterogeneous reactions the reaction rate may be
controlled by the rates of diffusion of the reacting species; rather than the chemical
kinetics.
3. The heat transfer factors: the removal, or addition, of the heat of reaction.
4. The safety factors: the confinement of hazardous reactants and products, and the
control of the reaction and the process conditions.
The need to satisfy these interrelated, and often contradictory factors, makes reactor
design a complex and difficult task. However, in many instances one of the factors will
predominate and will determine the choice of reactor type and the design method.
10.13.1. Principal types of reactor
The following characteristics are normally used to classify reactor designs:
1. Mode of operation: batch or continuous.
2. Phases present: homogeneous or heterogeneous.
3. Reactor geometry: flow pattern and manner of contacting the phases
(i) stirred tank reactor;
(ii) tubular reactor;
(iii) packed bed, fixed and moving;
(iv) fluidised bed.
Batch or continuous processing
In a batch process all the reagents are added at the commencement; the reaction proceeds,
the compositions changing with time, and the reaction is stopped and the product
withdrawn when the required conversion has been reached. Batch processes are suitable
for small-scale production and for processes where a range of different products, or grades,
is to be produced in the same equipment; for instance, pigments, dyestuffs and polymers.
In continuous processes the reactants are fed to the reactor and the products withdrawn
continuously; the reactor operates under steady-state conditions. Continuous production
will normally give lower production costs than batch production, but lacks the flexibility of
batch production. Continuous reactors will usually be selected for large-scale production.
Processes that do not fit the definition of batch or continuous are often referred to as
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CHEMICAL ENGINEERING
semi-continuous or semi-batch. In a semi-batch reactor some of the reactants may be
added, or some of the products withdrawn, as the reaction proceeds. A semi-continuous
process can be one which is interrupted periodically for some purpose; for instance, for
the regeneration of catalyst.
Homogeneous and heterogeneous reactions
Homogeneous reactions are those in which the reactants, products, and any catalyst used
form one continuous phase: gaseous or liquid.
Homogeneous gas phase reactors will always be operated continuously; whereas liquid
phase reactors may be batch or continuous. Tubular (pipe-line) reactors are normally used
for homogeneous gas-phase reactions; for example, in the thermal cracking of petroleum
crude oil fractions to ethylene, and the thermal decomposition of dichloroethane to vinyl
chloride. Both tubular and stirred tank reactors are used for homogeneous liquid-phase
reactions.
In a heterogeneous reaction two or more phases exist, and the overriding problem in the
reactor design is to promote mass transfer between the phases. The possible combination
of phases are:
1. Liquid-liquid: immiscible liquid phases; reactions such as the nitration of toluene or
benzene with mixed acids, and emulsion polymerisations.
2. Liquid-solid: with one, or more, liquid phases in contact with a solid. The solid may
be a reactant or catalyst.
3. Liquid-solid-gas: where the solid is normally a catalyst; such as in the hydrogeneration of amines, using a slurry of platinum on activated carbon as a catalyst.
4. Gas-solid: where the solid may take part in the reaction or act as a catalyst. The
reduction of iron ores in blast furnaces and the combustion of solid fuels are
examples where the solid is a reactant.
5. Gas-liquid: where the liquid may take part in the reaction or act as a catalyst.
Reactor geometry (type)
The reactors used for established processes are usually complex designs which have been
developed (have evolved) over a period of years to suit the requirements of the process,
and are unique designs. However, it is convenient to classify reactor designs into the
following broad categories.
Stirred tank reactors
Stirred tank (agitated) reactors consist of a tank fitted with a mechanical agitator and
a cooling jacket or coils. They are operated as batch reactors or continuously. Several
reactors may be used in series.
The stirred tank reactor can be considered the basic chemical reactor; modelling on a
large scale the conventional laboratory flask. Tank sizes range from a few litres to several
thousand litres. They are used for homogeneous and heterogeneous liquid-liquid and
liquid-gas reactions; and for reactions that involve finely suspended solids, which are held
in suspension by the agitation. As the degree of agitation is under the designer’s control,
stirred tank reactors are particularly suitable for reactions where good mass transfer or
heat transfer is required.
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
485
When operated as a continuous process the composition in the reactor is constant and
the same as the product stream, and, except for very rapid reactions, this will limit the
conversion that can be obtained in one stage.
The power requirements for agitation will depend on the degree of agitation required
and will range from about 0.2 kW/m3 for moderate mixing to 2 kW/m3 for intense mixing.
Tubular reactor
Tubular reactors are generally used for gaseous reactions, but are also suitable for some
liquid-phase reactions.
If high heat-transfer rates are required, small-diameter tubes are used to increase the
surface area to volume ratio. Several tubes may be arranged in parallel, connected to a
manifold or fitted into a tube sheet in a similar arrangement to a shell and tube heat
exchanger. For high-temperature reactions the tubes may be arranged in a furnace.
The pressure-drop and heat-transfer coefficients in empty tube reactors can be calculated
using the methods for flow in pipes given in Volume 1.
Packed bed reactors
There are two basic types of packed-bed reactor: those in which the solid is a reactant,
and those in which the solid is a catalyst. Many examples of the first type can be found
in the extractive metallurgical industries.
In the chemical process industries the designer will normally be concerned with the
second type: catalytic reactors. Industrial packed-bed catalytic reactors range in size from
small tubes, a few centimetres diameter, to large diameter packed beds. Packed-bed
reactors are used for gas and gas-liquid reactions. Heat-transfer rates in large diameter
packed beds are poor and where high heat-transfer rates are required fluidised beds should
be considered.
Fluidised bed reactors
The essential features of a fluidised bed reactor is that the solids are held in suspension
by the upward flow of the reacting fluid; this promotes high mass and heat-transfer rates
and good mixing. Heat-transfer coefficients in the order of 200 W/m2 Ž C to jackets and
internal coils are typically obtained. The solids may be a catalyst; a reactant in fluidised
combustion processes; or an inert powder, added to promote heat transfer.
Though the principal advantage of a fluidised bed over a fixed bed is the higher heattransfer rate, fluidised beds are also useful where it is necessary to transport large quantities
of solids as part of the reaction processes, such as where catalysts are transferred to another
vessel for regeneration.
Fluidisation can only be used with relatively small sized particles, <300 m with gases.
A great deal of research and development work has been done on fluidised bed reactors
in recent years, but the design and scale up of large diameter reactors is still an uncertain
process and design methods are largely empirical.
The principles of fluidisation processes are covered in Volume 2, Chapter 6. The design
of fluidised bed reactors is discussed by Rase (1977).
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CHEMICAL ENGINEERING
10.13.2. Design procedure
A general procedure for reactor design is outlined below:
1. Collect together all the kinetic and thermodynamic data on the desired reaction
and the side reactions. It is unlikely that much useful information will be gleaned
from a literature search, as little is published in the open literature on commercially
attractive processes. The kinetic data required for reactor design will normally be
obtained from laboratory and pilot plant studies. Values will be needed for the rate
of reaction over a range of operating conditions: pressure, temperature, flow-rate and
catalyst concentration. The design of experimental reactors and scale-up is discussed
by Rase (1977).
2. Collect the physical property data required for the design; either from the literature,
by estimation or, if necessary, by laboratory measurements.
3. Identify the predominant rate-controlling mechanism: kinetic, mass or heat transfer.
Choose a suitable reactor type, based on experience with similar reactions, or from
the laboratory and pilot plant work.
4. Make an initial selection of the reactor conditions to give the desired conversion
and yield.
5. Size the reactor and estimate its performance.
Exact analytical solutions of the design relationships are rarely possible; semiempirical methods based on the analysis of idealised reactors will normally have to
be used.
6. Select suitable materials of construction.
7. Make a preliminary mechanical design for the reactor: the vessel design, heat-transfer
surfaces, internals and general arrangement.
8. Cost the proposed design, capital and operating, and repeat steps 4 to 8, as necessary,
to optimise the design.
In choosing the reactor conditions, particularly the conversion, and optimising the
design, the interaction of the reactor design with the other process operations must not
be overlooked. The degree of conversion of raw materials in the reactor will determine
the size, and cost, of any equipment needed to separate and recycle unreacted materials.
In these circumstances the reactor and associated equipment must be optimised as a unit.
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EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
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Volume 1: Gas-solid and solid-solid reactions
Volume 2: Fluid-fluid-solid reactions.
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SMITH, J. M. Chemical Engineering Kinetics (McGraw Hill, 1970).
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Operation, 2nd edn (Wiley, 1988).
British Standards
BS 410:
BS 490:
2000
...
Part 1:
Part 2:
BS 1796: 1989
Specification for test sieves.
Conveyor and elevator belting.
1972 Rubber and plastic belting of textile construction for general use.
1975 Rubber and plastics belting of textile construction for use on bucket elevators.
Method for test sieving.
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CHEMICAL ENGINEERING
10.15. NOMENCLATURE
Dimensions
in MLT
Ai
As
Av
A1
b
c
D
Dc
Dc1
Dc2
DT
Dv
d
ds
d1
d2
d50
fc
fv
hv
K
L
Lc
Lv
l
N
P
P
p
Q
Qp
Q1
Q2
r
re
rt
uc
ud
ug
us
ut
uO v
u1
u2
Vv
w
z1
z2
z3
p
c
1
Area of interface
Surface area of cyclone
Area for vapour flow
Area of cyclone inlet duct
Index in equation 10.11
Index in equation 10.11
Agitator diameter
Cyclone diameter
Diameter of standard cyclone
Diameter of proposed cyclone design
Tank diameter
minimum vessel diameter for separator
Particle diameter
Diameter of solid particle removed in a centrifuge
Mean diameter of particles separated in cyclone under standard conditions
Mean diameter of particles separated in proposed cyclone design
Particle diameter for which cyclone is 50 per cent efficient
Friction factor for cyclones
fraction of cross-sectional area occupied by vapour.
height above liquid level
Constant in equation 10.11
Cyclone feed volumetric flow-rate
Continuous phase volumetric flow-rate
length of separator
Length of decanter vessel
Agitator speed
Agitator shaft power
Press differential (pressure drop)
Agitator blade pitch
Volumetric flow-rate of liquid through a centrifuge
Volumetric liquid flow through a pump
Standard flow-rate in cyclone
Proposed flow-rate in cyclone
Radius of decanter vessel
Radius of cyclone exit pipe
Radius of circle to which centre line of cyclone inlet duct is tangential
Velocity of continuous phase in a decanter
Settling (terminal) velocity of dispersed phase in a decanter
Terminal velocity of solid particles settling under gravity
velocity in a separator
settling velocity
Maximum allowable vapour velocity in a separating vessel
Velocity in cyclone inlet duct
Velocity in cyclone exit duct
Gas, or vapour volumetric flow-rate
Width of interface in a decanter
Height to light liquid overflow from a decanter
Height to heavy liquid overflow from a decanter
Height to the interface in a decanter
Separating efficiency of a centrifuge
Pump efficiency
Liquid viscosity
Viscosity of continuous phase
Cyclone test fluid viscosity
L2
L2
L2
L2
L
L
L
L
L
L
L
L
L
L
L
L
L3 T 1
L3 T1
LT1
L
T1
ML2 T3
ML1 T2
L
L3 T1
L3 T1
L3 T1
L3 T1
L
L
L
LT1
LT1
LT1
LT1
LT1
LT1
LT1
LT1
L3 T1
L
L
L
L
ML1 T1
ML1 T1
ML1 T1
EQUIPMENT SELECTION, SPECIFICATION AND DESIGN
2
f
L
s
v
1
2
1
2
Viscosity of fluid in proposed cyclone design
Liquid density
Gas density
Liquid density
Density of solid
Vapour density
Light liquid density in a decanter
Heavy liquid density in a decanter
Difference in density between solid and liquid
Density difference under standard conditions in standard cyclone
Density difference in proposed cyclone design
Sigma value for centrifuges, defined by equation 10.1
Factor in Figure 10.48
Parameter in Figure 10.47
491
ML1 T1
ML3
ML3
ML3
ML3
ML3
ML3
ML3
ML3
ML3
ML3
L2
10.16. PROBLEMS
10.1. The product from a crystalliser is to be separated from the liquor using a
centrifuge. The concentration of the crystals is 6.5 per cent and the slurry feed
rate to the centrifuge will be 5.0 m3 /h. The density of the liquor is 995 kg/m3
and that of the crystals 1500 kg/m3 . The viscosity of the liquor is 0.7 mN m2 s.
The cut-off crystal size required is 5 m.
Select a suitable type of centrifuge to use for this duty.
10.2. Dissolved solids in the tar from the bottom of a distillation column are precipitated
by quenching the hot tar in oil. The solids are then separated from the oil and
burnt. The density of the solids is 1100 kg/m3 . The density of the liquid phase
after addition of the tar is 860 kg/m3 and its viscosity, at the temperature of the
mixture, 1.7 mN m2 s. The solid content of the oil and tar mixture is 10 per cent
and the flow-rate of the liquid phase leaving the separator will be 1000 kg/h. The
cut-off particle size required is 0.1 mm.
List the types of separator that could be considered for separating the solids from
the liquid. Bearing mind the nature of the process, what type of separator would
you recommend for this duty?
10.3. The solids from a dilute slurry are to be separated using hydrocyclones. The
density of the solids is 2900 kg/m3 , and liquid is water. A recovery of 95 per cent
of particles greater than 100 m is required. The minimum operating temperature
will be 10 Ž C and the maximum 30 Ž C.
Design a hydrocyclone system to handle 1200 1/m of this slurry.
10.4. A fluidised bed is used in the production of aniline by the hydrogenation
of nitrobenzene. Single-stage cyclones, followed by candle filters, are used to
remove fines from the gases leaving the fluidised bed.
The reactor operates at a temperature 270 Ž C and a pressure of 2.5 bara. The
reactor diameter is 10 m. Hydrogen is used in large excess in the reaction, and
for the purposes of this exercise the properties of the gas may be taken as those
of hydrogen at the reactor conditions. The density of the catalyst particles is
1800 kg/m3 .
492
CHEMICAL ENGINEERING
The estimated particle size distribution of the fines is:
Particle size, m
Percentage by
weight less than
50
40
30
20
10
5
2
100
70
40
20
10
5
2
A 70 per cent recovery of the solids is required in the cyclones.
For a gas flow rate of 100,000 m3 /h, at the reactor conditions, determine how
many cyclones operating in parallel are need and design a suitable cyclone.
Estimate the size distribution of the particles entering the filters.
10.5. In a process for the production of acrylic fibres by the emulsion polymerisation
of acrylonitrile, the unreacted monomer is recovered from water by distillation.
Acrylonitrile forms an azeotrope with water and the overhead product from the
column contain around 5 mol per cent water. The overheads are condensed and
the recovered acrylonitrile separated from the water in a decanter. The decanter
operating temperature will be 20 Ž C.
Size a suitable decanter for a feed-rate of 3000 kg/h.
10.6. In the production of aniline by the hydrogenation of nitrobenzene, the reactor
products are separated from unreacted hydrogen in a condenser. The condensate,
which is mainly water and aniline, together with a small amount of unreacted
nitrobenzene and cyclo-hexylamine, is fed to a decanter to separate the water and
aniline. The separation will not be complete, as aniline is slightly soluble in water,
and water in aniline. A typical material balance for the decanter is given below:
Basis 100 kg feed
water
aniline
nitrobenzene
cyclo-hexylamine
total
feed
23.8
72.2
3.2
0.8
100
aqueous stream
21.4
1.1
trace
0.8
23.3
organic stream
2.4
71.1
3.2
trace
76.7
Design a decanter for this duty, for a feed-rate of 3500 kg/h. Concentrate on
the separation of the water and aniline. The densities of water aniline solutions
are given in Appendix G, problem C.8. The decanter will operate at a maximum
temperature of 30 Ž C.
10.7. Water droplets are to be separated from air in a simple separation drum. The
flow-rate of the air is 1000 m3 /h, at stp, and it contains 75 kg of water. The
drum will operate at 1.1 bara pressure and 20 Ž C.
Size a suitable liquid vapour separator.
10.8. The vapours from a chlorine vaporiser will contain some liquid droplets. The vaporiser consists of a vertical, cylindrical, vessel with a submerged bundle for heating.
A vapour rate of 2500 kg/h is required and the vaporiser will operate at 6 bara.
Size the vessel to restrict the carryover of liquid droplets. The liquid hold-up time
need not be considered, as the liquid level will be a function of the thermal design.
CHAPTER 11
Separation Columns
(Distillation, Absorption and Extraction)
11.1. INTRODUCTION
This chapter covers the design of separating columns. Though the emphasis is on distillation processes, the basic construction features, and many of the design methods, also
apply to other multistage processes; such as stripping, absorption and extraction.
Distillation is probably the most widely used separation process in the chemical and
allied industries; its applications ranging from the rectification of alcohol, which has been
practised since antiquity, to the fractionation of crude oil.
Only a brief review of the fundamental principles that underlie the design procedures
will be given; a fuller discussion can be found in Volume 2, and in other text books; King
(1980), Hengstebeck (1976), Kister (1992).
A good understanding of methods used for correlating vapour-liquid equilibrium data
is essential to the understanding of distillation and other equilibrium-staged processes;
this subject was covered in Chapter 8.
In recent years, most of the work done to develop reliable design methods for distillation
equipment has been carried out by a commercial organisation, Fractionation Research
Inc., an organisation set up with the resources to carry out experimental work on fullsize columns. Since their work is of a proprietary nature, it is not published in the open
literature and it has not been possible to refer to their methods in this book. Fractionation Research’s design manuals will, however, be available to design engineers whose
companies are subscribing members of the organisation.
Distillation column design
The design of a distillation column can be divided into the following steps:
1.
2.
3.
4.
5.
6.
7.
Specify the degree of separation required: set product specifications.
Select the operating conditions: batch or continuous; operating pressure.
Select the type of contacting device: plates or packing.
Determine the stage and reflux requirements: the number of equilibrium stages.
Size the column: diameter, number of real stages.
Design the column internals: plates, distributors, packing supports.
Mechanical design: vessel and internal fittings.
The principal step will be to determine the stage and reflux requirements. This is
a relatively simple procedure when the feed is a binary mixture, but a complex
493
494
CHEMICAL ENGINEERING
and difficult task when the feed contains more than two components (multicomponent
systems).
11.2. CONTINUOUS DISTILLATION: PROCESS DESCRIPTION
The separation of liquid mixtures by distillation depends on differences in volatility
between the components. The greater the relative volatilities, the easier the separation.
The basic equipment required for continuous distillation is shown in Figure 11.1. Vapour
flows up the column and liquid counter-currently down the column. The vapour and liquid
are brought into contact on plates, or packing. Part of the condensate from the condenser
is returned to the top of the column to provide liquid flow above the feed point (reflux),
and part of the liquid from the base of the column is vaporised in the reboiler and returned
to provide the vapour flow.
Condenser
Top
product
Reflux
Side
streams
Multiple
feeds
Feed
Reboiler
Bottom
product
(a)
Figure 11.1.
(b)
Distillation column (a) Basic column (b) Multiple feeds and side streams
In the section below the feed, the more volatile components are stripped from the liquid
and this is known as the stripping section. Above the feed, the concentration of the more
volatile components is increased and this is called the enrichment, or more commonly, the
rectifying section. Figure 11.1a shows a column producing two product streams, referred
to as tops and bottoms, from a single feed. Columns are occasionally used with more
than one feed, and with side streams withdrawn at points up the column, Figure 11.1b.
This does not alter the basic operation, but complicates the analysis of the process, to
some extent.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
495
If the process requirement is to strip a volatile component from a relatively non-volatile
solvent, the rectifying section may be omitted, and the column would then be called a
stripping column.
In some operations, where the top product is required as a vapour, only sufficient liquid
is condensed to provide the reflux flow to the column, and the condenser is referred to
as a partial condenser. When the liquid is totally condensed, the liquid returned to the
column will have the same composition as the top product. In a partial condenser the
reflux will be in equilibrium with the vapour leaving the condenser. Virtually pure top
and bottom products can be obtained in a single column from a binary feed, but where the
feed contains more than two components, only a single “pure” product can be produced,
either from the top or bottom of the column. Several columns will be needed to separate
a multicomponent feed into its constituent parts.
11.2.1. Reflux considerations
The reflux ratio, R, is normally defined as:
RD
flow returned as reflux
flow of top product taken off
The number of stages required for a given separation will be dependent on the reflux ratio
used.
In an operating column the effective reflux ratio will be increased by vapour condensed
within the column due to heat leakage through the walls. With a well-lagged column the
heat loss will be small and no allowance is normally made for this increased flow in
design calculations. If a column is poorly insulated, changes in the internal reflux due
to sudden changes in the external conditions, such as a sudden rain storm, can have a
noticeable effect on the column operation and control.
Total reflux
Total reflux is the condition when all the condensate is returned to the column as reflux:
no product is taken off and there is no feed.
At total reflux the number of stages required for a given separation is the minimum
at which it is theoretically possible to achieve the separation. Though not a practical
operating condition, it is a useful guide to the likely number of stages that will be
needed.
Columns are often started up with no product take-off and operated at total reflux till
steady conditions are attained. The testing of columns is also conveniently carried out at
total reflux.
Minimum reflux
As the reflux ratio is reduced a pinch point will occur at which the separation can only be
achieved with an infinite number of stages. This sets the minimum possible reflux ratio
for the specified separation.
496
CHEMICAL ENGINEERING
Optimum reflux ratio
Practical reflux ratios will lie somewhere between the minimum for the specified separation
and total reflux. The designer must select a value at which the specified separation is
achieved at minimum cost. Increasing the reflux reduces the number of stages required,
and hence the capital cost, but increases the service requirements (steam and water) and
the operating costs. The optimum reflux ratio will be that which gives the lowest annual
operating cost. No hard and fast rules can be given for the selection of the design reflux
ratio, but for many systems the optimum will lie between 1.2 to 1.5 times the minimum
reflux ratio.
For new designs, where the ratio cannot be decided on from past experience, the effect
of reflux ratio on the number of stages can be investigated using the short-cut design
methods given in this chapter. This will usually indicate the best of value to use in more
rigorous design methods.
At low reflux ratios the calculated number of stages will be very dependent on the
accuracy of the vapour-liquid equilibrium data available. If the data are suspect a higher
than normal ratio should be selected to give more confidence in the design.
11.2.2. Feed-point location
The precise location of the feed point will affect the number of stages required for a
specified separation and the subsequent operation of the column. As a general rule, the
feed should enter the column at the point that gives the best match between the feed
composition (vapour and liquid if two phases) and the vapour and liquid streams in the
column. In practice, it is wise to provide two or three feed-point nozzles located round
the predicted feed point to allow for uncertainties in the design calculations and data, and
possible changes in the feed composition after start-up.
11.2.3. Selection of column pressure
Except when distilling heat-sensitive materials, the main consideration when selecting the
column operating-pressure will be to ensure that the dew point of the distillate is above
that which can be easily obtained with the plant cooling water. The maximum, summer,
temperature of cooling water is usually taken as 30Ž C. If this means that high pressures
will be needed, the provision of refrigerated brine cooling should be considered. Vacuum
operation is used to reduce the column temperatures for the distillation of heat-sensitive
materials and where very high temperatures would otherwise be needed to distil relatively
non-volatile materials.
When calculating the stage and reflux requirements it is usual to take the operating
pressure as constant throughout the column. In vacuum columns, the column pressure
drop will be a significant fraction of the total pressure and the change in pressure up the
column should be allowed for when calculating the stage temperatures. This may require
a trial and error calculation, as clearly the pressure drop cannot be estimated before an
estimate of the number of stages is made.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
497
11.3. CONTINUOUS DISTILLATION: BASIC PRINCIPLES
11.3.1. Stage equations
Material and energy balance equations can be written for any stage in a multistage process.
Figure 11.2 shows the material flows into and out of a typical stage n in a distillation
column. The equations for this stage are set out below, for any component i.
Vn, yn
Fn, Zn
Ln−1, xn−1
n
Sn, xn
qn
Vn+1, yn+1
Figure 11.2.
Ln, xn
Stage flows
material balance
VnC1 ynC1 C Ln1 xn1 C Fn zn D Vn yn C Ln xn C Sn xn
⊲11.1⊳
VnC1 HnC1 C Ln1 hn1 C Fhf C qn D Vn Hn C Ln hn C Sn hn
⊲11.2⊳
energy balance
where Vn
VnC1
Ln
Ln1
Fn
Sn
qn
n
z
D
D
D
D
D
D
D
D
D
x
y
H
h
hf
D
D
D
D
D
vapour flow from the stage,
vapour flow into the stage from the stage below,
liquid flow from the stage,
liquid flow into the stage from the stage above,
any feed flow into the stage,
any side stream from the stage,
heat flow into, or removal from, the stage,
any stage, numbered from the top of the column,
mol fraction of component i in the feed stream (note, feed may
be two-phase),
mol fraction of component i in the liquid streams,
mol fraction component i in the vapour streams,
specific enthalpy vapour phase,
specific enthalpy liquid phase,
specific enthalpy feed (vapour C liquid).
All flows are the total stream flows (mols/unit time) and the specific enthalpies are also
for the total stream (J/mol).
498
CHEMICAL ENGINEERING
It is convenient to carry out the analysis in terms of “equilibrium stages”. In an
equilibrium stage (theoretical plate) the liquid and vapour streams leaving the stage
are taken to be in equilibrium, and their compositions are determined by the vapourliquid equilibrium relationship for the system (see Chapter 8). In terms of equilibrium
constants:
yi D Ki xi
⊲11.3⊳
The performance of real stages is related to an equilibrium stage by the concept of plate
efficiencies for plate contactors, and “height of an equivalent theoretical plate” for packed
columns.
In addition to the equations arising from the material and energy balances over a
stage, and the equilibrium relationships, there will be a fourth relationship, the summation
equation for the liquid and vapour compositions:
xi,n D yi,n D 1.0
⊲11.4⊳
These four equations are the so-called MESH equations for the stage: Material balance,
Equilibrium, Summation and Heat (energy) balance, equations. MESH equations can be
written for each stage, and for the reboiler and condenser. The solution of this set of
equations forms the basis of the rigorous methods that have been developed for the
analysis for staged separation processes.
11.3.2. Dew points and bubble points
To estimate the stage, and the condenser and reboiler temperatures, procedures are required
for calculating dew and bubble points. By definition, a saturated liquid is at its bubble
point (any rise in temperature will cause a bubble of vapour to form), and a saturated
vapour is at its dew point (any drop in temperature will cause a drop of liquid to form).
Dew points and bubble points can be calculated from a knowledge of the vapour-liquid
equilibrium for the system. In terms of equilibrium constants, the bubble point is defined
by the equation:
bubble point:
yi D
Ki xi D 1.0
⊲11.5a⊳
yi
and dew point:
xi D
D 1.0
⊲11.5b⊳
Ki
For multicomponent mixtures the temperature that satisfies these equations, at a given
system pressure, must be found by trial and error.
For binary systems the equations can be solved more readily because the component
compositions are not independent; fixing one fixes the other.
ya D 1 yb
⊲11.6a⊳
xa D 1 xb
⊲11.6b⊳
Bubble- and dew-point calculations are illustrated in Example 11.9.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
499
11.3.3. Equilibrium flash calculations
In an equilibrium flash process a feed stream is separated into liquid and vapour streams
at equilibrium. The composition of the streams will depend on the quantity of the feed
vaporised (flashed). The equations used for equilibrium flash calculations are developed
below and a typical calculation is shown in Example 11.1.
Flash calculations are often needed to determine the condition of the feed to a distillation
column and, occasionally, to determine the flow of vapour from the reboiler, or condenser
if a partial condenser is used.
Single-stage flash distillation processes are used to make a coarse separation of the light
components in a feed; often as a preliminary step before a multicomponent distillation
column, as in the distillation of crude oil.
Figure 11.3 shows a typical equilibrium flash process. The equations describing this
process are:
V, yi
F, Zi
L, xi
Figure 11.3.
Flash distillation
Material balance, for any component, i
Fzi D Vyi C Lxi
⊲11.7⊳
Energy balance, total stream enthalpies:
Fhf D VH C Lh
⊲11.8⊳
If the vapour-liquid equilibrium relationship is expressed in terms of equilibrium
constants, equation 11.7 can be written in a more useful form:
Fzi D VKi xi C Lxi
V
D Lxi
Ki C 1
L
from which
LD
VD
i
Fzi
VKi
C1
L
Fzi
L
C1
VKi
⊲11.9⊳
and, similarly,
i
⊲11.10⊳
500
CHEMICAL ENGINEERING
The groups incorporating the liquid and vapour flow-rates and the equilibrium constants
have a general significance in separation process calculations.
The group L/VKi is known as the absorption factor Ai , and is the ratio of the mols of
any component in the liquid stream to the mols in the vapour stream.
The group VKi /L is called the stripping factor Si , and is the reciprocal of the absorption
factor.
Efficient techniques for the solution of the trial and error calculations necessary in
multicomponent flash calculations are given by several authors; Hengstebeck (1976) and
King (1980).
Example 11.1
A feed to a column has the composition given in the table below, and is at a pressure of
14 bar and a temperature of 60Ž C. Calculate the flow and composition of the liquid and
vapour phases. Take the equilibrium data from the Depriester charts given in Chapter 8.
Feed
ethane (C2 )
propane (C3 )
isobutane (iC4 )
n-pentane (nC5 )
kmol/h
20
20
20
20
zi
0.25
0.25
0.25
0.25
Solution
For two phases to exist the flash temperature must lie between the bubble point and dew
point of the mixture.
From equations 11.5a and 11.5b:
Ki zi > 1.0
zi
> 1.0
Ki
Check feed condition
C2
C3
iC4
nC5
Ki
Ki zi
zi /Ki
3.8
1.3
0.43
0.16
0.95
0.33
0.11
0.04
0.07
0.19
0.58
1.56
1.43
2.40
therefore the feed is a two phase mixture.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
501
Flash calculation
Try L/V D 1.5
C2
C3
iC4
nC5
Try L/V D 3.0
Ki
Ai D L/VKi
Vi D Fzi /⊲1 C Ai ⊳
Ai
Vi
3.8
1.3
0.43
0.16
0.395
1.154
3.488
9.375
14.34
9.29
4.46
1.93
0.789
2.308
6.977
18.750
11.17
6.04
2.51
1.01
Vcalc D 30.02
L/V D
80 30.02
D 1.67
30.02
Vcalc D 20.73
L/V D 2.80
Hengstebeck’s method is used to find the third trial value for L/V. The calculated values
are plotted against the assumed values and the intercept with a line at 45Ž (calculated D
assumed) gives the new trial value, 2.4.
Try L/V D 2.4
Ai
C2
C3
iC4
nC5
0.632
1.846
5.581
15.00
Vi
yi D Vi /V
xi D ⊲Fzi Vi ⊳/L
12.26
7.03
3.04
1.25
0.52
0.30
0.13
0.05
0.14
0.23
0.30
0.33
1.00
1.00
Vcal D 23.58
L D 80 23.58 D 56.42 kmol/h,
L/V calculated D 56.42/23.58 D 2.39 close enough to the assumed value of 2.4.
Adiabatic flash
In many flash processes the feed stream is at a higher pressure than the flash pressure
and the heat for vaporisation is provided by the enthalpy of the feed. In this situation the
flash temperature will not be known and must be found by trial and error. A temperature
must be found at which both the material and energy balances are satisfied.
11.4. DESIGN VARIABLES IN DISTILLATION
It was shown in Chapter 1 that to carry out a design calculation the designer must specify
values for a certain number of independent variables to define the problem completely,
and that the ease of calculation will often depend on the judicious choice of these design
variables.
In manual calculations the designer can use intuition in selecting the design variables
and, as he proceeds with the calculation, can define other variables if it becomes clear that
502
CHEMICAL ENGINEERING
the problem is not sufficiently defined. He can also start again with a new set of design
variables if the calculations become tortuous. When specifying a problem for a computer
method it is essential that the problem is completely and sufficiently defined.
In Chapter 1 it was shown that the number of independent variables for any problem is
equal to the difference between the total number of variables and the number of linking
equations and other relationships. Examples of the application of this formal procedure
for determining the number of independent variables in separation process calculations are
given by Gilliand and Reed (1942) and Kwauk (1956). For a multistage, multicomponent,
column, there will be a set of material and enthalpy balance equations and equilibrium
relationships for each stage (the MESH equations), and for the reboiler and condenser; for
each component. If there are more than a few stages the task of counting the variables and
equations becomes burdensome and mistakes are very likely to be made. A simpler, more
practical, way to determine the number of independent variables is the “description rule”
procedure given by Hanson et al. (1962). Their description rule states that to determine a
separation process completely the number of independent variables which must be set (by
the designer) will equal the number that are set in the construction of the column or that
can be controlled by external means in its operation. The application of this rule requires
the designer to visualise the column in operation and list the number of variables fixed by
the column construction; those fixed by the process; and those that have to be controlled
for the column to operate steadily and produce product within specification. The method
is best illustrated by considering the operation of the simplest type of column: with one
feed, no side streams, a total condenser, and a reboiler. The construction will fix the
number of stages above and below the feed point (two variables). The feed composition
and total enthalpy will be fixed by the processes upstream (1 C ⊲n 1⊳ variables, where n
is the number of components). The feed rate, column pressure and condenser and reboiler
duties (cooling water and steam flows) will be controlled (four variables).
Total number of variables fixed D 2 C 1 C ⊲n 1⊳ C 4 D n C 6
To design the column this number of variables must be specified completely to define the
problem, but the same variables need not be selected.
Typically, in a design situation, the problem will be to determine the number of stages
required at a specified reflux ratio and column pressure, for a given feed, and with the
product compositions specified in terms of two key components and one product flowrate. Counting up the number of variables specified it will be seen that the problem is
completely defined:
Feed flow, composition, enthalpy
D 2 C (n 1)
Reflux (sets qc )
D 1
Key component compositions, top and bottom D 2
Product flow
D 1
Column pressure
D 1
nC6
Note: specifying (n 1) component compositions completely defines the feed composition as the fractions add up to 1.
503
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
In theory any (n C 6) independent variables could have been specified to define the
problem, but it is clear that the use of the above variables will lead to a straightforward
solution of the problem.
When replacing variables identified by the application of the description rule it is
important to ensure that those selected are truly independent, and that the values assigned
to them lie within the range of possible, practical, values.
The number of independent variables that have to be specified to define a problem will
depend on the type of separation process being considered. Some examples of the application of the description rule to more complex columns are given by Hanson et al. (1962).
11.5. DESIGN METHODS FOR BINARY SYSTEMS
A good understanding of the basic equations developed for binary systems is essential to
the understanding of distillation processes.
The distillation of binary mixtures is covered thoroughly in Volume 2, Chapter 11,
and the discussion in this section is limited to a brief review of the most useful design
methods. Though binary systems are usually considered separately, the design methods
developed for multicomponent systems (Section 11.6) can obviously also be used for
binary systems. With binary mixtures fixing the composition of one component fixes the
composition of the other, and iterative procedures are not usually needed to determine
the stage and reflux requirements; simple graphical methods are normally used.
11.5.1. Basic equations
Sorel (1899) first derived and applied the basic stage equations to the analysis of binary
systems. Figure 11.4a shows the flows and compositions in the top part of a column.
Taking the system boundary to include the stage n and the condenser, gives the following
equations:
Vl
qc
yn, V´n
L´n+1, xn+1
Hn
hn+1
n
l
L0
D, xd , hd
l
qb
n
yn+1, Vn+1
Ln, xn
Hn+1 hn
(a)
Figure 11.4.
B, xb, hb
(b)
Column flows and compositions (a) Above feed (b) Below feed
504
CHEMICAL ENGINEERING
Material balance
VnC1 D Ln C D
⊲11.11⊳
VnC1 ynC1 D Ln xn C Dxd
⊲11.12⊳
VnC1 HnC1 D Ln hn C Dhd C qc
⊲11.13⊳
total flows
for either component
Energy balance
total stream enthalpies
where qc is the heat removed in the condenser.
Combining equations 11.11 and 11.12 gives
ynC1 D
Ln
D
xn C
xd
Ln C D
Ln C D
⊲11.14⊳
Combining equations 11.11 and 11.13 gives
VnC1 HnC1 D ⊲Ln C D⊳HnC1 D Ln hn C Dhd C qc
⊲11.15⊳
Analogous equations can be written for the stripping section, Figure 11.6b.
xnC1 D
V0n
B
yn C 0
xb
0
Vn C B
Vn C B
⊲11.16⊳
and
0
LnC1
hnC1 D ⊲V0n C B⊳hnC1 D V0n Hn C Bhb qb
⊲11.17⊳
At constant pressure, the stage temperatures will be functions of the vapour and liquid
compositions only (dew and bubble points) and the specific enthalpies will therefore also
be functions of composition
H D f⊲y⊳
⊲11.18a⊳
h D f⊲x⊳
⊲11.18b⊳
Lewis-Sorel method (equimolar overflow)
For most distillation problems a simplifying assumption, first proposed by Lewis (1909),
can be made that eliminates the need to solve the stage energy-balance equations. The
molar liquid and vapour flow rates are taken as constant in the stripping and rectifying
sections. This condition is referred to as equimolar overflow: the molar vapour and liquid
flows from each stage are constant. This will only be true where the component molar
latent heats of vaporisation are the same and, together with the specific heats, are constant
over the range of temperature in the column; there is no significant heat of mixing; and
the heat losses are negligible. These conditions are substantially true for practical systems
when the components form near-ideal liquid mixtures.
Even when the latent heats are substantially different the error introduced by assuming
equimolar overflow to calculate the number of stages is usually small, and acceptable.
With equimolar overflow equations 11.14 and 11.16 can be written without the
subscripts to denote the stage number:
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
ynC1 D
xnC1 D
L
D
xn C
xd
LCD
LCD
B
V0
yn C 0
xb
V0 C B
V CB
505
⊲11.19⊳
⊲11.20⊳
where L D the constant liquid flow in the rectifying section D the reflux flow, L0 , and V0
is the constant vapour flow in the stripping section.
Equations 11.19 and 11.20 can be written in an alternative form:
D
L
ynC1 D xn C xd
⊲11.21⊳
V
V
B
L0
yn D 0 xnC1 0 xb
⊲11.22⊳
V
V
where V is the constant vapour flow in the rectifying section D ⊲L C D⊳; and L 0 is the
constant liquid flow in the stripping section D V0 C B.
These equations are linear, with slopes L/V and L 0 /V0 . They are referred to as operating
lines, and give the relationship between the liquid and vapour compositions between
stages. For an equilibrium stage, the compositions of the liquid and vapour streams leaving
the stage are given by the equilibrium relationship.
11.5.2. McCabe-Thiele method
Equations 11.21 and 11.22 and the equilibrium relationship are conveniently solved by
the graphical method developed by McCabe and Thiele (1925). The method is discussed
fully in Volume 2. A simple procedure for the construction of the diagram is given below
and illustrated in Example 11.2.
Procedure
Refer to Figure 11.5, all compositions are those of the more volatile component.
1. Plot the vapour-liquid equilibrium curve from data available at the column operating
pressure. In terms of relative volatility:
yD
˛x
⊲1 C ⊲˛ 1⊳x⊳
⊲11.23⊳
where ˛ is the geometric average relative volatility of the lighter (more volatile)
component with respect to the heavier component (less volatile).
It is usually more convenient, and less confusing, to use equal scales for the x and
y axes.
2. Make a material balance over the column to determine the top and bottom
compositions, xd and xb , from the data given.
3. The top and bottom operating lines intersect the diagonal at xd and xb respectively;
mark these points on the diagram.
4. The point of intersection of the two operating lines is dependent on the phase
condition of the feed. The line on which the intersection occurs is called the q line
(see Volume 2). The q line is found as follows:
506
CHEMICAL ENGINEERING
Figure 11.5.
McCabe-Thiele diagram
(i) calculate the value of the ratio q given by
qD
heat to vaporise 1 mol of feed
molar latent heat of feed
(ii) plot the q line, slope D q/⊲q 1⊳, intersecting the diagonal at zf (the feed
composition).
5. Select the reflux ratio and determine the point where the top operating line extended
cuts the y axis:
xd
D
⊲11.24⊳
1CR
6. Draw in the top operating line, from xd on the diagonal to .
7. Draw in the bottom operating line; from xb on the diagonal to the point of intersection
of the top operating line and the q line.
8. Starting at xd or xb , step off the number of stages.
Note: The feed point should be located on the stage closest to the intersection of the
operating lines.
The reboiler, and a partial condenser if used, act as equilibrium stages. However, when
designing a column there is little point in reducing the estimated number of stages to
account for this; they can be considered additional factors of safety.
The efficiency of real contacting stages can be accounted for by reducing the height of
the steps on the McCabe-Thiele diagram, see diagram Figure 11.6. Stage efficiencies are
discussed in Section 11.10.
The McCabe-Thiele method can be used for the design of columns with side streams
and multiple feeds. The liquid and vapour flows in the sections between the feed and
take-off points are calculated and operating lines drawn for each section.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
507
Equilibrium
curve
A
Operating
line
B
C
Stage efficiency =
BC
AC
Figure 11.6.
Actual enrichment
=
Theoretical enrichment
Stage efficiency
Stage vapour and liquid flows not constant
The McCabe-Thiele method can be used when the condition of equimolar overflow cannot
be assumed, but the operating lines will not then be straight. They can be drawn by making
energy balances at a sufficient number of points to determine the approximate slope of
the lines; see Hengstebeck (1976). Alternatively the more rigorous graphical method
of Ponchon and Savarit derived in Volume 2 can be used. Nowadays, it should rarely
be necessary to resort to complex graphical methods when the simple McCabe-Thiele
diagram is not sufficiently accurate, as computer programs will normally be available for
the rigorous solution of such problems.
11.5.3. Low product concentrations
When concentrations of the more volatile component of either product is very low the
steps on the McCabe-Thiele diagram become very small and difficult to plot. This problem
can be overcome by replotting the top or bottom sections to a larger scale, or on log-log
paper. In a log plot the operating line will not be straight and must be drawn by plotting
points calculated using equations 11.21 and 11.22. This technique is described by Alleva
(1962) and is illustrated in Example 11.2.
If the operating and equilibrium lines are straight, and they usually can be taken as
such when the concentrations are small, the number of stages required can be calculated
using the equations given by Robinson and Gilliland (1950).
For the stripping section:
0
0
xr
K
1
1
s0
xb
C 1
log
1 0
⊲K 1⊳
0
s
NŁs D
C1
⊲11.25⊳
K0
log
s0
where NŁs D number of ideal stages required from xb to some reference point xr0 ,
xb D mol fraction of the more volatile component in the bottom product,
508
CHEMICAL ENGINEERING
xr0 D mol fraction of more volatile component at the reference point,
s0 D slope of the bottom operating line,
K0 D equilibrium constant for the more volatile component.
For the rectifying section:
log
NŁr D
where NŁr
xd
xr
K
s
D
D
D
D
D
⊲1 s⊳ C xr /xd ⊲s K⊳
1K
1
s
log
K
⊲11.26⊳
number of stages required from some reference point xr to the xd ,
mol fraction of the least volatile component in the top product,
mol fraction of least volatile component at reference point,
equilibrium constant for the least volatile component,
slope of top operating line.
Note: at low concentrations K D ˛.
The use of these equations is illustrated in Example 11.3.
Example 11.2
Acetone is to be recovered from an aqueous waste stream by continuous distillation. The
feed will contain 10 per cent w/w acetone. Acetone of at least 98 per cent purity is wanted,
and the aqueous effluent must not contain more than 50 ppm acetone. The feed will be
at 20Ž C. Estimate the number of ideal stages required.
Solution
There is no point in operating this column at other than atmospheric pressure. The
equilibrium data available for the acetone-water system were discussed in Chapter 8,
Section 8.4.
The data of Kojima et al. will be used.
Mol fraction x, liquid
Acetone y, vapour
bubble point Ž C
0.00
0.00
100.0
0.05
0.10
0.15
0.20
0.25
0.30
0.6381 0.7301 0.7716 0.7916 0.8034 0.8124
74.80 68.53 65.26 63.59 62.60 61.87
x
0.35
0.40
0.45
0.50
0.55
0.60
0.65
y
0.8201 0.8269 0.8376 0.8387 0.8455 0.8532 0.8615
Ž
C 61.26 60.75 60.35 59.95 59.54 59.12 58.71
x
y
Ž
C
0.70
0.75
0.80
0.85
0.90
0.95
0.8712 0.8817 0.8950 0.9118 0.9335 0.9627
58.29
57.90
57.49
57.08
56.68
56.30
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
509
The equilibrium curve can be drawn with sufficient accuracy to determine the stages
above the feed by plotting the concentrations at increments of 0.1. The diagram would
normally be plotted at about twice the size of Figure 11.7.
Figure 11.7.
McCabe-Thiele plot, Example 11.2
Molecular weights, acetone 58, water 18
10
58
D 0.033
10 90
C
58 18
98
58
top product D
D 0.94
98
2
C
58 18
18
D 15.5 ð 106
bottom product D 50 ð 106 ð
58
Mol fractions acetone feed D
Feed condition (q-line)
Bubble point of feed (interpolated) D 83Ž C
Latent heats, water 41,360, acetone 28,410 J/mol
510
CHEMICAL ENGINEERING
Mean specific heats, water 75.3, acetone 128 J/mol Ž C
Latent heat of feed D 28,410 ð 0.033 C (1 0.033) 41,360 D 40,933 J/mol
Specific heat of feed D (0.033 ð 128) C (1 0.033) 75.3 D 77.0 J/mol Ž C
Heat to vaporise 1 mol of feed D (83 20) 77.0 C 40,933 D 45,784 J
45,784
D 1.12
40,933
1.12
D 9.32
Slope of q line D
1.12 1
qD
For this problem the condition of minimum reflux occurs where the top operating line
just touches the equilibrium curve at the point where the q line cuts the curve.
From the Figure 11.7,
for the operating line at minimum reflux D 0.65
From equation 11.24, Rmin D 0.94/0.65 1 D 0.45
Take R D Rmin ð 3
As the flows above the feed point will be small, a high reflux ratio is justified; the
condenser duty will be small.
At R D 3 ð 0.45 D 1.35,
D
0.94
D 0.4
1 C 1.35
For this problem it is convenient to step the stages off starting at the intersection of the
operating lines. This gives three stages above the feed up to y D 0.8. The top section is
drawn to a larger scale, Figure 11.8, to determine the stages above y D 0.8: three to four
stages required; total stages above the feed 7.
1.0
1
xd
2
0.9
3
4
0.7
0.8
Figure 11.8.
0.9
1.0
Top section enlarged
Below the feed, one stage is required down to x D 0.04. A log-log plot is used to
determine the stages below this concentration. Data for log-log plot:
operating line slope, from Figure 11.7 D 0.45/0.09 D 5.0
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
511
operating line equation, y D 4.63⊲x xb ⊳ C xb
D 5.0x 62.0 ð 106
equilibrium line slope, from v l e data D 0.6381/0.05 D 12.8
Equilibrium line
Operating line
x D
4 ð 102
y D
y D
0.51
0.20
103
104
1.3 ð 102
4.9 ð 103
1.3 ð 103
4.4 ð 104
4 ð 105
5.1 ð 104
1.4 ð 104
2 ð 105
2.6 ð 104
3.8 ð 105
From Figure 11.9, number of stages required for this section D 8
10
10
0
8
−1
7
Equilibrium
line
−2
10
6
4
y
10
0.04
5
−3
Operating
line
3
2
10
1
−4
χb
10
−5
10
−5
−4
10
10
−3
10
−2
10
−1
x
Figure 11.9.
Log-log plot of McCabe-Thiele diagram
Total number of stages below feed D 9
Total stages D 7 C 9 D 16
Example 11.3
For the problem specified in Example 11.2, estimate the number of ideal stages required
below an acetone concentration of 0.04 (more volatile component), using the RobinsonGilliland equation.
Solution
From the McCabe-Thiele diagram in Example 11.2:
slope of bottom operating line, s0 D 5.0
slope of equilibrium line, K0 D 12.8
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CHEMICAL ENGINEERING
xb D 15.5 ð 106
12.8
0.04
1
1
5.0
15.5 ð 106
log
C 1
1
⊲12.8 1⊳
5.0
NŁs D
C 1 D 8.9, say 9 (11.25)
12.8
log
5.0
11.5.4. The Smoker equations
Smoker (1938) derived an analytical equation that can be used to determine the number
of stages when the relative volatility is constant. Though his method can be used for any
problem for which the relative volatilities in the rectifying and stripping sections can be
taken as constant, it is particularly useful for problems where the relative volatility is low;
for example, in the separation of close boiling isomers. If the relative volatility is close
to one, the number of stages required will be very large, and it will be impractical to
draw a McCabe-Thiele diagram. The derivation of the equations are outlined below and
illustrated in Example 11.4.
Derivation of the equations:
A straight operating line can be represented by the equation:
y D sx C c
⊲11.27⊳
and in terms of relative volatility the equilibrium values of y are given by:
˛x
⊲equation 11.23⊳
yD
1 C ⊲˛ 1⊳x
Eliminating y from these equations gives a quadratic in x:
⊲11.28⊳
s⊲˛ 1⊳x 2 C [s C b⊲˛ 1⊳ ˛]x C b D 0
For any particular distillation problem equation 11.28 will have only one real root k
between 0 and 1
⊲11.29⊳
s⊲˛ 1⊳k 2 C [s C b⊲˛ 1⊳ ˛]k C b D 0
k is the value of the x ordinate at the point where the extended operating lines intersect
the vapour-liquid equilibrium curve. Smoker shows that the number of stages required is
given by the equation:
Ł
x0 ⊲1 ˇxnŁ ⊳
˛
log
⊲11.30⊳
N D log Ł
Ł
xn ⊲1 ˇx0 ⊳
sc2
where
sc⊲˛ 1⊳
ˇD
⊲11.31⊳
˛ sc2
N D number of stages required to effect the separation represented by the concentration
change from
xnŁ to x0Ł ; x Ł D ⊲x k⊳ and x0Ł > xnŁ
c D 1 C ⊲˛ 1⊳k
⊲11.32⊳
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
513
s D slope of the operating line between xnŁ and x0Ł ,
˛ D relative volatility, assumed constant over xnŁ to x0Ł .
For a column with a single feed and no side streams:
Rectifying section
x0Ł D xd k
xnŁ D zf k
R
sD
RC1
xd
bD
RC1
⊲11.33⊳
⊲11.34⊳
x0Ł D zf k
xnŁ D xb k
Rzf C xd ⊲R C 1⊳xb
sD
⊲R C 1⊳⊲zf xb ⊳
⊲zf xd ⊳xb
bD
⊲R C 1⊳⊲zf xb ⊳
⊲11.37⊳
⊲11.38⊳
⊲11.35⊳
⊲11.36⊳
Stripping section
⊲11.39⊳
⊲11.40⊳
If the feed stream is not at its bubble point, zf is replaced by the value of x at the
intersection of operating lines, given by
zf
bC
q1
zfŁ D q
⊲11.41⊳
s
q1
All compositions for the more volatile component.
Example 11.4
A column is to be designed to separate a mixture of ethylbenzene and styrene. The feed
will contain 0.5 mol fraction styrene, and a styrene purity of 99.5 per cent is required,
with a recovery of 85 per cent. Estimate the number of equilibrium stages required at a
reflux ratio of 8. Maximum column bottom pressure 0.20 bar.
Solution
Ethylbenzene is the more volatile component.
3279.47
T 59.95
3328.57
styrene ln PŽ D 9.386
T 63.72
P bar, T Kelvin
Antoine equations, ethylbenzene, ln PŽ D 9.386
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CHEMICAL ENGINEERING
Material balance, basis 100 kmol feed:
at 85 per cent recovery, styrene in bottoms D 50 ð 0.85 D 42.5 kmol
42.5
ð 0.5 D 0.21 kmol
99.5
ethylbenzene in the tops D 50 0.21 D 49.79 kmol
at 99.5 per cent purity, ethylbenzene in bottoms D
styrene in tops D 50 42.5 D 7.5 kmol
mol fraction ethylbenzene in tops D
zf D 0.5, xb D 0.005, xd D 0.87
49.79
D 0.87
49.79 C 7.5
Column bottom temperature, from Antoine equation for styrene
3328.57
T 63.72
T D 366 K, 93.3Ž C
ln 0.2 D 9.386
At 93.3Ž C, vapour pressure of ethylbenzene
3279.47
D 0.27 bar
366.4 59.95
PŽ ethylbenzene
0.27
Relative volatility D
D
D 1.35
Ž
P styrene
0.20
ln PŽ D 9.386
The relative volatility will change as the compositions and (particularly for a vacuum
column) the pressure changes up the column. The column pressures cannot be estimated
until the number of stages is known; so as a first trial the relative volatility will be taken
as constant, at the value determined by the bottom pressure.
Rectifying section
8
D 0.89
8C1
0.87
D 0.097
bD
8C1
0.89⊲1.35 1⊳k 2 C [0.89 C 0.097⊲1.35 1⊳ 1.35]k C 0.097 D 0
sD
⊲11.35⊳
⊲11.36⊳
⊲11.29⊳
k D 0.290
x0Ł D 0.87 0.29 D 0.58
⊲11.33⊳
D 0.50 0.29 D 0.21
⊲11.34⊳
xnŁ
c D 1 C ⊲1.35 1⊳0.29 D 1.10
ˇD
0.89 ð 1.10⊲1.35 1⊳
D 1.255
1.35 0.89 ð 1.12
⊲11.32⊳
⊲11.31⊳
515
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
0.58⊲1 1.255 ð 0.21⊳
1.35
N D log
log
0.21⊲1 1.255 ð 0.58⊳
0.89 ð 1.12
D
⊲11.30⊳
log 7.473
D 8.87, say 9
log 1.254
Stripping section, feed taken as at its bubble point
sD
bD
8 ð 0.5 C 0.87 ⊲8 C 1⊳0.005
D 1.084
⊲8 C 1⊳⊲0.5 0.005⊳
⊲0.5 0.87⊳0.005
D 4.15 ð 104 ⊲essentially zero⊳
⊲8 C 1⊳⊲0.5 0.005⊳
⊲11.39⊳
⊲11.40⊳
1.084⊲1.35 1⊳k 2 C [1.084 4.15 ð 104 ⊲1.35 1⊳ 1.35]k 4.15 ð 104
x0Ł
k D 0.702
D 0.5 0.702 D 0.202
xnŁ D 0.005 0.702 D 0.697
⊲11.29⊳
⊲11.37⊳
⊲11.38⊳
c D 1 C ⊲1.35 1⊳0.702 D 1.246
⊲11.32⊳
ˇD
⊲11.31⊳
1.084 ð 1.246⊲1.35 1⊳
D 1.42
1.35 1.084 ð 1.2462
1.35
0.202⊲1 0.697 ð 1.42⊳
log
N D log
0.697⊲1 0.202 ð 1.42⊳
1.084 ð 1.2462
D
⊲11.30⊳
log[4.17 ð 103 ]
D 24.6, say 25
log 0.8
11.6. MULTICOMPONENT DISTILLATION: GENERAL
CONSIDERATIONS
The problem of determining the stage and reflux requirements for multicomponent
distillations is much more complex than for binary mixtures. With a multicomponent
mixture, fixing one component composition does not uniquely determine the other
component compositions and the stage temperature. Also when the feed contains more
than two components it is not possible to specify the complete composition of the top
and bottom products independently. The separation between the top and bottom products
is specified by setting limits on two “key” components, between which it is desired to
make the separation.
The complexity of multicomponent distillation calculations can be appreciated by
considering a typical problem. The normal procedure is to solve the MESH equations
(Section 11.3.1) stage-by-stage, from the top and bottom of the column toward the feed
point. For such a calculation to be exact, the compositions obtained from both the bottomup and top-down calculations must mesh at the feed point and match the feed composition.
But the calculated compositions will depend on the compositions assumed for the top
and bottom products at the commencement of the calculations. Though it is possible to
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CHEMICAL ENGINEERING
match the key components, the other components will not match unless the designer was
particularly fortunate in choosing the trial top and bottom compositions. For a completely
rigorous solution the compositions must be adjusted and the calculations repeated until
a satisfactory mesh at the feed point is obtained. Clearly, the greater the number of
components, the more difficult the problem. As was shown in Section 11.3.2, trial-anderror calculations will be needed to determine the stage temperatures. For other than ideal
mixtures, the calculations will be further complicated by the fact that the component
volatilities will be functions of the unknown stage compositions. If more than a few
stages are required, stage-by-stage calculations are complex and tedious; as illustrated in
Example 11.9.
Before the advent of the modern digital computer, various “short-cut” methods were
developed to simplify the task of designing multicomponent columns. A comprehensive
summary of the methods used for hydrocarbon systems is given by Edmister (1947 to
1949) in a series of articles in the journal The Petroleum Engineer. Though computer
programs will normally be available for the rigorous solution of the MESH equations,
short-cut methods are still useful in the preliminary design work, and as an aid in defining
problems for computer solution. Intelligent use of the short-cut methods can reduce the
computer time and costs.
The short-cut methods available can be divided into two classes:
1. Simplification of the rigorous stage-by-stage procedures to enable the calculations to
be done by hand, or graphically. Typical examples of this approach are the methods
given by Smith and Brinkley (1960) and Hengstebeck (1976). These are described
in Section 11.7 and Hengstebeck’s method is illustrated by a worked example.
2. Empirical methods, which are based on the performance of operating columns, or
the results of rigorous designs. Typical examples of these methods are Gilliland’s
correlation, which is given in Volume 2, Chapter 11, and the Erbar-Maddox
correlation given in Section 11.7.3.
11.6.1. Key components
Before commencing the column design, the designer must select the two “key”
components between which it is desired to make the separation. The light key will
be the component that it is desired to keep out of the bottom product, and the heavy
key the component to be kept out of the top product. Specifications will be set on the
maximum concentrations of the keys in the top and bottom products. The keys are known
as “adjacent keys” if they are “adjacent” in a listing of the components in order of
volatility, and “split keys” if some other component lies between them in the order; they
will usually be adjacent.
Which components are the key components will normally be clear, but sometimes,
particularly if close boiling isomers are present, judgement must be used in their selection.
If any uncertainty exists, trial calculations should be made using different components as
the keys to determine the pair that requires the largest number of stages for separation (the
worst case). The Fenske equation can be used for these calculations; see Section 11.7.3.
The “non-key” components that appear in both top and bottom products are known as
“distributed” components; and those that are not present, to any significant extent, in one
or other product, are known as “non-distributed” components.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
517
11.6.2. Number and sequencing of columns
As was mentioned in Section 11.2, in multicomponent distillations it is not possible to
obtain more than one pure component, one sharp separation, in a single column. If a
multicomponent feed is to be split into two or more virtually pure products, several
columns will be needed. Impure products can be taken off as side streams; and the
removal of a side stream from a stage where a minor component is concentrated will
reduce the concentration of that component in the main product.
For separation of N components, with one essentially pure component taken overhead,
or from the bottom of each column, (N 1) columns will be needed to obtain complete
separation of all components. For example, to separate a mixture of benzene, toluene and
xylene two columns are needed (3 1). Benzene is taken overhead from the first column
and the bottom product, essentially free of benzene, is fed to the second column. This
column separates the toluene and xylene.
The order in which the components are separated will determine the capital and
operating costs. Where there are several components the number of possible sequences
can be very large; for example, with five components the number is 14, whereas with
ten components it is near 5000. When designing systems that require the separation of
several components, efficient procedures are needed to determine the optimum sequence
of separation; see Doherty and Malone (2001), Smith (1995) and Kumar (1982).
Procedures for the sequencing of columns are also available in the commercial
process simulator programs; for example, DISTIL in Hyprotech’s suite of programs (see
Chapter 4, Table 4.1).
In this section, it is only possible to give some general guide rules.
Heuristic rules for optimum sequencing
1. Remove the components one at a time; as in the benzene-toluene-xylene example.
2. Remove any components that are present in large excess early in the sequence.
3. With difficult separations, involving close boiling components, postpone the most
difficult separation to late in the sequence.
Difficult separations will require many stages, so to reduce cost, the column diameter
should be made a small as possible. Column diameter is dependent on flow-rate; see
Section 11.11. The further down the sequence the smaller will be the amount of material
that the column has to handle.
Tall columns
Where a large number of stages is required, it may be necessary to split a column into two
separate columns to reduce the height of the column, even though the required separation
could, theoretically, have been obtained in a single column. This may also be done in
vacuum distillations, to reduce the column pressure drop and limit the bottom temperatures.
11.7. MULTICOMPONENT DISTILLATION: SHORT-CUT
METHODS FOR STAGE AND REFLUX REQUIREMENTS
Some of the more useful short-cut procedures which can be used to estimate stage and
reflux requirements without the aid of computers are given in this section. Most of the
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CHEMICAL ENGINEERING
short-cut methods were developed for the design of separation columns for hydrocarbon
systems in the petroleum and petrochemical systems industries, and caution must be
exercised when applying them to other systems. They usually depend on the assumption
of constant relative volatility, and should not be used for severely non-ideal systems.
Short-cut methods for non-ideal and azeotropic systems are given by Featherstone
(1971) (1973).
11.7.1. Pseudo-binary systems
If the presence of the other components does not significantly affect the volatility of the
key components, the keys can be treated as a pseudo-binary pair. The number of stages
can then be calculated using a McCabe-Thiele diagram, or the other methods developed
for binary systems. This simplification can often be made when the amount of the non-key
components is small, or where the components form near-ideal mixtures.
Where the concentration of the non-keys is small, say less than 10 per cent, they can
be lumped in with the key components. For higher concentrations the method proposed
by Hengstebeck (1946) can be used to reduce the system to an equivalent binary system.
Hengstebeck’s method is outlined below and illustrated in Example 11.5. Hengstebeck’s
book (1976) should be consulted for the derivation of the method and further examples of its
application.
Hengstebeck’s method
For any component i the Lewis-Sorel material balance equations (Section 11.5) and
equilibrium relationship can be written in terms of the individual component molar flow
rates; in place of the component composition:
vnC1,i D ln,i C di
⊲11.42⊳
vn,i D Kn,i
V
ln,i
L
⊲11.43⊳
for the stripping section:
l0nC1,i D v0n,i C bi
V0 0
l
L 0 n,i
liquid flow rate of any component i from stage n,
vapour flow rate of any component i from stage n,
flow rate of component i in the tops,
flow rate of component i in the bottoms,
equilibrium constant for component i at stage n.
v0n,i D Kn,i
where ln,i
vn,i
di
bi
Kn,i
D
D
D
D
D
the
the
the
the
the
⊲11.44⊳
⊲11.45⊳
The superscript 0 denotes the stripping section.
V and L are the total flow-rates, assumed constant.
To reduce a multicomponent system to an equivalent binary it is necessary to estimate
the flow-rate of the key components throughout the column. Hengstebeck makes use of
the fact that in a typical distillation the flow-rates of each of the light non-key components
approaches a constant, limiting, rate in the rectifying section; and the flows of each of the
heavy non-key components approach limiting flow-rates in the stripping section. Putting
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
519
the flow-rates of the non-keys equal to these limiting rates in each section enables the
combined flows of the key components to be estimated.
Rectifying section
⊲11.46⊳
Le D L li
Stripping section
Ve D V vi
⊲11.47⊳
Le0 D L 0 l0i
⊲11.48⊳
V0e D V0 v0i
⊲11.49⊳
where Ve and Le are the estimated flow rates of the combined keys,
li and vi are the limiting liquid and vapour rates of components lighter than the
keys in the rectifying section,
0
0
li and vi are the limiting liquid and vapour rates of components heavier than the
keys in the stripping section.
The method used to estimate the limiting flow-rates is that proposed by Jenny (1939).
The equations are:
di
li D
⊲11.50⊳
˛i 1
vi D li C di
v0i D
˛i bi
˛LK ˛i
l0i D v0i C bi
⊲11.51⊳
⊲11.52⊳
⊲11.53⊳
where ˛i D relative volatility of component i, relative to the heavy key (HK),
˛LK D relative volatility of the light key (LK), relative to the heavy key.
Estimates of the flows of the combined keys enable operating lines to be drawn for the
equivalent binary system. The equilibrium line is drawn by assuming a constant relative
volatility for the light key:
˛LK x
⊲equation 11.23⊳
yD
1 C ⊲˛LK 1⊳x
where y and x refer to the vapour and liquid concentrations of the light key.
Hengstebeck shows how the method can be extended to deal with situations where
the relative volatility cannot be taken as constant, and how to allow for variations in the
liquid and vapour molar flow rates. He also gives a more rigorous graphical procedure
based on the Lewis-Matheson method (see Section 11.8).
Example 11.5
Estimate the number of ideal stages needed in the butane-pentane splitter defined by the
compositions given in the table below. The column will operate at a pressure of 8.3 bar,
with a reflux ratio of 2.5. The feed is at its boiling point.
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CHEMICAL ENGINEERING
Note: a similar problem has been solved by Lyster et al. (1959) using a rigorous
computer method and it was found that ten stages were needed.
Feed (f)
Tops (d)
5
15
25
20
35
5
15
24
1
0
0
0
1
19
35
100
45
55 kmol
Propane, C3
i-Butane, iC4
n-Butane, nC4
i-Pentane, iC5
n-Pentane, nC5
Bottoms (b)
Solution
The top and bottom temperatures (dew points and bubble points) were calculated by the
methods illustrated in Example 11.9. Relative volatilities are given by equation 8.30:
˛i D
Ki
KHK
Equilibrium constants were taken from the Depriester charts (Chapter 8).
Relative volatilities
Top
Bottom
Temp. C
65
120
C3
iC4
(LK) nC4
(HK) iC5
nC5
5.5
2.7
2.1
1.0
0.84
4.5
2.5
2.0
1.0
0.85
Ž
Average
5.0
2.6
2.0
1.0
0.85
Calculations of non-key flows
Equations 11.50, 11.51, 11.52, 11.53
C3
iC4
nC5
˛i
di
li D di /⊲˛i 1⊳
vi D li C di
5
2.6
5
15
1.3
9.4
6.3
24.4
li D 10.7
vi D 30.7
˛i
bi
v0i D ˛i bi /⊲˛LK ˛i ⊳
l0i D v0i C bi
0.85
35
25.9
60.9
v0i D 25.9
l0i D 60.9
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
521
Flows of combined keys
Le
Ve
V0e
Le0
D 2.5 ð 45 10.7 D 101.8
D ⊲2.5 C 1⊳45 30.7 D 126.8
D ⊲2.5 C 1⊳45 25.9 D 131.6
D ⊲2.5 C 1⊳45 C 55 60.9 D 151.6
⊲11.46⊳
⊲11.47⊳
⊲11.49⊳
⊲11.48⊳
Slope of top operating line
Le
101.8
D 0.8
D
Ve
126.8
Slope of bottom operating line
Le0
151.6
D
D 1.15
V0e
131.6
1
flow LK
D
D 0.05
xb D
flow (LK C HK)
19 C 1
24
xd D
D 0.96
24 C 1
25
xf D
D 0.56
25 C 20
2x
2x
D
yD
1 C ⊲2 1⊳x
1Cx
x 0 0.20 0.40 0.60 0.80 1.0
y
0
0.33
0.57
0.75
0.89
1.0
The McCabe-Thiele diagram is shown in Figure 11.10.
Twelve stages required; feed on seventh from base.
Figure 11.10.
McCabe-Thiele diagram for Example 11.5
⊲11.23⊳
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CHEMICAL ENGINEERING
11.7.2. Smith-Brinkley method
Smith and Brinkley developed a method for determining the distribution of components in
multicomponent separation processes. Their method is based on the solution of the finitedifference equations that can be written for multistage separation processes, and can be
used for extraction and absorption processes, as well as distillation. Only the equations
for distillation will be given here. The derivation of the equations is given by Smith and
Brinkley (1960) and Smith (1963). For any component i (suffix i omitted in the equation
for clarity)
⊲1 SrNr Ns ⊳ C R⊲1 Sr ⊳
b
D
f
⊲1 SrNr Ns ⊳ C R⊲1 Sr ⊳ C GSrNr Ns ⊲1 SsNs C1 ⊳
⊲11.54⊳
where b/fis the fractional split of the component between the feed and the bottoms, and:
Nr D number of equilibrium stages above the feed,
Ns D number of equilibrium stages below the feed,
Sr D stripping factor, rectifying section = Ki V/L,
Ss D stripping factor, stripping section = K0i V0 /L 0 ,
V and L are the total molar vapour and liquid flow rates, and the superscript 0
denotes the stripping section.
G depends on the condition of the feed.
If the feed is mainly liquid:
Gi D
K0i L 1 Sr
Ki L 0 1 Ss i
and the feed stage is added to the stripping section.
If the feed is mainly vapour:
L 1 Sr
Gi D 0
L 1 Ss i
⊲11.55⊳
⊲11.56⊳
Equation 11.54 is for a column with a total condenser. If a partial condenser is used
the number of stages in the rectifying section should be increased by one.
The procedure for using the Smith-Brinkley method is as follows:
1. Estimate the flow-rates L, V and L 0 , V0 from the specified component separations
and reflux ratio.
2. Estimate the top and bottom temperatures by calculating the dew and bubble points
for assumed top and bottom compositions.
3. Estimate the feed point temperature.
4. Estimate the average component K values in the stripping and rectifying sections.
5. Calculate the values of Sr,i for the rectifying section and Ss,i for the stripping section.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
523
6. Calculate the fractional split of each component, and hence the top and bottom
compositions.
7. Compare the calculated with the assumed values and check the overall column
material balance.
8. Repeat the calculation until a satisfactory material balance is obtained. The usual
procedure is to adjust the feed temperature up and down till a satisfactory balance
is obtained.
Examples of the application of the Smith-Brinkley method are given by Smith (1963).
This method is basically a rating method, suitable for determining the performance of
an existing column, rather than a design method, as the number of stages must be known.
It can be used for design by estimating the number of stages by some other method
and using equation 11.54 to determine the top and bottom compositions. The estimated
stages can then be adjusted and the calculations repeated until the required specifications
are achieved. However, the Geddes-Hengstebeck method for estimating the component
splits, described in Section 11.7.4, is easier to use and satisfactory for preliminary design.
11.7.3. Empirical correlations
The two most frequently used empirical methods for estimating the stage requirements
for multicomponent distillations are the correlations published by Gilliland (1940) and by
Erbar and Maddox (1961). These relate the number of ideal stages required for a given
separation, at a given reflux ratio, to the number at total reflux (minimum possible) and
the minimum reflux ratio (infinite number of stages).
Gilliland’s correlation is given in Volume 2, Chapter 11.
The Erbar-Maddox correlation is given in this section, as it is now generally considered
to give more reliable predictions. Their correlation is shown in Figure 11.11; which gives
the ratio of number of stages required to the number at total reflux, as a function of the
reflux ratio, with the minimum reflux ratio as a parameter. To use Figure 11.11, estimates
of the number of stages at total reflux and the minimum reflux ratio are needed.
Minimum number of stages (Fenske equation)
The Fenske equation (Fenske, 1932) can be used to estimate the minimum stages
required at total reflux. The derivation of this equation for a binary system is given
in Volume 2, Chapter 11. The equation applies equally to multicomponent systems and
can be written as:
xi
Nm xi
D ˛i
⊲11.57⊳
xr d
xr b
where [xi /xr ] D the ratio of the concentration of any component i to the concentration of
a reference component r, and the suffixes d and b denote the distillate
(tops) (d) and the bottoms (b),
Nm D minimum number of stages at total reflux, including the reboiler,
˛i D average relative volatility of the component i with respect to the
reference component.
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CHEMICAL ENGINEERING
Figure 11.11.
Erbar-Maddox correlation (Erbar and Maddox, 1961)
Normally the separation required will be specified in terms of the key components, and
equation 11.57 can be rearranged to give an estimate of the number of stages.
xHK
xLK
log
xHK d xLK b
⊲11.58⊳
Nm D
log ˛LK
where ˛LK is the average relative volatility of the light key with respect to the heavy
key, and xLK and xHK are the light and heavy key concentrations. The relative volatility
is taken as the geometric mean of the values at the column top and bottom temperatures.
To calculate these temperatures initial estimates of the compositions must be made, so
the calculation of the minimum number of stages by the Fenske equation is a trialand-error procedure. The procedure is illustrated in Example 11.7. If there is a wide
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
525
difference between the relative volatilities at the top and bottom of the column the use
of the average value in the Fenske equation will underestimate the number of stages. In
these circumstances, a better estimate can be made by calculating the number of stages
in the rectifying and stripping sections separately; taking the feed concentration as the
base concentration for the rectifying section and as the top concentration for the stripping
section, and estimating the average relative volatilities separately for each section. This
procedure will also give an estimate of the feed point location.
Winn (1958) has derived an equation for estimating the number of stages at total reflux,
which is similar to the Fenske equation, but which can be used when the relative volatility
cannot be taken as constant.
If the number of stages is known, equation 11.57 can be used to estimate the split of
components between the top and bottom of the column at total reflux. It can be written
in a more convenient form for calculating the split of components:
di
Nm dr
D ˛i
⊲11.59⊳
bi
br
where di and bi are the flow-rates of the component i in the tops and bottoms, dr and br
are the flow-rates of the reference component in the tops and bottoms.
Note: from the column material balance:
di C bi D fi
where fi is the flow rate of component i in the feed.
Minimum reflux ratio
Colburn (1941) and Underwood (1948) have derived equations for estimating the
minimum reflux ratio for multicomponent distillations. These equations are discussed
in Volume 2, Chapter 11. As the Underwood equation is more widely used it is presented
in this section. The equation can be stated in the form:
˛i xi,d
⊲11.60⊳
D Rm C 1
˛i
where ˛i D the relative volatility of component i with respect to some reference
component, usually the heavy key,
Rm D the minimum reflux ratio,
xi,d D concentration of component i in the tops at minimum reflux
and is the root of the equation:
˛i xi,f
D1q
˛i
⊲11.61⊳
where xi,f D the concentration of component i in the feed, and q depends on
the condition of the feed and was defined in Section 11.5.2.
The value of must lie between the values of the relative volatility of the light and heavy
keys, and is found by trial and error.
526
CHEMICAL ENGINEERING
In the derivation of equations 11.60 and 11.61 the relative volatilities are taken as
constant. The geometric average of values estimated at the top and bottom temperatures
should be used. This requires an estimate of the top and bottom compositions. Though
the compositions should strictly be those at minimum reflux, the values determined at
total reflux, from the Fenske equation, can be used. A better estimate can be obtained
by replacing the number of stages at total reflux in equation 11.59 by an estimate of
the actual number; a value equal to Nm /0.6 is often used. The Erbar-Maddox method of
estimating the stage and reflux requirements, using the Fenske and Underwood equations,
is illustrated in Example 11.7.
Feed-point location
A limitation of the Erbar-Maddox, and similar empirical methods, is that they do not
give the feed-point location. An estimate can be made by using the Fenske equation to
calculate the number of stages in the rectifying and stripping sections separately, but this
requires an estimate of the feed-point temperature. An alternative approach is to use the
empirical equation given by Kirkbride (1944):
xf,HK
B
xb,LK 2
Nr
log
D 0.206 log
⊲11.62⊳
Ns
D
xf,LK
xd,HK
where Nr
Ns
B
D
xf,HK
xf,LK
xd,HK
xb,LK
D
D
D
D
D
D
D
D
number of stages above the feed, including any partial condenser,
number of stages below the feed, including the reboiler,
molar flow bottom product,
molar flow top product,
concentration of the heavy key in the feed,
concentration of the light key in the feed,
concentration of the heavy key in the top product,
concentration of the light key if in the bottom product.
The use of this equation is illustrated in Example 11.8.
11.7.4. Distribution of non-key components (graphical method)
The graphical procedure proposed by Hengstebeck (1946), which is based on the Fenske
equation, is a convenient method for estimating the distribution of components between
the top and bottom products.
Hengstebeck and Geddes (1958) have shown that the Fenske equation can be written
in the form:
di
log
D A C C log ˛i
⊲11.63⊳
bi
Specifying the split of the key components determines the constants A and C in the
equation.
The distribution of the other components can be readily determined by plotting the
distribution of the keys against their relative volatility on log-log paper, and drawing a
straight line through these two points. The method is illustrated in Example 11.6.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
527
Yaws et al. (1979) have shown that the components distributions calculated by
equation 11.63 compare well with those obtained by rigorous plate by plate calculations.
Chang (1980) gives a computer program, based on the Geddes-Hengstebeck equation,
for the estimation of component distributions.
Example 11.6
Use the Geddes-Hengstebeck method to check the component distributions for the
separation specified in Example 11.5
Summary of problem, flow per 100 kmol feed
Component
C3
iC4
nC4 (LK)
iC5 (HK)
nC5
˛i
5
2.6
2.0
1.0
0.85
Feed (fi )
Distillate (di )
Bottoms (bi )
24
1
1
19
5
15
25
20
35
Solution
The average volatilities will be taken as those estimated in Example 11.5. Normally,
the volatilities are estimated at the feed bubble point, which gives a rough indication
of the average column temperatures. The dew point of the tops and bubble point of the
bottoms can be calculated once the component distributions have been estimated, and the
calculations repeated with a new estimate of the average relative volatilities, as necessary.
24
di
D 24
D
bi
1
di
1
For the heavy key,
D 0.053
D
bi
19
For the light key,
These values are plotted on Figure 11.12.
The distribution of the non-keys are read from Figure 11.12 at the appropriate relative
volatility and the component flows calculated from the following equations:
Overall column material balance
fi D di C bi
from which
di D
fi
bi
C1
di
bi D
fi
di
C1
bi
528
CHEMICAL ENGINEERING
Figure 11.12.
˛i
C3
iC4
nC4
iC5
nC5
5
2.6
2.0
1.0
0.85
Component Distribution (Example 11.6)
fi
5
15
25
20
35
di /bi
40,000
150
21
0.053
0.011
di
bi
5
14.9
24
1
0.4
0
0.1
1
19
34.6
As these values are close to those assumed for the calculation of the dew points and
bubble points in Example 11.5, there is no need to repeat with new estimates of the
relative volatilities.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
529
Example 11.7
For the separation specified in Example 11.5, evaluate the effect of changes in reflux
ratio on the number of stages required. This is an example of the application of the
Erbar-Maddox method.
Solution
The relative volatilities estimated in Example 11.5, and the component distributions calculated in Example 11.6 will be used for this example.
Summary of data
C3
iC4
nC4 (LK)
iC5 (HK)
nC5
˛i
fi
di
bi
5
2.6
2.0
1
0.85
5
15
25
20
35
5
14.9
24
1
0.4
0
0.1
1
19
34.6
100
D D 45.3
B D 54.7
Minimum number of stages; Fenske equation, equation 11.58:
19
24
log
1
1
Nm D
D 8.8
log 2
Minimum reflux ratio; Underwood equations 11.60 and 11.61.
This calculation is best tabulated.
As the feed is at its boiling point q D 1
˛i xi,f
D0
˛i
⊲11.61⊳
Try
xi,f
0.05
0.15
0.25
0.20
0.35
D 1.35
˛i
˛i xi,f
D 1.5
D 1.3
D 1.35
5
2.6
2.0
1
0.85
0.25
0.39
0.50
0.20
0.30
0.071
0.355
1.000
0.400
0.462
0.068
0.300
0.714
0.667
0.667
0.068
0.312
0.769
0.571
0.600
D 0.564
0.252
0.022
close enough
530
CHEMICAL ENGINEERING
Equation 11.60
xi,d
˛i
˛i xi,d
˛i xi,d /⊲˛i ⊳
0.11
0.33
0.53
0.02
0.01
5
2.6
2.0
1
0.85
0.55
0.86
1.08
0.02
0.01
0.15
0.69
1.66
0.06
0.02
D 2.42
Rm C 1 D 2.42
Rm D 1.42
1.42
Rm
D
D 0.59
⊲Rm C 1⊳
2.42
Specimen calculation, for R D 2.0
2
R
D D 0.66
⊲R C 1⊳
3
from Figure 11.11
Nm
D 0.56
N
8.8
ND
D 15.7
0.56
for other reflux ratios
R
N
2
15.7
3
11.9
4
10.7
5
10.4
6
10.1
Note: Above a reflux ratio of 4 there is little change in the number of stages required,
and the optimum reflux ratio will be near this value.
Example 11.8
Estimate the position of the feed point for the separation considered in Example 11.7, for
a reflux ratio of 3.
Solution
Use the Kirkbride equation, equation 11.62. Product distributions taken from
Example 11.6,
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
531
1
D 0.018
54.7
1
xd,HK D
D 0.022
45.3
Nr
0.018 2
54.7 0.20
log
D 0.206 log
Ns
45.3 0.25
0.022
Nr
D 0.206 log⊲0.65⊳
log
Ns
xb,LK D
Nr
D 0.91
Ns
for R D 3, N D 12
number of stages, excluding the reboiler D 11
Nr C Ns D 11
Ns D 11 Nr D 11 0.91Ns
Ns D
11
D 5.76, say 6
1.91
Checks with the method used in Example 11.5, where the reflux ratio was 2.5.
Example 11.9
This example illustrates the complexity and trial and error nature of stage-by-stage
calculation.
The same problem specification has been used in earlier examples to illustrate the
shortcut design methods.
A butane-pentane splitter is to operate at 8.3 bar with the following feed composition:
Propane,
Isobutane,
Normal butane,
Isopentane,
Normal pentane,
Light key
Heavy key
C3
iC4
nC4
iC5
nC5
nC4
iC5
xf
f mol/100 mol feed
0.05
0.15
0.25
0.20
0.35
5
15
25
20
35
For a specification of not more than 1 mol of the light key in the bottom product and
not more than 1 mol of the heavy key in the top product, and a reflux ratio of 2.5, make
a stage-by-stage calculation to determine the product composition and number of stages
required.
532
CHEMICAL ENGINEERING
Solution
Only sufficient trial calculations will be made to illustrate the method used. Basis
100 mol feed.
Estimation of dew and bubble points
Bubble point
Dew point
yi D
xi D
Ki xi D 1.0
yi
D 1.0
Ki
⊲11.5a⊳
⊲11.5b⊳
The K values, taken from the De Priester charts (Chapter 8), are plotted in Figure (a) for
easy interpolation.
Figure (a). K-values at 8.3 bar
To estimate the dew and bubble points, assume that nothing heavier than the heavy key
appears in the tops, and nothing lighter than the light key in the bottoms.
C3
C4
nC4
iC5
nC5
d
xd
b
xb
5
15
24
1
0
0.11
0.33
0.54
0.02
0
0
1
19
35
0.02
0.34
0.64
45
55
533
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Bubble-point calculation, bottoms
Try 100Ž C
C3
iC4
nC4
iC5
nC5
Try 120Ž C
xb
Ki
Ki xi
Ki
Ki xi
0.02
0.34
0.64
1.85
0.94
0.82
0.04
0.32
0.52
2.1
1.1
0.96
0.04
0.37
0.61
Ki xi D 0.88
temp. too low
1.02
close enough
Try 70Ž C
Try 60Ž C
Dew-point calculation, tops
C3
iC4
nC4
iC5
nC5
xd
Ki
yi /Ki
Ki
yi /Ki
0.11
0.33
0.54
0.02
2.6
1.3
0.9
0.46
0.04
0.25
0.60
0.04
2.20
1.06
0.77
0.36
0.24
0.35
0.42
0.01
yi /Ki D 0.94
temp. too high
1.02
close enough
Bubble-point calculation, feed (liquid feed)
Try 80Ž C
C3
iC4
nC4
iC5
nC5
Try 90Ž C
Try 85Ž C
xf
Ki
xi Ki
Ki
xi Ki
Ki
xi Ki
0.05
0.15
0.25
0.20
0.35
2.9
1.5
1.1
0.5
0.47
0.15
0.23
0.28
0.11
0.16
3.4
1.8
1.3
0.66
0.56
0.17
0.27
0.33
0.13
0.20
3.15
1.66
1.21
0.60
0.48
0.16
0.25
0.30
0.12
0.17
0.93
temp. too low
1.10
temp. too high
1.00
satisfactory
Stage-by-stage calculations
Top down calculations, assume total condensation with no subcooling
y1 D xd D x0
It is necessary to estimate the composition of the “non-keys” so that they can be included
in the stage calculations. As a first trial the following values will be assumed:
534
CHEMICAL ENGINEERING
C3
iC4
nC4
iC5
nC5
xd
d
0.10
0.33
0.54
0.02
0.001
5
15
24
1
0.1
45.1
In each stage calculation it will necessary to estimate the stage temperatures to
determine the K values and liquid and vapour enthalpies. The temperature range from
top to bottom of the column will be approximately 120 60 D 60Ž C. An approximate calculation (Example 11.7) has shown that around fourteen ideal stages will be
needed; so the temperature change from stage to stage can be expected to be around
4 to 5Ž C.
Stage 1
VI
To = 60˚C, Lo
xo
=
xd
TI?
yI
I
xI
y2
LI
V2
?
L0 D R ð D D 2.5 ð 45.1 D 112.8
V1 D ⊲R C 1⊳D D 3.5 ð 45.1 D 157.9
Estimation of stage temperature and outlet liquid composition (x1 )
C3
iC4
nC4
iC5
nC5
Try T1 D 66Ž C
Try T1 D 65Ž C
y1
Ki
yi /Ki
Ki
yi /Ki
x1 D yi /Ki
Normalised
0.10
0.33
0.54
0.02
0.001
2.40
1.20
0.88
0.42
0.32
0.042
0.275
0.614
0.048
0.003
2.36
1.19
0.86
0.42
0.32
0.042
0.277
0.628
0.048
0.003
0.042
0.278
0.629
0.048
0.003
yi /Ki D 0.982
too low
0.998
close enough
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
535
Summary of stage equations
L0 C V2 D L1 C V1
(i)
L0 x0 C V2 y2 D L1 x1 C V1 y1
(ii)
h0 L0 C H2 V2 D h1 L1 C H1 V1
(iii)
h D f⊲x, T⊳
H D f⊲x, T⊳
The enthalpy relationship is plotted in Figures ⊲b⊳ and ⊲c⊳.
yi D Ki xi
Figures ⊲b⊳ and ⊲c⊳.
(iv)
(v)
(vi)
Enthalpy kJ/mol (adapted from J. B. Maxwell, Data Book of Hydrocarbons (Van
Nostrand, 1962))
Before a heat balance can be made to estimate L1 and V2 , an estimate of y2 and T2 is
needed. y2 is dependent on the liquid and vapour flows, so as a first trial assume that
536
CHEMICAL ENGINEERING
these are constant and equal to L0 and V1 ; then, from equations (i) and (ii),
L0
⊲x1 x0 ⊳ C y1
y2 D
V1
112.8
L0
D
D 0.71
V1
157.9
C3
iC4
nC4
iC5
nC5
x1
x0
y2 D 0.71⊲x1 x0 ⊳ C y1
0.042
0.278
0.629
0.048
0.003
0.10
0.33
0.54
0.02
0.001
0.057
0.294
0.604
0.041
0.013
y2
Normalised
0.057
0.292
0.600
0.041
0.013
1.009
close enough
Enthalpy data from Figures ⊲b⊳ and (c) J/mol
h0 ⊲T0 D 60Ž C⊳
C3
iC4
nC4
iC5
nC5
h1 ⊲T1 D 65Ž C⊳
x0
hi
hi xi
x1
hi
hi xi
0.10
0.33
0.54
0.02
0.001
20,400
23,400
25,200
27,500
30,000
2040
7722
13,608
550
30
0.042
0.278
0.629
0.048
0.003
21,000
24,900
26,000
28,400
30,700
882
6897
16,328
1363
92
h0 D 23,950
C3
iC4
nC4
iC5
nC5
h1 D 25,562
H1 ⊲T1 D 65Ž C⊳
H2 ⊲T2 D 70Ž C assumed⊳
v1
Hi
Hi y i
y2
Hi
Hi y i
0.10
0.33
0.54
0.02
0.001
34,000
41,000
43,700
52,000
54,800
3400
13,530
23,498
1040
55
0.057
0.292
0.600
0.041
0.013
34,800
41,300
44,200
52,500
55,000
1984
12,142
26,697
2153
715
H1 D 41,623
H2 D 43,691
Energy balance (equation iii)
23,950 ð 112.8 C 43,691V2 D 25,562L1 C 41,623 ð 157.9
43,691V2 D 255,626L1 C 3,870,712
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
537
Material balance (equation i)
112.8 C V2 D L1 C 157.9
substituting
43,691⊲L1 C 45.1⊳ D 25,562L1 C 3,870,712
L1 D 104.8
V2 D 104.8 C 45.1 D 149.9
L1
D 0.70
V2
Could revise calculated values for y2 but L1 /V2 is close enough to assumed value of 0.71,
so there would be no significant difference from first estimate.
Stage 2
V2 = 149.6
LI = 104.5
xI (known)
y2 (known)
2
L2
x2
V3
y3
Estimation of stage temperature and outlet liquid composition (x2 ).
T2 D 70Ž C (use assumed value as first trial)
C3
iC4
nC4
iC5
nC5
y2
Ki
x2 D y2 /Ki
x2
Normalised
0.057
0.292
0.600
0.041
0.013
2.55
1.30
0.94
0.43
0.38
0.022
0.226
0.643
0.095
0.034
0.022
0.222
0.630
0.093
0.033
1.020
close enough to 1.0
y3 D
L
⊲x2 x1 ⊳ C y2
V
538
CHEMICAL ENGINEERING
As a first trial take L/V as L1 /V1 D 0.70
C3
iC4
nC4
iC5
nC5
x2
x1
y3 D 0.70⊲x2 x1 ⊳ C y2
y3
Normalised
0.022
0.222
0.630
0.093
0.033
0.042
0.277
0.628
0.048
0.003
0.044
0.256
0.613
0.072
0.035
0.043
0.251
0.601
0.072
0.034
1.020
Enthalpy data from Figures (b) and (c)
h2 ⊲T2 D 70Ž C⊳
C3
iC4
nC4
iC5
nC5
H3 ⊲T3 D 75Ž C assumed⊳
x2
hi
hi x2
y3
Hi
0.022
0.222
0.630
0.093
0.033
21,900
25,300
27,000
29,500
31,600
482
5617
17,010
2744
1043
0.043
0.251
0.601
0.072
0.035
34,600
41,800
44,700
53,000
55,400
h2 D 26,896
Hi y 3
1488
10,492
26,865
3816
1939
H3 D 44,600
Energy balance
25,562 ð 104.8 C 44,600V3 D 4369 ð 149.9 C 26,896L2
Material balance
104.8 C V3 D 149.9 C L2
L2 D 105.0
V3 D 150.1
L2
D 0.70 checks with assumed value.
V3
Stage 3
As the calculated liquid and vapour flows are not changing much from stage to stage the
calculation will be continued with the value of L/V taken as constant at 0.7.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Try T3 D 75Ž C (assumed value)
C3
iC4
nC4
iC5
nC5
Ki
x3 D y3 /Ki
Normalised
y4 D 0.7⊲x3 x2 ⊳ C y3
2.71
1.40
1.02
0.50
0.38
0.016
0.183
0.601
0.144
0.092
0.015
0.177
0.580
0.139
0.089
0.38
0.217
0.570
0.104
0.074
1.036
Close enough
1.003
Stage 4
Try T4 D 81Ž C
C3
iC4
nC4
iC5
nC5
Ki
x4 D y4 /Ki
Normalised
y5 D 0.7⊲x4 x3 ⊳ C y4
2.95
1.55
1.13
0.55
0.46
0.013
0.140
0.504
0.189
0.161
0.013
0.139
0.501
0.188
0.166
0.039
0.199
0.515
0.137
0.118
1.007
1.008
Close enough
Stage 5
Try T5 D 85Ž C
C3
iC4
nC4
iC5
nC5
Ki
x5
Normalised
y6 D 0.7⊲x5 x4 ⊳ C y5
3.12
1.66
1.20
0.60
0.46
0.013
0.120
0.430
0.228
0.257
0.012
0.115
0.410
0.218
0.245
0.038
0.179
0.450
0.159
0.192
1.048
1.018
Close enough
539
540
CHEMICAL ENGINEERING
Stage 6
Try T6 D 90Ž C
C3
iC4
nC4
iC5
nC5
Try T6 D 92Ž C
Ki
x6
Ki
x6
Normalised
y7
3.35
1.80
1.32
0.65
0.51
0.011
0.099
0.341
0.245
0.376
3.45
1.85
1.38
0.69
0.53
0.011
0.097
0.376
0.230
0.362
0.011
0.095
0.318
0.224
0.350
0.037
0.166
0.386
0.163
0.268
1.072
too low
1.026
close enough
Note: ratio of LK to HK in liquid from this stage D
1.020
0.386
D 2.37
0.163
Stage 7
Try T6 D 97Ž C
C3
iC4
nC4
iC5
nC5
Ki
x7
Normalised
3.65
1.98
1.52
0.75
0.60
0.010
0.084
0.254
0.217
0.447
0.010
0.083
0.251
0.214
0.442
1.012
ratio
LK
0.251
D
D 1.17
HK
0.214
This is just below the ratio in the feed
D
25
D 1.25
20
So, the feed would be introduced at this stage.
But the composition of the non-key components on the plate does not match the feed
composition.
C3
iC4
nC4
iC5
nC5
xf
x7
0.05
0.15
0.25
0.20
0.35
0.10
0.084
0.254
0.217
0.447
So it would be necessary to adjust the assumed top composition and repeat the calculation.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
541
Bottom-up calculation
To illustrate the procedure the calculation will be shown for the reboiler and bottom stage,
assuming constant molar overflow.
With the feed at its boiling point and constant molar overflow the base flows can be
calculated as follows:
V0 D V0 D 157.9
L 0 D L0 C FEED D 112.8 C 100 D 212.8
V0
157.9
D
D 0.74
0
L
212.8
B1
V'
L'
It will be necessary to estimate the concentration of the non-key components in the
bottom product; as a first trial take:
iC4
0.001
C3
0.001
nC4
0.02
iC5
0.34
nC5
0.64
Reboiler
Check bubble-point estimate of 120Ž C
Try 120Ž C
C3
iC4
nC4
iC5
nC5
Try 118Ž C
xB
Ki
yB D Ki xB
Ki
yB
0.001
0.001
0.02
0.34
0.64
4.73
2.65
2.10
1.10
0.96
0.005
0.003
0.042
0.374
0.614
4.60
2.58
2.03
1.06
0.92
0.005
0.003
0.041
0.360
0.589
1.038
too high
0.998
close enough
yB
v' = 157.9
L' = 212.8
xBI
B = 55
xB
542
CHEMICAL ENGINEERING
Material balance:
xB1 L 0 D yB V0 C xB B
B
V0
yB C 0 xB
0
L
L
157.9
55
yB C
xB
D
212.8
212.8
D 0.74yB C 0.26xB
xB1 D
xB1
Stage 1 from base (B1)
C3
iC4
nC4
iC5
nC5
xB
yB
xB1
xB2 D 0.74⊲y1B yB ⊳ C x1B
0.001
0.001
0.02
0.34
0.64
0.005
0.003
0.041
0.361
0.590
0.004
0.002
0.020
0.356
0.603
0.014
0.036
0.019
0.357
0.559
0.985
The calculation is continued stage-by-stage up the column to the feed point (stage 7 from
the top). If the vapour composition at the feed point does not mesh with the top-down
calculation, the assumed concentration of the non-keys in the bottom product is adjusted
and the calculations repeated.
11.8. MULTICOMPONENT SYSTEMS: RIGOROUS SOLUTION
PROCEDURES (COMPUTER METHODS)
The application of digital computers has made the rigorous solution of the MESH equations
(Section 11.3.1) a practical proposition, and computer methods for the design of multicomponent separation columns will be available in most design organisations. Programs,
and computer time, can also be rented from commercial computing bureaux. A considerable amount of work has been done over the past twenty or so years to develop efficient
and reliable computer-aided design procedures for distillation and other staged processes.
A detailed discussion of this work is beyond the scope of this book and the reader is
referred to the specialist books that have been published on the subject, Smith (1963),
Holland (1997) and Kister (1992), and to the numerous papers that have appeared in the
chemical engineering literature. A good summary of the present state of the art is given
by Haas (1992).
Several different approaches have been taken to develop programs that are efficient in
the use of computer time, and suitable for the full range of multicomponent separation
processes that are used in the process industries. A design group will use those methods
that are best suited to the processes that it normally handles.
In this section only a brief outline of the methods that have been developed will be
given.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
543
The basic steps in any rigorous solution procedure will be:
1. Specification of the problem; complete specification is essential for computer
methods.
2. Selection of values for the iteration variables; for example, estimated stage temperatures, and liquid and vapour flows (the column temperature and flow profiles).
3. A calculation procedure for the solution of the stage equations.
4. A procedure for the selection of new values for the iteration variables for each set
of trial calculations.
5. A procedure to test for convergence; to check if a satisfactory solution has been
achieved.
It is convenient to consider the methods available under the following four headings:
1.
2.
3.
4.
Lewis-Matheson method.
Thiele-Geddes method.
Relaxation methods.
Linear algebra methods.
Rating and design methods
With the exception of the Lewis-Matheson method, all the methods listed above require the
specification of the number of stages below and above the feed point. They are therefore
not directly applicable to design: where the designer wants to determine the number of
stages required for a specified separation. They are strictly what are referred to as “rating
methods”; used to determine the performance of existing, or specified, columns. Given the
number of stages they can be used to determine product compositions. Iterative procedures
are necessary to apply rating methods to the design of new columns. An initial estimate
of the number of stages can be made using short-cut methods and the programs used to
calculate the product compositions; repeating the calculations with revised estimates till
a satisfactory design is obtained.
11.8.1. Lewis-Matheson method
The method proposed by Lewis and Matheson (1932) is essentially the application of
the Lewis-Sorel method (Section 11.5.1) to the solution of multicomponent problems.
Constant molar overflow is assumed and the material balance and equilibrium relationship
equations are solved stage by stage starting at the top or bottom of the column, in the
manner illustrated in Example 11.9. To define a problem for the Lewis-Matheson method
the following variables must be specified, or determined from other specified variables:
Feed composition, flow rate and condition.
Distribution of the key components.
One product flow.
Reflux ratio.
Column pressure.
Assumed values for the distribution of the non-key components.
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CHEMICAL ENGINEERING
The usual procedure is to start the calculation at the top and bottom of the column and
proceed toward the feed point. The initial estimates of the component distributions in the
products are then revised and the calculations repeated until the compositions calculated
from the top and bottom starts mesh, and match the feed at the feed point.
Efficient procedures for adjusting the compositions to achieve a satisfactory mesh at
the feed point are given by Hengstebeck (1976).
In some computer applications of the method, where the assumption of constant molar
overflow is not made, it is convenient to start the calculations by assuming flow and
temperature profiles. The stage component compositions can then be readily determined
and used to revise the profiles for the next iteration. With this modification the procedure
is similar to the Thiele-Geddes method discussed in the next section.
In general, the Lewis-Matheson method has not been found to be an efficient procedure
for computer solutions, other than for relatively straightforward problems. It is not suitable
for problems involving multiple feeds, and side-streams, or where more than one column
is needed.
The method is suitable for interactive programs run on programmable calculators and
Personal Computers. Such programs can be “semi-manual” in operation: the computer
solving the stage equations, while control of the iteration variables, and convergence is
kept by the designer. As the calculations are carried out one stage at a time, only a
relatively small computer memory is needed.
11.8.2. Thiele-Geddes method
Like the Lewis-Matheson method, the original method of Thiele and Geddes (1933) was
developed for manual calculation. It has subsequently been adapted by many workers
for computer applications. The variables specified in the basic method, or that must be
derived from other specified variables, are:
Reflux temperature.
Reflux flow rate.
Distillate rate.
Feed flows and condition.
Column pressure.
Number of equilibrium stages above and below the feed point.
The basic procedure used in the Thiele-Geddes method, with examples, is described in
books by Smith (1963) and Deshpande (1985). The application of the method to computers
is covered in a series of articles by Lyster et al. (1959) and Holland (1963).
The method starts with an assumption of the column temperature and flow profiles. The
stage equations are then solved to determine the stage component compositions and the
results used to revise the temperature profiles for subsequent trial calculations. Efficient
convergence procedures have been developed for the Thiele-Geddes method. The so-called
“theta method”, described by Lyster et al. (1959) and Holland (1963), is recommended.
The Thiele-Geddes method can be used for the solution of complex distillation problems,
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
545
and for other multi-component separation processes. A series of programs for the solution
of problems in distillation, extraction, stripping and absorption, which use an iterative
procedure similar to the Thiele-Geddes method, are given by Hanson et al. (1962).
11.8.3. Relaxation methods
With the exception of this method, all the methods described solve the stage equations for
the steady-state design conditions. In an operating column other conditions will exist at
start-up, and the column will approach the “design” steady-state conditions after a period
of time. The stage material balance equations can be written in a finite difference form,
and procedures for the solution of these equations will model the unsteady-state behaviour
of the column.
Rose et al. (1958) and Hanson and Sommerville (1963) have applied “relaxation
methods” to the solution of the unsteady-state equations to obtain the steady-state values.
The application of this method to the design of multistage columns is described by
Hanson and Sommerville (1963). They give a program listing and worked examples
for a distillation column with side-streams, and for a reboiled absorber.
Relaxation methods are not competitive with the “steady-state” methods in the use of
computer time, because of slow convergence. However, because they model the actual
operation of the column, convergence should be achieved for all practical problems. The
method has the potential of development for the study of the transient behaviour of column
designs, and for the analysis and design of batch distillation columns.
11.8.4. Linear algebra methods
The Lewis-Matheson and Thiele-Geddes methods use a stage-by-stage procedure to solve
the equations relating the component compositions to the column temperature and flow
profiles. However, the development of high-speed digital computers with large memories
makes possible the simultaneous solution of the complete set of MESH equations that
describe the stage compositions throughout the column.
If the equilibrium relationships and flow-rates are known (or assumed) the set of
material balance equations for each component is linear in the component compositions.
Amundson and Pontinen (1958) developed a method in which these equations are solved
simultaneously and the results used to provide improved estimates of the temperature and
flow profiles. The set of equations can be expressed in matrix form and solved using
the standard inversion routines available in modern computer systems. Convergence can
usually be achieved after a few iterations.
This approach has been further developed by other workers; notably Wang and Henke
(1966) and Naphtali and Sandholm (1971).
The linearisation method of Naphtali and Sandholm has been used by Fredenslund et al.
(1977) for the multicomponent distillation program given in their book. Included in their
book, and coupled to the distillation program, are methods for estimation of the liquidvapour relationships (activity coefficients) using the UNIFAC method (see Chapter 8,
Section 16.3). This makes the program particularly useful for the design of columns for
546
CHEMICAL ENGINEERING
new processes, where experimental data for the equilibrium relationships are unlikely to
be available. The program is recommended to those who do not have access to their own
“in house” programs.
11.9. OTHER DISTILLATION SYSTEMS
11.9.1. Batch distillation
In batch distillation the mixture to be distilled is charged as a batch to the still and
the distillation carried out till a satisfactory top or bottom product is achieved. The still
usually consists of a vessel surmounted by a packed or plate column. The heater may
be incorporated in the vessel or a separate reboiler used. Batch distillation should be
considered under the following circumstances:
1.
2.
3.
4.
Where
Where
Where
Where
the quantity to be distilled is small.
a range of products has to be produced.
the feed is produced at irregular intervals.
the feed composition varies over a wide range.
Where the choice between batch and continuous is uncertain an economic evaluation of
both systems should be made.
Batch distillation is an unsteady state process, the composition in the still (bottoms)
varying as the batch is distilled.
Two modes of operation are used.
1. Fixed reflux, where the reflux rate is kept constant. The compositions will vary
as the more volatile component is distilled off, and the distillation stopped when
the average composition of the distillate collected, or the bottoms left, meet the
specification required.
2. Variable reflux, where the reflux rate is varied throughout the distillation to produce a
fixed overhead composition. The reflux ratio will need to be progressively increased
as the fraction of the more volatile component in the base of the still decreases.
The basic theory of batch distillation is given in Volume 2, Chapter 11 and in several other
texts: Hart (1997), Perry et al. (1997) and Walas (1990). In the simple theoretical analysis
of batch distillation columns the liquid hold-up in the column is usually ignored. This
hold-up can have a significant effect on the separating efficiency and should be taken
into account when designing batch distillation columns. The practical design of batch
distillation columns is covered by Hengstebeck (1976), Ellerbe (1997) and Hart (1997).
11.9.2. Steam distillation
In steam distillation, steam is introduced into the column to lower the partial pressure
of the volatile components. It is used for the distillation of heat sensitive products and
for compounds with a high boiling point. It is an alternative to vacuum distillation.
The products must be immiscible with water. Some steam will normally be allowed to
condense to provide the heat required for the distillation. Live steam can be injected
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
547
directly into the column base, or the steam generated by a heater in the still or in an
external boiler.
The design procedures for columns employing steam distillation is essentially the same
as that for conventional columns, making allowance for the presence of steam in the
vapour; see Volume 2, Chapter 11.
Steam distillation is used extensively in the extraction of essential oils from plant
materials.
11.9.3. Reactive distillation
Reactive distillation is the name given to the process where the chemical reaction and
product separation are carried out simultaneously in one unit. Carrying out the reaction, with
separation and purification of the product by distillation, gives the following advantages:
1. Chemical equilibrium restrictions are overcome, as the product is removed as it
is formed.
2. Energy savings can be obtained, as the heat of reaction can be utilised for the
distillation.
3. Capital costs are reduced, as only one vessel is required.
The design of reactive distillation columns is complicated by the complex interactions
between the reaction and separation processes. A comprehensive discussion of the process
is given by Sundmacher and Kiene (2003).
Reactive distillation is used in the production of MTBE (methyl tertiary butyl ether)
and methyl acetate.
11.10. PLATE EFFICIENCY
The designer is concerned with real contacting stages; not the theoretical equilibrium
stage assumed for convenience in the mathematical analysis of multistage processes.
Equilibrium will rarely be attained in a real stage. The concept of a stage efficiency is
used to link the performance of practical contacting stages to the theoretical equilibrium
stage.
Three principal definitions of efficiency are used:
1. Murphree plate efficiency (Murphree, 1925), defined in terms of the vapour
compositions by:
yn yn1
⊲11.64⊳
EmV D
ye yn1
where ye is the composition of the vapour that would be in equilibrium with the
liquid leaving the plate. The Murphree plate efficiency is the ratio of the actual
separation achieved to that which would be achieved in an equilibrium stage (see
Figure 11.6). In this definition of efficiency the liquid and the vapour stream are
taken to be perfectly mixed; the compositions in equation 11.64 are the average
composition values for the streams.
2. Point efficiency (Murphree point efficiency). If the vapour and liquid compositions
are taken at a point on the plate, equation 11.64 gives the local or point
efficiency, Emv .
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CHEMICAL ENGINEERING
3. Overall column efficiency. This is sometimes confusingly referred to as the overall
plate efficiency.
number of ideal stages
Eo D
⊲11.65⊳
number of real stages
An estimate of the overall column efficiency will be needed when the design method used
gives an estimate of the number of ideal stages required for the separation.
In some methods, the Murphree plate efficiencies can be incorporated into the procedure
for calculating the number of stages and the number of real stages determined directly.
For the idealised situation where the operating and equilibrium lines are straight, the
overall column efficiency and the Murphree plate efficiency are related by an equation
derived by Lewis (1936):
mV
log 1 C EmV
1
L
⊲11.66⊳
E0 D
mV
log
L
where m D slope of the equilibrium line,
V D molar flow rate of the vapour,
L D molar flow rate of the liquid.
Equation 11.66 is not of much practical use in distillation, as the slopes of the operating
and equilibrium lines will vary throughout the column. It can be used by dividing the
column into sections and calculating the slopes over each section. For most practical
purposes, providing the plate efficiency does not vary too much, a simple average of the
plate efficiency calculated at the column top, bottom and feed points will be sufficiently
accurate.
11.10.1. Prediction of plate efficiency
Whenever possible the plate efficiencies used in design should be based on experimental
values for similar systems, obtained on full-sized columns. There is no entirely satisfactory
method for predicting plate efficiencies from the system physical properties and plate
design parameters. However, the methods given in this section can be used to make a
rough estimate where no reliable experimental values are available. They can also be
used to extrapolate data obtained from small-scale experimental columns. If the system
properties are at all unusual, experimental confirmation of the predicted values should
always be obtained. The small, laboratory scale, glass sieve plate column developed
by Oldershaw (1941) has been shown to give reliable values for scale-up. The use of
Oldershaw columns is described in papers by Swanson and Gester (1962), Veatch et al.
(1960) and Fair et al. (1983).
Some typical values of plate efficiency for a range of systems are given in Table 11.1.
More extensive compilations of experimental data are given by Vital et al. (1984) and
Kister (1992).
Plate, and overall column, efficiencies will normally be between 30 per cent and 70 per
cent, and as a rough guide a figure of 50 per cent can be assumed for preliminary designs.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Table 11.1.
549
Representative efficiencies, sieve plates
System
Water-methanol
Water-ethanol
Water-isopropanol
Water-acetone
Water-acetic acid
Water-ammonia
Water-carbon dioxide
Toluene-propanol
Toluene-ethylene dichloride
Toluene-methylethylketone
Toluene-cyclohexane
Toluene-methylcyclohexane
Toluene-octane
Heptane-cyclohexane
Propane-butane
Isobutane-n-butane
Benzene-toluene
Benzene-methanol
Benzene-propanol
Ethylbenzene-styrene
Column
dia., m
Pressure
kPa, abs
1.0
0.2
101
Efficiency %
EmV
Eo
80
90
70
0.15
0.46
0.3
0.08
0.46
0.05
0.15
2.4
0.15
1.2
2.4
90
101
101
80
75
90
80
65
101
27
101
165
165
95
2070
0.13
0.18
0.46
690
75
85
70
90
40
85
75
100
110
75
94
55
75
EmV D Murphree plate efficiency,
Eo D Overall column efficiency.
Efficiencies will be lower for vacuum distillations, as low weir heights are used to keep
the pressure drop small (see Section 11.10.4).
Multicomponent systems
The prediction methods given in the following sections, and those available in the open
literature, are invariably restricted to binary systems. It is clear that in a binary system
the efficiency obtained for each component must be the same. This is not so for a
multicomponent system; the heavier components will usually exhibit lower efficiencies
than the lighter components.
The following guide rules, adapted from a paper by Toor and Burchard (1960), can be
used to estimate the efficiencies for a multicomponent system from binary data:
1. If the components are similar, the multicomponent efficiencies will be similar to the
binary efficiency.
2. If the predicted efficiencies for the binary pairs are high, the multicomponent
efficiency will be high.
3. If the resistance to mass transfer is mainly in the liquid phase, the difference between
the binary and multicomponent efficiencies will be small.
4. If the resistance is mainly in the vapour phase, as it normally will be, the difference
between the binary and multicomponent efficiencies can be substantial.
The prediction of efficiencies for multicomponent systems is also discussed by Chan and
Fair (1984b). For mixtures of dissimilar compounds the efficiency can be very different
550
CHEMICAL ENGINEERING
from that predicted for each binary pair, and laboratory or pilot-plant studies should be
made to confirm any predictions.
11.10.2. O’Connell’s correlation
A quick estimate of the overall column efficiency can be obtained from the correlation
given by O’Connell (1946), which is shown in Figure 11.13. The overall column efficiency
is correlated with the product of the relative volatility of the light key component (relative
to the heavy key) and the molar average viscosity of the feed, estimated at the average
column temperature. The correlation was based mainly on data obtained with hydrocarbon
systems, but includes some values for chlorinated solvents and water-alcohol mixtures. It
has been found to give reliable estimates of the overall column efficiency for hydrocarbon
systems; and can be used to make an approximate estimate of the efficiency for other
systems. The method takes no account of the plate design parameters; and includes only
two physical property variables.
Eduljee (1958) has expressed the O’Connell correlation in the form of an equation:
Eo D 51 32.5 log⊲a ˛a ⊳
⊲11.67⊳
where a D the molar average liquid viscosity, mNs/m2 ,
˛a D average relative volatility of the light key.
Absorbers
O’Connell gave a similar correlation for the plate efficiency of absorbers; Figure 11.14.
Appreciably lower plate efficiencies are obtained in absorption than in distillation.
Figure 11.13.
Distillation column efficiencies (bubble-caps) (after O’Connell, 1946)
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Figure 11.14.
551
Absorber column efficiencies (bubble-caps) (after O’Connell, 1946)
In O’Connell’s paper, the plate efficiency is correlated with a function involving Henry’s
constant, the total pressure, and the solvent viscosity at the operating temperature.
To convert the original data to SI units, it is convenient to express this function in the
following form:
s P
s
x D 0.062
D 0.062
⊲11.68⊳
s HMs
s KMs
where H
P
s
Ms
s
K
D
D
D
D
D
D
the Henry’s law constant, Nm2 /mol fraction,
total pressure, N/m2 ,
solvent viscosity, mNs/m2 ,
molecular weight of the solvent,
solvent density, kg/m3 ,
equilibrium constant for the solute.
Example 11.10
Using O’Connell’s correlation, estimate the overall column efficiency and the number of
real stages required for the separation given in Example 11.5.
Solution
From Example 11.5, feed composition, mol fractions:
propane 0.05, i-butane 0.15, n-butane 0.25, i-pentane 0.20, n-pentane 0.35.
552
CHEMICAL ENGINEERING
Ž
Column-top temperature 65 C, bottom temperature 120Ž C.
Average relative volatility light key D 2.0
Take the viscosity at the average column temperature, 93Ž C,
viscosities, propane D 0.03 mNs/m2
butane D 0.12 mNs/m2
pentane D 0.14 mNs/m2
For feed composition, molar average viscosity D 0.03 ð 0.05 C 0.12⊲0.15 C 0.25⊳
C 0.14⊲0.20 C 0.35⊳
D 0.13 mNs/m2
˛a a D 2.0 ð 0.13 D 0.26
From Figure 11.13, Eo D 70 per cent
From Example 11.4, number of ideal stages D 12, one ideal stage will be the reboiler,
so number of actual stages
⊲12 1⊳
D 16
D
0.7
11.10.3. Van Winkle’s correlation
Van Winkle et al. (1972) have published an empirical correlation for the plate efficiency
which can be used to predict plate efficiencies for binary systems. Their correlation uses
dimensionless groups that include those system variables and plate parameters that are
known to affect plate efficiency. They give two equations, the simplest, and that which
they consider the most accurate, is given below. The data used to derive the correlation
covered both bubble-cap and sieve plates.
EmV D 0.07Dg0.14 Sc0.25 Re0.08
where Dg
uv
L
L
Sc
L
DLK
Re
hw
v
D
D
D
D
D
D
D
D
D
D
surface tension number D (L /L uv ),
superficial vapour velocity,
liquid surface tension,
liquid viscosity,
liquid Schmidt number D (L /L DLK ),
liquid density,
liquid diffusivity, light key component,
Reynolds number D (hw uv v /L (FA)),
weir height,
vapour density,
(FA) D fractional area D
(area of holes or risers)
(total column cross-sectional area)
The use of this method is illustrated in Example 11.13.
⊲11.69⊳
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
553
11.10.4. AIChE method
This method of predicting plate efficiency, published in 1958, was the result of a five-year
study of bubble-cap plate efficiency directed by the Research Committee of the American
Institute of Chemical Engineers.
The AIChE method is the most detailed method for predicting plate efficiencies that is
available in the open literature. It takes into account all the major factors that are known
to affect plate efficiency; this includes:
The
The
The
The
mass transfer characteristics of the liquid and vapour phases.
design parameters of the plate.
vapour and liquid flow-rates.
degree of mixing on the plate.
The method is well established, and in the absence of experimental values, or proprietary
prediction methods, should be used when more than a rough estimate of efficiency is
needed.
The approach taken is semi-empirical. Point efficiencies are estimated making use of
the “two-film theory”, and the Murphree efficiency estimated allowing for the degree of
mixing likely to be obtained on real plates.
The procedure and equations are given in this section without discussion of the
theoretical basis of the method. The reader should refer to the AIChE manual, AIChE
(1958); or to Smith (1963) who gives a comprehensive account of the method, and extends
its use to sieve plates. A brief discussion of the method is given in Volume 2; to which
reference can be made for the definition of any unfamiliar terms used in the equations.
Chan and Fair (1984a) have published an alternative method for point efficiencies on
sieve plates which they demonstrate gives closer predictions than the AIChE method.
AIChE method
The mass transfer resistances in the vapour and liquid phases are expressed in terms of
the number of transfer units, NG and NL . The point efficiency is related to the number of
transfer units by the equation:
1
mV
1
1
C
⊲11.70⊳
D
ð
ln⊲1 Emv ⊳
NG
L
NL
where m is the slope of the operating line and V and L the vapour and liquid molar flow
rates.
Equation 11.70 is plotted in Figure 11.15.
The number of gas phase transfer units is given by:
NG D
⊲0.776 C 4.57 ð 103 hw 0.24Fv C 105Lp ⊳
v 0.5
v Dv
where hw D weir height, mm,
p
Fv D the column vapour “F” factor = ua v ,
⊲11.71⊳
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CHEMICAL ENGINEERING
Figure 11.15.
Relationship between point efficiency and number of liquid and vapour transfer units
(Equation 11.70)
ua D vapour velocity based on the active tray area (bubbling area), see
Section 11.13.2, m/s,
Lp D the volumetric liquid flow rate across the plate, divided by the average width
of the plate, m3 /sm. The average width can be calculated by dividing the
active area by the length of the liquid path ZL ,
v D vapour viscosity, Ns/m2 ,
v D vapour density; kg/m3 ,
Dv D vapour diffusivity, m2 /s.
The number of liquid phase transfer units is given by:
NL D ⊲4.13 ð 108 DL ⊳0.5 ⊲0.21Fv C 0.15⊳tL
⊲11.72⊳
where DL D liquid phase diffusivity, m2 /s,
tL D liquid contact time, s,
given by:
tL D
Zc ZL
Lp
⊲11.73⊳
where ZL D length of the liquid path, from inlet downcomer to outlet weir, m,
Zc D liquid hold-up on the plate, m3 per m2 active area,
given by:
for bubble-cap plates
Zc D 0.042 C 0.19 ð 103 hw 0.014Fv C 2.5Lp
⊲11.74⊳
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
555
for sieve plates
Zc D 0.006 C 0.73 ð 103 hw 0.24 ð 103 Fv hw C 1.22Lp
⊲11.75⊳
The Murphree efficiency EmV is only equal to the point efficiency Emv if the liquid on
the plate is perfectly mixed. On a real plate this will not be so, and to estimate the plate
efficiency from the point efficiency some means of estimating the degree of mixing is
needed. The dimensionless Peclet number characterises the degree of mixing in a system.
For a plate the Peclet number is given by:
Pe D
Z2L
D e tL
⊲11.76⊳
where De is the “eddy diffusivity”, m2 /s.
A Peclet number of zero indicates perfect mixing and a value of 1 indicates plug flow.
For bubble-cap and sieve plates the eddy diffusivity can be estimated from the equation:
De D ⊲0.0038 C 0.017ua C 3.86Lp C 0.18 ð 103 hw ⊳2
⊲11.77⊳
The relation between the plate efficiency and point efficiency with the Peclet number as
a parameter is shown in Figure 11.16a and b. The application of the AIChE method is
illustrated in Example 11.12.
Figure 11.16.
Relationship between plate and point efficiency
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CHEMICAL ENGINEERING
Estimation of physical properties
To use the AIChE method, and Van Winkle’s correlation, estimates of the physical
properties are required. It is unlikely that experimental values will be found in the literature
for all systems that are of practical interest. The prediction methods given in Chapter 8,
and in the references given in that chapter, can be used to estimate values.
The AIChE design manual recommends the Wilke and Chang (1955) equation for
liquid diffusivities and the Wilke and Lee (1955) modification to the Hirschfelder, Bird
and Spotz equation for gas diffusivities.
Plate design parameters
The significance of the weir height in the AIChE equations should be noted. The weir height
was the plate parameter found to have the most significant effect on plate efficiency. Increasing
weir height will increase the plate efficiency, but at the expense of an increase in pressure
drop and entrainment. Weir heights will normally be in the range 40 to 100 mm for columns
operating at and above atmospheric pressure, but will be as low as 6 mm for vacuum columns.
This, in part, accounts for the lower plate efficiencies obtained in vacuum columns.
The length of the liquid path ZL is taken into account when assessing the plate-mixing
performance. The mixing correlation given in the AIChE method was not tested on largediameter columns, and Smith (1963) states that the correlation should not be used for largediameter plates. However, on a large plate the liquid path will normally be subdivided,
and the value of ZL will be similar to that in a small column.
The vapour “F” factor Fv is a function of the active tray area. Increasing Fv decreases
the number of gas-phase transfer units. The liquid flow term Lp is also a function of the
active tray area, and the liquid path length. It will only have a significant effect on the
number of transfer units if the path length is long. In practice the range of values for Fv ,
the active area, and the path length will be limited by other plate design considerations.
Multicomponent systems
The AIChE method was developed from measurements on binary systems. The AIChE
manual should be consulted for advice on its application to multicomponent systems.
11.10.5. Entrainment
The AIChE method, and that of Van Winkle, predict the “dry” Murphree plate efficiency.
In operation some liquid droplets will be entrained and carried up the column by the
vapour flow, and this will reduce the actual, operating, efficiency.
The dry-plate efficiency can be corrected for the effects of entrainment using the
equation proposed by Colburn (1936):
Ea D
EmV
1 C EmV
1
where Ea D actual plate efficiency, allowing for entrainment,
D the fractional entrainment D
entrained liquid
.
gross liquid flow
⊲11.78⊳
557
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Methods for predicting the entrainment from sieve plates are given in Section 11.13.5,
Figure 11.27; a similar method for bubble-cap plates is given by Bolles (1963).
11.11. APPROXIMATE COLUMN SIZING
An approximate estimate of the overall column size can be made once the number of
real stages required for the separation is known. This is often needed to make a rough
estimate of the capital cost for project evaluation.
Plate spacing
The overall height of the column will depend on the plate spacing. Plate spacings from
0.15 m (6 in.) to 1 m (36 in.) are normally used. The spacing chosen will depend on
the column diameter and operating conditions. Close spacing is used with small-diameter
columns, and where head room is restricted; as it will be when a column is installed in a
building. For columns above 1 m diameter, plate spacings of 0.3 to 0.6 m will normally
be used, and 0.5 m (18 in.) can be taken as an initial estimate. This would be revised, as
necessary, when the detailed plate design is made.
A larger spacing will be needed between certain plates to accommodate feed and sidestreams arrangements, and for manways.
Column diameter
The principal factor that determines the column diameter is the vapour flow-rate. The
vapour velocity must be below that which would cause excessive liquid entrainment or a
high-pressure drop. The equation given below, which is based on the well-known Souders
and Brown equation, Lowenstein (1961), can be used to estimate the maximum allowable
superficial vapour velocity, and hence the column area and diameter,
⊲L v ⊳ 1/2
2
⊲11.79⊳
uO v D ⊲0.171lt C 0.27lt 0.047⊳
v
where uO v D maximum allowable vapour velocity, based on the gross (total) column
cross-sectional area, m/s,
lt D plate spacing, m, (range 0.5 1.5).
The column diameter, Dc , can then be calculated:
Ow
4V
Dc D
v uO v
⊲11.80⊳
O w is the maximum vapour rate, kg/s.
where V
This approximate estimate of the diameter would be revised when the detailed plate
design is undertaken.
11.12. PLATE CONTACTORS
Cross-flow plates are the most common type of plate contactor used in distillation and
absorption columns. In a cross-flow plate the liquid flows across the plate and the vapour
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CHEMICAL ENGINEERING
Figure 11.17.
Typical cross-flow plate (sieve)
up through the plate. A typical layout is shown in Figure 11.17. The flowing liquid is
transferred from plate to plate through vertical channels called “downcomers”. A pool of
liquid is retained on the plate by an outlet weir.
Other types of plate are used which have no downcomers (non-cross-flow plates), the
liquid showering down the column through large openings in the plates (sometimes called
shower plates). These, and, other proprietary non-cross-flow plates, are used for special
purposes, particularly when a low-pressure drop is required.
Three principal types of cross-flow tray are used, classified according to the method
used to contact the vapour and liquid.
1. Sieve plate (perforated plate) (Figure 11.18)
This is the simplest type of cross-flow plate. The vapour passes up through perforations in
the plate; and the liquid is retained on the plate by the vapour flow. There is no positive
vapour liquid seal, and at low flow-rates liquid will “weep” through the holes, reducing
the plate efficiency. The perforations are usually small holes, but larger holes and slots
are used.
2. Bubble-cap plates (Figure 11.19)
In which the vapour passes up through short pipes, called risers, covered by a cap with a
serrated edge, or slots. The bubble-cap plate is the traditional, oldest, type of cross-flow
plate, and many different designs have been developed. Standard cap designs would now
be specified for most applications.
The most significant feature of the bubble-cap plate is that the use of risers ensures
that a level of liquid is maintained on the tray at all vapour flow-rates.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Figure 11.18.
Sieve plate
Figure 11.19.
Bubble-cap
559
3. Valve plates (floating cap plates) (Figure 11.20)
Valve plates are proprietary designs. They are essentially sieve plates with large-diameter
holes covered by movable flaps, which lift as the vapour flow increases.
As the area for vapour flow varies with the flow-rate, valve plates can operate efficiently
at lower flow-rates than sieve plates: the valves closing at low vapour rates.
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CHEMICAL ENGINEERING
Figure 11.20.
Simple valve
Some very elaborate valve designs have been developed, but the simple type shown in
Figure 11.20 is satisfactory for most applications.
Liquid flow pattern
Cross-flow trays are also classified according to the number of liquid passes on the plate.
The design shown in Figure 11.21a is a single-pass plate. For low liquid flow rates reverse
flow plates are used; Figure 11.21b. In this type the plate is divided by a low central
partition, and inlet and outlet downcomers are on the same side of the plate. Multiplepass plates, in which the liquid stream is sub-divided by using several downcomers, are
used for high liquid flow-rates and large diameter columns. A double-pass plate is shown
in Figure 11.21c.
11.12.1. Selection of plate type
The principal factors to consider when comparing the performance of bubble-cap, sieve
and valve plates are: cost, capacity, operating range, efficiency and pressure drop.
Cost. Bubble-cap plates are appreciably more expensive than sieve or valve plates. The
relative cost will depend on the material of construction used; for mild steel the ratios,
bubble-cap : valve : sieve, are approximately 3.0 : 1.5 : 1.0.
Capacity. There is little difference in the capacity rating of the three types (the diameter
of the column required for a given flow-rate); the ranking is sieve, valve, bubble-cap.
Operating range. This is the most significant factor. By operating range is meant the
range of vapour and liquid rates over which the plate will operate satisfactorily (the
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
561
(a)
(b)
(c)
Figure 11.21.
Liquid flow patterns on cross-flow trays. (a) Single pass (b) Reverse flow (c) Double pass
stable operating range). Some flexibility will always be required in an operating plant to
allow for changes in production rate, and to cover start-up and shut-down conditions. The
ratio of the highest to the lowest flow rates is often referred to as the “turn-down” ratio.
Bubble-cap plates have a positive liquid seal and can therefore operate efficiently at very
low vapour rates.
Sieve plates rely on the flow of vapour through the holes to hold the liquid on the plate,
and cannot operate at very low vapour rates. But, with good design, sieve plates can be
designed to give a satisfactory operating range; typically, from 50 per cent to 120 per
cent of design capacity.
Valve plates are intended to give greater flexibility than sieve plates at a lower cost
than bubble-caps.
Efficiency. The Murphree efficiency of the three types of plate will be virtually the
same when operating over their design flow range, and no real distinction can be made
between them; see Zuiderweg et al. (1960).
Pressure drop. The pressure drop over the plates can be an important design consideration, particularly for vacuum columns. The plate pressure drop will depend on the
detailed design of the plate but, in general, sieve plates give the lowest pressure drop,
followed by valves, with bubble-caps giving the highest.
Summary. Sieve plates are the cheapest and are satisfactory for most applications.
Valve plates should be considered if the specified turn-down ratio cannot be met with
sieve plates. Bubble-caps should only be used where very low vapour (gas) rates have to
be handled and a positive liquid seal is essential at all flow-rates.
11.12.2. Plate construction
The mechanical design features of sieve plates are described in this section. The same
general construction is also used for bubble-cap and valve plates. Details of the various
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CHEMICAL ENGINEERING
types of bubble-cap used, and the preferred dimensions of standard cap designs, can be
found in the books by Smith (1963) and Ludwig (1997). The manufacturers’ design
manuals should be consulted for details of valve plate design; Glitsch (1970) and
Koch (1960).
Two basically different types of plate construction are used. Large-diameter plates are
normally constructed in sections, supported on beams. Small plates are installed in the
column as a stack of pre-assembled plates.
Sectional construction
A typical plate is shown in Figure 11.22. The plate sections are supported on a ring welded
round the vessel wall, and on beams. The beams and ring are about 50 mm wide, with
the beams set at around 0.6 m spacing. The beams are usually angle or channel sections,
constructed from folded sheet. Special fasteners are used so the sections can be assembled
from one side only. One section is designed to be removable to act as a manway. This
reduces the number of manways needed on the vessel, which reduces the vessel cost.
Manway
Downcomer and weir
Calming area
Major beam
Plate
support
ring
Major beam
clamp, welded
to tower wall
Major beam
Minor beam support clamp
Minor beam
support clamp
Peripheral ring clamps
Subsupport plate ring
used with angle ring
Minor beam
support clamp
Subsupport
angle ring
Figure 11.22.
Typical sectional plate construction
Diagrams and photographs, of sectional plates, are given in Volume 2, Chapter 11.
Stacked plates (cartridge plates)
The stacked type of construction is used where the column diameter is too small for a
man to enter to assemble the plates, say less than 1.2 m (4 ft). Each plate is fabricated
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
563
complete with the downcomer, and joined to the plate above and below using screwed rods
(spacers); see Figure 11.23. The plates are installed in the column shell as an assembly
(stack) of ten, or so, plates. Tall columns have to be divided into flanged sections so that
plate assemblies can be easily installed and removed. The weir, and downcomer supports,
are usually formed by turning up the edge of the plate.
Downcomers
Packaged
for installation
Top
spacer
Stack of
8 plates
Spacer
Hexagonal
spacer
bars
Screwed male/female
bar ends
Base spigot
and bracket
Figure 11.23.
Typical stacked-plate construction
The plates are not fixed to the vessel wall, as they are with sectional plates, so there
is no positive liquid seal at the edge of the plate, and a small amount of leakage will
occur. In some designs the plate edges are turned up round the circumference to make
better contact at the wall. This can make it difficult to remove the plates for cleaning and
maintenance, without damage.
Downcomers
The segmental, or chord downcomer, shown in Figure 11.24a is the simplest and cheapest
form of construction and is satisfactory for most purposes. The downcomer channel is
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CHEMICAL ENGINEERING
(a)
(b)
(c)
(d)
Figure 11.24.
Segment (chord) downcomer designs. (a) Vertical apron (b) Inclined apron (c) Inlet weir
(d) Recessed well
formed by a flat plate, called an apron, which extends down from the outlet weir. The
apron is usually vertical, but may be sloped (Figure 11.24b) to increase the plate area
available for perforation. If a more positive seal is required at the downcomer at the outlet,
an inlet weir can be fitted (Figure 11.24c) or a recessed seal pan used (Figure 11.24d).
Circular downcomers (pipes) are sometimes used for small liquid flow-rates.
Side-stream and feed points
Where a side-stream is withdrawn from the column the plate design must be modified
to provide a liquid seal at the take-off pipe. A typical design is shown in Figure 11.25a.
When the feed stream is liquid it will be normally introduced into the downcomer leading
to the feed plate, and the plate spacing increased at this point; Figure 11.25b.
Structural design
The plate structure must be designed to support the hydraulic loads on the plate during
operation, and the loads imposed during construction and maintenance. Typical design
values used for these loads are:
Hydraulic load: 600 N/m2 live load on the plate, plus 3000 N/m2 over the
downcomer seal area.
Erection and maintenance: 1500 N concentrated load on any structural member.
It is important to set close tolerances on the weir height, downcomer clearance, and
plate flatness, to ensure an even flow of liquid across the plate. The tolerances specified
will depend on the dimensions of the plate but will typically be about 3 mm.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
565
(a)
(b)
Figure 11.25.
Feed and take-off nozzles
The plate deflection under load is also important, and will normally be specified as
not greater than 3 mm under the operating conditions for plates greater than 2.5 m, and
proportionally less for smaller diameters.
The mechanical specification of bubble-cap, sieve and valve plates is covered in a
series of articles by Glitsch (1960), McClain (1960), Thrift (1960a, b) and Patton and
Pritchard (1960).
11.13. PLATE HYDRAULIC DESIGN
The basic requirements of a plate contacting stage are that it should:
Provide good vapour-liquid contact.
Provide sufficient liquid hold-up for good mass transfer (high efficiency).
Have sufficient area and spacing to keep the entrainment and pressure drop within
acceptable limits.
Have sufficient downcomer area for the liquid to flow freely from plate to plate.
Plate design, like most engineering design, is a combination theory and practice. The
design methods use semi-empirical correlations derived from fundamental research work
combined with practical experience obtained from the operation of commercial columns.
Proven layouts are used, and the plate dimensions are kept within the range of values
known to give satisfactory performance.
566
CHEMICAL ENGINEERING
A short procedure for the hydraulic design of sieve plates is given in this section.
Design methods for bubble-cap plates are given by Bolles (1963) and Ludwig (1997).
Valve plates are proprietary designs and will be designed in consultation with the vendors.
Design manuals are available from some vendors; Glistsch (1970) and Koch (1960).
A detailed discussion of the extensive literature on plate design and performance will
not be given in this volume. Chase (1967) and Zuiderweg (1982) give critical reviews of
the literature on sieve plates.
Several design methods have been published for sieve plates: Kister (1992), Barnicki
and Davies (1989), Koch and Kuzniar (1966), Fair (1963), and Huang and Hodson (1958);
see also the book by Lockett (1986).
Operating range
Satisfactory operation will only be achieved over a limited range of vapour and liquid
flow rates. A typical performance diagram for a sieve plate is shown in Figure 11.26.
Flo
od
Area of
satisfactory
operation
Downcomer
back-up
limitation
Coning
Vapour rate
ing
ive
s
s
e
c
x
E
ment
entrain
g
Weepin
Liquid rate
Figure 11.26.
Sieve plate performance diagram
The upper limit to vapour flow is set by the condition of flooding. At flooding there
is a sharp drop in plate efficiency and increase in pressure drop. Flooding is caused by
either the excessive carry over of liquid to the next plate by entrainment, or by liquid
backing-up in the downcomers.
The lower limit of the vapour flow is set by the condition of weeping. Weeping occurs
when the vapour flow is insufficient to maintain a level of liquid on the plate. “Coning”
occurs at low liquid rates, and is the term given to the condition where the vapour pushes
the liquid back from the holes and jets upward, with poor liquid contact.
In the following sections gas can be taken as synonymous with vapour when applying
the method to the design of plates for absorption columns.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
567
11.13.1. Plate-design procedure
A trial-and-error approach is necessary in plate design: starting with a rough plate layout,
checking key performance factors and revising the design, as necessary, until a satisfactory
design is achieved. A typical design procedure is set out below and discussed in the
following sections. The normal range of each design variable is given in the discussion,
together with recommended values which can be used to start the design.
Procedure
1. Calculate the maximum and minimum vapour and liquid flow-rates, for the turn
down ratio required.
2. Collect, or estimate, the system physical properties.
3. Select a trial plate spacing (Section 11.11).
4. Estimate the column diameter, based on flooding considerations (Section 11.13.3).
5. Decide the liquid flow arrangement (Section 11.13.4).
6. Make a trial plate layout: downcomer area, active area, hole area, hole size, weir
height (Sections 11.13.8 to 11.13.10).
7. Check the weeping rate (Section 11.13.6), if unsatisfactory return to step 6.
8. Check the plate pressure drop (Section 11.13.14), if too high return to step 6.
9. Check downcomer back-up, if too high return to step 6 or 3 (Section 11.13.15).
10. Decide plate layout details: calming zones, unperforated areas. Check hole pitch,
if unsatisfactory return to step 6 (Section 11.13.11).
11. Recalculate the percentage flooding based on chosen column diameter.
12. Check entrainment, if too high return to step 4 (Section 11.13.5).
13. Optimise design: repeat steps 3 to 12 to find smallest diameter and plate spacing
acceptable (lowest cost).
14. Finalise design: draw up the plate specification and sketch the layout.
This procedure is illustrated in Example 11.11.
11.13.2. Plate areas
The following areas terms are used in the plate design procedure:
Ac D total column cross-sectional area,
Ad D cross-sectional area of downcomer,
An D net area available for vapour-liquid disengagement, normally equal to Ac Ad ,
for a single pass plate,
Aa D active, or bubbling, area, equal to Ac 2Ad for single-pass plates,
Ah D hole area, the total area of all the active holes,
Ap D perforated area (including blanked areas),
Aap D the clearance area under the downcomer apron.
11.13.3. Diameter
The flooding condition fixes the upper limit of vapour velocity. A high vapour velocity
is needed for high plate efficiencies, and the velocity will normally be between 70 to
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CHEMICAL ENGINEERING
90 per cent of that which would cause flooding. For design, a value of 80 to 85 per cent
of the flooding velocity should be used.
The flooding velocity can be estimated from the correlation given by Fair (1961):
L v
⊲11.81⊳
uf D K1
v
where uf D flooding vapour velocity, m/s, based on the net column cross-sectional area
An (see Section 11.13.2),
K1 D a constant obtained from Figure 11.27.
Figure 11.27.
Flooding velocity, sieve plates
The liquid-vapour flow factor FLV in Figure 11.27 is given by:
L w v
FLV D
Vw L
⊲11.82⊳
where Lw D liquid mass flow-rate, kg/s,
Vw D vapour mass flow-rate, kg/s.
The following restrictions apply to the use of Figure 11.27:
1. Hole size less than 6.5 mm. Entrainment may be greater with larger hole sizes.
2. Weir height less than 15 per cent of the plate spacing.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
569
3. Non-foaming systems.
4. Hole: active area ratio greater than 0.10; for other ratios apply the following corrections:
hole: active area
multiply K1 by
0.10
1.0
0.08
0.9
0.06
0.8
5. Liquid surface tension 0.02 N/m, for other surface tensions multiply the value of
K1 by [/0.02]0.2 .
To calculate the column diameter an estimate of the net area An is required. As a first
trial take the downcomer area as 12 per cent of the total, and assume that the hole active
area is 10 per cent.
Where the vapour and liquid flow-rates, or physical properties, vary significantly
throughout the column a plate design should be made for several points up the column.
For distillation it will usually be sufficient to design for the conditions above and below
the feed points. Changes in the vapour flow-rate will normally be accommodated by
adjusting the hole area; often by blanking off some rows of holes. Different column
diameters would only be used where there is a considerable change in flow-rate. Changes
in liquid rate can be allowed for by adjusting the liquid downcomer areas.
11.13.4. Liquid-flow arrangement
The choice of plate type (reverse, single pass or multiple pass) will depend on the liquid
flow-rate and column diameter. An initial selection can be made using Figure 11.28,
which has been adapted from a similar figure given by Huang and Hodson (1958).
Figure 11.28.
Selection of liquid-flow arrangement
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CHEMICAL ENGINEERING
11.13.5. Entrainment
Entrainment can be estimated from the correlation given by Fair (1961), Figure 11.29,
which gives the fractional entrainment (kg/kg gross liquid flow) as a function of the
liquid-vapour factor FLV , with the percentage approach to flooding as a parameter.
The percentage flooding is given by:
un actual velocity (based on net area)
⊲11.83⊳
percentage flooding D
uf (from equation 11.81)
The effect of entrainment on plate efficiency can be estimated using equation 11.78.
10
0
9
8
7
6
5
4
3
Per cent flood
2
95
Fractional entrainment, Ψ
10
−1
9
8
7
6
90
5
80
4
3
70
2
60
50
10
−2
9
8
7
45
6
40
5
35
4
3
30
2
10
−3
10−2
2
3
4
5
6 7 8 9
10
−1
2
3
4
5 6 7 8 9
FLV
Figure 11.29.
Entrainment correlation for sieve plates (Fair, 1961)
10
0
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
571
As a rough guide the upper limit of can be taken as 0.1; below this figure the effect
on efficiency will be small. The optimum design value may be above this figure, see
Fair (1963).
11.13.6. Weep point
The lower limit of the operating range occurs when liquid leakage through the plate
holes becomes excessive. This is known as the weep point. The vapour velocity at the
weep point is the minimum value for stable operation. The hole area must be chosen
so that at the lowest operating rate the vapour flow velocity is still well above the
weep point.
Several correlations have been proposed for predicting the vapour velocity at the weep
point; see Chase (1967). That given by Eduljee (1959) is one of the simplest to use, and
has been shown to be reliable.
The minimum design vapour velocity is given by:
uL h D
[K2 0.90⊲25.4 dh ⊳]
⊲v ⊳1/2
⊲11.84⊳
where uL h D minimum vapour velocity through the holes(based on the hole area), m/s,
dh D hole diameter, mm,
K2 D a constant, dependent on the depth of clear liquid on the plate, obtained
from Figure 11.30.
Figure 11.30.
Weep-point correlation (Eduljee, 1959)
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CHEMICAL ENGINEERING
The clear liquid depth is equal to the height of the weir hw plus the depth of the crest of
liquid over the weir how ; this is discussed in the next section.
11.13.7. Weir liquid crest
The height of the liquid crest over the weir can be estimated using the Francis weir
formula (see Volume 1, Chapter 5). For a segmental downcomer this can be written as:
Lw 2/3
how D 750
⊲11.85⊳
L lw
where lw D weir length, m,
how D weir crest, mm liquid,
Lw D liquid flow-rate, kg/s.
With segmental downcomers the column wall constricts the liquid flow, and the weir crest
will be higher than that predicted by the Francis formula for flow over an open weir. The
constant in equation 11.85 has been increased to allow for this effect.
To ensure an even flow of liquid along the weir, the crest should be at least 10 mm at
the lowest liquid rate. Serrated weirs are sometimes used for very low liquid rates.
11.13.8. Weir dimensions
Weir height
The height of the weir determines the volume of liquid on the plate and is an important
factor in determining the plate efficiency (see Section 11.10.4). A high weir will increase
the plate efficiency but at the expense of a higher plate pressure drop. For columns
operating above atmospheric pressure the weir heights will normally be between 40 mm
to 90 mm (1.5 to 3.5 in.); 40 to 50 mm is recommended. For vacuum operation
lower weir
heights are used to reduce the pressure drop; 6 to 12 mm 41 to 21 in. is recommended.
Inlet weirs
Inlet weirs, or recessed pans, are sometimes used to improve the distribution of liquid
across the plate; but are seldom needed with segmental downcomers.
Weir length
With segmental downcomers the length of the weir fixes the area of the downcomer. The
chord length will normally be between 0.6 to 0.85 of the column diameter. A good initial
value to use is 0.77, equivalent to a downcomer area of 12 per cent.
The relationship between weir length and downcomer area is given in Figure 11.31.
For double-pass plates the width of the central downcomer is normally 200 250 mm
(8 10 in.).
11.13.9. Perforated area
The area available for perforation will be reduced by the obstruction caused by structural
members (the support rings and beams), and by the use of calming zones.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
573
20
(A d / A c ) x 100, per cent
15
10
5
0.6
0.8
0.7
0.9
l w / Dc
Figure 11.31.
Relation between downcomer area and weir length
Calming zones are unperforated strips of plate at the inlet and outlet sides of the plate.
The width of each zone is usually made the same; recommended values are: below 1.5 m
diameter, 75 mm; above, 100 mm.
The width of the support ring for sectional plates will normally be 50 to 75 mm: the
support ring should not extend into the downcomer area. A strip of unperforated plate
will be left round the edge of cartridge-type trays to stiffen the plate.
The unperforated area can be calculated from the plate geometry. The relationship
between the weir chord length, chord height and the angle subtended by the chord is
given in Figure 11.32.
11.13.10. Hole size
The hole sizes used vary from 2.5 to 12 mm; 5 mm is the preferred size. Larger holes
are occasionally used for fouling systems. The holes are drilled or punched. Punching
is cheaper, but the minimum size of hole that can be punched will depend on the plate
thickness. For carbon steel, hole sizes approximately equal to the plate thickness can be
punched, but for stainless steel the minimum hole size that can be punched is about twice
the plate thickness. Typical plate thicknesses used are: 5 mm (3/16 in.) for carbon steel,
and 3 mm (12 gauge) for stainless steel.
When punched plates are used they should be installed with the direction of punching
upward. Punching forms a slight nozzle, and reversing the plate will increase the
pressure drop.
574
CHEMICAL ENGINEERING
130
Dc
θc
lw
0.4
110
0.3
Lh /Dc
lh
0.2
90 θco
0.1
70
0
0.6
0.7
0.8
50
0.9
Lw/Dc
Figure 11.32.
Relation between angle subtended by chord, chord height and chord length
11.13.11. Hole pitch
The hole pitch (distance between the hole centres) lp should not be less than 2.0 hole
diameters, and the normal range will be 2.5 to 4.0 diameters. Within this range the
pitch can be selected to give the number of active holes required for the total hole area
specified.
Square and equilateral triangular patterns are used; triangular is preferred. The total
hole area as a fraction of the perforated area Ap is given by the following expression, for
an equilateral triangular pitch:
2
dh
Ah
D 0.9
⊲11.86⊳
Ap
lp
This equation is plotted in Figure 11.33.
11.13.12. Hydraulic gradient
The hydraulic gradient is the difference in liquid level needed to drive the liquid flow
across the plate. On sieve plates, unlike bubble-cap plates, the resistance to liquid flow
will be small, and the hydraulic gradient is usually ignored in sieve-plate design. It can be
significant in vacuum operation, as with the low weir heights used the hydraulic gradient
can be a significant fraction of the total liquid depth. Methods for estimating the hydraulic
gradient are given by Fair (1963).
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
575
0.2
Ah / Ap
0.15
0.10
0.05
2.0
Figure 11.33.
2.5
3.0
IP / d h
3.5
4.0
Relation between hole area and pitch
11.13.13. Liquid throw
The liquid throw is the horizontal distance travelled by the liquid stream flowing over
the downcomer weir. It is only an important consideration in the design of multiple-pass
plates. Bolles (1963) gives a method for estimating the liquid throw.
11.13.14. Plate pressure drop
The pressure drop over the plates is an important design consideration. There are two
main sources of pressure loss: that due to vapour flow through the holes (an orifice loss),
and that due to the static head of liquid on the plate.
A simple additive model is normally used to predict the total pressure drop. The total
is taken as the sum of the pressure drop calculated for the flow of vapour through the
dry plate (the dry plate drop hd ); the head of clear liquid on the plate (hw C how ); and
a term to account for other, minor, sources of pressure loss, the so-called residual loss
hr . The residual loss is the difference between the observed experimental pressure drop
and the simple sum of the dry-plate drop and the clear-liquid height. It accounts for the
two effects: the energy to form the vapour bubbles and the fact that on an operating plate
the liquid head will not be clear liquid but a head of “aerated” liquid froth, and the froth
density and height will be different from that of the clear liquid.
It is convenient to express the pressure drops in terms of millimetres of liquid. In
pressure units:
Pt D 9.81 ð 103 ht L
⊲11.87⊳
where Pt D total plate pressure drop, Pa(N/m2 ),
ht D total plate pressure drop, mm liquid.
576
CHEMICAL ENGINEERING
Dry plate drop
The pressure drop through the dry plate can be estimated using expressions derived for
flow through orifices.
2
v
uh
hd D 51
⊲11.88⊳
C0 L
where the orifice coefficient C0 is a function of the plate thickness, hole diameter, and
the hole to perforated area ratio. C0 can be obtained from Figure 11.34; which has been
adapted from a similar figure by Liebson et al. (1957). uh is the velocity through the
holes, m/s.
0.95
s
es
kn ter
c
i
e
th
e iam
at
Pl le d
Ho
0.90
1.2
0.85
Orifice coefficient, C0
1.0
0.80
0.8
0.75
0.6
0.2
0.70
0.65
0
5
10
15
Per cent perforated area, Ah / Ap x 100
Figure 11.34.
Discharge coefficient, sieve plates (Liebson et al., 1957)
20
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
577
Residual head
Methods have been proposed for estimating the residual head as a function of liquid
surface tension, froth density and froth height. However, as this correction term is small
the use of an elaborate method for its estimation is not justified, and the simple equation
proposed by Hunt et al. (1955) can be used:
hr D
12.5 ð 103
L
⊲11.89⊳
Equation 11.89 is equivalent to taking the residual drop as a fixed value of 12.5 mm of
water ⊲ 12 in.⊳.
Total drop
The total plate drop is given by:
ht D hd C ⊲hw C how ⊳ C hr
⊲11.90⊳
If the hydraulic gradient is significant, half its value is added to the clear liquid height.
11.13.15. Downcomer design [back-up]
The downcomer area and plate spacing must be such that the level of the liquid and froth
in the downcomer is well below the top of the outlet weir on the plate above. If the level
rises above the outlet weir the column will flood.
The back-up of liquid in the downcomer is caused by the pressure drop over the plate
(the downcomer in effect forms one leg of a U-tube) and the resistance to flow in the
downcomer itself; see Figure 11.35.
Figure 11.35.
Downcomer back-up
578
CHEMICAL ENGINEERING
In terms of clear liquid the downcomer back-up is given by:
hb D ⊲hw C how ⊳ C ht C hdc
⊲11.91⊳
where hb D downcomer back-up, measured from plate surface, mm,
hdc D head loss in the downcomer, mm.
The main resistance to flow will be caused by the constriction at the downcomer outlet,
and the head loss in the downcomer can be estimated using the equation given by Cicalese
et al. (1947)
Lwd 2
hdc D 166
⊲11.92⊳
L Am
where Lwd D liquid flow rate in downcomer, kg/s,
Am D either the downcomer area Ad or the clearance area under the downcomer
Aap ; whichever is the smaller, m2 .
The clearance area under the downcomer is given by:
Aap D hap lw
⊲11.93⊳
where hap is height of the bottom edge
of the apron above the plate. This height is
normally set at 5 to 10 mm 14 to 12 in. below the outlet weir height:
hap D hw ⊲5 to 10 mm⊳
Froth height
To predict the height of “aerated” liquid on the plate, and the height of froth in the
downcomer, some means of estimating the froth density is required. The density of the
“aerated” liquid will normally be between 0.4 to 0.7 times that of the clear liquid. A
number of correlations have been proposed for estimating froth density as a function of
the vapour flow-rate and the liquid physical properties; see Chase (1967); however, none
is particularly reliable, and for design purposes it is usually satisfactory to assume an
average value of 0.5 of the liquid density.
This value is also taken as the mean density of the fluid in the downcomer; which means
that for safe design the clear liquid back-up, calculated from equation 11.91, should not
exceed half the plate spacing lt , to avoid flooding.
Allowing for the weir height:
hb 6> 12 ⊲lt C hw ⊳
⊲11.94⊳
This criterion is, if anything, oversafe, and where close plate spacing is desired a better
estimate of the froth density in the downcomer should be made. The method proposed
by Thomas and Shah (1964) is recommended.
Downcomer residence time
Sufficient residence time must be allowed in the downcomer for the entrained vapour to
disengage from the liquid stream; to prevent heavily “aerated” liquid being carried under
the downcomer.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
579
A time of at least 3 seconds is recommended.
The downcomer residence time is given by:
tr D
Ad hbc L
Lwd
⊲11.95⊳
where tr D residence time, s,
hbc D clear liquid back-up, m.
Example 11.11
Design the plates for the column specified in Example 11.2. Take the minimum feed rate
as 70 per cent of the maximum (maximum feed 10,000 kg/h). Use sieve plates.
Solution
As the liquid and vapour flow-rates and compositions will vary up the column, plate
designs should be made above and below the feed point. Only the bottom plate will be
designed in detail in this example.
From McCabe-Thiele diagram, Example 11.2:
Number of stages D 16
Slope of the bottom operating line D 5.0
Slope of top operating line D 0.57
Top composition 94 per cent mol. 98 per cent w/w.
Bottom composition essentially water.
Reflux ratio D 1.35
Flow-rates
Mol. weight feed D 0.033 ð 58 C ⊲1 0.033⊳18 D 19.32
Feed D 13,000/19.32 D 672.9 kmol/h
A mass balance on acetone gives:
Top product, D D 672.9 ð 0.033/0.94 D 23.6 kmol/h
Vapour rate, V D D⊲1 C R⊳ D 23.6⊲1 C 1.35⊳ D 55.5 kmol/h
An overall mass balance gives:
Bottom product, B D 672.9 23.6 D 649.3 kmol/h
Slope of the bottom operating line Lm 0 /Vm 0 D 5.0
and Vm 0 D Lm 0 B, from which:
vapour flow below feed, Vm 0 D 162.3 kmol/h
liquid flow below feed, Lm 0 D 811.6 kmol/h
Physical properties
Estimate base pressure, assume column efficiency of 60 per cent, take reboiler as equivalent to one stage.
16 1
Number of real stages D
D 25
0.6
580
CHEMICAL ENGINEERING
Assume 100 mm water, pressure drop per plate.
Column pressure drop D 100 ð 103 ð 1000 ð 9.81 ð 25 D 24,525 Pa
Top pressure, 1 atm (14.7 lb/in2 ) D 101.4 ð 103 Pa
Estimated bottom pressure D 101.4 ð 103 C 24,525
D 125,925 Pa D 1.26 bar
From steam tables, base temperature 106Ž C.
v D 0.72 kg/m3
L D 954 kg/m3
Surface tension 57 ð 103 N/m
Top, 98% w/w acetone, top temperature 57Ž C
From PPDS (see Chapter 8);
v D 2.05 kg/m3 , L D 753 kg/m3
Molecular weight 55.6
Surface tension 23 ð 103 N/m
Column diameter
0.72
D 0.14
954
2.05
top D 0.57
D 0.03
753
FLV bottom D 5.0
FLV
⊲11.82⊳
Take plate spacing as 0.5 m
From Figure 11.27
base K1 D 7.5 ð 102
top K1 D 9.0 ð 102
Correction for surface tensions
0.2
57
ð 7.5 ð 102 D 9.3 ð 102
base K1 D
20
0.2
23
ð 9.0 ð 102 D 9.3 ð 102
top K1 D
20
954 0.72
2
D 3.38 m/s
base uf D 9.3 ð 10
0.72
753 2.05
2
top uf D 9.3 ð 10
D 1.78 m/s
2.05
⊲11.81⊳
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
581
Design for 85 per cent flooding at maximum flow rate
base uOv D 3.38 ð 0.85 D 2.87 m/s
top uOv D 1.78 ð 0.85 D 1.51 m/s
Maximum volumetric flow-rate
162.3 ð 18
D 1.13 m3 /s
0.72 ð 3600
55.5 ð 55.6
top D
D 0.42 m3 /s
2.05 ð 3600
base D
Net area required
1.13
D 0.40 m2
2.87
0.42
top D
D 0.28 m2
1.51
As first trial take downcomer area as 12 per cent of total.
Column cross-sectioned area
0.40
D 0.46 m2
base D
0.88
0.28
D 0.32 m2
top D
0.88
Column diameter
0.46 ð 4
base D
D 0.77 m
0.34 ð 4
D 0.64 m
top D
Use same diameter above and below feed, reducing the perforated area for plates above
the feed.
Nearest standard pipe size (BS 1600); outside diameter 812.8 mm (32 in); standard
wall thickness 9.52 mm; inside diameter 794 mm.
bottom D
Liquid flow pattern
Maximum volumetric liquid rate D
811.6 ð 18
D 4.3 ð 103 m3 /s
3600 ð 954
The plate diameter is outside the range of Figure 11.28, but it is clear that a single pass
plate can be used.
Provisional plate design
Column diameter
Column area
Downcomer area
Net area
Dc
Ac
Ad
An
D
D
D
D
0.79 m
0.50 m2
0.12 ð 0.50 D 0.06 m2 , at 12 per cent
Ac Ad D 0.50 0.06 D 0.44 m2
582
CHEMICAL ENGINEERING
Active area Aa D Ac 2Ad D 0.50 0.12 D 0.38 m2
Hole area Ah take 10 per cent Aa as first trial D 0.038 m2
Weir length (from Figure 11.31) D 0.76 ð 0.79 D 0.60 m
Take weir height
Hole diameter
Plate thickness
50 mm
5 mm
5 mm
Check weeping
Maximum liquid rate D
811.6 ð 18
3600
D 4.06 kg/s
Minimum liquid rate, at 70 per cent turn-down D 0.7 ð 4.06 D 2.84 kg/s
maximum how D 750
4.06
954 ð 0.06
minimum how D 750
2.85
954 ð 0.60
2/3
D 27 mm liquid
2/3
D 22 mm liquid
⊲11.85⊳
at minimum rate hw C how D 50 C 22 D 72 mm
K2 D 30.6
From Figure 11.30,
uL h ⊲min⊳ D
30.6 0.90⊲25.4 5⊳
D 14 m/s
⊲0.72⊳1/2
⊲11.84⊳
minimum vapour rate
Ah
0.7 ð 1.13
D
D 20.8 m/s
0.038
actual minimum vapour velocity D
So minimum operating rate will be well above weep point.
Plate pressure drop
Dry plate drop
Maximum vapour velocity through holes
1.13
D 29.7 m/s
0.038
From Figure 11.34, for plate thickness/hole dia. D 1, and Ah /Ap ' Ah /Aa D 0.1,
C0 D 0.84
29.7 2 0.72
hd D 51
D 48 mm liquid
⊲11.88⊳
0.84
954
uOh D
residual head
hr D
12.5 ð 103
D 13.1 mm liquid
954
⊲11.89⊳
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
583
total plate pressure drop
ht D 48 C ⊲50 C 27⊳ C 13 D 138 mm liquid
Note: 100 mm was assumed to calculate the base pressure. The calculation could be
repeated with a revised estimate but the small change in physical properties will have
little effect on the plate design. 138 mm per plate is considered acceptable.
Downcomer liquid back-up
Downcomer pressure loss
Take hap D hw 10 D 40 mm.
Area under apron, Aap D 0.60 ð 40 ð 103 D 0.024 m2 .
As this is less than Ad D 0.06 m2 use Aap in equation 11.92
2
4.06
hdc D 166
D 5.2 mm
954 ð 0.024
⊲11.92⊳
say 6 mm.
Back-up in downcomer
hb D ⊲50 C 27⊳ C 138 C 6 D 221 mm
⊲11.91⊳
0.22 m
0.22 < 21 (plate spacing C weir height)
so plate spacing is acceptable
Check residence time
0.06 ð 0.22 ð 954
D 3.1 s
4.06
>3 s, satisfactory.
tr D
⊲11.95⊳
Check entrainment
1.13
D 2.57 m/s
0.44
2.57
D 76
per cent flooding D
3.38
uv D
FLV D 0.14, from Figure 11.29, D 0.018, well below 0.1.
As the per cent flooding is well below the design figure of 85, the column diameter
could be reduced, but this would increase the pressure drop.
Trial layout
Use cartridge-type construction. Allow 50 mm unperforated strip round plate edge; 50 mm
wide calming zones.
584
CHEMICAL ENGINEERING
θc
0.79 m
0.6 m
50 mm
50 mm
Perforated area
From Figure 11.32, at lw /Dc D 0.6/0.79 D 0.76
c D 99Ž
angle subtended by the edge of the plate D 180 99 D 81Ž
mean length, unperforated edge strips D ⊲0.79 50 ð 103 ⊳ ð 81/180 D 1.05 m
area of unperforated edge strips D 50 ð 103 ð 1.05 D 0.053 m2
mean length of calming zone, approx. D weir length C width of unperforated strip
D 0.6 C 50 ð 103 D 0.65 m
area of calming zones D 2⊲0.65 ð 50 ð 103 ⊳ D 0.065 m2
total area for perforations, Ap D 0.38 0.053 0.065 D 0.262 m2
Ah /Ap D 0.038/0.262 D 0.145
From Figure 11.33, lp /dh D 2.6; satisfactory, within 2.5 to 4.0.
Number of holes
Area of one hole D 1.964 ð 105 m2
0.038
Number of holes D
D 1935
1.964 ð 105
Plate specification
50 mm
Plate No.
Plate I.D.
Hole size
Hole pitch
Total no. holes
Active holes
Blanking area
40 mm
0.79 m
0.60 m
50 mm
1
0.79 m
5 mm
12.5 mm
1935
50 mm
Turn-down
Plate material
Downcomer
Plate spacing
Plate thickness
Plate pressure drop
70 per cent max rate
Mild steel
material Mild steel
0.5 m
5 mm
140 mm liquid D 1.3 kPa
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
585
Example 11.12
For the plate design in Example 11.11, estimate the plate efficiency for the plate on which
the concentration of acetone is 5 mol per cent. Use the AIChE method.
Solution
Plate will be in the stripping section (see Figure 11.7).
Plate dimensions:
active area D 0.38 m2 ,
length between downcomers (Figure 11.32) (liquid path, ZL ⊳ D 0.79 2 ð 0.134 D
0.52 m,
weir height D 50 mm.
Flow rates, check efficiency at minimum rates, at column base:
162.3
D 0.032 kmol/s
3600
811.6
liquid D 0.7
D 0.158 kmol/s
3600
vapour D 0.7
from the MaCable-Thiele diagram (Figure 11.7) at x D 0.05, assuming 60 per cent plate
efficiency, y ³ 0.4. The liquid composition, x D 0.05, will occur on around the ninth
plate from the bottom, the seventh from the top of the column. The pressure on this plate
will be approximately:
9 ð 138 ð 103 ð 1000 ð 982 C 101.4 ð 103 D 113.6 kPa
say, 1.14 bar
At this pressure the plate temperature will be 79Ž C, and the liquid and vapour physical
properties, from PPDS:
liquid
mol. weight D 20.02, L D 925 kg/m3 , L D 9.34 ð 103 Nm2 s,
D 60 ð 103 N/m
vapour
mol. weight D 34.04, v D 1.35 kg/m3 , v D 10.0 ð 106 Nm2 s,
DL D 4.64 ð 109 m2 /s (estimated using Wilke-Chang equation, Chapter 8)
Dv D 18.6 ð 106 m2 /s (estimated using Fuller equation, Chapter 8)
0.032 ð 34.04
D 0.81 m3 /s
1.35
0.158 ð 20.02
Liquid, volumetric flow-rate D
D 3.42 ð 103 m3 /s
925
Vapour, volumetric flow-rate D
586
CHEMICAL ENGINEERING
0.81
D 2.13 m/s
0.38
p
p
Fv D ua v D 2.13 m/s
ua D
Average width over active surface D 0.38/0.52 D 0.73 m
3.42 ð 103
D 4.69 ð 103 m2 /s
0.73
LD
NG D
⊲0.776 C 4.57 ð 103 ð 50 0.24 ð 2.48 C 105 ð 4.69 ð 103 ⊳
1/2
10.0 ð 106
1.35 ð 18.8 ð 106
D 1.44
3
Zc D 0.006 C 0.73 ð 10
3
ð 50 0.24 ð 10
ð 4.69 ð 103 D 18.5 ð 103 m3 /m2
tL D
⊲11.71⊳
ð 2.48 ð 50 C 1.22
3
18.5 ð 10 ð 0.52
D 2.05 s
4.69 ð 103
⊲11.75⊳
⊲11.73⊳
NL D ⊲4.13 ð 108 ð 4.64 ð 109 ⊳0.5 ð ⊲0.21 ð 2.48 C 0.15⊳ ð 2.05 D 1.9 ⊲11.72⊳
De D ⊲0.0038 C 0.017 ð 2.13 C 3.86 ð 4.69 ð 103 C 0.18 ð 103 ð 50⊳2
D 0.0045 m2 /s
⊲11.77⊳
2
Pe D
0.52
D 29.3
0.0045 ð 2.05
⊲11.76⊳
From the McCabe-Thiele diagram, at x D 0.05, the slope of the equilibrium line D 1.0.
V/L D 0.032/0.158 D 0.20
mV
D 1.0 ð 0.20 D 0.20
so,
L
mV
0.20
L
D 0.11
D
NL
1.9
From Figure 11.15 Emv D 0.70
mV
Ð Emv D 0.2 ð 0.58 D 0.12
L
From Figure 11.16 EmV /Emv D 1.02
EmV D 0.70 ð 1.02 D 0.714
So plate efficiency D 71 per cent.
Note: The slope of the equilibrium line is difficult to determine at x D 0.05, but any
error will not greatly affect the value of EmV .
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
587
Example 11.13
Calculate the plate efficiency for the plate design considered in Examples 11.11 and 11.12,
using Van Winkle’s correlation.
Solution
From Examples 11.12 and 11.11:
L D 925 kg/m3 ,
v D 1.35 kg/m3 ,
L D 0.34 ð 103 Ns/m2 ,
v D 10.0 ð 106 Ns/m2 ,
DLK D DL D 4.64 ð 109 m2 /s,
hw D 50 mm,
0.038
D 0.076,
0.50
0.81
D 1.62 m/s,
superficial vapour velocity D
0.50
60 ð 103 N/m
60 ð 103
D 109
0.34 ð 103 ð 1.62
0.34 ð 103
D 79,
925 ð 4.64 ð 109
50 ð 103 ð 1.62 ð 1.35
D 4232
0.34 ð 103 ð 0.076
FA (fractional area) D Ah /Ac D
uv D
L D
Dg D
Sc D
Re D
EmV D 0.07⊲109⊳0.14 ⊲79⊳0.25 ⊲4232⊳0.08
(11.69)
D 0.79 ⊲79 per cent⊳
11.14. PACKED COLUMNS
Packed columns are used for distillation, gas absorption, and liquid-liquid extraction; only
distillation and absorption will be considered in this section. Stripping (desorption) is the
reverse of absorption and the same design methods will apply.
The gas liquid contact in a packed bed column is continuous, not stage-wise, as in a
plate column. The liquid flows down the column over the packing surface and the gas
or vapour, counter-currently, up the column. In some gas-absorption columns co-current
flow is used. The performance of a packed column is very dependent on the maintenance
of good liquid and gas distribution throughout the packed bed, and this is an important
consideration in packed-column design.
588
CHEMICAL ENGINEERING
A schematic diagram, showing the main features of a packed absorption column, is
given in Figure 11.36. A packed distillation column will be similar to the plate columns
shown in Figure 11.1, with the plates replaced by packed sections.
Figure 11.36.
Packed absorption column
The design of packed columns using random packings is covered in books by Strigle
(1994) and Billet (1995).
Choice of plates or packing
The choice between a plate or packed column for a particular application can only be
made with complete assurance by costing each design. However, this will not always
be worthwhile, or necessary, and the choice can usually be made, on the basis of
experience by considering main advantages and disadvantages of each type; which are
listed below:
1. Plate columns can be designed to handle a wider range of liquid and gas flow-rates
than packed columns.
2. Packed columns are not suitable for very low liquid rates.
3. The efficiency of a plate can be predicted with more certainty than the equivalent
term for packing (HETP or HTU).
4. Plate columns can be designed with more assurance than packed columns. There
is always some doubt that good liquid distribution can be maintained throughout
a packed column under all operating conditions, particularly in large columns.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
589
5. It is easier to make provision for cooling in a plate column; coils can be installed
on the plates.
6. It is easier to make provision for the withdrawal of side-streams from plate columns.
7. If the liquid causes fouling, or contains solids, it is easier to make provision for
cleaning in a plate column; manways can be installed on the plates. With smalldiameter columns it may be cheaper to use packing and replace the packing when
it becomes fouled.
8. For corrosive liquids a packed column will usually be cheaper than the equivalent
plate column.
9. The liquid hold-up is appreciably lower in a packed column than a plate column.
This can be important when the inventory of toxic or flammable liquids needs to
be kept as small as possible for safety reasons.
10. Packed columns are more suitable for handling foaming systems.
11. The pressure drop per equilibrium stage (HETP) can be lower for packing than
plates; and packing should be considered for vacuum columns.
12. Packing should always be considered for small diameter columns, say less than
0.6 m, where plates would be difficult to install, and expensive.
Packed-column design procedures
The design of a packed column will involve the following steps:
1. Select the type and size of packing.
2. Determine the column height required for the specified separation.
3. Determine the column diameter (capacity), to handle the liquid and vapour flow
rates.
4. Select and design the column internal features: packing support, liquid distributor,
redistributors.
These steps are discussed in the following sections, and a packed-column design illustrated
in Example 11.14.
11.14.1. Types of packing
The principal requirements of a packing are that it should:
Provide a large surface area: a high interfacial area between the gas and liquid.
Have an open structure: low resistance to gas flow.
Promote uniform liquid distribution on the packing surface.
Promote uniform vapour gas flow across the column cross-section.
Many diverse types and shapes of packing have been developed to satisfy these requirements. They can be divided into two broad classes:
1. Packings with a regular geometry: such as stacked rings, grids and proprietary structured packings.
2. Random packings: rings, saddles and proprietary shapes, which are dumped into the
column and take up a random arrangement.
590
CHEMICAL ENGINEERING
(e)
Figure 11.37.
(f)
Types of packing (Norton Co.). (a) Raschig rings (b) Pall rings (c) Berl saddle ceramic
(d) Intalox saddle ceramic (e) Metal Hypac ( f ) Ceramic, super Intalox
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
591
Grids have an open structure and are used for high gas rates, where low pressure drop
is essential; for example, in cooling towers. Random packings and structured packing
elements are more commonly used in the process industries.
Random packing
The principal types of random packings are shown in Figure 11.37 (see p. 590). Design
data for these packings are given in Table 11.2. Data on a wider range of packing sizes
are given in Volume 2, Chapter 4. The design methods and data given in this section
can be used for the preliminary design of packed columns, but for detailed design it is
advisable to consult the packing manufacturer’s technical literature to obtain data for the
particular packing that will be used. The packing manufacturers should be consulted for
details of the many special types of packing that are available for special applications.
Raschig rings, Figure 11.37a, are one of the oldest specially manufactured types of
random packing, and are still in general use. Pall rings, Figure 11.37b, are essentially
Raschig rings in which openings have been made by folding strips of the surface into the
ring. This increases the free area and improves the liquid distribution characteristics. Berl
saddles, Figure 11.37c, were developed to give improved liquid distribution compared
to Raschig rings, Intalox saddles, Figure 11.37d, can be considered to be an improved
type of Berl saddle; their shape makes them easier to manufacture than Berl saddles. The
Hypac and Super Intalox packings shown in Figure 11.37e, f can be considered improved
types of Pall ring and Intalox saddle, respectively.
Table 11.2.
Design data for various packings
Size
Raschig rings
ceramic
Metal
(density for carbon steel)
Pall rings
metal
(density for carbon steel)
Plastics
(density for polypropylene)
Intalox saddles
ceramic
in.
mm
Bulk
density
(kg/m3 )
0.50
1.0
1.5
2.0
3.0
0.5
1.0
1.5
2.0
3.0
0.625
1.0
1.25
2.0
3.5
0.625
1.0
1.5
2.0
3.5
0.5
1.0
1.5
2.0
3.0
13
25
38
51
76
13
25
38
51
76
16
25
32
51
76
16
25
38
51
89
13
25
38
51
76
881
673
689
651
561
1201
625
785
593
400
593
481
385
353
273
112
88
76
68
64
737
673
625
609
577
Surface
area a
(m2 /m3 )
Packing
factor
Fp m1
368
190
128
95
69
417
207
141
102
72
341
210
128
102
66
341
207
128
102
85
480
253
194
108
2100
525
310
210
120
980
375
270
190
105
230
160
92
66
52
320
170
130
82
52
660
300
170
130
72
592
CHEMICAL ENGINEERING
Intalox saddles, Super Intalox and Hypac packings are proprietary design, and registered
trade marks of the Norton Chemical Process Products Ltd.
Ring and saddle packings are available in a variety of materials: ceramics, metals,
plastics and carbon. Metal and plastics (polypropylene) rings are more efficient than
ceramic rings, as it is possible to make the walls thinner.
Raschig rings are cheaper per unit volume than Pall rings or saddles but are less
efficient, and the total cost of the column will usually be higher if Raschig rings are
specified. For new columns, the choice will normally be between Pall rings and Berl or
Intalox saddles.
The choice of material will depend on the nature of the fluids and the operating temperature. Ceramic packing will be the first choice for corrosive liquids; but ceramics are
unsuitable for use with strong alkalies. Plastics packings are attacked by some organic
solvents, and can only be used up to moderate temperatures; so are unsuitable for distillation columns. Where the column operation is likely to be unstable metal rings should
be specified, as ceramic packing is easily broken. The choice of packings for distillation
and absorption is discussed in detail by Eckert (1963), Strigle (1994), Kister (1992) and
Billet (1995).
Packing size
In general, the largest size of packing that is suitable for the size of column should be
used, up to 50 mm. Small sizes are appreciably more expensive than the larger sizes.
Above 50 mm the lower cost per cubic metre does not normally compensate for the
lower mass transfer efficiency. Use of too large a size in a small column can cause poor
liquid distribution.
Recommended size ranges are:
Column diameter
Use packing size
<0.3 m (1 ft)
0.3 to 0.9 m (1 to 3 ft)
>0.9 m
<25 mm (1 in.)
25 to 38 mm (1 to 1.5 in.)
50 to 75 mm (2 to 3 in.)
Structured packing
The term structured packing refers to packing elements made up from wire mesh or
perforated metal sheets. The material is folded and arranged with a regular geometry,
to give a high surface area with a high void fraction. A typical example is shown in
Figure 11.38.
Structured packings are produced by a number of manufacturers. The basic construction
and performance of the various proprietary types available are similar. They are available
in metal, plastics and stoneware. The advantage of structured packings over random
packing is their low HETP (typically less than 0.5 m) and low pressure drop (around
100 Pa/m). They are being increasingly used in the following applications:
1. For difficult separations, requiring many stages: such as the separation of isotopes.
2. High vacuum distillation.
3. For column revamps: to increase capacity and reduce reflux ratio requirements.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Figure 11.38.
593
Make-up of structured packing. (Reproduced from Butcher (1988) with permission.)
The applications have mainly been in distillation, but structured packings can also be
used in absorption; in applications where high efficiency and low pressure drop are needed.
The cost of structured packings per cubic metre will be significantly higher than that
of random packings, but this is offset by their higher efficiency.
The manufacturers’ technical literature should be consulted for design data. A review
of the types available is given by Butcher (1988). Generalised methods for predicting the
capacity and pressure drop of structured packings are given by Fair and Bravo (1990)
and Kister and Gill (1992). The use of structured packings in distillation is discussed in
detail in the book by Kister (1992).
11.14.2. Packed-bed height
Distillation
For the design of packed distillation columns it is simpler to treat the separation as a
staged process, and use the concept of the height of an equivalent equilibrium stage to
convert the number of ideal stages required to a height of packing. The methods for
estimating the number of ideal stages given in Sections 11.5 to 11.8 can then be applied
to packed columns.
The height of an equivalent equilibrium stage, usually called the height of a theoretical
plate (HETP), is the height of packing that will give the same separation as an equilibrium
stage. It has been shown by Eckert (1975) that in distillation the HETP for a given type and
size of packing is essentially constant, and independent of the system physical properties;
providing good liquid distribution is maintained and the pressure drop is at least above
17 mm water per metre of packing height. The following values for Pall rings can be
used to make an approximate estimate of the bed height required.
Size, mm
25 (1 in.)
38 (1 21 in.)
50 (2 in.)
HETP, m
0.4 0.5
0.6 0.75
0.75 1.0
594
CHEMICAL ENGINEERING
The HETP for saddle packings will be similar to that for Pall rings providing the
pressure drop is at least 29 mm per m.
The HETP for Raschig rings will be higher than those for Pall rings or saddles, and the
values given above will only apply at an appreciably higher pressure drop, greater than
42 mm per m.
The methods for estimating the heights of transfer units, HTU, given in Section 11.14.3
can be used for distillation. The relationship between transfer units and the height of an
equivalent theoretical plate, HETP is given by:
mGm
HOG Ln
Lm
⊲11.96⊳
HETP D
mGm
Lm 1
from equation 11.105
HOG D HG C
mGm
Lm
HL
The slope of the operating line m will normally vary throughout a distillation so it will
be necessary to calculate the HETP for each plate or a series of plates.
Absorption
Though packed absorption and stripping columns can also be designed as staged process,
it is usually more convenient to use the integrated form of the differential equations set
up by considering the rates of mass transfer at a point in the column. The derivation of
these equations is given in Volume 2, Chapter 12.
Where the concentration of the solute is small, say less than 10 per cent, the flow of gas
and liquid will be essentially constant throughout the column, and the height of packing
required, Z, is given by:
y1
Gm
dy
ZD
⊲11.97⊳
KG aP y2 y ye
in terms of the overall gas phase mass transfer coefficient KG and the gas composition.
Or,
x1
Lm
dx
ZD
⊲11.98⊳
KL aCt x2 xe x
in terms of the overall liquid-phase mass-transfer coefficient KL and the liquid composition,
where Gm
Lm
a
P
Ct
y1 and y2
D
D
D
D
D
D
molar gas flow-rate per unit cross-sectional area,
molar liquid flow-rate per unit cross-sectional area,
interfacial surface area per unit volume,
total pressure,
total molar concentration,
the mol fractions of the solute in the gas at the bottom and top of the
column, respectively,
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
595
x1 and x2 D the mol fractions of the solute in the liquid at the bottom and top of the
column, respectively,
xe D the concentration in the liquid that would be in equilibrium with the gas
concentration at any point,
ye D the concentration in the gas that would be in equilibrium with the liquid
concentration at any point.
Top
ing
t
era
∆y
line
Op
y
e
(y-y )
e
iu
ibr
lin
uil
2
y
e
m
∆y
Solute concentration in gas
1
Base
The relation between the equilibrium concentrations and actual concentrations is shown
in Figure 11.39.
Eq
( xe
x)
xe
x
Solute concentration in liquid
Figure 11.39.
Gas absorption concentration relationships
For design purposes it is convenient to write equations 11.97 and 11.98 in terms of
“transfer units” (HTU); where the value of integral is the number of transfer units, and the
group in front of the integral sign, which has units of length, is the height of a transfer unit.
or
Z D HOG NOG
⊲11.99a⊳
Z D HOL NOL
⊲11.99b⊳
where HOG is the height of an overall gas-phase transfer unit
D
Gm
KG aP
NOG is the number of overall gas-phase transfer units
y1
dy
D
y2 y y e
⊲11.100⊳
⊲11.101⊳
HOL is the height of an overall liquid-phase transfer unit
D
Lm
KL aCt
⊲11.102⊳
596
CHEMICAL ENGINEERING
NOL is the number of overall liquid-phase transfer units
x1
dx
D
x
ex
x2
⊲11.103⊳
The number of overall gas-phase transfer units is often more conveniently expressed in
terms of the partial pressure of the solute gas.
p2
dp
NOG D
⊲11.104⊳
p 1 p pe
The relationship between the overall height of a transfer unit and the individual film
transfer units HL and HG , which are based on the concentration driving force across the
liquid and gas films, is given by:
Gm
HL
Lm
Lm
D HL C
HG
mGm
HOG D HG C m
⊲11.105⊳
HOL
⊲11.106⊳
where m is the slope of the equilibrium line and Gm /Lm the slope of the operating line.
The number of transfer units is obtained by graphical or numerical integration of
equations 11.101, 11.103 or 11.104.
Where the operating and equilibrium lines are straight, and they can usually be
considered to be so for dilute systems, the number of transfer units is given by:
NOG D
y1 y2
ylm
⊲11.107⊳
where ylm is the log mean driving force, given by:
ylm D
y1 y2
y1
ln
y2
⊲11.108⊳
where y1 D y1 ye ,
y2 D y2 ye .
If the equilibrium curve and operating lines can be taken as straight and the solvent
feed essentially solute free, the number of transfer units is given by:
mGm
mGm y1
1
ln 1
C
⊲11.109⊳
NOG D
mGm
Lm
y2
Lm
1
Lm
This equation is plotted in Figure 11.40, which can be used to make a quick estimate of
the number of transfer units required for a given separation.
It can be seen from Figure 11.40 that the number of stages required for a given
separation is very dependent on the flow rate Lm . If the solvent rate is not set by
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Figure 11.40.
597
Number of transfer units NOG as a function of y1 /y2 with mGm /Lm as parameter
other process considerations, Figure 11.40 can be used to make quick estimates of the
column height at different flow rates to find the most economic value. Colburn (1939) has
suggested that the optimum value for the term mGm /Lm will lie between 0.7 to 0.8.
Only physical absorption from dilute gases has been considered in this section. For a
discussion of absorption from concentrated gases and absorption with chemical reaction,
the reader should refer to Volume 2, or to the book by Treybal (1980). If the inlet gas
concentration is not too high, the equations for dilute systems can be used by dividing
the operating line up into two or three straight sections.
11.14.3. Prediction of the height of a transfer unit (HTU)
There is no entirely satisfactory method for predicting the height of a transfer unit. In
practice the value for a particular packing will depend not only on the physical properties
598
CHEMICAL ENGINEERING
and flow-rates of the gas and liquid, but also on the uniformity of the liquid distribution
throughout the column, which is dependent on the column height and diameter. This makes
it difficult to extrapolate data obtained from small size laboratory and pilot plant columns
to industrial size columns. Whenever possible estimates should be based on actual values
obtained from operating columns of similar size to that being designed.
Experimental values for several systems are given by Cornell et al. (1960), Eckert
(1963), and Vital et al. (1984). A selection of values for a range of systems is given
in Table 11.3. The composite mass transfer term KG a is normally used when reporting
experimental mass-transfer coefficients for packing, as the effective interfacial area for
mass transfer will be less than the actual surface area a of the packing.
Many correlations have been published for predicting the height of a transfer unit, and
the mass-transfer coefficients; several are reviewed in Volume 2, Chapter 12. The two
methods given in this section have been found to be reliable for preliminary design work,
and, in the absence of practical values, can be used for the final design with a suitable
factor of safety.
The approach taken by the authors of the two methods is fundamentally different, and
this provides a useful cross-check on the predicted values. Judgement must always be
used when using predictive methods in design, and it is always worthwhile trying several
methods and comparing the results.
Typical values for the HTU of random packings are:
25 mm (1 in.)
38 mm (1 21 in.)
50 mm (2 in.)
Table 11.3.
System
Absorption
Hydrocarbons
NH3 -Air-H2 O
Air-water
Acetone-water
Distillation
Pentane-propane
IPA-water
Methanol-water
Acetone-water
Formic acid-water
Acetone-water
MEK-toluene
0.3 to 0.6 m (1 to 2 ft)
0.5 to 0.75 m (1 21 to 2 12 ft)
0.6 to 1.0 m (2 to 3 ft)
Typical packing efficiencies
Pressure
kPa
Column
dia, m
6000
101
101
101
0.9
101
101
101
101
101
101
101
101
101
101
101
101
101
type
Packing
size, mm
0.6
Pall
Berl
Berl
Pall
50
50
50
50
0.46
0.46
0.41
0.20
0.46
0.36
0.91
0.38
0.38
1.07
0.38
0.38
0.38
Pall
Int.
Pall
Int.
Pall
Int.
Pall
Pall
Int.
Int.
Pall
Int.
Berl
25
25
25
25
25
25
50
38
50
38
25
25
25
Pall D Pall rings, Berl D Berl saddles, Int. D Intalox saddles
HTU
m
HETP
m
0.85
0.50
0.50
0.75
0.75
0.52
0.55
0.50
0.29
0.27
0.31
0.46
0.50
0.46
0.37
0.46
0.45
0.45
0.45
1.22
0.35
0.23
0.31
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
599
Cornell’s method
Cornell et al. (1960) reviewed the previously published data and presented empirical
equations for predicting the height of the gas and liquid film transfer units. Their correlation
takes into account the physical properties of the system, the gas and liquid flow-rates; and the
column diameter and height. Equations and figures are given for a range of sizes of Raschig
rings and Berl saddles. Only those for Berl saddles are given here, as it is unlikely that
Raschig rings would be considered for a new column. Though the mass-transfer efficiency
of Pall rings and Intalox saddles will be higher than that of the equivalent size Berl saddle,
the method can be used to make conservative estimates for these packings.
Bolles and Fair (1982) have extended the correlations given in the earlier paper to
include metal Pall rings.
Cornell’s equations are:
Dc 1.11
Z 0.33
⊲LwŁ f1 f2 f3 ⊳0.5 ⊲11.110⊳
HG D 0.011 h ⊲Sc⊳0.5
v
0.305
3.05
Z 0.15
K
HL D 0.305h ⊲Sc⊳0.5
⊲11.111⊳
3
L
3.05
where HG
HL
⊲Sc⊳v
⊲Sc⊳L
Dc
Z
K3
h
h
LwŁ
f1
f2
f3
D
D
D
D
D
D
D
D
D
D
D
D
D
height of a gas-phase transfer unit, m,
height of a liquid-phase transfer unit, m,
gas Schmidt number D ⊲v /v Dv ⊳,
liquid Schmidt number D ⊲L /L DL ⊳,
column diameter, m,
column height, m,
percentage flooding correction factor, from Figure 11.41,
HG factor from Figure 11.42,
HL factor from Figure 11.43,
liquid mass flow-rate per unit area column cross-sectional area, kg/m2 s,
liquid viscosity correction factor D ⊲L /w ⊳0.16 ,
liquid density correction factor D ⊲w /L ⊳1.25 ,
surface tension correction factor D ⊲w /L ⊳0.8 ,
Figure 11.41.
Percentage flooding correction factor
600
CHEMICAL ENGINEERING
100
in (mm)
1 1/2 (38)
80
1/2 (12)
1(25)
60
ψn
40
20
0
10
20
40
30
50
60
70
80
90
100
Percentage flooding
Figure 11.42.
Factor for HG for Berl saddles
Figure 11.43.
Factor for HL for Berl saddles
where the suffix w refers to the physical properties of water at 20Ž C; all other physical
properties are evaluated at the column conditions.
The terms (Dc /0.305) and (Z/3.05) are included in the equations to allow for the effects
of column diameter and packed-bed height. The “standard” values used by Cornell were
1 ft (0.305 m) for diameter, and 10 ft (3.05 m) for height. These correction terms will
clearly give silly results if applied over too wide a range of values. For design purposes the
diameter correction term should be taken as a fixed value of 2.3 for columns above 0.6 m
601
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
(2 ft) diameter, and the height correction should only be included when the distance between
liquid redistributors is greater than 3 m. To use Figures 11.41 and 11.42 an estimate of the
column percentage flooding is needed. This can be obtained from Figure 11.44, where a
flooding line has been included with the lines of constant pressure drop.
K4 at design pressure drop 1/2
Percentage flooding D
⊲11.112⊳
K4 at flooding
A full discussion of flooding in packed columns is given in Volume 2, Chapter 4.
Onda’s method
Onda et al. (1968) published useful correlations for the film mass-transfer coefficients kG
and kL and the effective wetted area of the packing aw , which can be used to calculate
HG and HL .
Their correlations were based on a large amount of data on gas absorption and distillation;
with a variety of packings, which included Pall rings and Berl saddles. Their method for
estimating the effective area of packing can also be used with experimentally determined
values of the mass-transfer coefficients, and values predicted using other correlations.
The equation for the effective area is:
0.75 Ł 0.1 Ł2 0.05 Ł2 0.2
aw
Lw
c
Lw
Lw a
⊲11.113⊳
D 1 exp 1.45
2
a
L
aL
L L a
L g
and for the mass coefficients:
Ł 2/3
Lw
L 1/3
L 1/2
kL
D 0.0051
⊲adp ⊳0.4
L g
aw L
L DL
Ł 0.7
Vw
v 1/3
kG RT
D K5
⊲adp ⊳2.0
a Dv
av
v Dv
where K5
LwŁ
VŁw
aw
a
dp
c
D
D
D
D
D
D
D
⊲11.114⊳
⊲11.115⊳
5.23 for packing sizes above 15 mm, and 2.00 for sizes below 15 mm,
liquid mass flow rate per unit cross-sectional area, kg/m2 s,
gas mass flow rate per unit column cross-sectional area, kg/m2 s,
effective interfacial area of packing per unit volume, m2 /m3 ,
actual area of packing per unit volume (see Table 11.3), m2 /m3 ,
packing size, m,
critical surface tension for the particular packing material given below:
Material
Ceramic
Metal (steel)
Plastic (polyethylene)
Carbon
c mN/m
61
75
33
56
602
CHEMICAL ENGINEERING
L D liquid surface tension, N/m,
kG D gas film mass transfer coefficient, kmol/m2 s atm or kmol/m2 s bar,
kL D liquid film mass transfer coefficient, kmol/m2 s (kmol/m3 ) D m/s.
Note: all the groups in the equations are dimensionless.
The units for kG will depend on the units used for the gas constant:
R D 0.08206 atm m3 /kmol K or
0.08314 bar m3 /kmol K
The film transfer unit heights are given by:
Gm
kG aw P
Lm
HL D
kL aw Ct
HG D
where P
Ct
Gm
Lm
D
D
D
D
⊲11.116⊳
⊲11.117⊳
column operating pressure, atm or bar,
total concentration, kmol/m3 D L /molecular weight solvent,
molar gas flow-rate per unit cross-sectional area, kmol/m2 s,
molar liquid flow-rate per unit cross-sectional area, kmol/m2 s.
Nomographs
A set of nomographs are given in Volume 2, Chapter 12 for the estimation of HG and
HL , and the wetting rate. These were taken from a proprietary publication, but are based
on a set of similar nomographs given by Czermann et al. (1958), who developed the
nomographs from correlations put forward by Morris and Jackson (1953) and other
workers.
The nomographs can be used to make a quick, rough, estimate of the column height,
but are an oversimplification, as they do not take into account all the physical properties
and other factors that affect mass transfer in packed columns.
11.14.4. Column diameter (capacity)
The capacity of a packed column is determined by its cross-sectional area. Normally, the
column will be designed to operate at the highest economical pressure drop, to ensure
good liquid and gas distribution. For random packings the pressure drop will not normally
exceed 80 mm of water per metre of packing height. At this value the gas velocity will
be about 80 per cent of the flooding velocity. Recommended design values, mm water
per m packing, are:
Absorbers and strippers
Distillation, atmospheric and moderate pressure
15 to 50
40 to 80
Where the liquid is likely to foam, these values should be halved.
603
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
For vacuum distillations the maximum allowable pressure drop will be determined by
the process requirements, but for satisfactory liquid distribution the pressure drop should
not be less than 8 mm water per m. If very low bottom pressures are required special low
pressure-drop gauze packings should be considered; such as Hyperfil, Multifil or Dixon
rings; see Volume 2, Chapter 4.
The column cross-sectional area and diameter for the selected pressure drop can be
determined from the generalised pressure-drop correlation given in Figure 11.44.
10.0
6.0
4.0
Parameter of curves is pressure drop
in mm of water/metre of packed
od height
ing
lin
e
(12
5)
Flo
(83
)
2.0
(42
)
1.0
(21
)
0.6
0.4
(8)
K4
0.2
(4)
0.1
0.06
0.04
0.02
0.01
0.01
0.02
0.04
0.06
0.1
0.2
0.4
0.6
1.0
2.0
4.0
6.0
10.0
FLV
FLV =
Figure 11.44.
L*W
V*W
ρ
V
ρ
L
Generalised pressure drop correlation, adapted from a figure by the Norton Co. with permission
Figure 11.44 correlates the liquid and vapour flow rates, system physical properties
and packing characteristics, with the gas mass flow-rate per unit cross-sectional area;
with lines of constant pressure drop as a parameter.
604
CHEMICAL ENGINEERING
The term K4 on Figure 11.44 is the function:
K4 D
L
L
v ⊲L v ⊳
13.1⊲VŁw ⊳2 Fp
0.1
⊲11.118⊳
where VŁw D gas mass flow-rate per unit column cross-sectional area, kg/m2 s
Fp D packing factor, characteristic of the size and type of packing,
see Table 11.3, m1 .
L D liquid viscosity, Ns/m2
L , v D liquid and vapour densities, kg/m3
The values of the flow factor FLV given in Figure 11.44 covers the range that will
generally give satisfactory column performance.
The ratio of liquid to gas flow will be fixed by the reflux ratio in distillation; and in
gas absorption will be selected to give the required separation with the most economic
use of solvent.
A new generalised correlation for pressure drop in packed columns, similar to
Figure 11.44, has been published by Leva (1992), (1995). The new correlations gives
a better prediction for systems where the density of the irrigating fluid is appreciably
greater than that of water. It can also be used to predict the pressure drop over dry
packing.
Example 11.14
Sulphur dioxide produced by the combustion of sulphur in air is absorbed in water. Pure
SO2 is then recovered from the solution by steam stripping. Make a preliminary design
for the absorption column. The feed will be 5000 kg/h of gas containing 8 per cent v/v
SO2 . The gas will be cooled to 20Ž C. A 95 per cent recovery of the sulphur dioxide is
required.
Solution
As the solubility of SO2 in water is high, operation at atmospheric pressure should be
satisfactory. The feed-water temperature will be taken as 20Ž C, a reasonable design value.
Solubility data
From Chemical Engineers Handbook, 5th edn, McGraw-Hill, 1973.
per cent w/w
solution
0.05
0.1
0.15
0.2
0.3
1.2
3.2
5.8
8.5
14.1
0.5
0.7
1.0
1.5
SO2
Partial press.
gas mmHg
26
39
Partial pressure of SO2 in the feed D ⊲8/100⊳ ð 760 D 60.8 mm Hg
59
92
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
605
Figure (d). SO2 absorber design (Example 11.14)
These figures are plotted in Figure ⊲d⊳.
Number of stages
Partial pressure in the exit gas at 95 per cent recovery D 60.8 ð 0.05 D 3.04 mm Hg
Over this range of partial pressure the equilibrium line is essentially straight so
Figure 11.40 can be used to estimate the number of stages needed.
The use of Figure 11.40 will slightly overestimate the number of stages and a more
accurate estimate would be made by graphical integration of equation 11.104; but this is
not justified in view of the uncertainty in the prediction of the transfer unit height.
Molecular weights: SO2 D 64, H2 O D 18, air D 29
Slope of equilibrium line
From the data: partial pressure at 1.0% w/w SO2 D 59 mm Hg.
59
D 0.0776
760
1
64
D 0.0028
Mol. fraction in liquid D
99
1
C
64 18
0.0776
mD
D 27.4
0.0028
Mol. fraction in vapour D
606
CHEMICAL ENGINEERING
To decide the most economic water flow-rate, the stripper design should be considered
together with the absorption design, but for the purpose of this example the absorption
design will be considered alone. Using Figure 11.40 the number of stages required at
different water rates will be determined and the “optimum” rate chosen:
p1
60.8
y1
D 20
D
D
y2
p2
3.04
Gm
Lm
0.5
0.6
0.7
0.8
NOG
3.7
4.1
6.3
8
m
0.9
1.0
10.8
19.0
It can be seen that the “optimum” will be between mGm /Lm D 0.6 to 0.8, as would
be expected. Below 0.6 there is only a small decrease in the number of stages required
with increasing liquid rate; and above 0.8 the number of stages increases rapidly with
decreasing liquid rate.
Check the liquid outlet composition at 0.6 and 0.8:
Material balance Lm x1 D Gm ⊲y1 y2 ⊳
so x1 D
m Gm
Gm
⊲0.08 ð 0.95⊳ D
⊲0.076⊳
Lm
27.4 Lm
at
mGm
D 0.6, x1 D 1.66 ð 103 mol fraction
Lm
at
mGm
D 0.8, x1 D 2.22 ð 103 mol fraction
Lm
Use 0.8, as the higher concentration will favour the stripper design and operation,
without significantly increasing the number of stages needed in the absorber.
NOG D 8
Column diameter
The physical properties of the gas can be taken as those for air, as the concentration of
SO2 is low.
1.39
5000
D 1.39 kg/s, D
D 0.048 kmol/s
Gas flow-rate D
3600
29
27.4
Liquid flow-rate D
ð 0.048 D 1.64 kmol/s
0.8
D 29.5 kg/s.
Select 38 mm ⊲1 21 in.⊳ ceramic Intalox saddles.
From Table 11.3, Fp D 170 m1
29
273
ð
D 1.21 kg/m3
Gas density at 20Ž C D
22.4 293
Liquid density ' 1000 kg/m3
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Liquid viscosity D 103 Ns/m2
Ł
29.5 1.21
LW
v
D
D 0.74
VŁW L
1.39 103
Design for a pressure drop of 20 mm H2 O/m packing
From Figure 11.44,
K4 D 0.35
At flooding K4 D 0.8
0.35
Percentage flooding D
ð 100 D 66 per cent, satisfactory.
0.8
From equation 11.118
K4 V ⊲L v ⊳ 1/2
VŁW D
13.1Fp ⊲L /L ⊳0.1
0.35 ð 1.21⊲1000 1.21⊳ 1/2
D
D 0.87 kg/m2 s
13.1 ð 170⊲103 /103 ⊳0.1
1.39
D 1.6 m2
0.87
4
Diameter D
ð 1.6 D 1.43 m
Round off to 1.50 m
Column area required D
Column area D
ð 1.52 D 1.77 m2
4
Packing size to column diameter ratio D
A larger packing size could be considered.
Percentage flooding at selected diameter
1.5
D 39,
38 ð 103
1.6
D 60 per cent,
1.77
Could consider reducing column diameter.
D 66 ð
Estimation of HOG
Cornell’s method
DL D 1.7 ð 109 m2 /s
Dv D 1.45 ð 105 m2 /s
v D 0.018 ð 103 Ns/m2
0.018 ð 103
D 1.04
⊲Sc⊳v D
1.21 ð 1.45 ð 105
607
608
CHEMICAL ENGINEERING
103
D 588
1000 ð 1.7 ð 109
29.5
D
D 16.7 kg/s m2
1.77
⊲Sc⊳L D
Ł
LW
From Figure 11.41, at 60 per cent flooding, K3 D 0.85.
From Figure 11.42, at 60 per cent flooding, h D 80.
Ł
From Figure 11.43, at LW
D 16.7, h D 0.1.
HOG can be expected to be around 1 m, so as a first estimate Z can be taken as
8 m. The column diameter is greater than 0.6 m so the diameter correction term will be
taken as 2.3.
8 0.15
0.5
D 0.7 m
⊲11.111⊳
HL D 0.305 ð 0.1⊲588⊳ ð 0.85
3.05
As the liquid temperature has been taken as 20Ž C, and the liquid is water,
f 1 D f2 D f 3 D 1
8 0.33
HG D 0.011 ð 80⊲1.04⊳0.5 ⊲2.3⊳
⊲16.7⊳0.5 D 0.7 m
3.05
HOG D 0.7 C 0.8 ð 0.7 D 1.3 m
⊲11.110⊳
⊲11.105⊳
Z D 8 ð 1.3 D 10.4 m, close enough to the estimated value.
Onda’s method
R D 0.08314 bar m3 /kmol K.
Surface tension of liquid, taken as water at 20Ž C D 70 ð 103 N/m
g D 9.81 m/s2
dp D 38 ð 103 m
From Table 11.3, for 38 mm Intalox saddles
a D 194 m2 /m3
c for ceramics D 61 ð 103 N/m
0.05
0.75
0.1
61 ð 103
17.6
17.62 ð 194
aW
D 1 exp 1.45
a
70 ð 103
194 ð 103
10002 ð 9.81
0.2
17.62
D 0.71
⊲11.113⊳
ð
1000 ð 70 ð 103 ð 194
aW D 0.71 ð 194 D 138 m2 /m3
1/3
2/3
1/2
103
17.6
103
D
0.0051
kL
103 ð 9.81
138 ð 103
103 ð 1.7 ð 109
ð ⊲194 ð 38 ð 103 ⊳0.4
⊲11.114⊳
kL D 2.5 ð 104 m/s
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
VŁW on actual column diameter D
0.08314 ð 293
kG
D 5.23
194 ð 1.45 ð 105
ð
609
1.39
D 0.79 kg/m2 s
1.77
0.7
0.79
⊲11.115⊳
194 ð 0.018 ð 103
1/3
0.018 ð 103
⊲194 ð 38 ð 103 ⊳2.0
1.21 ð 1.45 ð 105
kG D 5.0 ð 104 kmol/sm2 bar
0.79
D 0.027 kmol/m2 s
Gm D
29
16.7
Lm D
D 0.93 kmol/m2 s
18
0.027
D 0.39 m
5.0 ð
ð 138 ð 1.013
CT D total concentration, as water,
1000
D 55.6 kmol/m3
D
18
HG D
HL D
104
0.93
D 0.49 m
2.5 ð 104 ð 138 ð 55.6
HOG D 0.39 C 0.8 ð 0.49 D 0.78 m
⊲11.116⊳
⊲11.117⊳
⊲11.105⊳
Use higher value, estimated using Cornell’s method, and round up packed bed height
to 11 m.
11.14.5. Column internals
The internal fittings in a packed column are simpler than those in a plate column but must
be carefully designed to ensure good performance. As a general rule, the standard fittings
developed by the packing manufacturers should be specified. Some typical designs are
shown in Figures 11.45 to 11.54; and their use is discussed in the following paragraphs.
Packing support
The function of the support plate is to carry the weight of the wet packing, whilst allowing
free passage of the gas and liquid. These requirements conflict; a poorly designed support
will give a high pressure drop and can cause local flooding. Simple grid and perforated plate supports are used, but in these designs the liquid and gas have to vie for
the same openings. Wide-spaced grids are used to increase the flow area; with layers
of larger size packing stacked on the grid to support the small size random packing,
Figure 11.45.
The best design of packing support is one in which gas inlets are provided above the level
where the liquid flows from the bed; such as the gas-injection type shown in Figure 11.46
610
CHEMICAL ENGINEERING
Packing is
dumped over
courses of
cross partition
rings
Figure 11.45.
Stacked packing used to support random packing
Gas is distributed
directly into packed
bed –no hydrostatic
head –gas and liquid
flow through
separate openings
in plate
Gas-injection
support plate
Figure 11.46.
The principle of the gas-injection packing support
and 11.47. These designs have a low pressure drop and no tendency to flooding. They are
available in a wide range of sizes and materials: metals, ceramics and plastics.
Liquid distributors
The satisfactory performance of a plate column is dependent on maintaining a uniform
flow of liquid throughout the column, and good initial liquid distribution is essential.
Various designs of distributors are used. For small-diameter columns a central open feedpipe, or one fitted with a spray nozzle, may well be adequate; but for larger columns more
elaborate designs are needed to ensure good distribution at all liquid flow-rates. The two
most commonly used designs are the orifice type, shown in Figure 11.48, and the weir
type, shown in Figure 11.49. In the orifice type the liquid flows through holes in the plate
and the gas through short stand pipes. The gas pipes should be sized to give sufficient
area for gas flow without creating a significant pressure drop; the holes should be small
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
611
(a)
(b)
Figure 11.47.
Typical designs of gas-injection supports (Norton Co.). (a) Small diameter columns (b) Large
diameter columns
enough to ensure that there is a level of liquid on the plate at the lowest liquid rate, but
large enough to prevent the distributor overflowing at the highest rate. In the weir type
the liquid flows over notched weirs in the gas stand-pipes. This type can be designed to
cope with a wider range of liquid flow rates than the simpler orifice type.
For large-diameter columns, the trough-type distributor shown in Figure 11.50 can be
used, and will give good liquid distribution with a large free area for gas flow.
All distributors which rely on the gravity flow of liquid must be installed in the column
level, or maldistribution of liquid will occur.
A pipe manifold distributor, Figure 11.51, can be used when the liquid is fed to the
column under pressure and the flow-rate is reasonably constant. The distribution pipes
and orifices should be sized to give an even flow from each element.
612
CHEMICAL ENGINEERING
Figure 11.48.
Figure 11.49.
Orifice-type distributor (Norton Co.)
Weir-type distributor (Norton Co.)
Liquid redistributors
Redistributors are used to collect liquid that has migrated to the column walls and redistribute it evenly over the packing. They will also even out any maldistribution that has
occurred within the packing.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Figure 11.50.
613
Weir-trough distributors (Norton Co.)
Figure 11.51.
Pipe distributor (Norton Co.)
A full redistributor combines the functions of a packing support and a liquid distributor;
a typical design is shown in Figure 11.52.
The “wall-wiper” type of redistributor, in which a ring collects liquid from the column
wall and redirects it into the centre packing, is occasionally used in small-diameter
columns, less than 0.6 m. Care should be taken when specifying this type to select a
design that does not unduly restrict the gas flow and cause local flooding. A good design
is that shown in Figure 11.53.
614
CHEMICAL ENGINEERING
Support plate
Gas
Liquid
Figure 11.52.
Redistributor
Full redistributor
Optional installation
installed between tower flanges
Figure 11.53.
“Wall wiper” redistributor (Norton Co.)
The maximum bed height that should be used without liquid redistribution depends on
the type of packing and the process. Distillation is less susceptible to maldistribution than
absorption and stripping. As a general guide, the maximum bed height should not exceed
3 column diameters for Raschig rings, and 8 to 10 for Pall rings and saddles. In a largediameter column the bed height will also be limited by the maximum weight of packing
that can be supported by the packing support and column walls; this will be around 8 m.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
615
Hold-down plates
At high gas rates, or if surging occurs through mis-operation, the top layers of packing
can be fluidised. Under these conditions ceramic packing can break up and the pieces
filter down the column and plug the packing; metal and plastic packing can be blown out
of the column. Hold-down plates are used with ceramic packing to weigh down the top
layers and prevent fluidisation; a typical design is shown in Figure 11.54. Bed-limiters
are sometimes used with plastics and metal packings to prevent expansion of the bed
when operating at a high-pressure drop. They are similar to hold-down plates but are of
lighter construction and are fixed to the column walls. The openings in hold-down plates
and bed-limiters should be small enough to retain the packing, but should not restrict the
gas and liquid flow.
Figure 11.54.
Hold-down plate design (Norton Co.)
Installing packing
Ceramic and metal packings are normally dumped into the column “wet”, to ensure a
truly random distribution and prevent damage to the packing. The column is partially
filled with water and the packing dumped into the water. A height of water must be kept
above the packing at all times.
If the columns must be packed dry, for instance to avoid contamination of process fluids
with water, the packing can be lowered into the column in buckets or other containers.
Ceramic packings should not be dropped from a height of more than half a metre.
Liquid hold-up
An estimate of the amount of liquid held up in the packing under operating conditions
is needed to calculate the total load carried by the packing support. The liquid hold-up
will depend on the liquid rate and, to some extent, on the gas flow-rate. The packing
manufacturers’ design literature should be consulted to obtain accurate estimates. As a
616
CHEMICAL ENGINEERING
rough guide, a value of about 25 per cent of the packing weight can be taken for ceramic
packings.
11.14.6. Wetting rates
If very low liquid rates have to be used, outside the range of FLV given in Figure 11.44,
the packing wetting rate should be checked to make sure it is above the minimum recommended by the packing manufacturer.
Wetting rate is defined as:
wetting rate D
volumetric liquid rate per unit cross-sectional area
packing surface area per unit volume
A nomograph for the calculation of wetting rates is given in Volume 2, Chapter 4.
Wetting rates are frequently expressed in terms of mass or volume flow-rate per unit
column cross-sectional area.
Kister (1992) gives values for minimum wetting rates of 0.5 to 2 gpm/ft2 ⊲0.35 ð
3
10 to 1.4 ð 103 m3 s1 /m2 ⊳ for random packing and 0.1 to 0.2 gpm/ft2 (0.07 ð
103 to 0.14 ð 103 m3 s1 /m2 ) for structured packing. Norman (1961) recommends that
the liquid rate in absorbers should be kept above 2.7 kg/m2 s.
If the design liquor rate is too low, the diameter of the column should be reduced. For
some processes liquid can be recycled to increase the flow over the packing.
A substantial factor of safety should be applied to the calculated bed height for process
where the wetting rate is likely to be low.
11.15. COLUMN AUXILIARIES
Intermediate storage tanks will normally be needed to smooth out fluctuations in column
operation and process upsets. These tanks should be sized to give sufficient hold-up time
for smooth operation and control. The hold-up time required will depend on the nature
of the process and on how critical the operation is; some typical values for distillation
processes are given below:
Operation
Feed to a train of columns
Between columns
Feed to a column from storage
Reflux drum
Time, minutes
10
5
2
5
to
to
to
to
20
10
5
15
The time given is that for the level in the tank to fall from the normal operating level to
the minimum operating level if the feed ceases.
Horizontal or vertical tanks are used, depending on the size and duty. Where only a
small hold-up volume is required this can be provided by extending the column base, or,
for reflux accumulators, by extending the bottom header of the condenser.
The specification and sizing of surge tanks and accumulators is discussed in more detail
by Mehra (1979) and Evans (1980).
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
617
11.16. SOLVENT EXTRACTION (LIQUID LIQUID EXTRACTION)
Extraction should be considered as an alternative to distillation in the following situations:
1. Where the components in the feed have close boiling points. Extraction in a suitable
solvent may be more economic if the relative volatility is below 1.2.
2. If the feed components form an azeotrope.
3. If the solute is heat sensitive, and can be extracted in to a lower boiling solvent, to
reduce the heat history during recovery.
Solvent selection
The following factors need to be considered when selecting a suitable solvent for a given
extraction.
1. Affinity for solute: the selectivity, which is a measure of the distribution of the
solute between the two solvents (concentration of solute in feed-solvent divided by
the concentration in extraction-solvent). Selectivity is analogous to relative volatility
in distillation. The greater the difference in solubility of the solute between the two
solvents, the easier it will be to extract.
2. Partition ratio: this is the weight fraction of the solute in the extract divided by the
weight fraction in the raffinate. This determines the quantity of solvent needed. The
less solvent needed the lower will be the solvent and solvent recovery costs.
3. Density: the greater the density difference between the feed and extraction solvents
the easier it will be to separate the solvents.
4. Miscibility: ideally the two solvents should be immiscible. The greater the solubility
of the exaction solvent in the feed solvent the more difficult it will be to recover
the solvent from the raffinate, and the higher the cost.
5. Safety: if possible, and all other factors considered, a solvent should be chosen that
is not toxic nor dangerously inflammable.
6. Cost: the purchase cost of the solvent is important but should not be considered in
isolation from the total process costs. It may be worth considering a more expensive
solvent if it is more effective and easier to recover.
11.16.1. Extraction equipment
Extraction equipment can be divided into two broad groups:
1. Stage-wise extractors, in which the liquids are alternately contacted (mixed) and
then separated, in a series of stages. The “mixer-settler” contactor, is an example of
this type. Several mixer-settlers are often used in series to increase the effectiveness
of the extraction.
2. Differential extractors, in which the phases are continuously in contact in the extractor and are only separated at the exits; for example, in packed column extractors.
Extraction columns can be further sub-divided according to the method used to promote
contact between the phases: packed, plate, mechanically agitated, or pulsed columns.
Various types of proprietary centrifugal extractors are also used.
618
CHEMICAL ENGINEERING
The following factors need to be taken into consideration when selecting an extractor
for a particular application:
1.
2.
3.
4.
The
The
The
The
number of stages required.
throughputs.
settling characteristics of the phases.
available floor area and head room.
Hanson (1968) has given a selection guide based on these factors, which can be used to
select the type of equipment most likely to be suitable, Figure 11.55.
The process
Minimum contact
Yes
time essential?
No
Poor setting character
Yes
danger stable emulsions?
No
Small number of
stages required?
No
Appreciable number
of stages required?
Centrifugal contactor
Yes
Limited area
available?
Limited headroom
available?
Simple gravity
column
Yes
Mixer-settler
Limited area
available?
Limited headroom
available?
Yes
Yes
Figure 11.55.
Centrifugal contactor
Mixer-settler
Large throughput?
Small throughput?
Mechanically
agitated column
Pulsed column
Selection guide for liquid liquid contactors (after Hanson, 1968)
The fields of application of the various types of extraction equipment are also well
summarised in Volume 2, Chapter 13. The basic principles of liquid liquid extraction are
covered in several specialist texts: Treybal (1980), Robbins (1997), and Humphrey and
Keller (1997).
11.16.2. Extractor design
Number of stages
The primary task in the design of an extractor for a liquid liquid extraction process is
the determination of the number of stages needed to achieve the separation required.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
619
The stages my be arranged in three ways:
1. Fresh solvent fed to each stage, the raffinate passing from stage to stage.
2. The extracting solvent fed co-currently with the raffinate, from stage to stage.
3. The exacting solvent fed counter-current to the raffinate.
Counter-current flow is the most efficient method and the most commonly used. It will
give the greatest concentration of the solute in the extract, and the least use of solvent.
Equilibrium data
To determine the number of stages it best to plot the equilibrium data on a triangular
diagram, Figure 11.56. Each corner of the triangle represents 100% of the feed-solvent,
solute or extraction-solvent. Each side shows the composition of one of the binary pairs.
The ternary compositions are shown in the interior of the triangular. Mixtures within the
region bounded by the curve will separate into two phases. The tie-lines link the equilibrium
compositions of the separate phases. The tie-lines reduce in length toward the top of the
curve. The point where they disappear is called the plait point.
A Solute
Plait
point
Tie
lines
C
Feed
solvent
Figure 11.56.
B
Solvent
Equilibrium diagram solute distributed between two solvents
A fuller discussion of the various classes of diagram used to represent liquid liquid
equilibria is given in Volume 2, Chapter 13; see also Treybal (1980) and Humphrey
et al. (1984).
The most comprehensive source of equilibrium data for liquid liquid systems is the
DECHEMA data series, Sorensen and Arlt (1979). Equilibrium data for some systems is
also given by Perry et al. (1997).
The UNIQUAC and UNIFAC equations can be used to estimate liquid liquid equilibria,
see Chapter 8.
Number of stages
The number of stages required for a given separation can be determined from the triangular
diagram using a method analogous to the McCabe Thiele diagram used to determine the
620
CHEMICAL ENGINEERING
number of theoretical stages (plates) in distillation. The method set out below is for
counter-current extraction.
Procedure
Refer to Figures 11.56 and 11.57.
rn−1
F
f
rn
1
E1
e1
n
en
m
en−1
Figure 11.57.
R
rm
S
so
Counter-current extraction
Let the flow-rates be:
F D feed, of the solution to be extracted
E D extract
R D raffinate
S D the extracting solvent
and the compositions:
r D raffinate
e D extract
s D solvent
f D feed
Then a material balance over stage n gives:
F C EnC1 D Rn C E1
It can be shown that the difference in flow-rate between the raffinate leaving any stage,
Rn , and the extract entering the stage, En , is constant. Also, that the difference between
the amounts of each component entering and leaving a stage is constant. This means that
if lines are drawn on the triangular diagram linking the composition of the raffinate from
a stage and the extract entering from the next stage, they will pass through a common
pole when extrapolated. The number of stages needed can be found by making use of
this construction and the equilibrium compositions given by the tie-lines.
Construction
1. Draw the liquid liquid equilibrium data on triangular graph paper. Show sufficient
tie-lines to enable the equilibrium compositions to be determined at each stage.
2. Mark the feed and extraction-solvent compositions on the diagram. Join them with
a line. The composition of a mixture of the feed and solvent will lie on this line.
3. Calculate the composition of the mixture given by mixing the feed with the extraction
solvent. Mark this point, 0, on the line drawn in step 2.
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
621
4. Mark the final raffinate composition, rm on the equilibrium curve.
5. Draw a line from rm through the point 0. This will cut the curve at the final extract
composition, e1 .
Note: if the extract composition is specified, rather than the raffinate, draw the line
from e1 through 0 to find rm .
6. Draw a line from the solvent composition, S0 through rm and extend it beyond rm .
7. Draw a line from e1 through f and extend it to cross the line drawn in step 6, at
the pole point, P.
8. Find the composition of the raffinate leaving the first stage, r1 by judging the position
of the tie-line from e1 . Draw a line from the pole point, P, through r1 to cut the
curve at e2 , the extract leaving stage 2.
9. Repeat this procedure until sufficient stages have been drawn to reach the desired
raffinate final composition.
If an extended tie-line passes through the pole point P, an infinite number of stages will
be needed. This condition sets the minimum flow of extraction-solvent required. It is
analogous to a pinch point in distillation.
The method is illustrated in Example 11.15.
Example 11.15
Acetone is to be extracted from a solution in water, using 1,1,2-trichloroethane. The feed
concentration is 45.0 per cent w/w acetone. Determine the number of stages required to
reduce the concentration of acetone to below 10 per cent, using 32 kg of extraction-solvent
per 100 kg feed.
The equilibrium data for this system are given by Treybal et al. Ind. Eng. Chem. 38,
817 (1946).
Solution
Composition of feed C solvent, point o D 0.45 ð 100/⊲100 C 32⊳ D 0.34 D 34 per cent.
Draw line from TCE (trichloroethane) D 100 per cent, point s0 , to feed composition, f,
45 per cent acetone.
Mark point o on this line at 34 per cent acetone.
Mark required final raffinate composition, rm , on the equilibrium curve, at 10 per cent.
Draw line from this point through point o to find final extract composition, e1 .
Draw line from this point though the feed composition, f, extend this line to cut a line
extended from s0 through rm , at P.
Using the tie-lines plotted on the figure, judge the position that a tie-line would have from
e1 and mark it in, to find the point on the curve giving the composition of the raffinate
leaving the first stage, r1 .
Draw a line through from the pole point P through r1 , to find the point on the curve
giving the extract composition leaving the second stage, e2 .
Repeat these steps until the raffinate composition found is below 10 per cent.
From the diagram, Figure 11.58, it can be seen that five stages are needed.
622
Acetone
100%
r1
o
e3
e4
r3
r4
e5
rm
r5
100%
water
Figure 11.58.
Example 11.15
50%
e2
r2
P
CHEMICAL ENGINEERING
e1
50%
f
50%
so
100%
TCE
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
623
That the raffinate composition from stage 5 passes through the specified raffinate composition of 10 per cent is fortuitous. As the construction, particularly the judgement of
the position of the tie-lines, is approximate, the number of stages will be increased to
six. This should ensure that the specified raffinate composition of below 10 per cent
is met.
Immiscible solvents
If the solvents are immiscible the procedure for determining the number of stages required
is simplified. The equilibrium curve can be drawn on regular, orthogonal, graph paper.
An operating line, giving the relationship between the compositions of the raffinate and
extracts entering and leaving each stage, can then be drawn, and the stages stepped off.
The procedure is similar to the McCabe Thiele construction for determining the number
of stages in distillation; Section 11.5.2. The slope of the operating line is the ratio of the
final raffinate to fresh solvent flow-rates.
For a full discussion of the methods that can be used to determine the stage requirements
in liquid liquid extraction refer to Treybal (1980), Perry et al. (1997) and Robbins (1997).
Computer programs are available for the design of extraction processes and would
normally be included in the various commercial process simulation packages available;
see Chapter 4.
11.16.3. Extraction columns
The simplest form of extractor is a spray column. The column is empty; one liquid forms
a continuous phase and the other liquid flows up, or down, the column in the form of
droplets. Mass transfer takes places to, or from, the droplets to the continuous phase. The
efficiency of a spray tower will be low, particularly with large diameter columns, due
to back mixing. The efficiency of the basic, empty, spray column can be improved by
installing plates or packing.
Sieve plates are used, similar to those used for distillation and absorption. The stage
efficiency for sieve plates, expressed in terms the height of an equivalent theoretical stage
(HETS), will, typically, range from 1 to 2.5 m.
Random packings are also used; they are the same as those used in packed distillation
and absorption columns. The properties of random packings are given in Table 11.3.
Proprietary structured packing are also used.
Mass transfer in packed columns is a continuous, differential, process, so the transfer
unit method should be used to determine the column height, as used in absorption; see
Section 11.14.2. However, it often convenient to treat them as staged processes and use
the HETS for the packing employed. For random packings the HETS will, typically, range
from 0.5 to 1.5 m, depending on the type and size of packing used.
Flooding
No simple correlation is available to predict the flooding velocities in extraction columns,
and hence the column diameter needed. The more specialised texts should be consulted
to obtain guidance on the appropriate method to use for a particular problem; see Treybal
(1980), Perry et al. (1997) and Humphrey and Keller (1997).
624
CHEMICAL ENGINEERING
11.16.4. Supercritical fluid extraction
A recent development in liquid liquid extraction has been the use of supercritical fluids
as the extraction-solvent. Carbon dioxide at high pressure is the most commonly used
fluid. It is used in processes for the decaffeination of coffee and tea. The solvent can
be recovered from the extract solution as a gas, by reducing the pressure. Super critical
extraction processes are discussed by Humphrey and Keller (1997).
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(McGraw-Hill).
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625
FAIR, J. R. and BRAVO, J. L. (1990) Chem. Eng. Prog. 86, (1) 19. Distillation columns containing structured
packing.
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efficiency from laboratory Oldershaw data.
FEATHERSTONE, W. (1971) Brit. Chem. Eng. & Proc. Tech. 16 (12), 1121. Azeotropic systems, a rapid method
of still design.
FEATHERSTONE, W. (1973) Proc. Tech. Int. 18 (April/May), 185. Non-ideal systems A rapid method of
estimating still requirements.
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FREDENSLUND, A., GMEHLING, J. and RASMUSSEN, P. (1977) Vapour-liquid Equilibria using UNIFAC (Elsevier).
GEDDES, R. L. (1958) AIChE Jl 4, 389. General index of fractional distillation power for hydrocarbon mixtures.
GILLILAND, E. R. (1940) Ind. Eng. Chem. 32, 1220. Multicomponent rectification, estimation of the number of
theoretical plates as a function of the reflux ratio.
GILLILAND, E. R. and REED, C. E. (1942) Ind. Eng. Chem. 34, 551. Degrees of freedom in multicomponent
absorption and rectification.
GLITSCH, H. C. (1960) Pet. Ref. 39 (Aug) 91. Mechanical specification of trays.
GLITSCH, H. C. (1970) Ballast Tray Design Manual, Bulletin No. 4900 (W. Glistsch & Son, Dallas, Texas).
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HANSON, C. (1968) Chem. Eng., NY 75 (Aug. 26th) 76. Solvent extraction.
HANSON, D. N., DUFFIN, J. H. and SOMERVILLE, G. E. (1962) Computation of Multistage Separation Processes
(Reinhold).
HANSON, D. N. and SOMERVILLE, G. F. (1963) Advances in Chemical Engineering 4, 279. Computing multistage
vapor-liquid processes.
HART, D. R. (1997) Batch Distillation, in Distillation Design, Kister, H. Z. (McGraw-Hill).
HENGSTEBECK, R. J. (1946) Trans. Am. Inst. Chem. Eng. 42, 309. Simplified method for solving multicomponent
distillation problems.
HENGSTEBECK, R. J. (1976) Distillation: Principles and design procedures (Kriger).
HOLLAND, C. D. (1963) Multicomponent Distillation (Prentice-Hall).
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extraction.
HUNT, C.D’A., HANSON, D. N. and WILKE, C. R. (1955) AIChE Jl 1, 441. Capacity factors in the performance
of perforated-plate columns.
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KISTER, H. Z. (1992) Distillation Design (McGraw-Hill).
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structured packings.
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tray.
KUMAR, A. (1982) Process Synthesis and Engineering Design (McGraw-Hill).
KWAUK, M. (1956) AIChE Jl 2, 240. A system for counting variables in separation processes.
LEVA, M. (1992) Chem. Eng. Prog. 88, 65. Reconsider Packed-Tower Pressure-Drop Correlations.
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LEWIS, W. K. (1909) Ind. Eng. Chem. 1, 522. The theory of fractional distillation.
LEWIS, W. K. (1936) Ind. Eng. Chem. 28, 399. Rectification of binary mixtures.
LEWIS, W. K. and MATHESON, G. L. (1932) Ind. Eng. Chem. 24, 494. Studies in distillation.
LIEBSON, I., KELLEY, R. E. and BULLINGTON, L. A. (1957) Pet. Ref. 36 (Feb.) 127. How to design perforated
trays.
LOCKETT, M. J. (1986) Distillation Tray Fundamentals (Cambridge University Press).
LOWENSTEIN, J. G. (1961) Ind. Eng. Chem. 53 (Oct.) 44A. Sizing distillation columns.
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151 (Oct.) 139 and 39 (Aug.) 121 (in four parts). Figure distillation this way.
MCCABE, W. L. and THIELE, E. W. (1925) Ind. Eng. Chem. 17, 605. Graphical design of distillation columns.
626
CHEMICAL ENGINEERING
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MEHRA, Y. R. (1979) Chem. Eng., NY 86 (July 2nd) 87. Liquid surge capacity in horizontal and vertical vessels.
MORRIS, G. A. and JACKSON, J. (1953) Absorption Towers (Butterworths).
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NAPHTALI, L. M. and SANDHOLM, D. P. (1971) AIChE Jl 17, 148. Multicomponent separation calculations by
linearisation.
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absorbers.
OLDERSHAW, C. F. (1941) Ind. Eng. Chem. (Anal. ed.) 13, 265. Perforated plate columns for analytical batch
distillations.
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627
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
11.18. NOMENCLATURE
Dimensions
in MLT q
A
Aa
Aap
Ac
Ad
Ah
Ai
Am
An
Ap
a
aw
B
b
bi
Co
CT
c
D
Dc
De
DL
DLK
Dv
dh
di
dp
E
Ea
EmV
Em v
Eo
e
FA
F
Fn
Fp
Fv
FLV
f
fi
f1
f2
f3
G
Gm
g
H
HG
HL
HOG
HOL
H
Constant in equation 11.63
Active area of plate
Clearance area under apron
Total column cross-sectional area
Downcomer cross-sectional area
Total hole area
Absorption factor
Area term in equation 11.92
Net area available for vapour-liquid disengagement
Perforated area
Packing surface area per unit volume
Effective interfacial area of packing per unit volume
Mols of bottom product per unit time
Parameter in equation 11.28
Mols of component i in bottom product
Orifice coefficient in equation 11.88
Total molar concentration
Parameter defined by equation 11.32
Mols of distillate per unit time
Column diameter
Eddy diffusivity
Liquid diffusivity
Diffusivity of light key component
Diffusivity of vapour
Hole diameter
Mols of component i in distillate per unit time
Size of packing
Extract flow-rate
Actual plate efficiency, allowing for entrainment
Murphree plate efficiency
Murphree point efficiency
Overall column efficiency
Extract composition
Fractional area, equation 11.69
Feed, of the solution to be extracted
Feed rate to stage n
Packing factor
p
Column ‘F’ factor D ua v
Column liquid-vapour factor in Figure 11.27
Feed composition
Mols of component i in feed per unit time
Viscosity correction factor in equation 11.110
Liquid density correction factor in equation 11.110
Surface tension correction factor in equation 11.110
Feed condition factor defined by equations 11.55 and 11.56
Molar flow-rate of gas per unit area
Gravitational acceleration
Specific enthalpy of vapour phase
Height of gas film transfer unit
Height of liquid film transfer unit
Height of overall gas phase transfer unit
Height of overall liquid phase transfer unit
Henry’s constant
L2
L2
L2
L2
L2
L2
L2
L2
L1
L1
MT1
M
ML3
MT1
L
L2 T1
L2 T1
L2 T1
L2 T1
L
MT1
L
MT1
MT1
MT1
L1
M1/2 L1/2 T1
MT1
ML2 T1
LT2
L2 T2
L
L
L
L
ML1 T2
628
h
hap
hb
hbc
hd
hdc
hf
how
hr
ht
hw
K
K0
KG
Ki
KL
Kn
K1
K2
K3
K4
K5
k
kG
kL
L
Le
Lm
Lp
Lw
LwŁ
Lwd
li
l0i
lh
ln
lp
lt
lw
Ms
m
N
NG
NL
Nm
NOG
NOL
Nr
NŁr
Ns
NŁs
n
P
Po
CHEMICAL ENGINEERING
Specific enthalpy of liquid phase
Apron clearance
Height of liquid backed-up in downcomer
Downcomer back-up in terms of clear liquid head
Dry plate pressure drop, head of liquid
Head loss in downcomer
Specific enthalpy of feed stream
Height of liquid crest over downcomer weir
Plate residual pressure drop, head of liquid
Total plate pressure drop, head of liquid
Weir height
Equilibrium constant for least volatile component
Equilibrium constant for more volatile component
Overall gas phase mass transfer coefficient
Equilibrium constant for component i
Overall liquid phase mass transfer coefficient
Equilibrium constant on stage n
Constant in equation 11.81
Constant in equation 11.84
Percentage flooding factor in equation 11.111
Parameter in Fig. 11.44, defined by equation 11.118
Constant in equation 11.115
Root of equation 11.28
Gas film mass transfer coefficient
Liquid film mass transfer coefficient
Liquid flow-rate, mols per unit time
Estimated flow-rate of combined keys, liquid
Molar flow-rate of liquid per unit area
Volumetric flow-rate across plate divided by average plate
width
Liquid mass flow-rate
Liquid mass flow-rate per unit area
Liquid mass flow-rate through downcomer
Limiting liquid flow-rate of components lighter than the keys
in the rectifying section
Limiting liquid flow-rates of components heavier than the keys
in the stripping section
Weir chord height
Molar liquid flow rate of component from stage n
Pitch of holes (distance between centres)
Plate spacing in column
Weir length
Molecular weight of solvent
Slope of equilibrium line
Number of stages
Number of gas-film transfer units
Number of liquid-film transfer units
Number of stages at total reflux
Number of overall gas-phase transfer units
Number of overall liquid-phase transfer units
Number of equilibrium stages above feed
Number of stages in rectifying section (equation 11.26)
Number of equilibrium stages below feed
Number of stages in stripping section (equation 11.25)
Stage number
Total pressure
Vapour pressure
L2 T2
L
L
L
L
L
L2 T2
L
L
L
L
L1 T
LT1
LT1
L1 T
LT1
MT1
MT1
ML2 T1
L2 T1
MT1
MT2 T1
MT1
MT1
MT1
L
MT1
L
L
L
ML1 T2
ML1 T2
629
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
Pt
p
q
qb
qc
qn
R
R
R
Rm
r
S
Si
Sn
Sr
Ss
s
s
tL
tr
ua
uf
uh
un
uv
V
Ve
Vw
VŁw
vi
v0i
vn
x
xA
xB
xb
xd
xe
xi
xr
xnŁ
xoŁ
x1
x2
xr
y
yA
yB
ye
yi
y
ylm
y1
y2
Z
Total plate pressure drop
Partial pressure
Heat to vaporise one mol of feed divided by molar latent heat
Heat supplied to reboiler
Heat removed in condenser
Heat supplied to or removed from stage n
Universal gas constant
Reflux ratio
Raffinate flow-rate
Minimum reflux ratio
Raffinate composition
Extracting solvent flow-rate
Stripping factor
Side stream flow from stage n
Stripping factor for rectifying section (equation 11.54)
Stripping factor for stripping section (equation 11.54)
Slope of operating line
Solvent composition
Liquid contact time
Residence time in downcomer
Vapour velocity based on active area
Vapour velocity at flooding point
Vapour velocity through holes
Vapour velocity based on net cross-sectional area
Superficial vapour velocity (based on total cross-sectional area)
Vapour flow-rate mols per unit time
Estimated flow-rate of combined keys, vapour
Vapour mass flow-rate
Vapour mass flow-rate per unit area
Limiting vapour flow-rates of components lighter than the keys
in the rectifying section
Limiting vapour flow-rates of components heavier than the keys
in the stripping section
Molar vapour flow-rate of component from stage n
Mol fraction of component in liquid phase
Mol fraction of component A in binary mixture
Mol fraction of component B in binary mixture
Mol fraction of component in bottom product
Mol fraction of component in distillate
Equilibrium concentration
Mol fraction of component i
Concentration of reference component (equation 11.57)
Reference concentration in equation 11.30
Reference concentration in equation 11.30
Concentration of solute in solution at column base
Concentration of solute in solution at column top
Reference concentration equations 11.25 and 11.26
Mol fraction of component in vapour phase
Mol fraction of component A in a binary mixture
Mol fraction of component B in a binary mixture
Equilibrium concentration
Mol fraction of component i
Concentration driving force in the gas phase
Log mean concentration driving force
Concentration of solute in gas phase at column base
Concentration of solute in gas phase at column top
Height of packing
ML1 T2
ML1 T2
ML2 T3
ML2 T3
ML2 T3
L2 T2 q1
MT1
MT1
MT1
T
T
LT1
LT1
LT1
LT1
LT1
MT1
MT1
MT1
ML2 T1
MT1
MT1
MT1
L
630
CHEMICAL ENGINEERING
Liquid hold-up on plate
Length of liquid path
Mol fraction of component i in feed stream
Mol fraction of component in feed stream
Pseudo feed concentration defined by equation 11.41
Relative volatility
Relative volatility of component i
Average relative volatility of light key
Parameter defined by equation 11.31
Root of equation 11.61
Dynamic viscosity
Molar average liquid viscosity
Viscosity of solvent
Viscosity of water at 20° C
Density
Density of water at 20° C
Surface tension
Critical surface tension for packing material
Surface tension of water at 20° C
Intercept of operating line on Y axis
Factor in equation 11.43
Fractional entrainment
Factor in equation 11.42
Zc
ZL
zi
zf
Ł
zf
˛
˛i
˛a
ˇ
a
s
w
w
c
w
n
h
Dg
Pe
Re
Sc
L
L
ML1 T1
ML1 T1
ML1 T1
ML1 T1
ML3
ML3
MT2
MT2
MT2
Surface tension number
Peclet number
Reynolds number
Schmidt number
Suffixes
L
v
HK
LK
Liquid
Vapour
Heavy key
Light key
b
d
f
Bottoms
Distillate (Tops)
Feed
i
n
1
2
Component number
Stage number
Base of packed column
Top of packed column
Superscripts
0
Stripping section of column
Subscripts
m
n
Last stage
Stage number
11.19. PROBLEMS
11.1. At a pressure of 10 bar, determine the bubble and dew point of a mixture of
hydrocarbons, composition, mol per cent: n-butane 21, n-pentane 48, n-hexane 31.
The equilibrium K factors can be estimated using the De Priester charts in
Chapter 8.
11.2. The feed to a distillation column has the following composition, mol per cent:
propane 5.0, isobutane 15, n-butane 25, isopentane 20, n-pentane 35. The feed is
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
631
Ž
preheated to a temperature of 90 C, at 8.3 bar pressure. Estimate the proportion
of the feed which is vapour.
The equilibrium K factors are given in Example 11.9.
11.3. Propane is separated from propylene by distillation. The compounds have close
boiling points and the relative volatility will be low. For a feed composition of
10 per cent w/w propane, 90 per cent w/w propylene, estimate the number of
theoretical plates needed to produce propylene overhead with a minimum purity
of 99.5 mol per cent. The column will operate with a reflux ratio of 20. The
feed will be at its boiling point. Take the relative volatility as constant at 1.1.
11.4. The composition of the feed to a debutaniser is given below. Make a preliminary
design for a column to recover 98 per cent of the n-butane overhead and 95 per
cent of the isopentane from the column base. The column will operate at 14
bar and the feed will be at its boiling point. Use the short-cut methods and
follow the procedure set out below. Use the De Priester charts to determine the
relative volatility. The liquid viscosity can be estimated using the data given in
Appendix D.
(a)
(b)
(c)
(d)
(e)
(f)
(g)
Investigate the effect of reflux ratio on the number of theoretical stages.
Select the optimum reflux ratio.
Determine the number of stages at this reflux ratio.
Estimate the stage efficiency.
Determine the number of real stages.
Estimate the feed point.
Estimate the column diameter.
Feed composition:
propane
isobutane
n-butane
isopentane
normal pentane
normal hexane
C3
i-C4
n-C4
i-C5
n-C5
n-C6
kg/h
910
180
270
70
90
20
11.5. In a process for the manufacture of acetone, acetone is separated from acetic
acid by distillation. The feed to the column is 60 mol per cent acetone, the
balance acetic acid.
The column is to recover 95 per cent of the acetone in the feed with a purity of
99.5 mol per cent acetone. The column will operate at a pressure of 760 mmHg
and the feed will be preheated to 70 Ž C.
For this separation, determine:
(a)
(b)
(c)
(d)
the number of minimum number of stages required,
the minimum reflux ratio,
the number of theoretical stages for a reflux ratio 1.5 times the minimum,
the number of actual stages if the plate efficiency can be taken as 60 per cent.
632
CHEMICAL ENGINEERING
Equilibrium data for the system acetone acetic acid, at 760
fractions acetone:
liquid
phase
0.10 0.2
0.3
0.4
0.5
0.6
0.7
0.8
vapour
phase
0.31 0.56 0.73 0.84 0.91 0.95 0.97 0.98
boiling
point Ž C 103.8 93.1 85.8 79.7 74.6 70.2 66.1 62.6
mmHg, mol
0.9
0.99
59.2
Reference: Othmer, D. F. Ind. Eng. Chem. 35, 614 (1943).
11.6. In the manufacture of absolute alcohol by fermentation, the product is separated
and purified using several stages of distillation. In the first stage, a mixture of
5 mol per cent ethanol in water, with traces of acetaldehyde and fusel oil, is
concentrated to 50 mol per cent. The concentration of alcohol in the wastewater
is reduced to less than 0.1 mol per cent.
Design a sieve plate column to perform this separation, for a feed rate of
10,000 kg/hour. Treat the feed as a binary mixture of ethanol and water.
Take the feed temperature as 20 Ž C. The column will operate at 1 atmosphere.
Determine:
(a) the number of theoretical stages,
(b) an estimate of the stage efficiency,
(c) the number of actual stages needed.
Design a suitable sieve plate for conditions below the feed point.
Equilibrium data for the system ethanol water, at 760 mmHg, mol fractions
ethanol:
liquid
phase 0.019 0.072 0.124 0.234 0.327 0.508 0.573 0.676 0.747 0.894
vapour
phase 0.170 0.389 0.470 0.545 0.583 0.656 0.684 0.739 0.782 0.894
boiling
point
Ž
C
95.5 89.0 85.3 82.7 81.5 79.8 79.3 78.7 78.4 78.2
Reference: Carey, J. S. and Lewis, W. K. Ind. Eng. Chem. 24, 882 (1932).
11.7. In the manufacture of methyl ethyl ketone from butanol, the product is separated
from unreacted butanol by distillation. The feed to the column consists of a
mixture of 0.90 mol fraction MEK, 0.10 mol fraction 2-butanol, with a trace of
trichloroethane.
The feed rate to the column is 20 kmol/h and the feed temperature 35 Ž C. The
specifications required are: top product 0.99 mol fraction MEK; bottom product
0.99 mol fraction butanol.
Design a column for this separation. The column will operate at essentially
atmospheric pressure. Use a reflux ratio 1.5 times the minimum.
(a) determine the minimum reflux ratio,
(b) determine the number of theoretical stages,
633
SEPARATION COLUMNS (DISTILLATION, ABSORPTION AND EXTRACTION)
(c) estimate the stage efficiency,
(d) determine the number of actual stages needed,
(e) design a suitable sieve plate for conditions below the feed point.
Equilibrium data for the system MEK 2-butanol, mol fractions MEK:
liquid
phase
vapour
phase
boiling
point Ž C
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.23
0.41
0.53
0.64
0.73
0.80
0.86
0.91
0.95
97
94
92
90
87
85
84
82
80
11.8. A column is required to recover acetone from an aqueous solution. The feed
contains 5 mol per cent acetone. A product purity of 99.5 per cent w/w is
required and the effluent water must contain less than 100 ppm acetone.
The feed temperature will range from 10 to 25 Ž C. The column will operate at
atmospheric pressure. For a feed of 7500 kg/h, compare the designs for a sieve
plate and packed column, for this duty. Use a reflux ratio of 3. Compare the
capital and utility cost for the two designs.
No reboiler is required for this column; live steam can be used.
Equilibrium data for the system acetone water is given in Example 11.2.
11.9. In the manufacture of methyl ethyl ketone (MEK). the product MEK is extracted
from a solution in water using 1,1,2 trichloroethane as the solvent.
For a feed rate 2000 kg/h of solution, composition 30 per cent w/w MEK,
determine the number of stages required to recover 95 per cent of the dissolved
MEK; using 700 kg/h TCE, with counter-current flow.
Tie-line data for the system MEK water TCE percentages w/w, from Newman
et al., Ind. Eng. Chem. 41, 2039 (1949).
water-rich
MEK
18.15
12.78
9.23
6.00
2.83
1.02
phase
TCE
0.11
0.16
0.23
0.30
0.37
0.41
solvent-rich phase
MEK
TCE
75.00
19.92
58.62
38.65
44.38
54.14
31.20
67.80
16.90
82.58
5.58
94.42
11.10. Chlorine is to be removed from a vent stream by scrubbing with a 5 per cent w/w
aqueous solution of sodium hydroxide. The vent stream is essential nitrogen,
with a maximum concentration of 5.5 per cent w/w chlorine. The concentration
of chlorine leaving the scrubber must be less than 50 ppm by weight. The
maximum flow-rate of the vent stream to the scrubber will be 4500 kg/h. Design
a suitable packed column for this duty. The column will operate at 1.1 bar and
ambient temperature. If necessary, the aqueous stream may be recirculated to
maintain a suitable wetting rate.
Note: the reaction of chlorine with the aqueous solution will be rapid and there
will be essentially no back-pressure of chlorine from the solution.
CHAPTER 12
Heat-transfer Equipment
12.1. INTRODUCTION
The transfer of heat to and from process fluids is an essential part of most chemical
processes. The most commonly used type of heat-transfer equipment is the ubiquitous
shell and tube heat exchanger; the design of which is the main subject of this chapter.
The fundamentals of heat-transfer theory are covered in Volume 1, Chapter 9; and in
many other textbooks: Holman (2002), Ozisik (1985), Rohsenow et al. (1998), Kreith and
Bohn (2000), and Incropera and Dewitt (2001).
Several useful books have been published on the design of heat exchange equipment.
These should be consulted for fuller details of the construction of equipment and design
methods than can be given in this book. A selection of the more useful texts is listed in
the bibliography at the end of this chapter. The compilation edited by Schlünder (1983ff),
see also the edition by Hewitt (1990), is probably the most comprehensive work on heat
exchanger design methods available in the open literature. The book by Saunders (1988)
is recommended as a good source of information on heat exchanger design, especially for
shell-and-tube exchangers.
As with distillation, work on the development of reliable design methods for heat
exchangers has been dominated in recent years by commercial research organisations:
Heat Transfer Research Inc. (HTRI) in the United States and Heat Transfer and Fluid Flow
Service (HTFS) in the United Kingdom. HTFS was developed by the United Kingdom
Atomic Energy Authority and the National Physical Laboratory, but is now available from
Aspentech, see Chapter 4, Table 4.1. Their methods are of a proprietary nature and are
not therefore available in the open literature. They will, however, be available to design
engineers in the major operating and contracting companies, whose companies subscribe
to these organisations.
The principal types of heat exchanger used in the chemical process and allied industries,
which will be discussed in this chapter, are listed below:
1.
2.
3.
4.
5.
6.
7.
8.
9.
Double-pipe exchanger: the simplest type, used for cooling and heating.
Shell and tube exchangers: used for all applications.
Plate and frame exchangers (plate heat exchangers): used for heating and cooling.
Plate-fin exchangers.
Spiral heat exchangers.
Air cooled: coolers and condensers.
Direct contact: cooling and quenching.
Agitated vessels.
Fired heaters.
634
635
HEAT-TRANSFER EQUIPMENT
The word “exchanger” really applies to all types of equipment in which heat is exchanged
but is often used specifically to denote equipment in which heat is exchanged between
two process streams. Exchangers in which a process fluid is heated or cooled by a plant
service stream are referred to as heaters and coolers. If the process stream is vaporised the
exchanger is called a vaporiser if the stream is essentially completely vaporised; a reboiler
if associated with a distillation column; and an evaporator if used to concentrate a solution
(see Chapter 10). The term fired exchanger is used for exchangers heated by combustion
gases, such as boilers; other exchangers are referred to as “unfired exchangers”.
12.2. BASIC DESIGN PROCEDURE AND THEORY
The general equation for heat transfer across a surface is:
Q D UATm
where
Q
U
A
Tm
D
D
D
D
⊲12.1⊳
heat transferred per unit time, W,
the overall heat transfer coefficient, W/m2 Ž C,
heat-transfer area, m2 ,
the mean temperature difference, the temperature driving force, Ž C.
The prime objective in the design of an exchanger is to determine the surface area required
for the specified duty (rate of heat transfer) using the temperature differences available.
The overall coefficient is the reciprocal of the overall resistance to heat transfer, which
is the sum of several individual resistances. For heat exchange across a typical heatexchanger tube the relationship between the overall coefficient and the individual coefficients, which are the reciprocals of the individual resistances, is given by:
do
do ln
1
1
do
1
do
1
1
di
D
C
C
C
ð
C
ð
⊲12.2⊳
Uo
ho
hod
2kw
di
hid
di
hi
where Uo
ho
hi
hod
hid
kw
di
do
D
D
D
D
D
D
D
D
the overall coefficient based on the outside area of the tube, W/m2 Ž C,
outside fluid film coefficient, W/m2 Ž C,
inside fluid film coefficient, W/m2 Ž C,
outside dirt coefficient (fouling factor), W/m2 Ž C,
inside dirt coefficient, W/m2 Ž C,
thermal conductivity of the tube wall material, W/mŽ C,
tube inside diameter, m,
tube outside diameter, m.
The magnitude of the individual coefficients will depend on the nature of the heattransfer process (conduction, convection, condensation, boiling or radiation), on the
physical properties of the fluids, on the fluid flow-rates, and on the physical arrangement
of the heat-transfer surface. As the physical layout of the exchanger cannot be determined
until the area is known the design of an exchanger is of necessity a trial and error
procedure. The steps in a typical design procedure are given below:
636
CHEMICAL ENGINEERING
1. Define the duty: heat-transfer rate, fluid flow-rates, temperatures.
2. Collect together the fluid physical properties required: density, viscosity, thermal
conductivity.
3. Decide on the type of exchanger to be used.
4. Select a trial value for the overall coefficient, U.
5. Calculate the mean temperature difference, Tm .
6. Calculate the area required from equation 12.1.
7. Decide the exchanger layout.
8. Calculate the individual coefficients.
9. Calculate the overall coefficient and compare with the trial value. If the calculated
value differs significantly from the estimated value, substitute the calculated for
the estimated value and return to step 6.
10. Calculate the exchanger pressure drop; if unsatisfactory return to steps 7 or 4 or
3, in that order of preference.
11. Optimise the design: repeat steps 4 to 10, as necessary, to determine the cheapest
exchanger that will satisfy the duty. Usually this will be the one with the
smallest area.
Procedures for estimating the individual heat-transfer coefficients and the exchanger
pressure drops are given in this chapter.
12.2.1. Heat exchanger analysis: the effectiveness
NTU method
The effectiveness NTU method is a procedure for evaluating the performance of heat
exchangers, which has the advantage that it does not require the evaluation of the mean
temperature differences. NTU stands for the Number of Transfer Units, and is analogous
with the use of transfer units in mass transfer; see Chapter 11.
The principal use of this method is in the rating of an existing exchanger. It can be
used to determine the performance of the exchanger when the heat transfer area and
construction details are known. The method has an advantage over the use of the design
procedure outlined above, as an unknown stream outlet temperature can be determined
directly, without the need for iterative calculations. It makes use of plots of the exchanger
effectiveness versus NTU. The effectiveness is the ratio of the actual rate of heat transfer,
to the maximum possible rate.
The effectiveness NTU method will not be covered in this book, as it is more useful
for rating than design. The method is covered in books by Incropera and Dewitt (2001),
Ozisik (1985) and Hewitt et al. (1994). The method is also covered by the Engineering
Sciences Data Unit in their Design Guides 98003 to 98007 (1998). These guides give
large clear plots of effectiveness versus NTU and are recommended for accurate work.
12.3. OVERALL HEAT-TRANSFER COEFFICIENT
Typical values of the overall heat-transfer coefficient for various types of heat exchanger
are given in Table 12.1. More extensive data can be found in the books by Perry et al.
(1997), TEMA (1999), and Ludwig (2001).
637
HEAT-TRANSFER EQUIPMENT
Table 12.1.
Typical overall coefficients
Shell and tube exchangers
Hot fluid
Cold fluid
Heat exchangers
Water
Organic solvents
Light oils
Heavy oils
Gases
Coolers
Organic solvents
Light oils
Heavy oils
Gases
Organic solvents
Water
Gases
Heaters
Steam
Steam
Steam
Steam
Steam
Dowtherm
Dowtherm
Flue gases
Flue
Condensers
Aqueous vapours
Organic vapours
Organics (some non-condensables)
Vacuum condensers
Vaporisers
Steam
Steam
Steam
U (W/m2 ° C)
Water
Organic solvents
Light oils
Heavy oils
Gases
800
100
100
50
10
1500
300
400
300
50
Water
Water
Water
Water
Brine
Brine
Brine
250
350
60
20
150
600
15
750
900
300
300
500
1200
250
Water
Organic solvents
Light oils
Heavy oils
Gases
Heavy oils
Gases
Steam
Hydrocarbon vapours
1500
500
300
60
30
50
20
30
30
4000
1000
900
450
300
300
200
100
100
Water
Water
Water
Water
1000
700
500
200
1500
1000
700
500
Aqueous solutions
Light organics
Heavy organics
1000 1500
900 1200
600 900
Air-cooled exchangers
Process fluid
Water
Light organics
Heavy organics
Gases, 5 10 bar
10 30 bar
Condensing hydrocarbons
300
300
50
50
100
300
450
700
150
100
300
600
500
200
70
200
100
1000
300
150
500
150
Immersed coils
Coil
Pool
Natural circulation
Steam
Steam
Steam
Water
Water
Dilute aqueous solutions
Light oils
Heavy oils
Aqueous solutions
Light oils
(continued overleaf )
638
CHEMICAL ENGINEERING
Table 12.1.
(continued)
Immersed coils
Coil
Pool
Agitated
Steam
Steam
Steam
Water
Water
Dilute aqueous solutions
Light oils
Heavy oils
Aqueous solutions
Light oils
U (W/m2 ° C)
800
300
200
400
200
1500
500
400
700
300
500
250
200
200
700
500
500
300
2500
250
100
2500
250
2000
250
2500
250
5000
5000
5000
3500
5000
500
200
3500
500
4500
450
3500
500
7500
7000
7000
4500
Jacketed vessels
Jacket
Vessel
Steam
Steam
Water
Water
Dilute aqueous solutions
Light organics
Dilute aqueous solutions
Light organics
Gasketed-plate exchangers
Hot fluid
Cold fluid
Light organic
Light organic
Viscous organic
Light organic
Viscous organic
Light organic
Viscous organic
Condensing steam
Condensing steam
Process water
Process water
Dilute aqueous solutions
Condensing steam
Light organic
Viscous organic
Viscous organic
Process water
Process water
Cooling water
Cooling water
Light organic
Viscous organic
Process water
Cooling water
Cooling water
Process water
Figure 12.1, which is adapted from a similar nomograph given by Frank (1974), can
be used to estimate the overall coefficient for tubular exchangers (shell and tube). The
film coefficients given in Figure 12.1 include an allowance for fouling.
The values given in Table 12.1 and Figure 12.1 can be used for the preliminary sizing
of equipment for process evaluation, and as trial values for starting a detailed thermal
design.
12.4. FOULING FACTORS (DIRT FACTORS)
Most process and service fluids will foul the heat-transfer surfaces in an exchanger to a
greater or lesser extent. The deposited material will normally have a relatively low thermal
conductivity and will reduce the overall coefficient. It is therefore necessary to oversize
an exchanger to allow for the reduction in performance during operation. The effect of
fouling is allowed for in design by including the inside and outside fouling coefficients
in equation 12.2. Fouling factors are usually quoted as heat-transfer resistances, rather
than coefficients. They are difficult to predict and are usually based on past experience.
°C
2
flu
id
co
ef
fic
ie
nt
,W
/m
Condensation
aqueous vapours
00
25
oc
es
s
Boiling aqueous
0
Pr
225
Boiling organics
d
Condensation organic vapours
ate
ll
era
U,
W
ffic
coe
0
200
0
175
ov
tim
Es
0
50
t,
ien
HEAT-TRANSFER EQUIPMENT
0
0
20
Dilute aqueous
2 °C
/m
0
150
1
Paraffins
0
125
Heavy organics
00
Molten salts
0
100
10
Oils
Air and gas
high pressure
Residue
750
0
50
250
500
Air and gas
low pressure
500
1000
1500
2000
2500
3000
3500
4000
4500
Thermal fluid
Air and gas
Brines
River, well, Hot heat
sea water transfer oil
Boiling
water
Steam condensing
Condensate
Refrigerants
Figure 12.1.
2
Service fluid coefficient, W/m °C
Overall coefficients (join process side duty to service side and read U from centre scale)
639
Cooling tower water
640
CHEMICAL ENGINEERING
Estimating fouling factors introduces a considerable uncertainty into exchanger design;
the value assumed for the fouling factor can overwhelm the accuracy of the predicted
values of the other coefficients. Fouling factors are often wrongly used as factors of
safety in exchanger design. Some work on the prediction of fouling factors has been done
by HTRI; see Taborek et al. (1972). Fouling is the subject of books by Bott (1990) an
Garrett-Price (1985).
Typical values for the fouling coefficients and factors for common process and service
fluids are given in Table 12.2. These values are for shell and tube exchangers with plain
(not finned) tubes. More extensive data on fouling factors are given in the TEMA standards
(1999), and by Ludwig (2001).
Table 12.2.
Fluid
River water
Sea water
Cooling water (towers)
Towns water (soft)
Towns water (hard)
Steam condensate
Steam (oil free)
Steam (oil traces)
Refrigerated brine
Air and industrial gases
Flue gases
Organic vapours
Organic liquids
Light hydrocarbons
Heavy hydrocarbons
Boiling organics
Condensing organics
Heat transfer fluids
Aqueous salt solutions
Fouling factors (coefficients), typical values
Coefficient (W/m2 ° C)
Factor (resistance) (m2° C/W)
3000 12,000
1000 3000
3000 6000
3000 5000
1000 2000
1500 5000
4000 10,000
2000 5000
3000 5000
5000 10,000
2000 5000
5000
5000
5000
2000
2500
5000
5000
3000 5000
0.0003 0.0001
0.001 0.0003
0.0003 0.00017
0.0003 0.0002
0.001 0.0005
0.00067 0.0002
0.0025 0.0001
0.0005 0.0002
0.0003 0.0002
0.0002 0.0001
0.0005 0.0002
0.0002
0.0002
0.0002
0.0005
0.0004
0.0002
0.0002
0.0003 0.0002
The selection of the design fouling coefficient will often be an economic decision. The
optimum design will be obtained by balancing the extra capital cost of a larger exchanger
against the savings in operating cost obtained from the longer operating time between
cleaning that the larger area will give. Duplicate exchangers should be considered for
severely fouling systems.
12.5. SHELL AND TUBE EXCHANGERS: CONSTRUCTION
DETAILS
The shell and tube exchanger is by far the most commonly used type of heat-transfer
equipment used in the chemical and allied industries. The advantages of this type are:
1.
2.
3.
4.
The configuration gives a large surface area in a small volume.
Good mechanical layout: a good shape for pressure operation.
Uses well-established fabrication techniques.
Can be constructed from a wide range of materials.
HEAT-TRANSFER EQUIPMENT
641
5. Easily cleaned.
6. Well-established design procedures.
Essentially, a shell and tube exchanger consists of a bundle of tubes enclosed in a cylindrical shell. The ends of the tubes are fitted into tube sheets, which separate the shell-side
and tube-side fluids. Baffles are provided in the shell to direct the fluid flow and support
the tubes. The assembly of baffles and tubes is held together by support rods and spacers,
Figure 12.2.
Figure 12.2.
Baffle spacers and tie rods
Exchanger types
The principal types of shell and tube exchanger are shown in Figures 12.3 to 12.8.
Diagrams of other types and full details of their construction can be found in the heatexchanger standards (see Section 12.5.1.). The standard nomenclature used for shell and
tube exchangers is given below; the numbers refer to the features shown in Figures 12.3
to 12.8.
Nomenclature
Part number
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Shell
Shell cover
Floating-head cover
Floating-tube plate
Clamp ring
Fixed-tube sheet (tube plate)
Channel (end-box or header)
Channel cover
Branch (nozzle)
Tie rod and spacer
Cross baffle or tube-support plate
Impingement baffle
Longitudinal baffle
Support bracket
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
Floating-head support
Weir
Split ring
Tube
Tube bundle
Pass partition
Floating-head gland (packed gland)
Floating-head gland ring
Vent connection
Drain connection
Test connection
Expansion bellows
Lifting ring
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CHEMICAL ENGINEERING
The simplest and cheapest type of shell and tube exchanger is the fixed tube sheet design
shown in Figure 12.3. The main disadvantages of this type are that the tube bundle cannot
be removed for cleaning and there is no provision for differential expansion of the shell
and tubes. As the shell and tubes will be at different temperatures, and may be of different
materials, the differential expansion can be considerable and the use of this type is limited
to temperature differences up to about 80Ž C. Some provision for expansion can be made
by including an expansion loop in the shell (shown dotted on Figure 12.3) but their use
is limited to low shell pressure; up to about 8 bar. In the other types, only one end of the
tubes is fixed and the bundle can expand freely.
The U-tube (U-bundle) type shown in Figure 12.4 requires only one tube sheet and
is cheaper than the floating-head types; but is limited in use to relatively clean fluids as
the tubes and bundle are difficult to clean. It is also more difficult to replace a tube in
this type.
7
6
9
1
11
6
18
9
7
20
26
Figure 12.3.
14
10
14
25
9
25
9
Fixed-tube plate (based on figures from BS 3274: 1960)
Figure 12.4.
U-tube (based on figures from BS 3274: 1960)
Exchangers with an internal floating head, Figures 12.5 and 12.6, are more versatile
than fixed head and U-tube exchangers. They are suitable for high-temperature differentials
HEAT-TRANSFER EQUIPMENT
643
and, as the tubes can be rodded from end to end and the bundle removed, are easier to
clean and can be used for fouling liquids. A disadvantage of the pull-through design,
Figure 12.5, is that the clearance between the outermost tubes in the bundle and the shell
must be made greater than in the fixed and U-tube designs to accommodate the floatinghead flange, allowing fluid to bypass the tubes. The clamp ring (split flange design),
Figure 12.6, is used to reduce the clearance needed. There will always be a danger of
leakage occurring from the internal flanges in these floating head designs.
In the external floating head designs, Figure 12.7, the floating-head joint is located
outside the shell, and the shell sealed with a sliding gland joint employing a stuffing box.
Because of the danger of leaks through the gland, the shell-side pressure in this type is
usually limited to about 20 bar, and flammable or toxic materials should not be used on
the shell side.
Figure 12.5.
Figure 12.6.
Internal floating head without clamp ring (based on figures from BS 3274: 1960)
Internal floating head with clamp ring (based on figures from BS 3274: 1960)
644
CHEMICAL ENGINEERING
Figure 12.7.
Figure 12.8.
External floating head, packed gland (based on figures from BS 3274: 1960)
Kettle reboiler with U-tube bundle (based on figures from BS 3274: 1960)
12.5.1. Heat-exchanger standards and codes
The mechanical design features, fabrication, materials of construction, and testing of
shell and tube exchangers is covered by British Standard, BS 3274. The standards of the
American Tubular Heat Exchanger Manufacturers Association, the TEMA standards, are
also universally used. The TEMA standards cover three classes of exchanger: class R
covers exchangers for the generally severe duties of the petroleum and related industries;
class C covers exchangers for moderate duties in commercial and general process applications; and class B covers exchangers for use in the chemical process industries. The British
and American standards should be consulted for full details of the mechanical design
features of shell and tube exchangers; only brief details will be given in this chapter.
The standards give the preferred shell and tube dimensions; the design and manufacturing tolerances; corrosion allowances; and the recommended design stresses for materials
of construction. The shell of an exchanger is a pressure vessel and will be designed in
accordance with the appropriate national pressure vessel code or standard; see Chapter 13,
Section 13.2. The dimensions of standard flanges for use with heat exchangers are given
in BS 3274, and in the TEMA standards.
645
HEAT-TRANSFER EQUIPMENT
In both the American and British standards dimensions are given in feet and inches, so
these units have been used in this chapter with the equivalent values in SI units given in
brackets.
12.5.2. Tubes
Dimensions
Tube diameters in the range 85 in. (16 mm) to 2 in. (50 mm) are used. The smaller
diameters 85 to 1 in. (16 to 25 mm) are preferred for most duties, as they will give
more compact, and therefore cheaper, exchangers. Larger tubes are easier to clean by
mechanical methods and would be selected for heavily fouling fluids.
The tube thickness (gauge) is selected to withstand the internal pressure and give an
adequate corrosion allowance. Steel tubes for heat exchangers are covered by BS 3606
(metric sizes); the standards applicable to other materials are given in BS 3274. Standard
diameters and wall thicknesses for steel tubes are given in Table 12.3.
Table 12.3.
Standard dimensions for steel tubes
Outside diameter (mm)
16
20
25
30
38
50
Wall thickness (mm)
1.2
1.6
1.6
1.6
1.6
2.0
2.0
2.0
2.0
2.0
2.0
2.6
2.6
2.6
2.6
2.6
3.2
3.2
3.2
3.2
The preferred lengths of tubes for heat exchangers are: 6 ft. (1.83 m), 8 ft (2.44 m),
12 ft (3.66 m), 16 ft (4.88 m) 20 ft (6.10 m), 24 ft (7.32 m). For a given surface area,
the use of longer tubes will reduce the shell diameter; which will generally result in a
lower cost exchanger, particularly for high shell pressures. The optimum tube length to
shell diameter will usually fall within the range of 5 to 10.
If U-tubes are used, the tubes on the outside of the bundle will be longer than those
on the inside. The average length needs to be estimated for use in the thermal design.
U-tubes will be bent from standard tube lengths and cut to size.
The tube size is often determined by the plant maintenance department standards, as
clearly it is an advantage to reduce the number of sizes that have to be held in stores for
tube replacement.
As a guide, 43 in. (19 mm) is a good trial diameter with which to start design calculations.
Tube arrangements
The tubes in an exchanger are usually arranged in an equilateral triangular, square, or
rotated square pattern; see Figure 12.9.
The triangular and rotated square patterns give higher heat-transfer rates, but at the
expense of a higher pressure drop than the square pattern. A square, or rotated square
arrangement, is used for heavily fouling fluids, where it is necessary to mechanically clean
646
CHEMICAL ENGINEERING
Pt
t
P
Pt
Flow
Triangular
Square
Figure 12.9.
Rotated square
Tube patterns
Shell inside diameter − bundle diameter, mm
100
90
Pull-through floating head
80
70
60
Split-ring floating head
50
40
Outside packed head
30
20
10
Fixed and U-tube
0
0.2
0.4
0.6
0.8
Bundle diameter, m
Figure 12.10.
1.0
1.2
Shell-bundle clearance
the outside of the tubes. The recommended tube pitch (distance between tube centres)
is 1.25 times the tube outside diameter; and this will normally be used unless process
requirements dictate otherwise. Where a square pattern is used for ease of cleaning, the
recommended minimum clearance between the tubes is 0.25 in. (6.4 mm).
647
HEAT-TRANSFER EQUIPMENT
Tube-side passes
The fluid in the tube is usually directed to flow back and forth in a number of “passes”
through groups of tubes arranged in parallel, to increase the length of the flow path. The
number of passes is selected to give the required tube-side design velocity. Exchangers
are built with from one to up to about sixteen tube passes. The tubes are arranged into
the number of passes required by dividing up the exchanger headers (channels) with
partition plates (pass partitions). The arrangement of the pass partitions for 2, 4 and
6 tube passes are shown in Figure 12.11. The layouts for higher numbers of passes are
given by Saunders (1988).
12.5.3. Shells
The British standard BS 3274 covers exchangers from 6 in. (150 mm) to 42 in.
(1067 mm) diameter; and the TEMA standards, exchangers up to 60 in. (1520 mm).
Up to about 24 in. (610 mm) shells are normally constructed from standard, close
tolerance, pipe; above 24 in. (610 mm) they are rolled from plate.
For pressure applications the shell thickness would be sized according to the pressure
vessel design standards, see Chapter 13. The minimum allowable shell thickness is given
in BS 3274 and the TEMA standards. The values, converted to SI units and rounded, are
given below:
Minimum shell thickness
Nominal shell
dia., mm
150
200 300
330 580
610 740
760 990
1010 1520
1550 2030
2050 2540
Carbon steel
pipe
plate
7.1
9.3
9.5
7.9
7.9
9.5
11.1
12.7
12.7
Alloy
steel
3.2
3.2
3.2
4.8
6.4
6.4
7.9
9.5
The shell diameter must be selected to give as close a fit to the tube bundle as is
practical; to reduce bypassing round the outside of the bundle; see Section 12.9. The
clearance required between the outermost tubes in the bundle and the shell inside diameter
will depend on the type of exchanger and the manufacturing tolerances; typical values
are given in Figure 12.10 (as given on p. 646).
12.5.4. Tube-sheet layout (tube count)
The bundle diameter will depend not only on the number of tubes but also on the number of
tube passes, as spaces must be left in the pattern of tubes on the tube sheet to accommodate
the pass partition plates.
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CHEMICAL ENGINEERING
1
2
3
5
4
6
Six tube passes
1
2
3
4
Four passes
1
2
Two passes
Figure 12.11.
Tube arrangements, showing pass-partitions in headers
An estimate of the bundle diameter Db can be obtained from equation 12.3b, which
is an empirical equation based on standard tube layouts. The constants for use in this
equation, for triangular and square patterns, are given in Table 12.4.
Db
do
n1
Nt
K1
1/n1
Nt D K1
Db D do
,
⊲12.3a⊳
,
⊲12.3b⊳
where Nt D number of tubes,
Db D bundle diameter, mm,
do D tube outside diameter, mm.
If U-tubes are used the number of tubes will be slightly less than that given by
equation 12.3a, as the spacing between the two centre rows will be determined by the
minimum allowable radius for the U-bend. The minimum bend radius will depend on the
tube diameter and wall thickness. It will range from 1.5 to 3.0 times the tube outside
diameter. The tighter bend radius will lead to some thinning of the tube wall.
649
HEAT-TRANSFER EQUIPMENT
An estimate of the number of tubes in a U-tube exchanger (twice the actual number
of U-tubes), can be made by reducing the number given by equation 12.3a by one centre
row of tubes.
The number of tubes in the centre row, the row at the shell equator, is given by:
Db
Tubes in centre row D
Pt
where pt D tube pitch, mm.
The tube layout for a particular design will normally be planned with the aid of computer
programs. These will allow for the spacing of the pass partition plates and the position
of the tie rods. Also, one or two rows of tubes may be omitted at the top and bottom of
the bundle to increase the clearance and flow area opposite the inlet and outlet nozzles.
Tube count tables which give an estimate of the number of tubes that can be accommodated in standard shell sizes, for commonly used tube sizes, pitches and number of
passes, can be found in several books: Kern (1950), Ludwig (2001), Perry et al. (1997),
and Saunders (1988).
Some typical tube arrangements are shown in Appendix I.
Table 12.4.
Constants for use in equation 12.3
Triangular pitch, pt D 1.25do
No. passes
K1
n1
1
2
4
6
8
0.319
2.142
0.249
2.207
0.175
2.285
0.0743
2.499
0.0365
2.675
Square pitch, pt D 1.25do
No. passes
K1
n1
1
2
4
6
8
0.215
2.207
0.156
2.291
0.158
2.263
0.0402
2.617
0.0331
2.643
12.5.5. Shell types (passes)
The principal shell arrangements are shown in Figure 12.12a e. The letters E, F, G, H, J
are those used in the TEMA standards to designate the various types. The E shell is the
most commonly used arrangement.
Two shell passes (F shell) are occasionally used where the shell and tube side temperature differences will be unsuitable for a single pass (see Section 12.6). However, it is
difficult to obtain a satisfactory seal with a shell-side baffle and the same flow arrangement
can be achieved by using two shells in series. One method of sealing the longitudinal
shell-side baffle is shown in Figure 12.12f.
The divided flow and split-flow arrangements (G and J shells) are used to reduce the
shell-side pressure drop; where pressure drop, rather than heat transfer, is the controlling
factor in the design.
12.5.6. Shell and tube designation
A common method of describing an exchanger is to designate the number of shell and
tube passes: m/n; where m is the number of shell passes and n the number of tube passes.
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CHEMICAL ENGINEERING
Figure 12.12. Shell types (pass arrangements). (a) One-pass shell (E shell) (b) Split flow (G shell) (c) Divided
flow (J shell) (d) Two-pass shell with longitudinal baffle (F shell) (e) Double split flow (H shell)
So 1/2 describes an exchanger with 1 shell pass and 2 tube passes, and 2/4 an exchanger
with 2 shell passes and 4 four tube passes.
12.5.7. Baffles
Baffles are used in the shell to direct the fluid stream across the tubes, to increase the fluid velocity and so improve the rate of transfer. The most commonly used type of baffle is the single
segmental baffle shown in Figure 12.13a, other types are shown in Figures 12.13b, c and d.
Only the design of exchangers using single segmental baffles will be considered in this
chapter.
If the arrangement shown in Figure 12.13a were used with a horizontal condenser the
baffles would restrict the condensate flow. This problem can be overcome either by rotating
the baffle arrangement through 90Ž , or by trimming the base of the baffle, Figure 12.14.
The term “baffle cut” is used to specify the dimensions of a segmental baffle. The baffle
cut is the height of the segment removed to form the baffle, expressed as a percentage of
the baffle disc diameter. Baffle cuts from 15 to 45 per cent are used. Generally, a baffle
cut of 20 to 25 per cent will be the optimum, giving good heat-transfer rates, without
excessive drop. There will be some leakage of fluid round the baffle as a clearance must
be allowed for assembly. The clearance needed will depend on the shell diameter; typical
values, and tolerances, are given in Table 12.5.
651
HEAT-TRANSFER EQUIPMENT
Figure 12.13.
Types of baffle used in shell and tube heat exchangers. (a) Segmental (b) Segmental and strip
(c) Disc and doughnut (d) Orifice
Figure 12.14.
Table 12.5.
Baffles for condensers
Typical baffle clearances and tolerances
Shell diameter, Ds
Baffle diameter
Pipe shells
6 to 25 in. (152 to 635 mm)
Plate shells
6 to 25 in. (152 to 635 mm)
Ds
1
16
Ds
1
8 in. (3.2 mm)
3
16 in. (4.8 mm)
27 to 42 in. (686 to 1067 mm)
Ds
in. (1.6 mm)
Tolerance
1
C 32
in. (0.8 mm)
1
C0, 32
in. (0.8 mm)
1
C0, 16
in. (1.6 mm)
652
CHEMICAL ENGINEERING
Another leakage path occurs through the clearance between the tube holes in the baffle
1
in. (0.8 mm).
and the tubes. The maximum design clearance will normally be 32
The minimum thickness to be used for baffles and support plates are given in the
standards. The baffle spacings used range from 0.2 to 1.0 shell diameters. A close baffle
spacing will give higher heat transfer coefficients but at the expense of higher pressure
drop. The optimum spacing will usually be between 0.3 to 0.5 times the shell diameter.
12.5.8. Support plates and tie rods
1
in.
Where segmental baffles are used some will be fabricated with closer tolerances, 64
(0.4 mm), to act as support plates. For condensers and vaporisers, where baffles are not
needed for heat-transfer purposes, a few will be installed to support the tubes.
The minimum spacings to be used for support plates are given in the standards. The
spacing ranges from around 1 m for 16 mm tubes to 2 m for 25 mm tubes.
The baffles and support plate are held together with tie rods and spacers. The number of
rods required will depend on the shell diameter, and will range from 4, 16 mm diameter
rods, for exchangers under 380 mm diameter; to 8, 12.5 mm rods, for exchangers of
1 m diameter. The recommended number for a particular diameter can be found in the
standards.
12.5.9. Tube sheets (plates)
In operation the tube sheets are subjected to the differential pressure between shell and
tube sides. The design of tube sheets as pressure-vessel components is covered by BS 5500
and is discussed in Chapter 13. Design formulae for calculating tube sheet thicknesses
are also given in the TEMA standards.
Thrust
collar
Hardened
rollers
Drive
Tube
Tapered
mandrel
Figure 12.15.
Tube
sheet
Tube rolling
The joint between the tubes and tube sheet is normally made by expanding the tube by
rolling with special tools, Figure 12.15. Tube rolling is a skilled task; the tube must be
expanded sufficiently to ensure a sound leaf-proof joint, but not overthinned, weakening
the tube. The tube holes are normally grooved, Figure 12.16a, to lock the tubes more
firmly in position and to prevent the joint from being loosened by the differential expansion
HEAT-TRANSFER EQUIPMENT
Figure 12.16.
653
Tube/tube sheet joints
of the shell and tubes. When it is essential to guarantee a leak-proof joint the tubes
can be welded to the sheet, Figure 12.16b. This will add to the cost of the exchanger;
not only due to the cost of welding, but also because a wider tube spacing will be
needed.
The tube sheet forms the barrier between the shell and tube fluids, and where it is
essential for safety or process reasons to prevent any possibility of intermixing due to
leakage at the tube sheet joint, double tube-sheets can be used, with the space between
the sheets vented; Figure 12.16c.
To allow sufficient thickness to seal the tubes the tube sheet thickness should not be less
than the tube outside diameter, up to about 25 mm diameter. Recommended minimum
plate thicknesses are given in the standards.
The thickness of the tube sheet will reduce the effective length of the tube slightly,
and this should be allowed for when calculating the area available for heat transfer. As
a first approximation the length of the tubes can be reduced by 25 mm for each tube
sheet.
12.5.10. Shell and header nozzles (branches)
Standard pipe sizes will be used for the inlet and outlet nozzles. It is important to avoid
flow restrictions at the inlet and outlet nozzles to prevent excessive pressure drop and flowinduced vibration of the tubes. As well as omitting some tube rows (see Section 12.5.4),
the baffle spacing is usually increased in the nozzle zone, to increase the flow area. For
vapours and gases, where the inlet velocities will be high, the nozzle may be flared, or
special designs used, to reduce the inlet velocities; Figure 12.17a and b (see p. 654).
The extended shell design shown in Figure 12.17b also serves as an impingement plate.
Impingement plates are used where the shell-side fluid contains liquid drops, or for highvelocity fluids containing abrasive particles.
12.5.11. Flow-induced tube vibrations
Premature failure of exchanger tubes can occur through vibrations induced by the shellside fluid flow. Care must be taken in the mechanical design of large exchangers where
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CHEMICAL ENGINEERING
Tube-sheet
Impingement
plate
Flared nozzle
Shell
(a)
(b)
Figure 12.17.
Inlet nozzle designs
the shell-side velocity is high, say greater than 3 m/s, to ensure that tubes are adequately
supported.
The vibration induced by the fluid flowing over the tube bundle is caused principally
by vortex shedding and turbulent buffeting. As fluid flows over a tube vortices are shed
from the down-stream side which cause disturbances in the flow pattern and pressure
distribution round the tube. Turbulent buffeting of tubes occurs at high flow-rates due to
the intense turbulence at high Reynolds numbers.
The buffeting caused by vortex shedding or by turbulent eddies in the flow stream
will cause vibration, but large amplitude vibrations will normally only occur above a
certain critical flow velocity. Above this velocity the interaction with the adjacent tubes
can provide a feed back path which reinforces the vibrations. Resonance will also occur
if the vibrations approach the natural vibration frequency of the unsupported tube length.
Under these conditions the magnitude of the vibrations can increase dramatically leading
to tube failure. Failure can occur either through the impact of one tube on another or
through wear on the tube where it passes through the baffles.
For most exchanger designs, following the recommendations on support sheet spacing
given in the standards will be sufficient to protect against premature tube failure from
vibration. For large exchangers with high velocities on the shell-side the design should be
analysed to check for possible vibration problems. The computer aided design programs
for shell-and-tube exchanger design available from commercial organisations, such as
HTFS and HTRI (see Section 12.1), include programs for vibration analysis.
Much work has been done on tube vibration over the past 20 years, due to an increase in
the failure of exchangers as larger sizes and higher flow-rates have been used. Discussion
of this work is beyond the scope of this book; for review of the methods used see Saunders
(1988) and Singh and Soler (1992).
See also, the Engineering Science Data Unit Design Guide ESDU 87019, which gives a
clear explanation of mechanisms causing tube vibration in shell and tube heat exchangers,
and their prediction and prevention.
HEAT-TRANSFER EQUIPMENT
655
12.6. MEAN TEMPERATURE DIFFERENCE (TEMPERATURE
DRIVING FORCE)
Before equation 12.1 can be used to determine the heat transfer area required for a
given duty, an estimate of the mean temperature difference Tm must be made. This
will normally be calculated from the terminal temperature differences: the difference
in the fluid temperatures at the inlet and outlet of the exchanger. The well-known
“logarithmic mean” temperature difference (see Volume 1, Chapter 9) is only applicable
to sensible heat transfer in true co-current or counter-current flow (linear temperatureenthalpy curves). For counter-current flow, Figure 12.18a, the logarithmic mean temperature is given by:
⊲T1 t2 ⊳ ⊲T2 t1 ⊳
Tlm D
⊲12.4⊳
⊲T1 t2 ⊳
ln
⊲T2 t1 ⊳
where Tlm
T1
T2
t1
t2
D
D
D
D
D
log mean temperature difference,
hot fluid temperature, inlet,
hot fluid temperature, outlet,
cold fluid temperature, inlet,
cold fluid temperature, outlet.
The equation is the same for co-current flow, but the terminal temperature differences
will be (T1 t1 ) and (T2 t2 ). Strictly, equation 12.4 will only apply when there is no
change in the specific heats, the overall heat-transfer coefficient is constant, and there are
no heat losses. In design, these conditions can be assumed to be satisfied providing the
temperature change in each fluid stream is not large.
In most shell and tube exchangers the flow will be a mixture of co-current, countercurrent and cross flow. Figures 12.18b and c show typical temperature profiles for an
exchanger with one shell pass and two tube passes (a 1 : 2 exchanger). Figure 12.18c
shows a temperature cross, where the outlet temperature of the cold stream is above that
of the hot stream.
The usual practice in the design of shell and tube exchangers is to estimate the “true
temperature difference” from the logarithmic mean temperature by applying a correction
factor to allow for the departure from true counter-current flow:
Tm D Ft Tlm
⊲12.5⊳
where Tm D true temperature difference, the mean temperature difference for use in
the design equation 12.1,
Ft D the temperature correction factor.
The correction factor is a function of the shell and tube fluid temperatures, and the number
of tube and shell passes. It is normally correlated as a function of two dimensionless
temperature ratios:
RD
⊲T1 T2 ⊳
⊲t2 t1 ⊳
⊲12.6⊳
656
Figure 12.18.
CHEMICAL ENGINEERING
Temperature profiles (a) Counter-current flow (b) 1 : 2 exchanger (c) Temperature cross
and
SD
⊲t2 t1 ⊳
⊲T1 t1 ⊳
⊲12.7⊳
R is equal to the shell-side fluid flow-rate times the fluid mean specific heat; divided
by the tube-side fluid flow-rate times the tube-side fluid specific heat.
S is a measure of the temperature efficiency of the exchanger.
For a 1 shell : 2 tube pass exchanger, the correction factor is given by:
⊲1 S⊳
2
⊲R C 1⊳ ln
⊲1 RS⊳
⊲12.8⊳
Ft D
2 S[R C 1 ⊲R2 C 1⊳]
⊲R 1⊳ ln
2 S[R C 1 C ⊲R2 C 1⊳]
The derivation of equation 12.8 is given by Kern (1950). The equation for a
1 shell : 2 tube pass exchanger can be used for any exchanger with an even number
HEAT-TRANSFER EQUIPMENT
657
of tube passes, and is plotted in Figure 12.19. The correction factor for 2 shell passes and
4, or multiples of 4, tube passes is shown in Figure 12.20, and that for divided and split
flow shells in Figures 12.21 and 12.22.
Figure 12.19.
Temperature correction factor: one shell pass; two or more even tube passes
Temperature correction factor plots for other arrangements can be found in the TEMA
standards and the books by Kern (1950) and Ludwig (2001). Mueller (1973) gives a
comprehensive set of figures for calculating the log mean temperature correction factor,
which includes figures for cross-flow exchangers.
The following assumptions are made in the derivation of the temperature correction
factor Ft , in addition to those made for the calculation of the log mean temperature
difference:
1. Equal heat transfer areas in each pass.
2. A constant overall heat-transfer coefficient in each pass.
3. The temperature of the shell-side fluid in any pass is constant across any crosssection.
4. There is no leakage of fluid between shell passes.
Though these conditions will not be strictly satisfied in practical heat exchangers, the
Ft values obtained from the curves will give an estimate of the “true mean temperature
difference” that is sufficiently accurate for most designs. Mueller (1973) discusses these
658
CHEMICAL ENGINEERING
Figure 12.20.
Temperature correction factor: two shell passes; four or multiples of four tube passes
Figure 12.21.
Temperature correction factor: divided-flow shell; two or more even-tube passes
HEAT-TRANSFER EQUIPMENT
Figure 12.22.
659
Temperature correction factor, split flow shell, 2 tube pass
assumptions, and gives Ft curves for conditions when all the assumptions are not met;
see also Butterworth (1973) and Emerson (1973).
The shell-side leakage and bypass streams (see Section 12.9) will affect the mean
temperature difference, but are not normally taken into account when estimating the
correction factor Ft . Fisher and Parker (1969) give curves which show the effect of
leakage on the correction factor for a 1 shell pass : 2 tube pass exchanger.
The value of Ft will be close to one when the terminal temperature differences are
large, but will appreciably reduce the logarithmic mean temperature difference when the
temperatures of shell and tube fluids approach each other; it will fall drastically when
there is a temperature cross. A temperature cross will occur if the outlet temperature of
the cold stream is greater than the inlet temperature of the hot stream, Figure 12.18c.
Where the Ft curve is near vertical values cannot be read accurately, and this will
introduce a considerable uncertainty into the design.
An economic exchanger design cannot normally be achieved if the correction factor
Ft falls below about 0.75. In these circumstances an alternative type of exchanger should
be considered which gives a closer approach to true counter-current flow. The use of
two or more shells in series, or multiple shell-side passes, will give a closer approach to
true counter-current flow, and should be considered where a temperature cross is likely
to occur.
Where both sensible and latent heat is transferred, it will be necessary to divide
the temperature profile into sections and calculate the mean temperature difference for
each section.
660
CHEMICAL ENGINEERING
12.7. SHELL AND TUBE EXCHANGERS: GENERAL DESIGN
CONSIDERATIONS
12.7.1. Fluid allocation: shell or tubes
Where no phase change occurs, the following factors will determine the allocation of the
fluid streams to the shell or tubes.
Corrosion. The more corrosive fluid should be allocated to the tube-side. This will
reduce the cost of expensive alloy or clad components.
Fouling. The fluid that has the greatest tendency to foul the heat-transfer surfaces should be
placed in the tubes. This will give better control over the design fluid velocity, and the higher
allowable velocity in the tubes will reduce fouling. Also, the tubes will be easier to clean.
Fluid temperatures. If the temperatures are high enough to require the use of special
alloys placing the higher temperature fluid in the tubes will reduce the overall cost. At
moderate temperatures, placing the hotter fluid in the tubes will reduce the shell surface
temperatures, and hence the need for lagging to reduce heat loss, or for safety reasons.
Operating pressures. The higher pressure stream should be allocated to the tube-side.
High-pressure tubes will be cheaper than a high-pressure shell.
Pressure drop. For the same pressure drop, higher heat-transfer coefficients will be
obtained on the tube-side than the shell-side, and fluid with the lowest allowable pressure
drop should be allocated to the tube-side.
Viscosity. Generally, a higher heat-transfer coefficient will be obtained by allocating
the more viscous material to the shell-side, providing the flow is turbulent. The critical
Reynolds number for turbulent flow in the shell is in the region of 200. If turbulent flow
cannot be achieved in the shell it is better to place the fluid in the tubes, as the tube-side
heat-transfer coefficient can be predicted with more certainty.
Stream flow-rates. Allocating the fluids with the lowest flow-rate to the shell-side will
normally give the most economical design.
12.7.2. Shell and tube fluid velocities
High velocities will give high heat-transfer coefficients but also a high-pressure drop. The
velocity must be high enough to prevent any suspended solids settling, but not so high as
to cause erosion. High velocities will reduce fouling. Plastic inserts are sometimes used
to reduce erosion at the tube inlet. Typical design velocities are given below:
Liquids
Tube-side, process fluids: 1 to 2 m/s, maximum 4 m/s if required to reduce fouling; water:
1.5 to 2.5 m/s.
Shell-side: 0.3 to 1 m/s.
Vapours
For vapours, the velocity used will depend on the operating pressure and fluid density; the
lower values in the ranges given below will apply to high molecular weight materials.
Vacuum
Atmospheric pressure
High pressure
50 to 70 m/s
10 to 30 m/s
5 to 10 m/s
HEAT-TRANSFER EQUIPMENT
661
12.7.3. Stream temperatures
The closer the temperature approach used (the difference between the outlet temperature of
one stream and the inlet temperature of the other stream) the larger will be the heat-transfer
area required for a given duty. The optimum value will depend on the application, and can
only be determined by making an economic analysis of alternative designs. As a general
guide the greater temperature difference should be at least 20Ž C, and the least temperature
difference 5 to 7Ž C for coolers using cooling water, and 3 to 5Ž C using refrigerated brines.
The maximum temperature rise in recirculated cooling water is limited to around 30Ž C.
Care should be taken to ensure that cooling media temperatures are kept well above
the freezing point of the process materials. When the heat exchange is between process
fluids for heat recovery the optimum approach temperatures will normally not be lower
than 20Ž C.
12.7.4. Pressure drop
In many applications the pressure drop available to drive the fluids through the exchanger
will be set by the process conditions, and the available pressure drop will vary from a
few millibars in vacuum service to several bars in pressure systems.
When the designer is free to select the pressure drop an economic analysis can be made
to determine the exchanger design which gives the lowest operating costs, taking into
consideration both capital and pumping costs. However, a full economic analysis will
only be justified for very large, expensive, exchangers. The values suggested below can
be used as a general guide, and will normally give designs that are near the optimum.
Liquids
Viscosity <1 mN s/m2
35 kN/m2
2
1 to 10 mN s/m 50 70 kN/m2
Gas and vapours
High vacuum
Medium vacuum
1 to 2 bar
Above 10 bar
0.4 0.8 kN/m2
0.1 ð absolute pressure
0.5 ð system gauge pressure
0.1 ð system gauge pressure
When a high-pressure drop is utilised, care must be taken to ensure that the resulting high
fluid velocity does not cause erosion or flow-induced tube vibration.
12.7.5. Fluid physical properties
The fluid physical properties required for heat-exchanger design are: density, viscosity,
thermal conductivity and temperature-enthalpy correlations (specific and latent heats).
Sources of physical property data are given in Chapter 8. The thermal conductivities of
commonly used tube materials are given in Table 12.6.
662
CHEMICAL ENGINEERING
Table 12.6.
Metal
Aluminium
Brass
(70 Cu, 30 Zn)
Copper
Nickel
Cupro-nickel (10 per cent Ni)
Monel
Stainless steel (18/8)
Steel
Titanium
Conductivity of metals
Temperature (° C)
kw ⊲W/m° C⊳
0
100
0
100
400
0
100
0
212
0 100
0 100
0 100
0
100
600
0 100
202
206
97
104
116
388
378
62
59
45
30
16
45
45
36
16
In the correlations used to predict heat-transfer coefficients, the physical properties
are usually evaluated at the mean stream temperature. This is satisfactory when the
temperature change is small, but can cause a significant error when the change in temperature is large. In these circumstances, a simple, and safe, procedure is to evaluate the
heat-transfer coefficients at the stream inlet and outlet temperatures and use the lowest
of the two values. Alternatively, the method suggested by Frank (1978) can be used; in
which equations 12.1 and 12.3 are combined:
QD
A[U2 ⊲T1 t2 ⊳ U1 ⊲T2 t1 ⊳]
U2 ⊲T1 t2 ⊳
ln
U1 ⊲T2 t1 ⊳
⊲12.9⊳
where U1 and U2 are evaluated at the ends of the exchanger. Equation 12.9 is derived
by assuming that the heat-transfer coefficient varies linearly with temperature.
If the variation in the physical properties is too large for these simple methods to
be used it will be necessary to divide the temperature-enthalpy profile into sections and
evaluate the heat-transfer coefficients and area required for each section.
12.8. TUBE-SIDE HEAT-TRANSFER COEFFICIENT AND
PRESSURE DROP (SINGLE PHASE)
12.8.1. Heat transfer
Turbulent flow
Heat-transfer data for turbulent flow inside conduits of uniform cross-section are usually
correlated by an equation of the form:
c
a
b
Nu D CRe Pr
⊲12.10⊳
w
HEAT-TRANSFER EQUIPMENT
where Nu
Re
Pr
and: hi
de
D
D
D
D
D
Nusselt number D ⊲hi de /kf ⊳,
Reynolds number D ⊲ut de /⊳ D ⊲Gt de /⊳,
Prandtl number D ⊲Cp /kf ⊳
inside coefficient, W/m2 Ž C,
equivalent (or hydraulic mean) diameter, m
de D
ut
kf
Gt
w
Cp
D
D
D
D
D
D
663
4 ð cross-sectional area for flow
D di for tubes,
wetted perimeter
fluid velocity, m/s,
fluid thermal conductivity, W/mŽ C,
mass velocity, mass flow per unit area, kg/m2 s,
fluid viscosity at the bulk fluid temperature, Ns/m2 ,
fluid viscosity at the wall,
fluid specific heat, heat capacity, J/kgŽ C.
The index for the Reynolds number is generally taken as 0.8. That for the Prandtl number
can range from 0.3 for cooling to 0.4 for heating. The index for the viscosity factor is
normally taken as 0.14 for flow in tubes, from the work of Sieder and Tate (1936), but some
workers report higher values. A general equation that can be used for exchanger design is:
0.14
Nu D CRe0.8 Pr 0.33
⊲12.11⊳
w
where C D 0.021 for gases,
D 0.023 for non-viscous liquids,
D 0.027 for viscous liquids.
It is not really possible to find values for the constant and indexes to cover the complete
range of process fluids, from gases to viscous liquids, but the values predicted using
equation 12.11 should be sufficiently accurate for design purposes. The uncertainty in
the prediction of the shell-side coefficient and fouling factors will usually far outweigh
any error in the tube-side value. Where a more accurate prediction than that given by
equation 12.11 is required, and justified, the data and correlations given in the Engineering
Science Data Unit reports are recommended: ESDU 92003 and 93018 (1998).
Butterworth (1977) gives the following equation, which is based on the ESDU work:
St D ERe0.205 Pr 0.505
⊲12.12⊳
where St D Stanton number D ⊲Nu/RePr⊳ D ⊲hi /ut Cp ⊳
and
E D 0.0225 exp⊲0.0225⊲ln Pr⊳2 ⊳.
Equation 12.12 is applicable at Reynolds numbers greater than 10,000.
Hydraulic mean diameter
In some texts the equivalent (hydraulic mean) diameter is defined differently for use in
calculating the heat transfer coefficient in a conduit or channel, than for calculating the
pressure drop. The perimeter through which the heat is being transferred is used in place
of the total wetted perimeter. In practice, the use of de calculated either way will make
664
CHEMICAL ENGINEERING
little difference to the value of the estimated overall coefficient; as the film coefficient is
only, roughly, proportional to de0.2 .
It is the full wetted perimeter that determines the flow regime and the velocity gradients
in a channel. So, in this book, de determined using the full wetted perimeter will be used
for both pressure drop and heat transfer calculations. The actual area through which
the heat is transferred should, of course, be used to determine the rate of heat transfer;
equation 12.1.
Laminar flow
Below a Reynolds number of about 2000 the flow in pipes will be laminar. Providing the
natural convection effects are small, which will normally be so in forced convection, the
following equation can be used to estimate the film heat-transfer coefficient:
0.33 0.14
de
⊲12.13⊳
Nu D 1.86⊲RePr⊳0.33
L
w
Where L is the length of the tube in metres.
If the Nusselt number given by equation 12.13 is less than 3.5, it should be taken as 3.5.
In laminar flow the length of the tube can have a marked effect on the heat-transfer
rate for length to diameter ratios less than 500.
Transition region
In the flow region between laminar and fully developed turbulent flow heat-transfer coefficients cannot be predicted with certainty, as the flow in this region is unstable, and the
transition region should be avoided in exchanger design. If this is not practicable the coefficient should be evaluated using both equations 12.11 and 12.13 and the least value taken.
Heat-transfer factor, jh
It is often convenient to correlate heat-transfer data in terms of a heat transfer “j” factor,
which is similar to the friction factor used for pressure drop (see Volume 1, Chapters 3
and 9). The heat-transfer factor is defined by:
0.14
jh D StPr 0.67
⊲12.14⊳
w
The use of the jh factor enables data for laminar and turbulent flow to be represented
on the same graph; Figure 12.23. The jh values obtained from Figure 12.23 can be used
with equation 12.14 to estimate the heat-transfer coefficients for heat-exchanger tubes and
commercial pipes. The coefficient estimated for pipes will normally be conservative (on
the high side) as pipes are rougher than the tubes used for heat exchangers, which are
finished to closer tolerances. Equation 12.14 can be rearranged to a more convenient form:
0.14
hi di
0.33
D jh RePr
⊲12.15⊳
kf
w
Note. Kern (1950), and other workers, define the heat transfer factor as:
0.14
1/3
jH D NuPr
w
2
10−1
9
8
7
6
5
L/D = 24
HEAT-TRANSFER EQUIPMENT
4
48
Heat transfer factor, jh
3
120
2
240
500
10−2
9
8
7
6
5
4
3
2
10−3
1
10
2
3
4
5
6 7 89
2
10
2
3
4
5 6 789
3
2
10
3
4
5 6 789
4
10
2
3
4
5 6 789
5
10
2
3
4
5 6 789
6
10
Reynolds number, Re
Figure 12.23.
Tube-side heat-transfer factor
665
666
CHEMICAL ENGINEERING
The relationship between jh and jH is given by:
jH D jh Re
Viscosity correction factor
The viscosity correction factor will normally only be significant for viscous liquids.
To apply the correction an estimate of the wall temperature is needed. This can be
made by first calculating the coefficient without the correction and using the following
relationship to estimate the wall temperature:
hi ⊲tw t⊳ D U⊲T t⊳
⊲12.16⊳
where t D tube-side bulk temperature (mean),
tw D estimated wall temperature,
T D shell-side bulk temperature (mean).
Usually an approximate estimate of the wall temperature is sufficient, but trial-and-error
calculations can be made to obtain a better estimate if the correction is large.
Coefficients for water
Though equations 12.11 and 12.13 and Figure 12.23 may be used for water, a more
accurate estimate can be made by using equations developed specifically for water. The
physical properties are conveniently incorporated into the correlation. The equation below
has been adapted from data given by Eagle and Ferguson (1930):
hi D
where hi
t
ut
di
D
D
D
D
4200⊲1.35 C 0.02t⊳ut0.8
d0.2
i
⊲12.17⊳
inside coefficient, for water, W/m2 Ž C,
water temperature, Ž C,
water velocity, m/s,
tube inside diameter, mm.
12.8.2. Tube-side pressure drop
There are two major sources of pressure loss on the tube-side of a shell and tube exchanger:
the friction loss in the tubes and the losses due to the sudden contraction and expansion
and flow reversals that the fluid experiences in flow through the tube arrangement.
The tube friction loss can be calculated using the familiar equations for pressure-drop
loss in pipes (see Volume 1, Chapter 3). The basic equation for isothermal flow in pipes
(constant temperature) is:
0 2
L ut
P D 8jf
⊲12.18⊳
di
2
where jf is the dimensionless friction factor and L 0 is the effective pipe length.
HEAT-TRANSFER EQUIPMENT
667
The flow in a heat exchanger will clearly not be isothermal, and this is allowed for by
including an empirical correction factor to account for the change in physical properties
with temperature. Normally only the change in viscosity is considered:
u2 m
⊲12.19⊳
P D 8jf ⊲L 0 /di ⊳ t
2 w
m D 0.25 for laminar flow, Re < 2100,
D 0.14 for turbulent flow, Re > 2100.
Values of jf for heat exchanger tubes can be obtained from Figure 12.24; commercial
pipes are given in Chapter 5.
The pressure losses due to contraction at the tube inlets, expansion at the exits, and
flow reversal in the headers, can be a significant part of the total tube-side pressure drop.
There is no entirely satisfactory method for estimating these losses. Kern (1950) suggests
adding four velocity heads per pass. Frank (1978) considers this to be too high, and
recommends 2.5 velocity heads. Butterworth (1978) suggests 1.8. Lord et al. (1970) take
the loss per pass as equivalent to a length of tube equal to 300 tube diameters for straight
tubes, and 200 for U-tubes; whereas Evans (1980) appears to add only 67 tube diameters
per pass.
The loss in terms of velocity heads can be estimated by counting the number of flow
contractions, expansions and reversals, and using the factors for pipe fittings to estimate
the number of velocity heads lost. For two tube passes, there will be two contractions,
two expansions and one flow reversal. The head loss for each of these effects (see
Volume 1, Chapter 3) is: contraction 0.5, expansion 1.0, 180Ž bend 1.5; so for two passes
the maximum loss will be
2 ð 0.5 C 2 ð 1.0 C 1.5 D 4.5 velocity heads
D 2.25 per pass
From this, it appears that Frank’s recommended value of 2.5 velocity heads per pass is
the most realistic value to use.
Combining this factor with equation 12.19 gives
m
ut2
L
Pt D Np 8jf
C 2.5
⊲12.20⊳
di
w
2
where Pt
Np
ut
L
D
D
D
D
tube-side pressure drop, N/m2 (Pa),
number of tube-side passes,
tube-side velocity, m/s,
length of one tube.
Another source of pressure drop will be the flow expansion and contraction at the
exchanger inlet and outlet nozzles. This can be estimated by adding one velocity head for
the inlet and 0.5 for the outlet, based on the nozzle velocities.
−1
10
−2
10−3
1
9
8
7
6
5
1
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
1
9
8
7
6
5
4
4
3
3
2
2
1
9
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
1
9
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
1
1
101
2
3
4
2
5 6 7 8 91
2
10
3
4
5 6 7 8 91
2
3
10
3
4
5 6 7 8 91
2
3
4
4
10
Reynolds number, Re
Figure 12.24. Tube-side friction factors
Note: The friction factor jf is the same as the friction factor for pipes ⊲D ⊲R/u2 ⊳⊳, defined in Volume 1 Chapter 3.
5 6 7 8 91
2
5
10
3
4
5 6 7 8 91
10
1
6
CHEMICAL ENGINEERING
Friction factor, j
f
10
0
668
10
HEAT-TRANSFER EQUIPMENT
669
12.9. SHELL-SIDE HEAT-TRANSFER AND PRESSURE DROP
(SINGLE PHASE)
12.9.1. Flow pattern
The flow pattern in the shell of a segmentally baffled heat exchanger is complex, and this
makes the prediction of the shell-side heat-transfer coefficient and pressure drop very much
more difficult than for the tube-side. Though the baffles are installed to direct the flow
across the tubes, the actual flow of the main stream of fluid will be a mixture of cross flow
between the baffles, coupled with axial (parallel) flow in the baffle windows; as shown
in Figure 12.25. Not all the fluid flow follows the path shown in Figure 12.25; some will
leak through gaps formed by the clearances that have to be allowed for fabrication and
assembly of the exchanger. These leakage and bypass streams are shown in Figure 12.26,
which is based on the flow model proposed by Tinker (1951, 1958). In Figure 12.26,
Tinker’s nomenclature is used to identify the various streams, as follows:
Stream A is the tube-to-baffle leakage stream. The fluid flowing through the clearance
between the tube outside diameter and the tube hole in the baffle.
Cross flow
Axial flow
Figure 12.25.
Figure 12.26.
Idealised main stream flow
Shell-side leakage and by-pass paths
670
CHEMICAL ENGINEERING
Stream B is the actual cross-flow stream.
Stream C is the bundle-to-shell bypass stream. The fluid flowing in the clearance area
between the outer tubes in the bundle (bundle diameter) and the shell.
Stream E is the baffle-to-shell leakage stream. The fluid flowing through the clearance
between the edge of a baffle and the shell wall.
Stream F is the pass-partition stream. The fluid flowing through the gap in the tube
arrangement due to the pass partition plates. Where the gap is vertical it will
provide a low-pressure drop path for fluid flow.
Note. There is no stream D.
The fluid in streams C, E and F bypasses the tubes, which reduces the effective heattransfer area.
Stream C is the main bypass stream and will be particularly significant in pull-through
bundle exchangers, where the clearance between the shell and bundle is of necessity large.
Stream C can be considerably reduced by using sealing strips; horizontal strips that block
the gap between the bundle and the shell, Figure 12.27. Dummy tubes are also sometimes
used to block the pass-partition leakage stream F.
Figure 12.27.
Sealing strips
The tube-to-baffle leakage stream A does not bypass the tubes, and its main effect is
on pressure drop rather than heat transfer.
The clearances will tend to plug as the exchanger becomes fouled and this will increase
the pressure drop; see Section 12.9.6.
12.9.2. Design methods
The complex flow pattern on the shell-side, and the great number of variables involved,
make it difficult to predict the shell-side coefficient and pressure drop with complete
assurance. In methods used for the design of exchangers prior to about 1960 no attempt
was made to account for the leakage and bypass streams. Correlations were based on
the total stream flow, and empirical methods were used to account for the performance
of real exchangers compared with that for cross flow over ideal tube banks. Typical
of these “bulk-flow” methods are those of Kern (1950) and Donohue (1955). Reliable
predictions can only be achieved by comprehensive analysis of the contribution to heat
transfer and pressure drop made by the individual streams shown in Figure 12.26. Tinker
(1951, 1958) published the first detailed stream-analysis method for predicting shell-side
heat-transfer coefficients and pressure drop, and the methods subsequently developed
HEAT-TRANSFER EQUIPMENT
671
have been based on his model. Tinker’s presentation is difficult to follow, and his method
difficult and tedious to apply in manual calculations. It has been simplified by Devore
(1961, 1962); using standard tolerance for commercial exchangers and only a limited
number of baffle cuts. Devore gives nomographs that facilitate the application of the
method in manual calculations. Mueller (1973) has further simplified Devore’s method
and gives an illustrative example.
The Engineering Sciences Data Unit has also published a method for estimating shellside the pressure drop and heat transfer coefficient, EDSU Design Guide 83038 (1984). The
method is based on a simplification of Tinker’s work. It can be used for hand calculations, but
as iterative procedures are involved it is best programmed for use with personal computers.
Tinker’s model has been used as the basis for the proprietary computer methods
developed by Heat Transfer Research Incorporated; see Palen and Taborek (1969), and
by Heat Transfer and Fluid Flow Services; see Grant (1973).
Bell (1960, 1963) developed a semi-analytical method based on work done in the
cooperative research programme on shell and tube exchangers at the University of
Delaware. His method accounts for the major bypass and leakage streams and is suitable
for a manual calculation. Bell’s method is outlined in Section 12.9.4 and illustrated in
Example 12.3.
Though Kern’s method does not take account of the bypass and leakage streams, it
is simple to apply and is accurate enough for preliminary design calculations, and for
designs where uncertainty in other design parameters is such that the use of more elaborate
methods is not justified. Kern’s method is given in Section 12.9.3 and is illustrated in
Examples 12.1 and 12.3.
12.9.3. Kern’s method
This method was based on experimental work on commercial exchangers with standard
tolerances and will give a reasonably satisfactory prediction of the heat-transfer coefficient
for standard designs. The prediction of pressure drop is less satisfactory, as pressure drop
is more affected by leakage and bypassing than heat transfer. The shell-side heat transfer
and friction factors are correlated in a similar manner to those for tube-side flow by using
a hypothetical shell velocity and shell diameter. As the cross-sectional area for flow will
vary across the shell diameter, the linear and mass velocities are based on the maximum
area for cross-flow: that at the shell equator. The shell equivalent diameter is calculated
using the flow area between the tubes taken in the axial direction (parallel to the tubes)
and the wetted perimeter of the tubes; see Figure 12.28.
d0
pt
Figure 12.28.
pt
Equivalent diameter, cross-sectional areas and wetted perimeters
672
CHEMICAL ENGINEERING
Shell-side jh and jf factors for use in this method are given in Figures 12.29 and
12.30, for various baffle cuts and tube arrangements. These figures are based on data
given by Kern (1950) and by Ludwig (2001).
The procedure for calculating the shell-side heat-transfer coefficient and pressure drop
for a single shell pass exchanger is given below:
Procedure
1. Calculate the area for cross-flow As for the hypothetical row of tubes at the shell
equator, given by:
⊲pt do ⊳Ds lB
⊲12.21⊳
As D
pt
where pt
do
Ds
lB
D
D
D
D
tube pitch,
tube outside diameter,
shell inside diameter, m,
baffle spacing, m.
The term ⊲pt do ⊳/pt is the ratio of the clearance between tubes and the total
distance between tube centres.
2. Calculate the shell-side mass velocity Gs and the linear velocity us :
Ws
Gs D
As
us D
Gs
where Ws D fluid flow-rate on the shell-side, kg/s,
D shell-side fluid density, kg/m3 .
3. Calculate the shell-side equivalent diameter (hydraulic diameter), Figure 12.28. For
a square pitch arrangement:
2
pt d2o
4
1.27 2
4
D
⊲pt 0.785d2o ⊳
⊲12.22⊳
de D
do
do
For an equilateral triangular pitch arrangement:
2
pt
1 do
4
ð 0.87pt 2
1.10 2
2
4
D
⊲pt 0.917d2o ⊳
⊲12.23⊳
de D
do
do
2
where de D equivalent diameter, m.
4. Calculate the shell-side Reynolds number, given by:
Gs de
us de
D
⊲12.24⊳
Re D
5. For the calculated Reynolds number, read the value of jh from Figure 12.29 for the
selected baffle cut and tube arrangement, and calculate the shell-side heat transfer
100
1
1
9
8
7
6
5
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7891
−2
1 10
9
8
7
6
5
4
4
3
3
2
−1
Heat transfer factor, jn
10
1
9
8
7
6
5
1
9
8
7
6
5
Baffle cuts, percent
and
15
25
35
45
4
3
2
−2
10
2
4
3
2
1
9
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
10−3 1
1
2
1
10
3
4
2
5 6 7 8 91
3
4
5 6 7 8 91
2
2
3
4
5 6 7 8 91
3
10
2
3
4
4
10
−3
10
10
5 6 7 8 91
2
5
10
3
4
−4
10
HEAT-TRANSFER EQUIPMENT
15
25
35
45
1
5 6 7891
6
10
Reynolds number Re
Shell-side heat-transfer factors, segmental baffles
673
Figure 12.29.
1
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
1
9
8
7
6
5
4
4
3
3
2
2
1
9
8
7
6
5
1
9
8
7
6
5
4
4
Baffle cuts, percent
and
15
25
35
45
3
2
10−11
3
2
9
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
10−21
1
101
2
3
4
5 6 7 8 91
102
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
103
2
3
104
Reynolds number, Re
Figure 12.30.
Shell-side friction factors, segmental baffles
4
5 6 7 8 91
105
2
3
4
5 6 7 8 91
1
106
CHEMICAL ENGINEERING
Friction factor, jf
100
1
9
8
7
6
5
674
101
675
HEAT-TRANSFER EQUIPMENT
coefficient hs from:
Nu D
hs de
D jh RePr 1/3
kf
w
0.14
⊲12.25⊳
The tube wall temperature can be estimated using the method given for the tube-side,
Section 12.8.1.
6. For the calculated shell-side Reynolds number, read the friction factor from
Figure 12.30 and calculate the shell-side pressure drop from:
2 0.14
L us
Ds
⊲12.26⊳
Ps D 8jf
de
lB
2
w
where L D tube length,
lB D baffle spacing.
The term (L/lB ) is the number of times the flow crosses the tube bundle D ⊲Nb C 1⊳,
where Nb is the number of baffles.
Shell nozzle-pressure drop
The pressure loss in the shell nozzles will normally only be significant with gases. The
nozzle pressure drop can be taken as equivalent to 1 21 velocity heads for the inlet and
1
2 for the outlet, based on the nozzle area or the free area between the tubes in the row
immediately adjacent to the nozzle, whichever is the least.
Example 12.1
Design an exchanger to sub-cool condensate from a methanol condenser from 95Ž C to
40Ž C. Flow-rate of methanol 100,000 kg/h. Brackish water will be used as the coolant,
with a temperature rise from 25Ž to 40Ž C.
Solution
Only the thermal design will be considered.
This example illustrates Kern’s method.
Coolant is corrosive, so assign to tube-side.
Heat capacity methanol D 2.84 kJ/kgŽ C
100,000
ð 2.84⊲95 40⊳ D 4340 kW
3600
Heat capacity water D 4.2 kJ/kgŽ C
Heat load D
Cooling water flow D
Tlm D
4340
D 68.9 kg/s
4.2⊲40 25⊳
⊲95 40⊳ ⊲40 25⊳
D 31Ž C
⊲95 40⊳
ln
⊲40 25⊳
⊲12.4⊳
676
CHEMICAL ENGINEERING
Use one shell pass and two tube passes
95 40
D 3.67
40 25
40 25
SD
D 0.21
95 25
RD
From Figure 12.19
⊲12.6⊳
⊲12.7⊳
Ft D 0.85
Tm D 0.85 ð 31 D 26Ž C
From Figure 12.1
U D 600 W/m2 Ž C
Provisional area
4340 ð 103
⊲12.1⊳
D 278 m2
26 ð 600
Choose 20 mm o.d., 16 mm i.d., 4.88-m-long tubes 34 in. ð 16 ft , cupro-nickel.
Allowing for tube-sheet thickness, take
AD
L D 4.83 m
Area of one tube D 4.83 ð 20 ð 103 D 0.303 m2
278
D 918
Number of tubes D
0.303
As the shell-side fluid is relatively clean use 1.25 triangular pitch.
918 1/2.207
D 826 mm
Bundle diameter Db D 20
0.249
Use a split-ring floating head type.
From Figure 12.10, bundle diametrical clearance D 68 mm,
shell diameter, Ds D 826 C 68 D 894 mm.
(Note. nearest standard pipe sizes are 863.6 or 914.4 mm).
Shell size could be read from standard tube count tables.
Tube-side coefficient
40 C 25
D 33Ž C
2
Tube cross-sectional area D ð 162 D 201 mm2
4
Mean water temperature D
Tubes per pass D
918
D 459
2
Total flow area D 459 ð 201 ð 106 D 0.092 m2
⊲12.3b⊳
HEAT-TRANSFER EQUIPMENT
Water mass velocity D
677
68.9
D 749 kg/s m2
0.092
Density water D 995 kg/m3
Water linear velocity D
hi D
749
D 0.75 m/s
995
4200⊲1.35 C 0.02 ð 33⊳0.750.8
D 3852 W/m2 Ž C
160.2
(12.17)
The coefficient can also be calculated using equation 12.15; this is done to illustrate
use of this method.
0.14
hi di
D jh RePr 0.33
kf
w
Viscosity of water D 0.8 mNs/m2
Thermal conductivity D 0.59 W/mŽ C
Re D
udi
995 ð 0.75 ð 16 ð 103
D 14,925
D
0.8 ð 103
Cp
4.2 ð 103 ð 0.8 ð 103
D
D 5.7
kf
0.59
Neglect
w
Pr D
L
4.83 ð 103
D 302
D
di
16
From Figure 12.23, jh D 3.9 ð 103
hi D
0.59
ð 3.9 ð 103 ð 14,925 ð 5.70.33 D 3812 W/m2 Ž C
16 ð 103
Checks reasonably well with value calculated from equation 12.17; use lower figure.
Shell-side coefficient
894
Ds
D
D 178 mm.
5
5
Tube pitch D 1.25 ð 20 D 25 mm
Choose baffle spacing D
⊲25 20⊳
894 ð 178 ð 106 D 0.032 m2
25
1
100,000
Mass velocity, GS D
ð
D 868 kg/s m2
3600
0.032
1.1 2
⊲25 0.917 ð 202 ⊳ D 14.4 mm
Equivalent diameter de D
20
Cross-flow area As D
⊲12.21⊳
⊲12.23⊳
678
CHEMICAL ENGINEERING
Mean shell side temperature D
95 C 40
D 68Ž C
2
Methanol density D 750 kg/m3
Viscosity D 0.34 mNs/m2
Heat capacity D 2.84 kJ/kgŽ C
Thermal conductivity D 0.19 W/mŽ C
Gs de
868 ð 14.4 ð 103
Re D
D 36,762
D
0.34 ð 103
Cp
2.84 ð 103 ð 0.34 ð 103
D
Pr D
D 5.1
kf
0.19
⊲12.24⊳
Choose 25 per cent baffle cut, from Figure 12.29
jh D 3.3 ð 103
Without the viscosity correction term
0.19
ð 3.3 ð 103 ð 36,762 ð 5.11/3 D 2740 W/m2 Ž C
14.4 ð 103
Estimate wall temperature
hs D
Mean temperature difference D 68 33 D 35Ž C
across all resistances
U
600
across methanol film D
ð T D
ð 35 D 8Ž C
ho
2740
Mean wall temperature D 68 8 D 60Ž C
w D 0.37 mNs/m2
w
0.14
D 0.99
which shows that the correction for a low-viscosity fluid is not significant.
Overall coefficient
Thermal conductivity of cupro-nickel alloys D 50 W/mŽ C.
Take the fouling coefficients from Table 12.2; methanol (light organic) 5000 Wm2Ž C1 ,
brackish water (sea water), take as highest value, 3000 Wm2Ž C1
20
3
20 ð 10 ln
1
1
1
16
C
C
D
Uo
2740 5000
2 ð 50
⊲12.2⊳
1
20
1
20
ð
C
ð
C
16 3000 16 3812
Uo D 738 W/m2 Ž C
well above assumed value of 600 W/m2 Ž C.
679
HEAT-TRANSFER EQUIPMENT
Pressure drop
Tube-side
From Figure 12.24, for Re D 14,925
jf D 4.3 ð 103
Neglecting the viscosity correction term
3
995 ð 0.752
3 4.83 ð 10
Pt D 2 8 ð 4.3 ð 10
C 2.5
16
2
⊲12.20⊳
D 7211 N/m2 D 7.2 kPa ⊲1.1 psi⊳
low, could consider increasing the number of tube passes.
Shell side
Linear velocity D
Gs
868
D
D 1.16 m/s
750
From Figure 12.30, at Re D 36,762
jf D 4 ð 102
Neglect viscosity correction
Ps D 8 ð 4 ð 102
894
14.4
4.83 ð 103
178
750 ð 1.162
2
⊲12.26⊳
D 272,019 N/m2
D 272 kPa (39 psi) too high,
could be reduced by increasing the baffle pitch. Doubling the pitch halves the shell-side
velocity, which reduces the pressure drop by a factor of approximately (1/2)2
Ps D
272
D 68 kPa (10 psi), acceptable
4
This will reduce the shell-side heat-transfer coefficient by a factor of ⊲1/2⊳0.8 ⊲ho /
Re0.8 / us0.8 ⊳
ho D 2740 ð ⊲ 12 ⊳0.8 D 1573 W/m2 Ž C
This gives an overall coefficient of 615 W/m2 Ž C
of 600 W/m2 Ž C.
still above assumed value
Example 12.2
Gas oil at 200Ž C is to be cooled to 40Ž C. The oil flow-rate is 22,500 kg/h. Cooling water
is available at 30Ž C and the temperature rise is to be limited to 20Ž C. The pressure drop
allowance for each stream is 100 kN/m2 .
Design a suitable exchanger for this duty.
680
CHEMICAL ENGINEERING
Solution
Only the thermal design will be carried out, to illustrate the calculation procedure for an
exchanger with a divided shell.
T1 = 200°C
•
T2 = 40°C
•
•
t2 = 50°C
•
t1 = 30°C
Tlm D
⊲200 40⊳ ⊲40 30⊳
D 51.7Ž C
⊲200 50⊳
Ln
⊲40 30⊳
⊲12.4⊳
R D ⊲200 50⊳/⊲50 30⊳ D 8.0
⊲12.6⊳
S D ⊲50 30⊳/⊲200 30⊳ D 0.12
⊲12.7⊳
These values do not intercept on the figure for a single shell-pass exchanger, Figure 12.19,
so use the figure for a two-pass shell, Figure 12.20, which gives
Ft D 0.94, so
Tm D 0.94 ð 51.7 D 48.6Ž C
Physical properties
Water, from steam tables:
Temperature, Ž C
Cp , kJ kg1Ž C1
k, kWm1Ž C1
, mNm2 s
, kg m3
30
4.18
618 ð 106
797 ð 103
995.2
40
4.18
631 ð 106
671 ð 103
992.8
50
4.18
643 ð 106
544 ð 103
990.1
Gas oil, from Kern, Process Heat Transfer, McGraw-Hill :
Temperature, Ž C
Cp , kJ kg1Ž C1
k, Wm1Ž C1
, mNm2 s
, kg m3
200
2.59
0.13
0.06
830
120
2.28
0.125
0.17
850
40
1.97
0.12
0.28
870
681
HEAT-TRANSFER EQUIPMENT
Duty:
Oil flow-rate D 22,500/3600 D 6.25 kg/s
Q D 6.25 ð 2.28 ð ⊲200 40⊳ D 2280 kW
2280
D 27.27 kg/h
4.18⊲50 30⊳
From Figure 12.1, for cooling tower water and heavy organic liquid, take
Water flow-rate D
U D 500 Wm2 C1
Area required D
2280 ð 103
D 94 m2
500 ð 48.6
Tube-side coefficient
Select 20 mm o.d., 16 mm i.d. tubes, 4 m long, triangular pitch 1.25do , carbon steel.
Surface area of one tube D ð 20 ð 103 ð 4 D 0.251 m2
Number of tubes required D 94/0.251 D 375, say 376, even number
Cross-sectional area, one tube D ⊲16 ð 103 ⊳2 D 2.011 ð 104 m2
4
Total tube area D 376 ð 2.011 ð 104 D 0.0756 m2
Put water through tube for ease of cleaning.
Tube velocity, one pass D 27.27/⊲992.8 ð 0.0756⊳ D 0.363 m/s
Too low to make effective use of the allowable pressure drop, try 4 passes.
ut D 4 ð 0.363 D 1.45 m/s
A floating head will be needed due to the temperature difference. Use a pull through type.
Tube-side heat transfer coefficient
4200⊲1.35 C 0.02 ð 40⊳1.450.8
D 6982 Wm2Ž C1
⊲12.17⊳
hi D
160.2
Shell-side coefficient
From Table 12.4 and equation 12.3b, for 4 passes, 1.25do triangular pitch
Bundle diameter, Db D 20⊲376/0.175⊳1/2.285 D 575 mm
From Figure 12.10, for pull through head, clearance D 92 mm
Shell diameter, Ds D 575 C 92 D 667 mm (26 in pipe)
Use 25 per cent cut baffles, baffle arrangement for divided shell as shown below:
Baffles
682
CHEMICAL ENGINEERING
Take baffle spacing as 1/5 shell diameter D 667/5 D 133 mm
Tube pitch, pt D 1.25 ð 20 D 25 mm
Area for flow, As , will be half that given by equation 12.21
25 20
As D 0.5 ð
ð 0.667 ð 0.133 D 0.00887 m2
25
Gs D 6.25/0.00887 D 704.6 kg/s
us D 704.6/850 D 0.83 m/s, looks reasonable
de D
1.10 2
⊲25 0.917 ð 202 ⊳ D 14.2 mm
20
Re D
0.83 ð 14.2 ð 103 ð 850
D 58,930
0.17 ð 103
⊲12.23⊳
From Figure 12.29, jh D 2.6 ð 103
Pr D ⊲2.28 ð 103 ð 0.17 ð 103 ⊳/0.125 D 3.1
Nu D 2.6 ð 103 ð 58,930 ð 3.11/3 D 223.4
3
⊲12.25⊳
2Ž
hs D ⊲223.4 ð 0.125⊳/⊲14.2 ð 10 ⊳ D 1967 Wm
1
C
Overall coefficient
Take fouling factors as 0.00025 for cooling tower water and 0.0002 for gas oil (light
organic). Thermal conductivity for carbon steel tubes 45 Wm1Ž C1 .
20 ð 103 ln⊲20/16⊳
2 ð 45
C 20/16⊲1/6982 C 0.00025⊳ D 0.00125
1/Uo D 1/1967 C 0.0002 C
Uo D 1/0.00125 D 800 Wm2Ž C1
⊲12.2⊳
Well above the initial estimate of 500 Wm2Ž C1 , so design has adequate area for the
duty required.
Pressure drops
Tube-side
Re D
1.45 ð 16 ð 103 ð 992.8
D 34,378
670 ð 106
⊲3.4 ð 104 ⊳
From Figure 12.24, jf D 3.5 ð 103 . Neglecting the viscosity correction
4
1.452
3
D 39,660
C
2.5
992.8
ð
Pt D 4 8 ð 3.5 ð 10 ð
16 ð 103
2
D 40 kN/m2
Well within the specification, so no need to check the nozzle pressure drop.
⊲12.20⊳
HEAT-TRANSFER EQUIPMENT
683
Shell-side
From Figure 12.30, for Re D 58,930, js D 3.8 ð 102
With a divided shell, the path length D 2 ð ⊲L/lb ⊳
Neglecting the viscosity correction factor,
662 ð 103
0.832
2ð4
2
Ps D 8 ð 3.8 ð 10
ð
ð
850
ð
D 251,481
14.2 ð 103
132 ð 103
2
D 252 kN/m2
⊲12.26⊳
Well within the specification, no need to check nozzle pressure drops.
So the proposed thermal design is satisfactory. As the calculated pressure drops are
below that allowed, there is some scope for improving the design.
Example 12.3
Design a shell-and-tube exchanger for the following duty.
20,000 kg/h of kerosene (42Ž API) leaves the base of a kerosene side-stripping column
at 200Ž C and is to be cooled to 90Ž C by exchange with 70,000 kg/h light crude oil
(34Ž API) coming from storage at 40Ž C. The kerosene enters the exchanger at a pressure
of 5 bar and the crude oil at 6.5 bar. A pressure drop of 0.8 bar is permissible on
both streams. Allowance should be made for fouling by including a fouling factor of
0.0003 (W/m2 Ž C)1 on the crude stream and 0.0002 (W/m2 Ž C)1 on the kerosene stream.
Solution
The solution to this example illustrates the iterative nature of heat exchanger design calculations. An algorithm for the design of shell-and-tube exchangers is shown in Figure A
(see p. 684). The procedure set out in this figure will be followed in the solution.
Step 1: Specification
The specification is given in the problem statement.
20,000 kg/h of kerosene (42Ž API) at 200Ž C cooled to 90Ž C, by exchange with
70,000 kg/h light crude oil (34Ž API) at 40Ž C.
The kerosene pressure 5 bar, the crude oil pressure 6.5 bar.
Permissible pressure drop of 0.8 bar on both streams.
Fouling
factors:
crude
stream
0.00035 (W/m2 Ž C)1,
kerosene
stream
2 Ž 1
0.0002 (W/m C) .
To complete the specification, the duty (heat transfer rate) and the outlet temperature
of the crude oil needed to be calculated.
The mean temperature of the kerosene D ⊲200 C 90⊳/2 D 145Ž C.
At this temperature the specific heat capacity of 42Ž API kerosene is 2.47 kJ/kgŽ C
(physical properties from D. Q. Kern, Process Heat Transfer, McGraw-Hill).
Duty D
20,000
ð 2.47⊲200 90⊳ D 1509.4 kW
3600
684
CHEMICAL ENGINEERING
Step 1
Specification
Define duty
Make energy balance if needed
to calculate unspecified flow
rates or temperatures
Step 10
Decide baffle spacing and
estimate shell-side heat
transfer coefficient
Step 11
Step 2
Calculate overall heat transfer
coefficient including fouling
factors, Uo,calc
Collect physical properties
Step 3
No
Assume value of overall
coefficient Uo, ass
Step 4
0<
Step 12
Set Uo,ass = Uo, calc
Decide number of shell and
tube passes Calculate ∆Tlm,
correction factor, F, and ∆Tm
Uo,calc - Uo,ass
< 30%
Uo,ass
Yes
Estimate tube- and shell-side
pressure drops
Step 5
Determine heat transfer area
required: A o= q /Uo,ass ∆Tm
No
Step 6
Pressure drops
within specification?
Step 13
Decide type, tube size, material
layout Assign fluids to shell or
tube side
Yes
Estimate cost of exchanger
Step 7
Calculate number of tubes
Yes
Step 14
Can design be
optimized to reduce cost?
Step 8
No
Calculate shell diameter
Accept design
Step 9
Estimate tube-side heat
transfer coefficient
Figure A. Design procedure for shell-and-tube heat exchangers
Example 12.2 and Figure A were developed by the author for the Open University Course T333 Principles
and Applications of Heat Transfer. They are reproduced here by permission of the Open University.
As a first trial take the mean temperature of the crude oil as equal to the inlet temperature, 40Ž C; specific heat capacity at this temperature D 2.01 kJ/kgŽ C.
An energy balance gives:
7000
ð 2.01⊲t2 40⊳ D 1509.4
3600
t2 D 78.6Ž C and the stream mean temperature D ⊲40 C 78.6⊳/2 D 59.3Ž C.
685
HEAT-TRANSFER EQUIPMENT
Ž
The specific heat at this temperature is 2.05 kJ/kg C. A second trial calculation using
this value gives t2 D 77.9Ž C and a new mean temperature of 58.9Ž C. There is no significant
change in the specific heat at this mean temperature from the value used, so take the crude
stream outlet temperature to be 77.9Ž C, say 78Ž C.
Step 2: Physical Properties
Kerosene
inlet
mean
outlet
temperature
specific heat
thermal conductivity
density
viscosity
200
2.72
0.130
690
0.22
145
2.47
0.132
730
0.43
90
2.26
0.135
770
0.80
Crude oil
outlet
mean
inlet
temperature
specific heat
thermal conductivity
density
viscosity
78
2.09
0.133
800
2.4
59
2.05
0.134
820
3.2
40
2.01
0.135
840
4.3
Ž
C
kJ/kgŽ C
W/mŽ C
kg/m3
mN sm2
Ž
C
kJ/kgŽ C
W/mŽ C
kg/m3
mN sm2
Step 3: Overall coefficient
For an exchanger of this type the overall coefficient will be in the range 300 to
500 W/m2 Ž C, see Figure 12.1 and Table 12.1; so start with 300 W/m2 Ž C.
Step 4: Exchanger type and dimensions
An even number of tube passes is usually the preferred arrangement, as this positions the
inlet and outlet nozzles at the same end of the exchanger, which simplifies the pipework.
Start with one shell pass and 2 tube passes.
Tlm D
RD
SD
⊲200 78⊳ ⊲90 40⊳
D 80.7Ž C
⊲200 78⊳
ln
⊲90 40⊳
⊲200 90⊳
D 2.9
⊲78 40⊳
⊲78 40⊳
D 0.24
⊲200 40⊳
From Figure 12.19, Ft D 0.88, which is acceptable.
So,
Tm D 0.88 ð 80.7 D 71.0Ž C
⊲12.4⊳
⊲12.6⊳
⊲12.7⊳
686
CHEMICAL ENGINEERING
Step 5: Heat transfer area
Ao D
1509.4 ð 103
D 70.86 m2
300 ð 71.0
(12.1)
Step 6: Layout and tube size
Using a split-ring floating head exchanger for efficiency and ease of cleaning.
Neither fluid is corrosive, and the operating pressure is not high, so a plain carbon steel
can be used for the shell and tubes.
The crude is dirtier than the kerosene, so put the crude through the tubes and the
kerosene in the shell.
Use 19.05 mm (3/4 inch) outside diameter, 14.83 mm inside diameter, 5 m Long tubes
(a popular size) on a triangular 23.81 mm pitch (pitch/dia. D 1.25).
Step 7: Number of tubes
Area of one tube (neglecting thickness of tube sheets)
D ð 19.05 ð 103 ð 5 D 0.2992 m2
Number of tubes D 70.89/0.2992 D 237, say 240
So, for 2 passes, tubes per pass D 120
Check the tube-side velocity at this stage to see if it looks reasonable.
Tube cross-sectional area D
⊲14.83 ð 103 ⊳2 D 0.0001727 m2
4
So area per pass D 120 ð 0.0001727 D 0.02073 m2
70,000
1
ð
D 0.0237 m3 /s
3600
820
0.0237
Tube-side velocity, ut D
D 1.14 m/s
0.02073
Volumetric flow D
The velocity is satisfactory, between 1 to 2 m/s, but may be a little low. This will show
up when the pressure drop is calculated.
Step 8: Bundle and shell diameter
From Table 12.4, for 2 tube passes, K1 D 0.249, n1 D 2.207,
so,
Db D 19.05
240
0.249
1/2.207
D 428 mm ⊲0.43 m⊳
⊲12.3b⊳
For a split-ring floating head exchanger the typical shell clearance from Figure 12.10
is 56 mm, so the shell inside diameter,
Ds D 428 C 56 D 484 mm
HEAT-TRANSFER EQUIPMENT
687
Step 9: Tube-side heat transfer coefficient
820 ð 1.14 ð 14.83 ð 103
D 4332, ⊲4.3 ð 103 ⊳
3.2 ð 103
2.05 ð 103 ð 3.2 ð 103
D 48.96
Pr D
0.134
L
5000
D
D 337
di
14.83
Re D
From Figure 12.23, jh D 3.2 ð 103
Nu D 3.2 ð 103 ⊲4332⊳⊲48.96⊳0.33 D 50.06
0.134
hi D 50.06 ð
D 452 W/m2 Ž C
14.83 ð 103
⊲12.15⊳
This is clearly too low if Uo is to be 300 W/m2 Ž C. The tube-side velocity did look
low, so increase the number of tube passes to 4. This will halve the cross-sectional area
in each pass and double the velocity.
New
and
ut D 2 ð 1.14 D 2.3 m/s
Re D 2 ð 4332 D 8664⊲8.7 ð 103 ⊳
jh D 3.8 ð 103
0.134
ð 3.8 ð 103 ⊲8664⊳⊲48.96⊳0.33
hi D
14.83 ð 103
D 1074 W/m2 Ž C
Step 10: Shell-side heat transfer coefficient
Kern’s method will be used.
With 4 tube passes the shell diameter will be larger than that calculated for 2 passes.
For 4 passes K1 D 0.175 and n1 D 2.285.
240 1/2.285
D 450 mm, ⊲0.45 m⊳
⊲12.3b⊳
Db D 19.05
0.175
The bundle to shell clearance is still around 56 mm, giving:
Ds D 506 mm ⊲about 20 inches⊳
As a first trial take the baffle spacing D Ds /5, say 100 mm. This spacing should give
good heat transfer without too high a pressure drop.
⊲23.81 19.05⊳
⊲12.21⊳
506 ð 100 D 10,116 mm2 D 0.01012 m2
As D
23.81
1.10
de D
⊲12.23⊳
⊲23.812 0.917 ð 19.052 ⊳ D 13.52 mm
19.05
1
20,000
ð
D 0.0076 m3 /s
Volumetric flow-rate on shell-side D
3600
730
688
CHEMICAL ENGINEERING
Shell-side velocity D
Re D
Pr D
0.076
D 0.75 m/s
0.01012
730 ð 0.75 ð 13.52 ð 103
D 17,214, ⊲1.72 ð 104 ⊳
0.43 ð 103
2.47 ð 103 ð 0.43 ð 103
D 8.05
0.132
Use segmental baffles with a 25% cut. This should give a reasonable heat transfer coefficient without too large a pressure drop.
From Figure 12.29, jh D 4.52 ð 103 .
Neglecting the viscosity correction:
0.132
⊲12.25⊳
hs D
ð 103 ð 4.52 ð 103 ð 17,214 ð 8.050.33 D 1505 W/m2 Ž C
13.52
Step 11: Overall coefficient
1
D
Uo
3
19.05 ð 10 Ln
1
19.05
C 0.00035
C
1074
14.83
2 ð 55
19.05
14.83
C
1
C 0.0002
1505
Uo D 386 W/m2 Ž C
(12.2)
This is above the initial estimate of 300 W/m2 Ž C. The number of tubes could possibly
be reduced, but first check the pressure drops.
Step 12: Pressure drop
Tube-side
240 tubes, 4 passes, tube i.d. 14.83 mm, ut 2.3 m/s,
Re D 8.7 ð 103 . From Figure 12.24, jf D 5 ð 103 .
⊲820 ð 2.32 ⊳
5000
Pt D 4 8 ð 5 ð 103
C 2.5
14.83
2
D 4⊲13.5 C 2.5⊳
⊲12.20⊳
⊲820 ð 2.32 ⊳
2
D 138,810 N/m2 , 1.4 bar
This exceeds the specification. Return to step 6 and modify the design.
Modified design
The tube velocity needs to be reduced. This will reduce the heat transfer coefficient, so
the number of tubes must be increased to compensate. There will be a pressure drop
across the inlet and outlet nozzles. Allow 0.1 bar for this, a typical figure (about 15% of
the total); which leaves 0.7 bar across the tubes. Pressure drop is roughly proportional
HEAT-TRANSFER EQUIPMENT
689
to the square of the velocity and ut is proportional to the number of tubes per pass. So
the pressure drop calculated for 240 tubes can be used to estimate the number of tubes
required.
Tubes needed D 240/⊲0.6/1.4⊳0.5 D 365
Say, 360 with 4 passes.
Retain 4 passes as the heat transfer coefficient will be too low with 2 passes.
Second trial design: 360 tubes 19.05 mm o.d., 14.83 mm i.d., 5 m long, triangular
pitch 23.81 mm.
360 1/2.285
D 537 mm, ⊲0.54 m⊳
⊲12.3b⊳
Db D 19.05
0.175
From Figure 12.10 clearance with this bundle diameter D 59 mm
Ds D 537 C 59 D 596 mm
Cross-sectional area per pass D
Tube velocity ut D
Re D
360
⊲14.83 ð 103 ⊳2 D 0.01555 m2
4
4
0.0237
D 1.524 m/s
0.01555
820 ð 1.524 ð 14.83 ð 103
D 5792
3.2 ð 103
L/d is the same as the first trial, 337
jh D 3.6 ð 103
0.134
3
ð 10
hi D
3.6 ð 103 ð 5792 ð 48.960.33 D 680 W/m2 Ž C ⊲12.15⊳
14.83
This looks satisfactory, but check the pressure drop before doing the shell-side calculation.
jf D 5.5 ð 103
⊲820 ð 1.5242 ⊳
5000
3
D 66,029 N/m2 , 0.66 bar
C 2.5
Pt D 4 8 ð 5.5 ð 10
14.83
2
⊲12.20⊳
Well within specification.
Keep the same baffle cut and spacing.
As D
⊲23.81 19.05⊳
596 ð 100 D 11,915 mm2 , 0.01192 m2
23.81
us D
0.0076
D 0.638 m/s
0.01193
de D 13.52 mm, as before
Re D
730 ð 0.638 ð 13.52 ð 103
D 14,644, ⊲1.5 ð 104 ⊳
0.43 ð 103
⊲12.21⊳
690
CHEMICAL ENGINEERING
Pr D 8.05
jh D 4.8 ð 103 , jf D 4.6 ð 102
0.132
4.8 ð 103 ð 14,644 ð ⊲8.05⊳0.33 D 1366 W/m2 Ž C, looks OK
hs D
13.52 ð 103
⊲12.25⊳
2
596
5000 ⊲730 ð 0.638 ⊳
Ps D 8 ð 4.6 ð 102
D 120,510 N/m2 , 1.2 bar
13.52
100
2
⊲12.26⊳
Too high; the specification only allowed 0.8 overall, including the loss over the nozzles.
Check the overall coefficient to see if there is room to modify the shell-side design.
19.05
19.05 ð 103 ln
1
19.05
1
1
14.88
D
C 0.00035
C
C
C 0.0002
Uo
683
14.83
2 ð 55
1366 ⊲12.2⊳
Uo D 302 W/m2 Ž C
Uo required D
so Uo required D
Q
,
⊲Ao Tlm ⊳
Ao D 360 ð 0.2992 D 107.7 m2 ,
1509.4 ð 103
D 197 W/m2 Ž C
⊲107.7 ð 71⊳
The estimated overall coefficient is well above that required for design, 302 compared
to 192 W/m2 Ž C, which gives scope for reducing the shell-side pressure drop.
Allow a drop of 0.1 bar for the shell inlet and outlet nozzles, leaving 0.7 bar for the
shell-side flow. So, to
keep within the specification, the shell-side velocity will have to
be reduced by around ⊲1/2⊳ D 0.707. To achieve this the baffle spacing will need to
be increased to 100/0.707 D 141, say 140 mm.
⊲23.81 19.05⊳
596 ð 140 D 6681 mm2 , 0.167 m2
23.81
0.0076
us D
D 0.455 m/s,
0.0167
As D
⊲12.21⊳
Giving: Re D 10,443, hs D 1177 W/m2 Ž C, Ps D 0.47 bar, and Uo D 288 Wm2 Ž C1 .
The pressure drop is now well within the specification.
Step 13: Estimate cost
The cost of this design can be estimated using the methods given in Chapter 6.
Step 14: Optimisation
There is scope for optimising the design by reducing the number of tubes, as the pressure
drops are well within specification and the overall coefficient is well above that needed.
However, the method used for estimating the coefficient and pressure drop on the shell-side
(Kern’s method) is not accurate, so keeping to this design will give some margin of safety.
HEAT-TRANSFER EQUIPMENT
691
Viscosity correction factor
The viscosity correction factor ⊲/w ⊳0.14 was neglected when calculating the heat transfer
coefficients and pressure drops. This is reasonable for the kerosene as it has a relatively
low viscosity, but it is not so obviously so for the crude oil. So, before firming up the
design, the effect of this factor on the tube-side coefficient and pressure drop will be
checked.
First, an estimate of the temperature at the tube wall, tw is needed.
The inside area of the tubes D ð 14.83 ð 103 ð 5 ð 360 D 83.86 m2
Heat flux D Q/A D 1509.4 ð 103 /83.86 D 17,999 W/m2
As a rough approximation
⊲tw t⊳hi D 17,999
where t is the mean bulk fluid temperature D 59Ž C.
tw D
So,
17,999
C 59 D 86Ž C.
680
The crude oil viscosity at this temperature D 2.1 ð 103 Ns/m2 .
0.14
0.14
3.2 ð 103
Giving
D
D 1.06
w
2.1 ð 103
Only a small factor, so the decision to neglect it was justified. Applying the correction
would increase the estimated heat transfer coefficient, which is in the right direction. It
would give a slight decrease in the estimated pressure drop.
Summary: the proposed design
Split ring, floating head, 1 shell pass, 4 tube passes.
360 carbon steel tubes, 5 m long, 19.05 mm o.d., 14.83 mm i.d., triangular pitch,
pitch 23.18 mm.
Heat transfer area 107.7 m2 (based on outside diameter).
Shell i.d. 597 mm (600 mm), baffle spacing 140 mm, 25% cut.
Tube-side coefficient 680 W/m2 Ž C, clean.
Shell-side coefficient 1366 W/m2 Ž C, clean.
Overall coefficient, estimated 288 W/m2 Ž C, dirty.
Overall coefficient required 197 W/m2 Ž C, dirty.
Dirt/Fouling factors:
Tube-side (crude oil) 0.00035 (W/m2 Ž C)1 .
Shell-side (kerosene) 0.0002 (W/m2 Ž C)1 .
Pressure drops:
Tube-side, estimated 0.40 bar, C0.1 for nozzles; specified 0.8 bar overall.
Shell-side, estimated 0.45 bar, C0.1 for nozzles; specified 0.8 bar overall.
692
CHEMICAL ENGINEERING
Optimisation using a CAD program
The use of a proprietary computer program (HTFS, M-TASC) to find the lowest cost
design that meets the specification resulted in the design set out below. The program
selected longer tubes, to minimise the cost. This has resulted in an exchanger with a shell
length to diameter ratio of greater than 10 : 1. This could cause problems in supporting
the shell, and in withdrawing the tube bundle for maintenance.
The CAD program was rerun with the tube length restricted to 3500 mm, to produce
a more compact design. This gave a design with 349 tubes, 4 passes, in a shell 540 mm
diameter. The setting plan for this design is shown in Figure B.
4475
304
598
2714
A
T2
B
S1
T1
C
S2
A
B
857
C
2217
2906
Pulling length
Section BB
Section CC
All measurements are in mm
Warnings
- This setting plan is approximate only
For accurate setting plan use full
mechanical design package
Figure B.
Nom bore Rating lb
90
150
80
150
125
150
125
150
Shell
Tube
Pressure bar
5
6.5
TempertureC
300
190
Passes
1
4
kg
1754
2758
3678
T1
T2
S1
S2
255
205
205
594 593
575 575
Section AA
Baffle arrangement diagrammatic (orientation below)
Baffle
orientation
Weight Bundle/Dry/Wet
Tube in
Tube out
Shell in
Shell out
HTFS SETTING PLAN
AES
610 - 3500
Setting out plan for compact design. (Courtesy of Heat Transfer and Fluid Flow Service, Harwell)
CAD design
Split ring, floating head, 1 shell pass, 2 tube passes.
168 carbon steel tubes, 6096 mm, 19.05 mm o.d., 14.83 mm i.d., triangular pitch,
pitch 23.18 mm.
HEAT-TRANSFER EQUIPMENT
693
Heat transfer area 61 m2 .
Shell i.d. 387, baffle spacing 77.9 mm, 15% cut.
Tube-side coefficient 851 W/m2 Ž C, clean.
Shell-side coefficient 1191 W/m2 Ž C, clean.
Overall coefficient estimated 484 Wm2 Ž C1 clean.
Overall coefficient estimated 368 Wm2 Ž C1 dirty.
Pressure drops, including drop over nozzles:
Tube-side, estimated 0.5 bar.
Shell-side, estimated 0.5 bar.
12.9.4. Bell’s method
In Bell’s method the heat-transfer coefficient and pressure drop are estimated from correlations for flow over ideal tube-banks, and the effects of leakage, bypassing and flow in
the window zone are allowed for by applying correction factors.
This approach will give more satisfactory predictions of the heat-transfer coefficient
and pressure drop than Kern’s method; and, as it takes into account the effects of leakage
and bypassing, can be used to investigate the effects of constructional tolerances and the
use of sealing strips. The procedure in a simplified and modified form to that given by
Bell (1963), is outlined below.
The method is not recommended when the by-pass flow area is greater than 30% of
the cross-flow area, unless sealing strips are used.
Heat-transfer coefficient
The shell-side heat transfer coefficient is given by:
hs D hoc Fn Fw Fb FL
⊲12.27⊳
where hoc D heat transfer coefficient calculated for cross-flow over an ideal tube bank,
no leakage or bypassing.
Fn D correction factor to allow for the effect of the number of vertical tube rows,
Fw D window effect correction factor,
Fb D bypass stream correction factor,
FL D leakage correction factor.
The total correction will vary from 0.6 for a poorly designed exchanger with large clearances to 0.9 for a well-designed exchanger.
hoc , ideal cross-flow coefficient
The heat-transfer coefficient for an ideal cross-flow tube bank can be calculated using the
heat transfer factors jh given in Figure 12.31. Figure 12.31 has been adapted from a similar
figure given by Mueller (1973). Mueller includes values for more tube arrangements than
are shown in Figure 12.31. As an alternative to Figure 12.31, the comprehensive data given
2
3
4
5 6 7 8 91
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
1.25
10−1 1
1
9
8
7
6
5
1.25
4
4
3
3
2
2
10−2 19
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
10−3
1
101
2
3
4
5 6 7 8 91
2
3
4
5 6 7 8 91
2
3
4
103
102
5 6 7 8 91
2
104
Reynolds number, Re
Figure 12.31.
Heat-transfer factor for cross-flow tube banks
3
4
5 6 7 8 91
105
2
3
4
5 6 7 8 91
1
106
CHEMICAL ENGINEERING
9
8
7
6
5
Heat transfer factor, jh
2
694
1
100 19
HEAT-TRANSFER EQUIPMENT
695
in the Engineering Sciences Data Unit Design Guide on heat transfer during cross-flow of
fluids over tube banks, ESDU 73031 (1973), can be used; see Butterworth (1977).
The Reynolds number for cross-flow through a tube bank is given by:
Re D
us do
Gs do
D
where Gs D mass flow rate per unit area, based on the total flow and free area at the
bundle equator. This is the same as Gs calculated for Kern’s method,
do D tube outside diameter.
The heat-transfer coefficient is given by:
hoc do
D jh RePr 1/3
kf
w
0.14
⊲12.28⊳
Fn , tube row correction factor
The mean heat-transfer coefficient will depend on the number of tubes crossed.
Figure 12.31 is based on data for ten rows of tubes. For turbulent flow the correction
factor Fn is close to 1.0. In laminar flow the heat-transfer coefficient may decrease with
increasing rows of tubes crossed, due to the build up of the temperature boundary layer.
The factors given below can be used for the various flow regimes; the factors for turbulent
flow are based on those given by Bell (1963).
Ncv is number of constrictions crossed D number of tube rows between the baffle tips;
see Figure 12.39, and Section 12.9.5.
1. Re > 2000, turbulent;
take Fn from Figure 12.32.
Figure 12.32.
Tube row correction factor Fn
2. Re > 100 to 2000, transition region,
take Fn D 1.0;
3. Re < 100, laminar region,
Fn / ⊲N0c ⊳0.18 ,
(12.29)
where N0c is the number of rows crossed in series from end to end of the shell, and
depends on the number of baffles. The correction factor in the laminar region is not
696
CHEMICAL ENGINEERING
well established, and Bell’s paper, or the summary given by Mueller (1973), should be
consulted if the design falls in this region.
Fw , window correction factor
This factor corrects for the effect of flow through the baffle window, and is a function of
the heat-transfer area in the window zones and the total heat-transfer area. The correction
factor is shown in Figure 12.33 plotted versus Rw , the ratio of the number of tubes in the
window zones to the total number in the bundle, determined from the tube layout diagram.
1.2
1.1
1.0
Fw
0.9
0.8
0.7
0.6
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Rw
Figure 12.33.
Window correction factor
For preliminary calculations Rw can be estimated from the bundle and window crosssectional areas, see Section 12.9.5.
Fb , bypass correction factor
This factor corrects for the main bypass stream, the flow between the tube bundle and the
shell wall, and is a function of the shell to bundle clearance, and whether sealing strips
are used:
Ab
2Ns 1/3
Fb D exp ˛
1
⊲12.30⊳
As
Ncv
697
HEAT-TRANSFER EQUIPMENT
where ˛ D 1.5 for laminar flow, Re < 100,
˛ D 1.35 for transitional and turbulent flow Re > 100,
Ab D clearance area between the bundle and the shell, see Figure 12.39 and
Section 12.9.5,
As D maximum area for cross-flow, equation 12.21,
Ns D number of sealing strips encountered by the bypass stream in the
cross-flow zone,
Ncv D the number of constrictions, tube rows, encountered in the cross-flow section.
Equation 12.30 applies for Ns Ncv /2.
Where no sealing strips are used, Fb can be obtained from Figure 12.34.
1.0
0.9
0.8
R e > 100
Fb
R e < 100
0.7
0.6
0.5
0
0.1
0.2
0.3
0.4
Ab / As
Figure 12.34.
Bypass correction factor
FL , Leakage correction factor
This factor corrects for the leakage through the tube-to-baffle clearance and the baffle-toshell clearance.
⊲Atb C 2Asb ⊳
⊲12.31⊳
FL D 1 ˇL
AL
698
CHEMICAL ENGINEERING
0.5
0.4
0.3
βL
0.2
0.1
0
0.1
0.3
0.2
0.4
0.5
0.6
0.7
0.8
AL /As
Figure 12.35.
Coefficient for FL , heat transfer
where ˇL D a factor obtained from Figure 12.35,
Atb D the tube to baffle clearance area, per baffle, see Figure 12.39 and
Section 12.9.5,
Asb D shell-to-baffle clearance area, per baffle, see Figure 12.39 and Section 12.9.5,
AL D total leakage area D ⊲Atb C Asb ⊳.
Typical values for the clearances are given in the standards, and are discussed in
Section 12.5.6. The clearances and tolerances required in practical exchangers are
discussed by Rubin (1968).
Pressure drop
The pressure drops in the cross-flow and window zones are determined separately, and
summed to give the total shell-side pressure drop.
Cross-flow zones
The pressure drop in the cross-flow zones between the baffle tips is calculated from
correlations for ideal tube banks, and corrected for leakage and bypassing.
Pc D Pi F0b F0L
⊲12.32⊳
where Pc D the pressure drop in a cross-flow zone between the baffle tips, corrected
for by-passing and leakage,
Pi D the pressure drop calculated for an equivalent ideal tube bank,
F0b D by-pass correction factor,
F0L D leakage correction factor.
HEAT-TRANSFER EQUIPMENT
699
1Pi ideal tube bank pressure drop
The number of tube rows has little effect on the friction factor and is ignored.
Any suitable correlation for the cross-flow friction factor can be used; for that given
in Figure 12.36, the pressure drop across the ideal tube bank is given by:
u2 0.14
⊲12.33⊳
Pi D 8jf Ncv s
2
w
where Ncv D number of tube rows crossed (in the cross-flow region),
us D shell side velocity, based on the clearance area at the bundle equator,
equation 12.21,
jf D friction factor obtained from Figure 12.36, at the appropriate Reynolds
number, Re D ⊲us do /⊳.
F 0b , bypass correction factor for pressure drop
Bypassing will affect the pressure drop only in the cross-flow zones. The correction
factor is calculated from the equation used to calculate the bypass correction factor for
heat transfer, equation 12.30, but with the following values for the constant ˛.
Laminar region, Re < 100, ˛ D 5.0
Transition and turbulent region, Re > 100, ˛ D 4.0
The correction factor for exchangers without sealing strips is shown in Figure 12.37.
F 0L , leakage factor for pressure drop
Leakages will affect the pressure drop in both the cross-flow and window zones. The
factor is calculated using the equation for the heat-transfer leakage-correction factor,
equation 12.31, with the values for the coefficient ˇL0 taken from Figure 12.38.
Window-zone pressure drop
Any suitable method can be used to determine the pressure drop in the window area; see
Butterworth (1977). Bell used a method proposed by Colburn. Corrected for leakage, the
window drop for turbulent flow is given by:
u2
⊲12.34⊳
Pw D F0L ⊲2 C 0.6Nwv ⊳ z
2
where uz D the geometric mean velocity,
p
uz D uw us ,
uw D the velocity in the window zone, based on the window area less the area
occupied by the tubes Aw , see Section 12.9.5,
Ws
uw D
⊲12.35⊳
Aw
Ws D shell-side fluid mass flow, kg/s,
Nwv D number of restrictions for cross-flow in window zone, approximately equal
to the number of tube rows.
700
101 1 1
2
3
4
5 6 7 891
2
3
4
5 6 7891
2
3
4
5 6 7891
2
3
4
5 6 789 1
2
3
4
5 6 7891
9
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
9
8
7
6
5
1
9
8
7
6
5
1.25
4
4
3
3
1.25
2
2
10−1 1
9
8
7
6
5
1
9
8
7
6
5
4
4
3
3
2
2
10−2 1
1
1
101
2
3
4
5 6 7 891
2
3
4
5 6 7891
102
2
3
4
5 6 7891
103
2
104
Reynolds number, Re
Figure 12.36.
Friction factor for cross-flow tube banks
3
4
5 6 789 1
105
2
3
4
5 6 7891
106
CHEMICAL ENGINEERING
Friction factor, jt
100 1
701
HEAT-TRANSFER EQUIPMENT
1.0
0.9
0.8
0.7
0.6
F b′
Re >100
0.5
Re <100
0.4
0.3
0.2
0
0.1
0.2
0.3
0.4
Ab / As
Bypass factor for pressure drop F0b
Figure 12.37.
0.7
0.6
0.5
0.4
β′L 0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
AL/As
Figure 12.38.
Coefficient for F0L , pressure drop
0.8
702
CHEMICAL ENGINEERING
End zone pressure drop
There will be no leakage paths in an end zone (the zone between tube sheet and baffle).
Also, there will only be one baffle window in these zones; so the total number of restrictions in the cross-flow zone will be Ncv C Nwv . The end zone pressure drop Pe will
therefore be given by:
⊲Nwv C Ncv ⊳
F0b
⊲12.36⊳
Pe D Pi
Ncv
Total shell-side pressure drop
Summing the pressure drops over all the zones in series from inlet to outlet gives:
Ps D 2 end zones C ⊲Nb 1⊳ cross-flow zones C Nb window zones
Ps D 2Pe C Pc ⊲Nb 1⊳ C Nb Pw
⊲12.37⊳
where Nb is the number of baffles D [⊲L/lB ⊳ 1].
An estimate of the pressure loss incurred in the shell inlet and outlet nozzles must be
added to that calculated by equation 12.37; see Section 12.9.3.
End zone lengths
The spacing in the end zones will often be increased to provide more flow area at the inlet
and outlet nozzles. The velocity in these zones will then be lower and the heat transfer
and pressure drop will be reduced slightly. The effect on pressure drop will be more
marked than on heat transfer, and can be estimated by using the actual spacing in the end
zone when calculating the cross-flow velocity in those zones.
12.9.5. Shell and bundle geometry
The bypass and leakage areas, window area, and the number of tubes and tube rows in the
window and cross-flow zones can be determined precisely from the tube layout diagram.
For preliminary calculations they can be estimated with sufficient accuracy by considering
the tube bundle and shell geometry.
With reference to Figures 12.39 and 12.40:
Hc D
Hb D
Bb D
b D
Db D
baffle cut height D Ds ð Bc , where Bc is the baffle cut as a fraction,
height from the baffle chord to the top of the tube bundle,
“bundle cut” D Hb /Db ,
angle subtended by the baffle chord, rads,
bundle diameter.
Then:
Db
Ds ⊲0.5 Bc ⊳
2
⊲Db 2Hb ⊳
Ncv D
p0t
Hb D
⊲12.38⊳
⊲12.39⊳
703
HEAT-TRANSFER EQUIPMENT
Figure 12.39.
Clearance and flow areas in the shell-side of a shell and tube exchanger
Hc
Hb
θb
Db
Ds
Figure 12.40.
Baffle and tube geometry
704
CHEMICAL ENGINEERING
Nwv D
Hb
p0t
⊲12.40⊳
where p0t is the vertical tube pitch
p0t D pt for square pitch,
p0t D 0.87pt for equilateral triangular pitch.
The number of tubes in a window zone Nw is given by:
Nw D Nt ð Ra0
⊲12.41⊳
where Ra0 is the ratio of the bundle cross-sectional area in the window zone to the total
bundle cross-sectional area, Ra0 can be obtained from Figure 12.41, for the appropriate
“bundle cut”, Bb .
Figure 12.41.
Baffle geometrical factors
The number of tubes in a cross-flow zone Nc is given by
and
Nc D Nt 2Nw
⊲12.42⊳
Rw D
⊲12.43⊳
2Nw
Nt
2
Ds
d2o
ð Ra Nw
Aw D
4
4
⊲12.44⊳
705
HEAT-TRANSFER EQUIPMENT
Ra is obtained from Figure 12.41, for the appropriate baffle cut Bc
ct do
⊲Nt Nw ⊳
⊲12.45⊳
2
where ct is the diametrical tube-to-baffle clearance; the difference between the hole and
tube diameter, typically 0.8 mm.
Atb D
c s Ds
⊲2 b ⊳
2
where cs is the baffle-to-shell clearance, see Table 12.5.
Asb D
⊲12.46⊳
b can be obtained from Figure 12.41, for the appropriate baffle cut, Bc
Ab D lB ⊲Ds Db ⊳
⊲12.47⊳
where lB is the baffle spacing.
12.9.6. Effect of fouling on pressure drop
Bell’s method gives an estimate of the shell-side pressure drop for the exchanger in the
clean condition. In service, the clearances will tend to plug up, particularly the small
clearance between the tubes and baffle, and this will increase the pressure drop. Devore
(1961) has estimated the effect of fouling on pressure drop by calculating the pressure
drop in an exchange in the clean condition and with the clearance reduced by fouling,
using Tinker’s method. He presented his results as ratios of the fouled to clean pressure
drop for various fouling factors and baffle spacings.
The ratios given in Table 12.7, which are adapted from Devore’s figures, can be used
to make a rough estimate of the effect of fouling on pressure drop.
Table 12.7.
Ratio of fouled to clean pressure drop
Fouling coefficient
(W/m2 ° C)
Laminar flow
6000
2000
<1000
Turbulent flow
6000
2000
<1000
Shell diameter/baffle spacing
1.0
2.0
5.0
1.06
1.19
1.32
1.20
1.44
1.99
1.28
1.55
2.38
1.12
1.37
1.64
1.38
2.31
3.44
1.55
2.96
4.77
12.9.7. Pressure-drop limitations
Though Bell’s method will give a better estimate of the shell-side pressure drop than
Kern’s, it is not sufficiently accurate for the design of exchangers where the allowable
pressure drop is the overriding consideration. For such designs, a divided-flow model
based on Tinker’s work should be used. If a proprietary computer program is not available,
706
CHEMICAL ENGINEERING
the ESDU Design Guide, ESDU 83038 (1984) is recommended. Devore’s method can also
be considered, providing the exchanger layout conforms with those covered in his work.
Example 12.4
Using Bell’s method, calculate the shell-side heat transfer coefficient and pressure drop
for the exchanger designed in Example 12.1.
Summary of proposed design
Number of tubes
Shell i.d.
Bundle diameter
Tube o.d.
Pitch 1.25
Tube length
Baffle pitch
D 918
894
826
20
25
4830
356
mm
mm
mm
mm
mm
mm
Physical properties from Example 12.1
Solution
Heat-transfer coefficient
Ideal bank coefficient, hoc
25 20
ð 894 ð 356 ð 106 D 0.062 m2
25
100,000
1
ð
D 448 kg/s m2
Gs D
3600
0.062
As D
Re D
⊲12.21⊳
Gs do
448 ð 20 ð 103
D 26,353
D
0.34 ð 103
From Figure 12.31 jh D 5.3 ð 103 .
Prandtl number, from Example 12.1 D 5.1
Neglect viscosity correction factor (/w ).
hoc D
0.19
ð 5.3 ð 103 ð 26,353 ð 5.11/3 D 2272 W/m2 Ž C
20 ð 103
Tube row correction factor, Fn
Tube vertical pitch p0t D 0.87 ð 25 D 21.8 mm
Baffle cut height Hc D 0.25 ð 894 D 224 mm
Height between baffle tips D 894 2 ð 224 D 446 mm
Ncv D
From Figure 12.32 Fn D 1.03.
446
D 20
21.8
⊲12.28⊳
707
HEAT-TRANSFER EQUIPMENT
Window correction factor, Fw
224 mm
190 mm
446 mm
826
894⊲0.5 0.25⊳ D 190 mm
2
“Bundle cut” D 190/826 D 0.23 (23 per cent)
From Figure 12.41 at cut of 0.23
Hb D
(12.38)
Ra0 D 0.18
Tubes in one window area, Nw D 918 ð 0.18 D 165
Tubes in cross-flow area, Nc D 918 2 ð 165 D 588
Rw D
2 ð 165
D 0.36
918
⊲12.41⊳
⊲12.42⊳
⊲12.43⊳
From Figure 12.33 Fw D 1.02.
Bypass correction, Fb
Ab D ⊲894 826⊳356 ð 106 D 0.024 m2
0.024
Ab
D
D 0.39
As
0.062
Fb D exp[1.35 ð 0.39] D 0.59
⊲12.47⊳
⊲12.30⊳
Very low, sealing strips needed; try one strip for each five vertical rows.
1
Ns
D
Ncv
5
Fb D exp[1.35 ð 0.39⊲1 ⊲ 25 ⊳1/3 ⊳] D 0.87
(12.30)
Leakage correction, FL
Using clearances as specified in the Standards,
Atb D
tube-to-baffle
1
32
in. D 0.8 mm
baffle-to-shell
3
16
in. D 4.8 mm
0.8
ð 20⊲918 165⊳ D 18.9 ð 103 mm2 D 0.019 m2
2
(12.45)
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CHEMICAL ENGINEERING
From Figure 12.41, 25 per cent cut (0.25), b D 2.1 rads.
Asb D
4.8
ð 894⊲2 2.1⊳ D 8.98 ð 103 mm2 D 0.009 m2
2
⊲12.46⊳
AL D ⊲0.019 C 0.009⊳ D 0.028 m2
0.028
AL
D
D 0.45
As
0.062
From Figure 12.35 ˇL D 0.3.
⊲0.019 C 2 ð 0.009⊳
FL D 1 0.3
D 0.60
0.028
⊲12.31⊳
Shell-side coefficient
hs D 2272 ð 1.03 ð 1.02 ð 0.87 ð 0.60 D 1246 W/m2 Ž C
(12.27)
Appreciably lower than that predicted by Kern’s method.
Pressure drop
Cross-flow zone
From Figure 12.36 at Re D 26,353, for 1.25 pitch, jf D 5.6 ð 102
us D
448
Gs
D
D 0.60 m/s
750
Neglecting viscosity term (/w ).
Pi D 8 ð 5.6 ð 102 ð 20 ð
⊲˛ D 4.0⊳
F0b
750 ð 0.62
D 1209.6 N/m2
2
⊲12.33⊳
⊲12.30⊳
D exp[4.0 ð 0.39⊲1
⊲ 52 ⊳1/3 ⊳]
D 0.66
From Figure 12.38 ˇL0 D 0.52.
F0L
⊲0.019 C 2 ð 0.009⊳
D 0.31
D 1 0.52
0.028
⊲12.31⊳
Pc D 1209.6 ð 0.66 ð 0.31 D 248 N/m2
Window zone
From Figure 12.41, for baffle cut 25 per cent (0.25) Ra D 0.19.
ð 8942 ð 0.19 165 ð ð 202
Aw D
4
4
D 67.4 ð 103 mm2 D 0.067 m2
⊲12.44⊳
HEAT-TRANSFER EQUIPMENT
709
1
1
100,000
ð
ð
D 0.55 m/s
3600
750 0.067
p
p
uz D uw us D 0.55 ð 0.60 D 0.57 m/s
uw D
Nwv D
190
D8
21.8
⊲12.40⊳
Pw D 0.31⊲2 C 0.6 ð 8⊳
750 ð 0.572
D 257 N/m2
2
⊲12.34⊳
End zone
⊲8 C 20⊳
Pe D 1209.6
0.66 D 1118 N/m2
20
(12.36)
Total pressure drop
4830
1 D 12
356
Ps D 2 ð 1118 C 248⊲12 1⊳ C 12 ð 257 D 8048 N/m2
Number of baffles Nb D
⊲12.37⊳
D 8.05 kPa (1.2 psi)
This for the exchanger in the clean condition. Using the factors given in Table 12.7 to
estimate the pressure drop in the fouled condition
Ps D 1.4 ð 8.05 D 11.3 kPa
Appreciably lower than that predicted by Kern’s method. This shows the unsatisfactory
nature of the methods available for predicting the shell-side pressure drop.
12.10. CONDENSERS
This section covers the design of shell and tube exchangers used as condensers. Direct
contact condensers are discussed in Section 12.13.
The construction of a condenser will be similar to other shell and tube exchangers, but
with a wider baffle spacing, typically lB D Ds .
Four condenser configurations are possible:
1.
2.
3.
4.
Horizontal, with condensation in the shell, and the cooling medium in the tubes.
Horizontal, with condensation in the tubes.
Vertical, with condensation in the shell.
Vertical, with condensation in the tubes.
Horizontal shell-side and vertical tube-side are the most commonly used types of
condenser. A horizontal exchanger with condensation in the tubes is rarely used as
a process condenser, but is the usual arrangement for heaters and vaporisers using
condensing steam as the heating medium.
710
CHEMICAL ENGINEERING
12.10.1. Heat-transfer fundamentals
The fundamentals of condensation heat transfer are covered in Volume 1, Chapter 9.
The normal mechanism for heat transfer in commercial condensers is filmwise condensation. Dropwise condensation will give higher heat-transfer coefficients, but is unpredictable; and is not yet considered a practical proposition for the design of condensers
for general purposes.
The basic equations for filmwise condensation were derived by Nusselt (1916), and his
equations form the basis for practical condenser design. The basic Nusselt equations are
derived in Volume 1, Chapter 9. In the Nusselt model of condensation laminar flow is
assumed in the film, and heat transfer is assumed to take place entirely by conduction
through the film. In practical condensers the Nusselt model will strictly only apply at low
liquid and vapour rates, and where the flowing condensate film is undisturbed. Turbulence
can be induced in the liquid film at high liquid rates, and by shear at high vapour rates. This
will generally increase the rate of heat transfer over that predicted using the Nusselt model.
The effect of vapour shear and film turbulence are discussed in Volume 1, Chapter 9, see
also Butterworth (1978) and Taborek (1974).
Developments in the theory of condensation and their application in condenser design
are reviewed by Owen and Lee (1983).
Physical properties
The physical properties of the condensate for use in the following equations, are evaluated
at the average condensate film temperature: the mean of the condensing temperature and
the tube-wall temperature.
12.10.2. Condensation outside horizontal tubes
L ⊲L v ⊳g 1/3
⊲12.48⊳
L
mean condensation film coefficient, for a single tube, W/m2 Ž C
condensate thermal conductivity, W/mŽ C,
condensate density, kg/m3 ,
vapour density, kg/m3 ,
condensate viscosity, Ns/m2 ,
gravitational acceleration, 9.81 m/s2 ,
the tube loading, the condensate flow per unit length of tube, kg/m s.
⊲hc ⊳1 D 0.95kL
where ⊲hc ⊳1
kL
L
v
L
g
D
D
D
D
D
D
D
In a bank of tubes the condensate from the upper rows of tubes will add to that condensing
on the lower tubes. If there are Nr tubes in a vertical row and the condensate is assumed to
flow smoothly from row to row, Figure 12.42a, and if the flow remains laminar, the mean
coefficient predicted by the Nusselt model is related to that for the top tube by:
⊲hc ⊳Nr D ⊲hc ⊳1 Nr1/4
⊲12.49⊳
In practice, the condensate will not flow smoothly from tube to tube, Figure 12.42b, and
the factor of ⊲Nr ⊳1/4 applied to the single tube coefficient in equation 12.49 is considered
to be too conservative. Based on results from commercial exchangers, Kern (1950)
711
HEAT-TRANSFER EQUIPMENT
Vapour
flow
(a)
Figure 12.42.
(b)
Condensate flow over tube banks
suggests using an index of 1/6. Frank (1978) suggests multiplying single tube coefficient
by a factor of 0.75.
Using Kern’s method, the mean coefficient for a tube bundle is given by:
L ⊲L v ⊳g 1/3 1/6
⊲hc ⊳b D 0.95kL
Nr
⊲12.50⊳
L h
where h D
and
L
Wc
Nt
Nr
D
D
D
D
Wc
LNt
tube length,
total condensate flow,
total number of tubes in the bundle,
average number of tubes in a vertical tube row.
Nr can be taken as two-thirds of the number in the central tube row.
For low-viscosity condensates the correction for the number of tube rows is generally
ignored.
A procedure for estimating the shell-side heat transfer in horizontal condensers is given
in the Engineering Sciences Data Unit Design Guide, ESDU 84023.
12.10.3. Condensation inside and outside vertical tubes
For condensation inside and outside vertical tubes the Nusselt model gives:
L ⊲L v ⊳g 1/3
⊲hc ⊳v D 0.926kL
L v
⊲12.51⊳
where ⊲hc ⊳v D mean condensation coefficient, W/m2 Ž C,
v D vertical tube loading, condensate rate per unit tube perimeter, kg/m s
712
CHEMICAL ENGINEERING
for a tube bundle
v D
Wc
Wc
or
Nt do
Nt di
Equation 12.51 will apply up to a Reynolds number of 30; above this value waves on
the condensate film become important. The Reynolds number for the condensate film is
given by:
4v
Rec D
L
The presence of waves will increase the heat-transfer coefficient, so the use
of equation 12.51 above a Reynolds number of 30 will give conservative (safe)
estimates. The effect of waves on condensate film on heat transfer is discussed by
Kutateladze (1963).
Above a Reynolds number of around 2000, the condensate film becomes turbulent.
The effect of turbulence in the condensate film was investigated by Colburn (1934) and
Colburn’s results are generally used for condenser design, Figure 12.43. Equation 12.51
is also shown on Figure 12.43. The Prandtl number for the condensate film is given by:
Prc D
Figure 12.43.
Cp L
kL
Condensation coefficient for vertical tubes
Figure 12.43 can be used to estimate condensate film coefficients in the absence of appreciable vapour shear. Horizontal and downward vertical vapour flow will increase the
rate of heat transfer, and the use of Figure 12.43 will give conservative values for most
practical condenser designs.
Boyko and Kruzhilin (1967) developed a correlation for shear-controlled condensation
in tubes which is simple to use. Their correlation gives the mean coefficient between two
points at which the vapour quality is known. The vapour quality x is the mass fraction of
HEAT-TRANSFER EQUIPMENT
713
the vapour present. It is convenient to represent the Boyko-Kruzhilin correlation as:
1/2
1/2
0 J1 C J2
⊲hc ⊳BK D hi
⊲12.52⊳
2
L v
where
JD1C
x
v
and the suffixes 1 and 2 refer to the inlet and outlet conditions respectively. hi0 is the tubeside coefficient evaluated for single-phase flow of the total condensate (the condensate at
point 2). That is, the coefficient that would be obtained if the condensate filled the tube
and was flowing alone; this can be evaluated using any suitable correlation for forced
convection in tubes; see Section 12.8.
Boyko and Kruzhilin used the correlation:
kL
hi0 D 0.021
Re0.8 Pr 0.43
⊲12.53⊳
di
In a condenser the inlet stream will normally be saturated vapour and the vapour will be
totally condensed.
For these conditions equation 12.52 becomes:
L /v
0 1C
⊲hc ⊳BK D hi
⊲12.54⊳
2
For the design of condensers with condensation inside the tubes and downward vapour
flow, the coefficient should be evaluated using Figure 12.43 and equation 12.52, and the
higher value selected.
Flooding in vertical tubes
When the vapour flows up the tube, which will be the usual arrangement for a reflux
condenser, care must be taken to ensure that the tubes do not flood. Several correlations
have been published for the prediction of flooding in vertical tubes, see Perry et al. (1997).
One of the simplest to apply, which is suitable for use in the design of condensers handling
low-viscosity condensates, is the criterion given by Hewitt and Hall-Taylor (1970); see
also Butterworth (1977). Flooding should not occur if the following condition is satisfied:
1/2 1/4
[uv1/2 v1/4 C uL L ] < 0.6[gdi ⊲L v ⊳]1/4
⊲12.55⊳
where uv and uL are the velocities of the vapour and liquid, based on each phase flowing
in the tube alone; and di is in metres. The critical condition will occur at the bottom of
the tube, so the vapour and liquid velocities should be evaluated at this point.
Example 12.5
Estimate the heat-transfer coefficient for steam condensing on the outside, and on the
inside, of a 25 mm o.d., 21 mm i.d. vertical tube 3.66 m long. The steam condensate rate
714
CHEMICAL ENGINEERING
is 0.015 kg/s per tube and condensation takes place at 3 bar. The steam will flow down
the tube.
Solution
Physical properties, from steam tables:
Saturation temperature D 133.5Ž C
L D 931 kg/m3
v D 1.65 kg/m3
kL D 0.688 W/mŽ C
L D 0.21 mNs/m2
Prc D 1.27
Condensation outside the tube
0.015
D 0.191 kg/s m
25 ð 103
4 ð 0.191
D 3638
Rec D
0.21 ð 103
v D
From Figure 12.43
1/3
2L
hc
D 1.65 ð 101
kL L ⊲L v ⊳g
hc D 1.65 ð 101 ð 0.688
D 6554 W/m2 Ž C
⊲0.21 ð 103 ⊳2
931⊲931 1.65⊳9.81
1/3
Condensation inside the tube
0.015
D 0.227 kg/s m
21 ð 103
4 ð 0.227
D 4324
Rec D
0.21 ð 103
v D
From Figure 12.43
1
hc D 1.72 ð 10
⊲0.21 ð 103 ⊳2
ð 0.688
931⊲931 1.65⊳9.81
1/3
D 6832 W/m2 Ž C
Boyko-Kruzhilin method
Cross-sectional area of tube D ⊲21 ð 103 ⊳2
D 3.46 ð 104 m2
4
HEAT-TRANSFER EQUIPMENT
715
Fluid velocity, total condensation
ut D
Re D
0.015
D 0.047 m/s
931 ð 3.46 ð 104
udi
931 ð 0.047 ð 21 ð 103
D
D 4376
L
0.21 ð 103
0.688
⊲4376⊳0.8 ⊲1.27⊳0.43 D 624 W/m2 Ž C
21 ð 103
1 C 931/1.65
D 7723 W/m2 Ž C
hc D 624
2
hi0 D 0.021 ð
⊲12.53⊳
⊲12.54⊳
Take higher value, hc D 7723 W/m2 Ž C
Example 12.6
It is proposed to use an existing distillation column, which is fitted with a dephlegmator
(reflux condenser) which has 200 vertical, 50 mm i.d., tubes, for separating benzene from
a mixture of chlorobenzenes. The top product will be 2500 kg/h benzene and the column
will operate with a reflux ratio of 3. Check if the tubes are likely to flood. The condenser
pressure will be 1 bar.
Solution
The vapour will flow up and the liquid down the tubes. The maximum flow rates of both
will occur at the base of the tube.
Vapour flow D ⊲3 C 1⊳2500 D 10,000 kg/h
Liquid flow D 3 ð 2500 D 7500 kg/h
Total area tubes D ⊲50 ð 103 ⊳2 ð 200 D 0.39 m2
4
Densities at benzene boiling point
L D 840 kg/m3 ,
v D 2.7 kg/m3
Vapour velocity (vapour flowing alone in tube)
uv D
10,000
D 2.64 m/s
3600 ð 0.39 ð 2.7
Liquid velocity (liquid alone)
uL D
7500
D 0.006 m/s
3600 ð 0.39 ð 840
From equation 12.55 for no flooding
1/2 1/4
[uv1/2 v1/4 C uL L ] < 0.6[gdi ⊲L v ⊳]1/4
716
CHEMICAL ENGINEERING
[⊲2.64⊳1/2 ⊲2.7⊳1/4 C ⊲0.006⊳1/2 ⊲840⊳1/4 ] < 0.6[9.81 ð 50 ð 103 ⊲840 2.7⊳]1/4
[2.50] < [2.70]
Tubes should not flood, but there is little margin of safety.
12.10.4. Condensation inside horizontal tubes
Where condensation occurs in a horizontal tube the heat-transfer coefficient at any point
along the tube will depend on the flow pattern at that point. The various patterns that
can exist in two-phase flow are shown in Figure 12.44; and are discussed in Volume 1,
Chapter 5. In condensation, the flow will vary from a single-phase vapour at the inlet
to a single-phase liquid at the outlet; with all the possible patterns of flow occurring
between these points. Bell et al. (1970) give a method for following the change in flow
pattern as condensation occurs on a Baker flow-regime map. Correlations for estimating
the average condensation coefficient have been published by several workers, but there
is no generally satisfactory method that will give accurate predictions over a wide flow
range. A comparison of the published methods is given by Bell et al. (1970).
Vapour
Annular
flow
Figure 12.44.
Slug
flow
Bubbly
flow
Liquid
Flow patterns, vapour condensing in a horizontal tube
Two flow models are used to estimate the mean condensation coefficient in horizontal
tubes: stratified flow, Figure 12.45a, and annular flow, Figure 12.45b. The stratified flow
model represents the limiting condition at low condensate and vapour rates, and the
annular model the condition at high vapour and low condensate rates. For the stratified flow model, the condensate film coefficient can be estimated from the Nusselt
equation, applying a suitable correction for the reduction in the coefficient caused by
(a)
Figure 12.45.
(b)
Flow patterns in condensation. (a) Stratified flow (b) Annular flow
HEAT-TRANSFER EQUIPMENT
717
the accumulation of condensate in the bottom of the tube. The correction factor will
typically be around 0.8, so the coefficient for stratified flow can be estimated from:
L ⊲L v ⊳g 1/3
⊲hc ⊳s D 0.76kL
⊲12.56⊳
L h
The Boyko-Kruzhilin equation, equation 12.52, can be used to estimate the coefficient for
annular flow.
For condenser design, the mean coefficient should be evaluated using the correlations
for both annular and stratified flow and the higher value selected.
12.10.5. Condensation of steam
Steam is frequently used as a heating medium. The film coefficient for condensing steam
can be calculated using the methods given in the previous sections; but, as the coefficient
will be high and will rarely be the limiting coefficient, it is customary to assume a typical,
conservative, value for design purposes. For air-free steam a coefficient of 8000 W/m2 Ž C
(1500 Btu/h ft2 Ž F) can be used.
12.10.6. Mean temperature difference
A pure, saturated, vapour will condense at a fixed temperature, at constant pressure. For
an isothermal process such as this, the simple logarithmic mean temperature difference
can be used in the equation 12.1; no correction factor for multiple passes is needed. The
logarithmic mean temperature difference will be given by:
Tlm D
⊲t t1 ⊳
2
Tsat t1
ln
Tsat t2
⊲12.57⊳
where Tsat D saturation temperature of the vapour,
t1 D inlet coolant temperature,
t2 D outlet coolant.
When the condensation process is not exactly isothermal but the temperature change is
small; such as where there is a significant change in pressure, or where a narrow boiling
range multicomponent mixture is being condensed; the logarithmic temperature difference
can still be used but the temperature correction factor will be needed for multipass
condensers. The appropriate terminal temperatures should be used in the calculation.
12.10.7. Desuperheating and sub-cooling
When the vapour entering the condenser is superheated, and the condensate leaving the
condenser is cooled below its boiling point (sub-cooled), the temperature profile will be
as shown in Figure 12.46.
718
CHEMICAL ENGINEERING
Figure 12.46.
Condensation with desuperheating and sub-cooling
Desuperheating
If the degree of superheat is large, it will be necessary to divide the temperature profile
into sections and determine the mean temperature difference and heat-transfer coefficient
separately for each section. If the tube wall temperature is below the dew point of the
vapour, liquid will condense directly from the vapour on to the tubes. In these circumstances it has been found that the heat-transfer coefficient in the superheating section is
close to the value for condensation and can be taken as the same. So, where the amount
of superheating is not too excessive, say less than 25 per cent of the latent heat load,
and the outlet coolant temperature is well below the vapour dew point, the sensible heat
load for desuperheating can be lumped with the latent heat load. The total heat-transfer
area required can then be calculated using a mean temperature difference based on the
saturation temperature (not the superheat temperature) and the estimated condensate film
heat-transfer coefficient.
Sub-cooling of condensate
Some sub-cooling of the condensate will usually be required to control the net positive
suction head at the condensate pump (see Chapter 5, and Volume 1, Chapter 8), or to
cool a product for storage. Where the amount of sub-cooling is large, it is more efficient
to sub-cool in a separate exchanger. A small amount of sub-cooling can be obtained in a
condenser by controlling the liquid level so that some part of the tube bundle is immersed
in the condensate.
In a horizontal shell-side condenser a dam baffle can be used, Figure 12.47a. A
vertical condenser can be operated with the liquid level above the bottom tube sheet,
Figure 12.47b.
The temperature difference in the sub-cooled region will depend on the degree of
mixing in the pool of condensate. The limiting conditions are plug flow and complete
mixing. The temperature profile for plug flow is that shown in Figure 12.46. If the pool is
perfectly mixed, the condensate temperature will be constant over the sub-cooling region
and equal to the condensate outlet temperature. Assuming perfect mixing will give a very
719
HEAT-TRANSFER EQUIPMENT
Liquid
level
Dam baffle
(a)
(b)
Figure 12.47.
Arrangements for sub-cooling
conservative (safe) estimate of the mean temperature difference. As the liquid velocity
will be low in the sub-cooled region the heat-transfer coefficient should be estimated
using correlations for natural convection (see Volume 1, Chapter 9); a typical value would
be 200 W/m2 Ž C.
12.10.8. Condensation of mixtures
The correlations given in the previous sections apply to the condensation of a single
component; such as an essentially pure overhead product from a distillation column. The
design of a condenser for a mixture of vapours is a more difficult task.
The term “mixture of vapours” covers three related situations of practical interest:
1. Total condensation of a multicomponent mixture; such as the overheads from a
multicomponent distillation.
2. Condensation of only part of a multicomponent vapour mixture, all components of
which are theoretically condensable. This situation will occur where the dew point of
some of the lighter components is above the coolant temperature. The uncondensed
component may be soluble in the condensed liquid; such as in the condensation of
some hydrocarbons mixtures containing light “gaseous” components.
3. Condensation from a non-condensable gas, where the gas is not soluble to any extent
in the liquid condensed. These exchangers are often called cooler-condensers.
The following features, common to all these situations, must be considered in the
developing design methods for mixed vapour condensers:
1. The condensation will not be isothermal. As the heavy component condenses out
the composition of the vapour, and therefore its dew point, change.
2. Because the condensation is not isothermal there will be a transfer of sensible heat
from the vapour to cool the gas to the dew point. There will also be a transfer of
sensible heat from the condensate, as it must be cooled from the temperature at
which it condensed to the outlet temperature. The transfer of sensible heat from the
720
CHEMICAL ENGINEERING
vapour can be particularly significant, as the sensible-heat transfer coefficient will
be appreciably lower than the condensation coefficient.
3. As the composition of the vapour and liquid change throughout the condenser their
physical properties vary.
4. The heavy component must diffuse through the lighter components to reach the
condensing surface. The rate of condensation will be governed by the rate of
diffusion, as well as the rate of heat transfer.
Temperature profile
To evaluate the true temperature difference (driving force) in a mixed vapour condenser
a condensation curve (temperature vs. enthalpy diagram) must be calculated; showing
the change in vapour temperature versus heat transferred throughout the condenser,
Figure 12.48. The temperature profile will depend on the liquid-flow pattern in the
condenser. There are two limiting conditions of condensate-vapour flow:
Temperature
Integral
Differential
Coolant
temperature
Heat transferred
Figure 12.48.
Condensation curves
1. Differential condensation: in which the liquid separates from the vapour from which
it has condensed. This process is analogous to differential, or Rayleigh, distillation,
and the condensation curve can be calculated using methods similar to those for determining the change in composition in differential distillation; see Volume 2, Chapter 11.
2. Integral condensation: in which the liquid remains in equilibrium with the uncondensed vapour. The condensation curve can be determined using procedures similar
to those for multicomponent flash distillation given in Chapter 11. This will be
a relatively simple calculation for a binary mixture, but complex and tedious for
mixtures of more than two components.
HEAT-TRANSFER EQUIPMENT
721
It is normal practice to assume that integral condensation occurs. The conditions for
integral condensation will be approached if condensation is carried out in one pass, so that
the liquid and vapour follow the same path; as in a vertical condenser with condensation
inside or outside the tubes. In a horizontal shell-side condenser the condensate will tend to
separate from the vapour. The mean temperature difference will be lower for differential
condensation, and arrangements where liquid separation is likely to occur should generally
be avoided for the condensation of mixed vapours.
Where integral condensation can be considered to occur, the use of a corrected
logarithmic mean temperature difference based on the terminal temperatures will generally
give a conservative (safe) estimate of the mean temperature difference, and can be used
in preliminary design calculations.
Estimation of heat-transfer coefficients
Total condensation. For the design of a multicomponent condenser in which the vapour is
totally condensed, an estimate of the mean condensing coefficient can be made using the
single component correlations with the liquid physical properties evaluated at the average
condensate composition. It is the usual practice to apply a factor of safety to allow
for the sensible-heat transfer and any resistance to mass transfer. Frank (1978) suggests
a factor of 0.65, but this is probably too pessimistic. Kern (1950) suggests increasing
the area calculated for condensation alone by the ratio of the total heat (condensing
C sensible) to the condensing load. Where a more exact estimate of the coefficient is
required, and justified by the data, the rigorous methods developed for partial condensation
can be used.
Partial condensation. The methods developed for partial condensation and condensation
from a non-condensable gas can be divided into two classes:
1. Empirical methods: approximate methods, in which the resistance to heat transfer
is considered to control the rate of condensation, and the mass transfer resistance is
neglected. Design methods have been published by Silver (1947), Bell and Ghaly
(1973) and Ward (1960).
2. Analytical methods: more exact procedures, which are based on some model of
the heat and mass transfer process, and which take into account the diffusional
resistance to mass transfer. The classic method is that of Colburn and Hougen
(1934); see also Colburn and Drew (1937) and Porter and Jeffreys (1963). The
analytical methods are complex, requiring step-by-step, trial and error, calculations,
or graphical procedures. They are suited for computer solution using numerical
methods; and proprietary design programs are available. Examples of the application
of the Colburn and Drew method are given by Kern (1950) and Jeffreys (1961). The
method is discussed briefly in Volume 1, Chapter 9.
An assessment of the methods available for the design of condensers where the condensation is from a non-condensable gas is given by McNaught (1983).
Approximate methods. The local coefficient for heat transfer can be expressed in terms
of the local condensate film coefficient hc0 and the local coefficient for sensible-heat
722
CHEMICAL ENGINEERING
transfer from the vapour (the gas film coefficient) hg0 , by a relationship first proposed by
Silver (1947):
1
1
Z
D 0 C 0
⊲12.58⊳
0
hcg
hc
hg
0
where hcg
D the local effective cooling-condensing coefficient
ZD
and
⊲Hs /Ht ⊳
⊲dT/dHt ⊳
x
Cpg
D
D
D
D
Hs
dT
D xCpg
,
Ht
dHt
the ratio of the change in sensible heat to the total enthalpy change.
slope of the temperature enthalpy curve,
vapour quality, mass fraction of vapour,
vapour (gas) specific heat.
The term dT/dHt can be evaluated from the condensation curve; hc0 from the single
component correlations; and hg0 from correlations for forced convection.
If this is done at several points along the condensation curve the area required can be
determined by graphical or numerical integration of the expression:
Qt
dQ
AD
⊲12.59⊳
U⊲T
v tc ⊳
0
where Qt
U
Tv
tc
D
D
D
D
total heat transferred,
0
overall heat transfer coefficient, from equation 12.1, using hcg
,
local vapour (gas) temperature,
local cooling medium temperature.
Gilmore (1963) gives an integrated form of equation 12.57, which can be used for the
approximate design of partial condensers
1
Qg 1
1
D
C
hcg
hc
Qt hg
⊲12.60⊳
where hcg D mean effective coefficient,
hc D mean condensate film coefficient, evaluated from the single-component
correlations, at the average condensate composition, and total condensate
loading,
hg D mean gas film coefficient, evaluated using the average vapour flowrate : arithmetic mean of the inlet and outlet vapour (gas) flow-rates,
Qg D total sensible-heat transfer from vapour (gas),
Qt D total heat transferred: latent heat of condensation C sensible heat for
cooling the vapour (gas) and condensate.
As a rough guide, the following rules of thumb suggested by Frank (1978) can be used
to decide the design method to use for a partial condenser (cooler-condenser):
1. Non-condensables <0.5 per cent: use the methods for total condensation; ignore the
presence of the uncondensed portion.
723
HEAT-TRANSFER EQUIPMENT
2. Non-condensables >70 per cent: assume the heat transfer is by forced convection
only. Use the correlations for forced convection to calculate the heat-transfer coefficient, but include the latent heat of condensation in the total heat load transferred.
3. Between 0.5 to 70 per cent non-condensables: use methods that consider both mechanisms of heat transfer.
In partial condensation it is usually better to put the condensing stream on the shellside, and to select a baffle spacing that will maintain high vapour velocities, and therefore
high sensible-heat-transfer coefficients.
Fog formation. In the condensation of a vapour from a non-condensable gas, if the
bulk temperature of the gas falls below the dew point of the vapour, liquid can condense
out directly as a mist or fog. This condition is undesirable, as liquid droplets may
be carried out of the condenser. Fog formation in cooler-condensers is discussed by
Colburn and Edison (1941) and Lo Pinto (1982). Steinmeyer (1972) gives criteria for
the prediction of fog formation. Demisting pads can be used to separate entrained liquid
droplets.
12.10.9. Pressure drop in condensers
The pressure drop on the condensing side is difficult to predict as two phases are present
and the vapour mass velocity is changing throughout the condenser.
A common practice is to calculate the pressure drop using the methods for single-phase
flow and apply a factor to allow for the change in vapour velocity. For total condensation,
Frank (1978) suggests taking the pressure drop as 40 per cent of the value based on the
inlet vapour conditions; Kern (1950) suggests a factor of 50 per cent.
An alternative method, which can also be used to estimate the pressure drop in a partial
condenser, is given by Gloyer (1970). The pressure drop is calculated using an average
vapour flow-rate in the shell (or tubes) estimated as a function of the ratio of the vapour
flow-rate in and out of the shell (or tubes), and the temperature profile.
Ws (average) D Ws (inlet) ð K2
⊲12.61⊳
K2 is obtained from Figure 12.49.
Tin /Tout in Figure 12.49 is the ratio of the terminal temperature differences.
These methods can be used to make a crude estimate of the likely pressure drop. A
reliable prediction can be obtained by treating the problem as one of two-phase flow.
For tube-side condensation the general methods for two-phase flow in pipes can be used;
see Collier and Thome (1994); and Volume 1, Chapter 5. As the flow pattern will be
changing throughout condensation, some form of step-wise procedure will need to be
used. Two-phase flow on the shell-side is discussed by Grant (1973), who gives a method
for predicting the pressure drop based on Tinker’s shell-side flow model.
A method for estimating the pressure drop on the shell-side of horizontal condensers
is given in the Engineering Sciences Data Unit Design Guide, ESDU 84023 (1985).
Pressure drop is only likely to be a major consideration in the design of vacuum
condensers; and where reflux is returned to a column by gravity flow from the condenser.
724
CHEMICAL ENGINEERING
Figure 12.49.
Factor for average vapour flow-rate for pressure-drop calculation (Gloyer, 1970)
Example 12.7
Design a condenser for the following duty: 45,000 kg/h of mixed light hydrocarbon
vapours to be condensed. The condenser to operate at 10 bar. The vapour will enter
the condenser saturated at 60Ž C and the condensation will be complete at 45Ž C. The
average molecular weight of the vapours is 52. The enthalpy of the vapour is 596.5 kJ/kg
and the condensate 247.0 kJ/kg. Cooling water is available at 30Ž C and the temperature
rise is to be limited to 10Ž C. Plant standards require tubes of 20 mm o.d., 16.8 mm i.d.,
4.88 m (16 ft) long, of admiralty brass. The vapours are to be totally condensed and no
sub-cooling is required.
Solution
Only the thermal design will be done. The physical properties of the mixture will be taken
as the mean of those for n-propane (MW D 44) and n-butane (MW D 58), at the average
temperature.
45,000
⊲596.5 247.0⊳ D 4368.8 kW
3600
4368.8
Cooling water flow D
D 104.5 kg/s
⊲40 30⊳4.18
Heat transferred from vapour D
Assumed overall coefficient (Table 12.1) D 900 W/m2 Ž C
Mean temperature difference: the condensation range is small and the change in
saturation temperature will be linear, so the corrected logarithmic mean temperature
HEAT-TRANSFER EQUIPMENT
725
difference can be used.
RD
SD
⊲60 45⊳
D 1.5
⊲40 30⊳
⊲12.6⊳
⊲40 30⊳
D 0.33
⊲60 30⊳
⊲12.7⊳
60°C
45°C
40°C
30°C
Try a horizontal exchanger, condensation in the shell, four tube passes. For one shell
pass, four tube passes, from Figure 12.19, Ft D 0.92
⊲60 40⊳ ⊲45 30⊳
D 17.4Ž C
Tlm D
⊲60 40⊳
ln
⊲45 30⊳
Tm D 0.92 ð 17.4 D 16Ž C
Trial area D
4368.8 ð 103
D 303 m2
900 ð 16
Surface area of one tube D 20 ð 103 ð 4.88 D 0.305 m2 (ignore tube sheet
thickness)
303
D 992
Number of tubes D
0.305
Use square pitch, Pt D 1.25 ð 20 mm D 25 mm.
Tube bundle diameter
992 1/2.263
Db D 20
D 954 mm
⊲12.3b⊳
0.158
Number of tubes in centre row Nr D Db /Pt D 954/25 D 38
Shell-side coefficient
Estimate tube wall temperature, Tw ; assume condensing coefficient of 1500 W/m2 Ž C,
Mean temperature
60 C 45
D 52.5Ž C
2
40 C 30
Tube-side D
D 35Ž C
2
Shell-side D
726
CHEMICAL ENGINEERING
⊲52.5 Tw ⊳1500 D ⊲52.5 35⊳900
Tw D 42.0Ž C
Mean temperature condensate D
52.5 C 42.0
D 47Ž C
2
Physical properties at 47Ž C
L D 0.16 mNs/m2
L D 551 kg/m3
kL D 0.13 W/mŽ C
vapour density at mean vapour temperature
273
10
52
ð
ð
D 19.5 kg/m3
v D
22.4 ⊲273 C 52.5⊳
1
h D
Nr D
Wc
45,000
1
ð
D 2.6 ð 103 kg/s m
D
LNt
3600
4.88 ð 992
2
3
ð 38 D 25
hc D 0.95 ð 0.13
551⊲551 19.5⊳9.81
0.16 ð 103 ð 2.6 ð 103
1/3
ð 251/6
⊲12.50⊳
D 1375 W/m2 Ž C
Close enough to assumed value of 1500 W/m2 Ž C, so no correction to Tw needed.
Tube-side coefficient
992
⊲16.8 ð 103 ⊳2 ð
D 0.055 m2
4
4
Density of water, at 35Ž C D 993 kg/m3
1
104.5
ð
D 1.91 m/s
Tube velocity D
993
0.055
Tube cross-sectional area D
4200⊲1.35 C 0.02 ð 35⊳1.910.8
16.80.2
2Ž
D 8218 W/m C
hi D
⊲12.17⊳
Fouling factors: as neither fluid is heavily fouling, use 6000 W/m2 Ž C for each side.
kw D 50 W/mŽ C
Overall coefficient
20
20 ð 10 ln
1
1
1
16.8
D
C
C
U
1375 6000
2 ð 50
3
U D 786 W/m2 Ž C
C
20
1
20
1
ð
C
ð
16.8 6000 16.8 8218
⊲12.2⊳
727
HEAT-TRANSFER EQUIPMENT
Significantly lower than the assumed value of 900 W/m2 Ž C.
Repeat calculation using new trial value of 750 W/m2 Ž C.
4368 ð 103
D 364 m2
750 ð 16
364
Number of tubes D
D 1194
0.305
1194 1/2.263
D 1035 mm
Db D 20
0.158
Area D
⊲12.36⊳
1035
D 41
25
1
45,000
ð
D 2.15 ð 103 kg/m s
h D
3600
4.88 ð 1194
Number of tubes in centre row D
Nr D
2
3
ð 41 D 27
hc D 0.95 ð 0.13
551⊲551 19.5⊳9.81
0.16 ð 103 ð 2.15 ð 103
1/3
ð 271/6
⊲12.50⊳
D 1447 W/m2 Ž C
992
D 1.59 m/s
1194
1.590.8
D 7097 W/m2 Ž C
hi D 4200⊲1.35 C 0.02 ð 35⊳
16.80.2
20
20 ð 103 ln
1
1
1
16.8
D
C
C
U
1447 6000
2 ð 50
1
20
1
20
ð
C
ð
C
16.8 6000 16.8 7097
New tube velocity D 1.91 ð
U D 773 W/m2 Ž C
(12.17)
(12.2)
Close enough to estimate, firm up design.
Shell-side pressure drop
Use pull-through floating head, no need for close clearance.
Select baffle spacing D shell diameter, 45 per cent cut.
From Figure 12.10, clearance D 95 mm.
Shell i.d. D 1035 C 95 D 1130 mm
Use Kern’s method to make an approximate estimate.
Cross-flow area As D
⊲25 20⊳
1130 ð 1130 ð 106
25
D 0.255 m2
⊲12.21⊳
728
CHEMICAL ENGINEERING
Mass flow-rate, based on inlet conditions
1
45,000
ð
D 49.02 kg/s m2
Gs D
3600
0.255
1.27 2
Equivalent diameter, de D
⊲25 0.785 ð 202 ⊳
20
D 19.8 mm
⊲12.22⊳
Vapour viscosity D 0.008 mNs/m2
Re D
From Figure 12.30, jf D 2.2 ð 102
49.02 ð 19.8 ð 103
D 121,325
0.008 ð 103
49.02
Gs
D
D 2.51 m/s
v
19.5
Take pressure drop as 50 per cent of that calculated using the inlet flow; neglect
viscosity correction.
4.88 19.5⊲2.51⊳2
1
2 1130
8 ð 2.2 ð 10
⊲12.26⊳
Ps D
2
19.8
1.130
2
us D
D 1322 N/m2
D 1.3 kPa
Negligible; more sophisticated method of calculation not justified.
Tube-side pressure drop
Viscosity of water D 0.6 mN s/m2
ut di
1.59 ð 993 ð 16.8 ð 103
Re D
D
D 44,208
0.6 ð 103
From Figure 12.24, jf D 3.5 ð 103 .
Neglect viscosity correction.
Pt D 4 8 ð 3.5 ð 103
D 53,388 N/m2
4.88
16.8 ð 103
993 ð 1.592
C 2.5
2
⊲12.20⊳
D 53 kPa ⊲7.7 psi⊳,
acceptable.
12.11. REBOILERS AND VAPORISERS
The design methods given in this section can be used for reboilers and vaporisers.
Reboilers are used with distillation columns to vaporise a fraction of the bottom product;
whereas in a vaporiser essentially all the feed is vaporised.
HEAT-TRANSFER EQUIPMENT
729
Three principal types of reboiler are used:
1. Forced circulation, Figure 12.50: in which the fluid is pumped through the
exchanger, and the vapour formed is separated in the base of the column. When
used as a vaporiser a disengagement vessel will have to be provided.
Figure 12.50.
Forced-circulation reboiler
2. Thermosyphon, natural circulation, Figure 12.51: vertical exchangers with vaporisation in the tubes, or horizontal exchangers with vaporisation in the shell. The liquid
circulation through the exchanger is maintained by the difference in density between
the two-phase mixture of vapour and liquid in the exchanger and the single-phase
liquid in the base of the column. As with the forced-circulation type, a disengagement
vessel will be needed if this type is used as a vaporiser.
3. Kettle type, Figure 12.52: in which boiling takes place on tubes immersed in a pool
of liquid; there is no circulation of liquid through the exchanger. This type is also,
more correctly, called a submerged bundle reboiler.
In some applications it is possible to accommodate the bundle in the base of the
column, Figure 12.53; saving the cost of the exchanger shell.
Choice of type
The choice of the best type of reboiler or vaporiser for a given duty will depend on the
following factors:
1. The nature of the process fluid, particularly its viscosity and propensity to fouling.
2. The operating pressure: vacuum or pressure.
3. The equipment layout, particularly the headroom available.
Forced-circulation reboilers are especially suitable for handling viscous and heavily
fouling process fluids; see Chantry and Church (1958). The circulation rate is predictable
and high velocities can be used. They are also suitable for low vacuum operations, and for
low rates of vaporisation. The major disadvantage of this type is that a pump is required
and the pumping cost will be high. There is also the danger that leakage of hot fluid will
occur at the pump seal; canned-rotor type pumps can be specified to avoid the possibility
of leakage.
730
CHEMICAL ENGINEERING
Figure 12.51.
Horizontal thermosyphon reboiler
Figure 12.52.
Figure 12.53.
Kettle reboiler
Internal reboiler
731
HEAT-TRANSFER EQUIPMENT
Thermosyphon reboilers are the most economical type for most applications, but are not
suitable for high viscosity fluids or high vacuum operation. They would not normally be
specified for pressures below 0.3 bar. A disadvantage of this type is that the column base
must be elevated to provide the hydrostatic head required for the thermosyphon effect.
This will increase the cost of the column supporting-structure. Horizontal reboilers require
less headroom than vertical, but have more complex pipework. Horizontal exchangers are
more easily maintained than vertical, as tube bundle can be more easily withdrawn.
Kettle reboilers have lower heat-transfer coefficients than the other types, as there is no
liquid circulation. They are not suitable for fouling materials, and have a high residence
time. They will generally be more expensive than an equivalent thermosyphon type as a
larger shell is needed, but if the duty is such that the bundle can be installed in the column
base, the cost will be competitive with the other types. They are often used as vaporisers,
as a separate vapour-liquid disengagement vessel is not needed. They are suitable for
vacuum operation, and for high rates of vaporisation, up to 80 per cent of the feed.
12.11.1. Boiling heat-transfer fundamentals
The complex phenomena involved in heat transfer to a boiling liquid are discussed in
Volume 1, Chapter 9. A more detailed account is given by Collier and Thome (1994),
Tong and Tang (1997) and Hsu and Graham (1976). Only a brief discussion of the subject
will be given in this section: sufficient for the understanding of the design methods given
for reboilers and vaporisers.
The mechanism of heat transfer from a submerged surface to a pool of liquid depends
on the temperature difference between the heated surface and the liquid; Figure 12.54. At
low-temperature differences, when the liquid is below its boiling point, heat is transferred
by natural convection. As the surface temperature is raised incipient boiling occurs, vapour
1400
1200
1000
800
2
Heat flux, W/m x 10
−3
Critical
flux
600
400
200
100
200
400 600
1000
2000
Surface temperature, °C
Figure 12.54.
Typical pool boiling curve (water at 1 bar)
732
CHEMICAL ENGINEERING
bubbles forming and breaking loose from the surface. The agitation caused by the rising
bubbles, and other effects caused by bubble generation at the surface, result in a large
increase in the rate of heat transfer. This phenomenon is known as nucleate boiling.
As the temperature is raised further the rate of heat transfer increases until the heat
flux reaches a critical value. At this point, the rate of vapour generation is such that
dry patches occur spontaneously over the surface, and the rate of heat transfer falls
off rapidly. At higher temperature differences, the vapour rate is such that the whole
surface is blanketed with vapour, and the mechanism of heat transfer is by conduction
through the vapour film. Conduction is augmented at high temperature differences by
radiation.
The maximum heat flux achievable with nucleate boiling is known as the critical heat
flux. In a system where the surface temperature is not self-limiting, such as a nuclear
reactor fuel element, operation above the critical flux will result in a rapid increase in the
surface temperature, and in the extreme situation the surface will melt. This phenomenon
is known as “burn-out”. The heating media used for process plant are normally selflimiting; for example, with steam the surface temperature can never exceed the saturation
temperature. Care must be taken in the design of electrically heated vaporisers to ensure
that the critical flux can never be exceeded.
The critical flux is reached at surprisingly low temperature differences; around 20 to
30Ž C for water, and 20 to 50Ž C for light organics.
Estimation of boiling heat-transfer coefficients
In the design of vaporisers and reboilers the designer will be concerned with two types of
boiling: pool boiling and convective boiling. Pool boiling is the name given to nucleate
boiling in a pool of liquid; such as in a kettle-type reboiler or a jacketed vessel. Convective
boiling occurs where the vaporising fluid is flowing over the heated surface, and heat
transfer takes place both by forced convection and nucleate boiling; as in forced circulation
or thermosyphon reboilers.
Boiling is a complex phenomenon, and boiling heat-transfer coefficients are difficult
to predict with any certainty. Whenever possible experimental values obtained for the
system being considered should be used, or values for a closely related system.
12.11.2. Pool boiling
In the nucleate boiling region the heat-transfer coefficient is dependent on the nature
and condition of the heat-transfer surface, and it is not possible to present a universal
correlation that will give accurate predictions for all systems. Palen and Taborek (1962)
have reviewed the published correlations and compared their suitability for use in reboiler
design.
The correlation given by Forster and Zuber (1955) can be used to estimate pool
boiling coefficients, in the absence of experimental data. Their equation can be written in
the form:
0.79
0.49
kL C0.45
pL L
⊲12.62⊳
hnb D 0.00122 0.5 0.29 0.24 0.24 ⊲Tw Ts ⊳0.24 ⊲pw ps ⊳0.75
L v
733
HEAT-TRANSFER EQUIPMENT
where hnb
kL
CpL
L
L
v
Tw
Ts
pw
ps
D
D
D
D
D
D
D
D
D
D
D
D
nucleate, pool, boiling coefficient, W/m2 Ž C,
liquid thermal conductivity, W/mŽ C,
liquid heat capacity, J/kgŽ C,
liquid density, kg/m3 ,
liquid viscosity, Ns/m2 ,
latent heat, J/kg,
vapour density, kg/m3 ,
wall, surface temperature, Ž C,
saturation temperature of boiling liquid Ž C,
saturation pressure corresponding to the wall temperature, Tw , N/m2 ,
saturation pressure corresponding to Ts , N/m2 ,
surface tension, N/m.
The reduced pressure correlation given by Mostinski (1963) is simple to use and gives
values that are as reliable as those given by more complex equations.
1.2
10
P 0.17
P
P
0.69
0.7
hnb D 0.104⊲Pc ⊳ ⊲q⊳
1.8
C4
C 10
⊲12.63⊳
Pc
Pc
Pc
where P D operating pressure, bar,
Pc D liquid critical pressure, bar,
q D heat flux, W/m2 .
Note. q D hnb ⊲Tw Ts ⊳.
Mostinski’s equation is convenient to use when data on the fluid physical properties
are not available.
Equations 12.62 and 12.63 are for boiling single component fluids; for mixtures the
coefficient will generally be lower than that predicted by these equations. The equations
can be used for close boiling range mixtures, say less than 5Ž C; and for wider boiling
ranges with a suitable factor of safety (see Section 12.11.6).
Critical heat flux
It is important to check that the design, and operating, heat flux is well below the critical
flux. Several correlations are available for predicting the critical flux. That given by
Zuber et al. (1961) has been found to give satisfactory predictions for use in reboiler and
vaporiser design. In SI units, Zuber’s equation can be written as:
qc D 0.131[g⊲L v ⊳v2 ]1/4
⊲12.64⊳
where qc D maximum, critical, heat flux, W/m2 ,
g D gravitational acceleration, 9.81 m/s2 .
Mostinski also gives a reduced pressure equation for predicting the maximum critical
heat flux:
0.9
0.35
P
P
4
1
⊲12.65⊳
qc D 3.67 ð 10 Pc
Pc
Pc
734
CHEMICAL ENGINEERING
Film boiling
The equation given by Bromley (1950) can be used to estimate the heat-transfer coefficient
for film boiling on tubes. Heat transfer in the film-boiling region will be controlled
by conduction through the film of vapour, and Bromley’s equation is similar to the
Nusselt equation for condensation, where conduction is occurring through the film of
condensate.
3
1/4
k ⊲L v ⊳v g
hfb D 0.62 v
⊲12.66⊳
v do ⊲Tw Ts ⊳
where hfb is the film boiling heat-transfer coefficient; the suffix v refers to the vapour
phase and do is in metres. It must be emphasised that process reboilers and vaporisers will
always be designed to operate in the nucleate boiling region. The heating medium would
be selected, and its temperature controlled, to ensure that in operation the temperature
difference is well below that at which the critical flux is reached. For instance, if direct
heating with steam would give too high a temperature difference, the steam would be
used to heat water, and hot water used as the heating medium.
Example 12.8
Estimate the heat-transfer coefficient for the pool boiling of water at 2.1 bar, from a
surface at 125Ž C. Check that the critical flux is not exceeded.
Solution
Physical properties, from steam tables:
Saturation temperature, Ts
L
CpL
kL
L
pw at 125Ž C
ps
D
D
D
D
D
D
D
D
D
121.8Ž C
941.6 kg/m3 , v D 1.18 kg/m3
4.25 ð 103 J/kgŽ C
687 ð 103 W/mŽ C
230 ð 106 Ns/m2
2198 ð 103 J/kg
55 ð 103 N/m
2.321 ð 105 N/m2
2.1 ð 105 N/m2
Use the Foster-Zuber correlation, equation 12.62:
hb D 1.22 ð 103
⊲687 ð 103 ⊳0.79 ⊲4.25 ð 103 ⊳0.45 ⊲941.6⊳0.49
⊲55 ð 103 ⊳0.5 ⊲230 ð 106 ⊳0.29 ⊲2198 ð 103 ⊳0.24 1.180.24
ð ⊲125 121.8⊳0.24 ⊲2.321 ð 105 2.10 ð 105 ⊳0.75
D 3738 W/m2 Ž C
HEAT-TRANSFER EQUIPMENT
735
Use the Zuber correlation, equation 12.65:
qc D 0.131 ð 2198 ð 103 [55 ð 103 ð 9.81⊲941.6 1.18⊳1.182 ]1/4
D 1.48 ð 106 W/m2
Actual flux D ⊲125 121.8⊳3738 D 11,962 W/m2 ,
well below critical flux.
12.11.3. Convective boiling
The mechanism of heat transfer in convective boiling, where the boiling fluid is flowing
through a tube or over a tube bundle, differs from that in pool boiling. It will depend
on the state of the fluid at any point. Consider the situation of a liquid boiling inside a
vertical tube; Figure 12.55. The following conditions occur as the fluid flows up the tube.
1. Single-phase flow region: at the inlet the liquid is below its boiling point (sub-cooled)
and heat is transferred by forced convection. The equations for forced convection
can be used to estimate the heat-transfer coefficient in this region.
2. Sub-cooled boiling: in this region the liquid next to the wall has reached boiling
point, but not the bulk of the liquid. Local boiling takes place at the wall, which
increases the rate of heat transfer over that given by forced convection alone.
Figure 12.55.
Convective boiling in a vertical tube
736
CHEMICAL ENGINEERING
3. Saturated boiling region: in this region bulk boiling of the liquid is occurring in a
manner similar to nucleate pool boiling. The volume of vapour is increasing and
various flow patterns can form (see Volume 2, Chapter 14). In a long tube, the flow
pattern will eventually become annular: where the liquid phase is spread over the
tube wall and the vapour flows up the central core.
4. Dry wall region: Ultimately, if a large fraction of the feed is vaporised, the wall
dries out and any remaining liquid is present as a mist. Heat transfer in this region
is by convection and radiation to the vapour. This condition is unlikely to occur in
commercial reboilers and vaporisers.
Saturated, bulk, boiling is the principal mechanism of interest in the design of reboilers
and vaporisers.
A comprehensive review of the methods available for predicting convective boiling
coefficients is given by Webb and Gupte (1992). The methods proposed by Chen
(1966) and Shah (1976) are convenient to use in manual calculations and are accurate
enough for preliminary design work. Chen’s method is outlined below and illustrated in
Example 12.9.
Chen’s method
In forced-convective boiling the effective heat-transfer coefficient hcb can be considered
0
0
and hnb
.
to be made up of convective and nucleate boiling components; hfc
0
0
hcb D hfc
C hnb
⊲12.67⊳
0
can be estimated using the equations for singleThe convective boiling coefficient hfc
phase forced-convection heat transfer modified by a factor fc to account for the effects
of two-phase flow:
0
hfc
D hfc ð fc
⊲12.68⊳
The forced-convection coefficient hfc is calculated assuming that the liquid phase is
flowing in the conduit alone.
The two-phase correction factor fc is obtained from Figure 12.56; in which the term
1/Xtt is the Lockhart-Martinelli two-phase flow parameter with turbulent flow in both
phases (See Volume 1, Chapter 5). This parameter is given by:
0.9 0.5 0.1
1
L
x
v
D
⊲12.69⊳
Xtt
1x
v
L
where x is the vapour quality, the mass fraction of vapour.
The nucleate boiling coefficient can be calculated using correlations for nucleate pool
boiling modified by a factor fs to account for the fact that nucleate boiling is more
difficult in a flowing liquid.
0
hnb
D hnb ð fs
⊲12.70⊳
The suppression factor fs is obtained from Figure 12.57. It is a function of the liquid
Reynolds number ReL and the forced-convection correction factor fc .
HEAT-TRANSFER EQUIPMENT
Convective boiling enhancement factor
737
Figure 12.56.
738
1.0
0.9
0.8
0.6
CHEMICAL ENGINEERING
Suppression factor, fs
0.7
0.5
0.4
0.3
0.2
0.1
0
4
10
2
3
4
5
6
7
8
9 10
5
2
1.25
ReLf c
Figure 12.57.
Nucleate boiling suppression factor
3
4
5
6
7
8
9 10
6
HEAT-TRANSFER EQUIPMENT
739
ReL is evaluated assuming that only the liquid phase is flowing in the conduit, and will
be given by:
⊲1 x⊳Gde
ReL D
⊲12.71⊳
L
where G is the total mass flow rate per unit flow area.
Chen’s method was developed from experimental data on forced convective boiling in
vertical tubes. It can be applied, with caution, to forced convective boiling in horizontal
tubes, and annular conduits (concentric pipes). Butterworth (1977) suggests that, in the
absence of more reliable methods, it may be used to estimate the heat-transfer coefficient
for forced convective boiling in cross-flow over tube bundles; using a suitable cross-flow
correlation to predict the forced-convection coefficient. Shah’s method was based on data
for flow in horizontal and vertical tubes and annuli.
A major problem that will be encountered when applying convective boiling correlations
to the design of reboilers and vaporisers is that, because the vapour quality changes
progressively throughout the exchanger, a step-by-step procedure will be needed. The
exchanger must be divided into sections and the coefficient and heat transfer area estimated
sequentially for each section.
Example 12.9
A fluid whose properties are essentially those of o-dichlorobenzene is vaporised in the
tubes of a forced convection reboiler. Estimate the local heat-transfer coefficient at a point
where 5 per cent of the liquid has been vaporised. The liquid velocity at the tube inlet is
2 m/s and the operating pressure is 0.3 bar. The tube inside diameter is 16 mm and the
local wall temperature is estimated to be 120Ž C.
Solution
Physical properties:
boiling point 136Ž C
L D 1170 kg/m3
L D 0.45 mNs/m2
v D 0.01 mNs/m2
v D 1.31 kg/m3
kL D 0.11 W/mŽ C
CpL D 1.25 kJ/kgŽ C
Pc D 41 bar
The forced-convective boiling coefficient will be estimated using Chen’s method.
With 5 per cent vapour, liquid velocity (for liquid flow in tube alone)
D 2 ð 0.95 D 1.90 m/s
ReL D
1170 ð 1.90 ð 16 ð 103
D 79,040
0.45 ð 103
740
CHEMICAL ENGINEERING
From Figure 12.23, jh D 3.3 ð 103
1.25 ð 103 ð 0.45 ð 103
D 5.1
0.11
Neglect viscosity correction term.
0.11
hfc D
ð 3.3 ð 103 ⊲79,040⊳⊲5.1⊳0.33
16 ð 103
Pr D
D 3070 W/m2 Ž C
0.1
1
0.05 0.9 1170 0.5 0.01 ð 103
D
Xtt
1 0.05
1.31
0.45 ð 103
⊲12.15⊳
⊲12.69⊳
D 1.44
From Figure 12.56, fc D 3.2
0
hfc
D 3.2 ð 3070 D 9824 W/m2 Ž C
Using Mostinski’s correlation to estimate the nucleate boiling coefficient
hnb D 0.104 ð 410.69 [hnb ⊲136 120⊳]0.7
0.3 1.2
0.3 10
0.3 0.17
C4
C 10
ð 1.8
41
41
41
⊲12.63⊳
0.7
hnb D 7.43hnb
hnb D 800 W/m2 Ž C
Re L f1.25
D 79,040 ð 3.21.25 D 338,286
c
From Figure 12.57, fs D 0.13,
0
hnb
D 0.13 ð 800 D 104 W/m2 Ž C
hcb D 9824 C 104 D 9928 W/m2 Ž C
12.11.4. Design of forced-circulation reboilers
The normal practice in the design of forced-convection reboilers is to calculate the heattransfer coefficient assuming that the heat is transferred by forced convection only. This
will give conservative (safe) values, as any boiling that occurs will invariably increase the
rate of heat transfer. In many designs the pressure is controlled to prevent any appreciable
vaporisation in the exchanger. A throttle value is installed in the exchanger outlet line,
and the liquid flashes as the pressure is let down into the vapour-liquid separation vessel.
If a significant amount of vaporisation does occur, the heat-transfer coefficient can be
evaluated using correlations for convective boiling, such as Chen’s method.
Conventional shell and tube exchanger designs are used, with one shell pass and two
tube passes, when the process fluid is on the shell side; and one shell and one tube pass
when it is in the tubes. High tube velocities are used to reduce fouling, 3 9 m/s.
Because the circulation rate is set by the designer, forced-circulation reboilers can be
designed with more certainty than natural circulation units.
741
HEAT-TRANSFER EQUIPMENT
The critical flux in forced-convection boiling is difficult to predict. Kern (1950)
recommends that for commercial reboiler designs the heat flux should not exceed
63,000 W/m2 (20,000 Btu/ft2 h) for organics and 95,000 W/m2 (30,000 Btu/ft2 h) for
water and dilute aqueous solutions. These values are now generally considered to be
too pessimistic.
12.11.5. Design of thermosyphon reboilers
The design of thermosyphon reboilers is complicated by the fact that, unlike a forcedconvection reboiler, the fluid circulation rate cannot be determined explicitly. The circulation rate, heat-transfer rate and pressure drop are all interrelated, and iterative design
procedures must be used. The fluid will circulate at a rate at which the pressure losses
in the system are just balanced by the available hydrostatic head. The exchanger, column
base and piping can be considered as the two legs of a U-tube; Figure 12.58. The driving
force for circulation round the system is the difference in density of the liquid in the
“cold” leg (the column base and inlet piping) and the two-phase fluid in the “hot” leg
(the exchanger tubes and outlet piping).
Figure 12.58.
Liquid
Liquid-vapour
Liquid level
Vertical thermosyphon reboiler, liquid and vapour flows
To calculate the circulation rate it is necessary to make a pressure balance round the
system.
A typical design procedure will include the following steps:
1. Calculate the vaporisation rate required; from the specified duty.
2. Estimate the exchanger area; from an assumed value for the overall heat-transfer
coefficient. Decide the exchanger layout and piping dimensions.
3. Assume a value for the circulation rate through the exchanger.
4. Calculate the pressure drop in the inlet piping (single phase).
5. Divide the exchanger tube into sections and calculate the pressure drop sectionby-section up the tube. Use suitable methods for the sections in which the flow is
two-phase. Include the pressure loss due to the fluid acceleration as the vapour rate
increases. For a horizontal reboiler, calculate the pressure drop in the shell, using
a method suitable for two-phase flow.
742
CHEMICAL ENGINEERING
6. Calculate the pressure drop in the outlet piping (two-phase).
7. Compare the calculated pressure drop with the available differential head; which
will depend on the vapour voidage, and hence the assumed circulation rate. If a
satisfactory balance has been achieved, proceed. If not, return to step 3 and repeat
the calculations with a new assumed circulation rate.
8. Calculate the heat-transfer coefficient and heat-transfer rate section-by-section up
the tubes. Use a suitable method for the sections in which the boiling is occurring;
such as Chen’s method.
9. Calculate the rate of vaporisation from the total heat-transfer rate, and compare
with the value assumed in step 1. If the values are sufficiently close, proceed. If
not, return to step 2 and repeat the calculations for a new design.
10. Check that the critical heat flux is not exceeded at any point up the tubes.
11. Repeat the complete procedure as necessary to optimise the design.
It can be seen that to design a thermosyphon reboiler using hand calculations would be
tedious and time-consuming. The iterative nature of the procedure lends itself to solution
by computers. Sarma et al. (1973) discuss the development of a computer program for
vertical thermosyphon reboiler design, and give algorithms and design equations.
Extensive work on the performance and design of thermosyphon reboilers has been
carried out by HTFS and HTRI, and proprietary design programs are available from these
organisations.
In the absence of access to a computer program the rigorous design methods given
by Fair (1960, 1963) or Hughmark (1961, 1964, 1969) can be used for thermosyphon
vertical reboilers. Collins (1976) and Fair and Klip (1983) give methods for the design
of horizontal, shell-side thermsyphon reboilers. The design and performance of this type
of reboiler is also reviewed in a paper by Yilmaz (1987).
Approximate methods can be used for preliminary designs. Fair (1960) gives a method
in which the heat transfer and pressure drop in the tubes are based on the average of the
inlet and outlet conditions. This simplifies step 5 in the design procedure but trial-anderror calculations are still needed to determine the circulation rate. Frank and Prickett
(1973) programmed Fair’s rigorous design method for computer solution and used it,
together with operating data on commercial exchangers, to derive a general correlation
of heat-transfer rate with reduced temperature for vertical thermosyphon reboilers. Their
correlation, converted to SI units, is shown in Figure 12.59. The basis and limitations of
the correlation are listed below:
1. Conventional designs: tube lengths 2.5 to 3.7 m (8 to 12 ft) (standard length 2.44 m),
preferred diameter 25 mm (1 in.).
2. Liquid in the sump level with the top tube sheet.
3. Process side fouling coefficient 6000 W/m2 Ž C.
4. Heating medium steam, coefficient including fouling, 6000 W/m2 Ž C.
5. Simple inlet and outlet piping.
6. For reduced temperatures greater than 0.8, use the limiting curve (that for aqueous
solutions).
7. Minimum operating pressure 0.3 bar.
8. Inlet fluid should not be appreciably sub-cooled.
9. Extrapolation is not recommended.
743
HEAT-TRANSFER EQUIPMENT
solu
tion
s
70,000
T
r =0
.7
T
r =0
.8
Aqu
e
ous
60,000
T
r =
0.6
50,000
Heat flux, W/m2
40,000
30,000
20,000
10,000
0
10
Figure 12.59.
20
30
40
50
Mean overall temperature difference, °C
60
Vertical thermosyphon design correlation
For heating media other than steam and process side fouling coefficients different from
6000 W/m2 Ž C, the design heat flux taken from Figure 12.59 may be adjusted as follows:
U0 D
and
q0
T0
1
1
1
1
1
1
D 0
C
C
Uc
U
6000 hs
6000 hid
⊲12.72⊳
744
where q0
hs
hid
Uc
CHEMICAL ENGINEERING
D
D
D
D
flux read from Figure 12.59 at T0 ,
new shell side coefficient W/m2 Ž C,
fouling coefficient on the process (tube) side W/m2 Ž C,
corrected overall coefficient.
The use of Frank and Prickett’s method is illustrated in Example 12.10.
Limitations on the use of Frank and Pricket’s method
A study by van Edmonds (1994), using the HTFS TREB4 program, found that Frank and
Pricket’s method gave acceptable predictions for pure components and binary mixtures
with water, but that the results were unreliable for other mixtures. Also, van Edmonds’
results predicted higher flux values than those obtained by Pricket and Frank.
For preliminary designs for pure components, or near pure components, Pricket and
Frank’s method should give a conservative estimate of the operating heat flux. It is not
recommended for mixtures, other than binary mixtures with water.
Approximate design method for mixtures
For mixtures, the simplified analysis used by Kern (1954) can be used to obtain an
approximate estimate of the number of tubes required; see also Aerstin and Street (1978)
and Hewitt et al. (1994).
This method uses simple, unsophisticated, methods to estimate the two-phase pressure
drop through the exchanger and piping, and the convective boiling heat transfer coefficient.
The calculation procedure is set out below and illustrated in Example 12.11
Procedure
1. Determine the heat duty.
2. Estimate the heat transfer area, using the maximum allowable heat flux. Take as
39,700 W/m2 for vertical and 47,300 W/m2 for horizontal reboilers.
3. Choose the tube diameters and length. Calculate the number of tubes required.
4. Estimate the recirculation ratio, not less than 3.
5. Calculated the vapour flow rate leaving the reboiler for the duty and liquid heat of
vaporisation.
6. Calculate the liquid flow rate leaving the reboiler for the vapour rate and recirculation ratio.
7. Estimate the two-phase pressure drop though the tubes, due to friction. Use the
homogenous model or another simple method, such as the Lochart Martenelli
equation; see Volume 1, Chapter 5.
8. Estimate the static head in the tubes.
9. Estimate the available head.
10. Compare the total estimated pressure drop and the available head. If the available
head is greater by a sufficient amount to allow for the pressure drop through the
inlet and outlet piping, proceed. If the available head is not sufficient, return to
step 2, and increase the number of tubes.
11. Calculate the convective heat transfer coefficient using simple methods, such as
assuming convection only, or Chens’ method; see Section 12.11.3.
HEAT-TRANSFER EQUIPMENT
745
12. Calculate the overall heat transfer coefficient.
13. Calculate the required overall coefficient and compare with that estimated. If
satisfactory, accept the design, if unsatisfactory return to step 2 and increase the
estimated area.
Maximum heat flux
Thermosyphon reboilers can suffer from flow instabilities if too high a heat flux is used.
The liquid and vapour flow in the tubes is not smooth but tends to pulsate, and at high
heat fluxes the pulsations can become large enough to cause vapour locking. A good
practice is to install a flow restriction in the inlet line, a valve or orifice plate, so that the
flow resistance can be adjusted should vapour locking occur in operation.
Kern recommends that the heat flux in thermosyphon reboilers, based on the total
heat-transfer area, should not exceed 37,900 W/m2 (12,000 Btu/ft2 h). For horizontal
thermosyphon reboilers, Collins recommends a maximum flux ranging from 47,300 W/m2
for 20-mm tubes to 56,800 W/m2 for 25-mm tubes (15,000 to 18,000 Btu/ft2 h). These
“rule of thumb” values are now thought to be too conservative; see Skellence et al.
(1968) and Furzer (1990). Correlations for determining the maximum heat flux for vertical
thermosyphons are given by Lee et al. (1956) and Palen et al. (1974); and for horizontal
thermosyphons by Yilmaz (1987).
General design considerations
The tube lengths used for vertical thermosyphon reboilers vary from 1.83 m (6 ft) for
vacuum service to 3.66 m (12 ft) for pressure operation. A good size for general applications is 2.44 m (8 ft) by 25 mm internal diameter. Larger tube diameters, up to 50 mm,
are used for fouling systems.
The top tube sheet is normally aligned with the liquid level in the base of the column;
Figure 12.58. The outlet pipe should be as short as possible, and have a cross-sectional
area at least equal to the total cross-sectional area of the tubes.
Example 12.10
Make a preliminary design for a vertical thermosyphon for a column distilling crude
aniline. The column will operate at atmospheric pressure and a vaporisation rate of
6000 kg/h is required. Steam is available at 22 bar (300 psig). Take the column bottom
pressure as 1.2 bar.
Solution
Physical properties, taken as those of aniline:
Boiling point at 1.2 bar 190Ž C
Molecular weight 93.13
Tc 699 K
Latent heat 42,000 kJ/kmol
Steam saturation temperature 217Ž C.
746
CHEMICAL ENGINEERING
Mean overall T D ⊲217 190⊳ D 27Ž C.
Reduced temperature, Tr D
⊲190 C 273⊳
D 0.66
699
From Figure 12.59, design heat flux D 25,000 W/m2
Heat load D
Area required D
6000 42,000
ð
D 751 kW
3600
93.13
751 ð 103
D 30 m2
25,000
Use 25 mm i.d., 30 mm o.d., 2.44 m long tubes.
Area of one tube D 25 ð 103 ð 2.44 D 0.192 m2
30
Number of tubes D
D 157
0.192
Approximate diameter of bundle, for 1.25 square pitch
157 1/2.207
D 595 mm
Db D 30
0.215
⊲12.3b⊳
A fixed tube sheet will be used for a vertical thermosyphon reboiler. From Figure 12.10,
shell diametrical clearance D 14 mm,
Shell inside dia. D 595 C 14 D 609 mm
Outlet pipe diameter; take area as equal to total tube cross-sectional area
D 157⊲25 ð 103 ⊳2 D 0.077 m2
4
0.077 ð 4
Pipe diameter D
D 0.31 m
Example 12.11
Make a preliminary design for a vertical thermosyphon reboiler for the column specified
in Example 11.9. Take the vapour rate required to be 36 kmol/h.
From example 8.3:
Operating pressure 8.3 (neglecting pressure drop over column).
Bottoms composition: C3 0.001, iC4 0.001, nC4 0.02, iC5 0.34, nC5 0.64, kmol.
Bubble point of mixture, approximately, 120Ž C.
Solution
The concentrations of C3 and iC4 are small enough to be neglected.
Take the liquid: vapour ratio as 3 : 1.
Estimate the liquid and vapour compositions leaving the reboiler:
747
HEAT-TRANSFER EQUIPMENT
Vapour rate, V D 36/3600 D 0.1 kmol/s
L/V D 3, so liquid rate, L D 3 V D 0.3 kmol/s and feed, F D L C V D 0.4 kmol/s.
The vapour and liquid compositions leaving the reboiler can be estimated using the same
procedure as that for a flash calculation; see Section 11.3.3.
Ki
Ai D Ki ð L/V Vi D zi /⊲1 C AI ⊳ yi D Vi /V xi D ⊲Fzi Vi ⊳/L
2.03
6.09
0.001
0.010
0.023
nC4
iC5
1.06
3.18
0.033
0.324
0.343
nC5
0.92
2.76
0.068
0.667
0.627
0.102
1.001
0.993
Totals
(near enough correct)
Enthalpies of vaporisation, from Figures (b) and (c) Example 11.9, kJ/mol
nC4
iC5
nC5
Total
xi
0.02
0.35
0.63
Hi
50
58
61
hi
34
41
42
Hi hi
16
17
19
xi ⊲Hi hi ⊳
0.32
5.95
11.97
18.24
Exchanger duty, feed to reboiler taken as at its boiling point
D vapour flow-rate ð heat of vaporisation
D 0.1 ð 103 ð 18.24 D 1824 kW
Take the maximum flux as 37,900 W/m2 ; see Section 12.11.5.
Heat transfer area required D 1,824,000/37,900 D 48.1 m2
Use 25 mm i.d., 2.5 m long tubes, a popular size for vertical thermosyphon reboilers.
Area of one tube D 25 ð 103 ð 2.5 D 0.196 m2
Number of tubes required D 48.1/0.196 D 246
Liquid density at base of exchanger D 520 kg/m3
Relative molecular mass at tube entry D 58 ð 0.02 C 72⊲0.34 C 0.64⊳ D 71.7
vapour at exit D 58 ð 0.02 C 72⊲0.35 C 0.63⊳ D 71.7
Two-phase fluid density at tube exit:
volume of vapour D 0.1 ð ⊲22.4./8.3⊳ ð ⊲393/273⊳ D 0.389 m3
volume of liquid D ⊲0.3 ð 71.7⊳/520 D 0.0413 m3
total volume D 0.389 C 0.0413 D 0.430 m3
⊲0.4 ð 71.7⊳
ð 71.7 D 66.7 kg/m3
exit density D
0.430
Friction loss
Mass flow-rate D 0.4 ð 71.7 D 28.68 kg/s
⊲25 ð 103 ⊳2
Cross-sectional area of tube D
D 0.00049 m2
4
748
CHEMICAL ENGINEERING
Total cross-sectional area of bundle D 246 ð 0.00049 D 0.121 m2
Mass flux, G D mass flow/area D 28.68/0.121 D 237.0 kg m2 s1
At tube exit, pressure drop per unit lengths, using the homogeneous model:
homogeneous velocity D G/m D 237/66.7 D 3.55 m/s
Viscosity, taken as that of liquid, D 0.12 mN sm2
Re D
66.7 ð 3.55 ð 25 ð 103
m ud
D
D 49,330, ⊲4.9 ð 104 ⊳
0.12 ð 103
Friction factor, from Fig. 12.24 D 3.2 ð 103
3.552
1
ð
66.7
ð
D 430 N/m2 per m
25 ð 103
2
At tube entry, liquid only, pressure drop per unit length:
Pf D 8 ð 3.2 ð 103 ð
⊲12.19⊳
velocity D G/L D 237.0/520 D 0.46 m/s
Re D
L ud
520 ð 0.46 ð 25 ð 103
D 49,833, ⊲5.0 ð 104 ⊳
D
0.12 ð 103
Friction factor, from Fig 12.24 D 3.2 ð 103
0.462
1
ð
520
ð
D 56 N/m2 per m
25 ð 103
2
Taking the pressure drop change as linear along the tube,
Mean pressure drop per unit length D ⊲430 C 56⊳/2 D 243 N/m2
Pressure drop over tube 243 ð 2.5 D 608 N/m2
The viscosity correction factor is neglected in this rough calculation.
Pf D 8 ð 3.2 ð 103 ð
⊲12.19⊳
Static pressure in tubes
Making the simplifying assumption that the variation in density in the tubes is linear from
bottom to top, the static pressure will be given by:
Ps D g
L
0
gL
dx
D
ð Ln⊲v0 /vi ⊳
vi C x⊲v0 vi ⊳/L
⊲v0 vi ⊳
where vi and v0 are the inlet and outlet specific volumes.
vi D 1/520 D 0.00192 and v0 D 1/66.7 D 0.0150 m3 /kg
Ps D
9.8 ð 2.5
ð Ln⊲0.0150/0.00192⊳ D 3850 N/m2
⊲0.0150 0.00192⊳
Total pressure drop over tubes D 346 C 3850 D 4250 N/m2
Available head (driving force)
Pa D L gL D 520 ð 9.8 ð 2.5 D 12,740 N/m2
HEAT-TRANSFER EQUIPMENT
749
Which is adequate to maintain a circulation ratio of 3 : 1, including allowances for the
pressure drop across the piping.
Heat transfer
The convective boiling coefficient will be calculated using Chen’s method; see Section
12.13.3.
As the heat flux is known and only a rough estimate of the coefficient is required, use
Mostinski’s equation to estimate the nucleate boiling coefficient; Section 12.11.2.
Take the critical pressure as that for n-pentane, 33.7 bar.
hnb D 0.104⊲33.7⊳0.69 ⊲37,900⊳0.7 [1.8⊲8.3/33.7⊳0.17
C 4⊲8.3/33.7⊳1.2 C 10⊲8.3/33.7⊳10 ]
D 1888.6⊲1.418 C 0.744 C 0.000⊳ D 4083 Wm2Ž C1
⊲12.63⊳
Vapour quality, x D mass vapour/total mass flow D 0.1/0.4 D 0.25
Viscosity of vapour D 0.0084 mNm2 s
Vapour density at tube exit D ⊲0.1 ð 71.7⊳/0.389 D 18.43 kg/m3
1/Xtt D [0.25/⊲1 0.25⊳]0.9 [520/18.43]0.5 [0.0084/0.12]0.1 D 1.51
⊲12.69⊳
Specific heat of liquid D 2.78 kJkg1Ž C1 , thermal conductivity of liquid D
0.12 Wm1Ž C1 .
PrL D ⊲2.78 ð 103 ð 0.12 ð 103 ⊳/0.12 D 2.78
Mass flux, liquid phase only flowing in tubes D ⊲0.3 ð 71.7⊳/0.121 D 177.8 kg m2 s1
Velocity D 177.8/520 D 0.34 m/s
ReL D
520 ð 0.34 ð 25 ð 103
D 36,833 ⊲3.7 ð 104 ⊳
0.12 ð 103
From Figure 12.23 jh D 3.3 ð 103 ,
Nu D 3.3 ð 103 ð 36,833 ð 2.780.33 D 170.3
hi D 170.3 ð ⊲0.12/25 ð 103 ⊳ D 817 Wm2Ž C1
again, neglecting the viscosity correction factor.
From Figure 12.56, the convective boiling factor, fc D 3.6
ReL ð fc 1.25 D 36,883 ð 3.61.25 D 182,896 ⊲1.8 ð 105 ⊳
From Figure 12.57 the nucleate boiling suppression factor, fs D 0.23
So, hcb D 3.6 ð 817 C 0.23 ð 4083 D 3880 Wm2Ž C1
This value has been calculated at the outlet conditions.
⊲12.15⊳
750
CHEMICAL ENGINEERING
Assuming that the coefficient changes linearly for the inlet to outlet, then the average
coefficient will be given by:
[inlet coefficient (all liquid) C outlet coefficient (liquid C vapour)]/2
ReL at inlet D 36,833 ð 0.4/0.3 D 49,111 ⊲4.9 ð 104 ⊳
From Figure 12.23, jh D 3.2 ð 103
Nu D 3.2 ð 103 ð 49,111 ð 2.780.33 D 220.2
3
2Ž
hi D 220.2 ð ⊲0.12/25 ð 10 ⊳ D 1057 Wm
⊲12.15⊳
C
1
Mean coefficient D ⊲1057 C 3880⊳/2 D 2467 Wm2Ž C1
The overall coefficient, U, neglecting the resistance of the tube wall, and taking the steam
coefficient as 8000 Wm2Ž C1 , is given by:
1/U D 1/8000 C 1/2467 D 5.30 ð 104
U D 1886 Wm2Ž C1
The overall coefficient required for the design D duty/TLM
TLM D 158.8 120 D 38.8Ž C, taking both streams as isothermal
So, U required D 37,900/38.3 D 990 Wm2Ž C1
So the area available in the proposed design is more than adequate and will take care of
any fouling.
The analysis could be improved by dividing the tube length into sections, calculating
the heat transfer coefficient and pressure drop over each section, and totalling.
More accurate, but more complex, methods could be used to predict the two-phase
pressure drop and heat transfer coefficients.
The pressure drop over the inlet and outlet pipes could also be estimated, taking into
account the bends, and expansions and contractions.
An allowance could also be included for the energy (pressure drop) required to accelerate the liquid vapour mixtures as the liquid is vaporised. This can be taken as two
velocity head, based on the mean density.
12.11.6. Design of kettle reboilers
Kettle reboilers, and other submerged bundle equipment, are essentially pool boiling
devices, and their design is based on data for nucleate boiling.
In a tube bundle the vapour rising from the lower rows of tubes passes over the upper
rows. This has two opposing effects: there will be a tendency for the rising vapour to
blanket the upper tubes, particularly if the tube spacing is close, which will reduce the
heat-transfer rate; but this is offset by the increased turbulence caused by the rising vapour
bubbles. Palen and Small (1964) give a detailed procedure for kettle reboiler design in
HEAT-TRANSFER EQUIPMENT
751
which the heat-transfer coefficient calculated using equations for boiling on a single tube
is reduced by an empirically derived tube bundle factor, to account for the effects of
vapour blanketing. Later work by Heat Transfer Research Inc., reported by Palen et al.
(1972), showed that the coefficient for bundles was usually greater than that estimated for
a single tube. On balance, it seems reasonable to use the correlations for single tubes to
estimate the coefficient for tube bundles without applying any correction (equations 12.62
or 12.63).
The maximum heat flux for stable nucleate boiling will, however, be less for a tube
bundle than for a single tube. Palen and Small (1964) suggest modifying the Zuber
equation for single tubes (equation 12.64) with a tube density factor. This approach was
supported by Palen et al. (1972).
The modified Zuber equation can be written as:
pt
p
qcb D Kb
[g⊲L v ⊳v2 ]0.25
⊲12.74⊳
do
Nt
where qcb D maximum (critical) heat flux for the tube bundle, W/m2 ,
Kb D 0.44 for square pitch arrangements,
D 0.41 for equilateral triangular pitch arrangements,
pt D tube pitch,
do D tube outside diameter,
Nt D total number of tubes in the bundle,
Note. For U-tubes Nt will be equal to twice the number of actual U-tubes.
Palen and Small suggest that a factor of safety of 0.7 be applied to the maximum flux
estimated from equation 12.74. This will still give values that are well above those which
have traditionally been used for the design of commercial kettle reboilers; such as that
of 37,900 W/m2 (12,000 Btu/ft2 h) recommended by Kern (1950). This has had important
implications in the application of submerged bundle reboilers, as the high heat flux allows
a smaller bundle to be used, which can then often be installed in the base of the column;
saving the cost of shell and piping.
General design considerations
A typical layout is shown in Figure 12.8. The tube arrangement, triangular or square pitch,
will not have a significant effect on the heat-transfer coefficient. A tube pitch of between
1.5 to 2.0 times the tube outside diameter should be used to avoid vapour blanketing.
Long thin bundles will be more efficient than short fat bundles.
The shell should be sized to give adequate space for the disengagement of the vapour
and liquid. The shell diameter required will depend on the heat flux. The following values
can be used as a guide:
Heat flux W/m2
Shell dia./Bundle dia.
25,000
25,000 to 40,000
40,000
1.2 to 1.5
1.4 to 1.8
1.7 to 2.0
752
CHEMICAL ENGINEERING
The freeboard between the liquid level and shell should be at least 0.25 m. To avoid
excessive entrainment, the maximum vapour velocity uO v (m/s) at the liquid surface should
be less than that given by the expression:
L v
uO v < 0.2
v
1/2
⊲12.75⊳
When only a low rate of vaporisation is required a vertical cylindrical vessel with
a heating jacket or coils should be considered. The boiling coefficients for internal
submerged coils can be estimated using the equations for nucleate pool boiling.
Mean temperature differences
When the fluid being vaporised is a single component and the heating medium is steam (or
another condensing vapour), both shell and tubes side processes will be isothermal and the
mean temperature difference will be simply the difference between the saturation temperatures. If one side is not isothermal the logarithmic mean temperature difference should be
used. If the temperature varies on both sides, the logarithmic temperature difference must
be corrected for departures from true cross- or counter-current flow (see Section 12.6).
If the feed is sub-cooled, the mean temperature difference should still be based on the
boiling point of the liquid, as the feed will rapidly mix with the boiling pool of liquid;
the quantity of heat required to bring the feed to its boiling point must be included in the
total duty.
Mixtures
The equations for estimating nucleate boiling coefficients given in Section 12.11.1 can be
used for close boiling mixtures, say less than 5Ž C, but will overestimate the coefficient if
used for mixtures with a wide boiling range. Palen and Small (1964) give an empirical
correction factor for mixtures which can be used to estimate the heat-transfer coefficient
in the absence of experimental data:
⊲hnb ⊳ mixture D fm ⊲hnb ⊳ single component
⊲12.76⊳
where fm D exp[0.0083⊲Tbo Tbi ⊳]
and Tbo D temperature of the vapour mixture leaving the reboiler Ž C,
Tbi D temperature of the liquid entering the reboiler Ž C.
The inlet temperature will be the saturation temperature of the liquid at the base of the
column, and the vapour temperature the saturation temperature of the vapour returned to
the column. The composition of these streams will be fixed by the distillation column
design specification.
Example 12.12
Design a vaporiser to vaporise 5000 kg/h n-butane at 5.84 bar. The minimum temperature
of the feed (winter conditions) will be 0Ž C. Steam is available at 1.70 bar (10 psig).
HEAT-TRANSFER EQUIPMENT
753
90
45
Tube outer limit dia.
420 mm
Tube O.D 30mm
52 Tube holes
26 u-tubes
Tube sheet layout, U-tubes, Example 12.9
Solution
Only the thermal design and general layout will be done. Select kettle type.
Physical properties of n-butane at 5.84 bar:
boiling point D 56.1Ž C
latent heat D 326 kJ/kg
mean specific heat, liquid D 2.51 kJ/kgŽ C
critical pressure, Pc D 38 bar
Heat loads:
sensible heat (maximum) D ⊲56.1 0⊳2.51 D 140.8 kJ/kg
total heat load D ⊲140.8 C 326⊳ ð
5000
D 648.3 kW,
3600
add 5 per cent for heat losses
maximum heat load (duty) D 1.05 ð 648.3
D 681 kW
From Figure 12.1 assume U D 1000 W/m2 Ž C.
Mean temperature difference; both sides isothermal, steam saturation temperature at
1.7 bar D 115.2Ž C
Tm D 115.2 56.1 D 59.1Ž C
681 ð 103
D 11.5 m2
1000 ð 59.1
Select 25 mm i.d., 30 mm o.d. plain U-tubes,
Area (outside) required D
Nominal length 4.8 m (one U-tube)
Number of U tubes D
11.5
D 25
⊲30 ð 103 ⊳4.8
754
CHEMICAL ENGINEERING
Use square pitch arrangement, pitch D 1.5 ð tube o.d.
D 1.5 ð 30 D 45 mm
Draw a tube layout diagram, take minimum bend radius
1.5 ð tube o.d. D 45 mm
Proposed layout gives 26 U-tubes, tube outer limit diameter 420 mm.
Boiling coefficient
Use Mostinski’s equation:
heat flux, based on estimated area,
hnb
681
D 59.2 kW/m2
qD
11.5
5.84 1.2
5.84 10
5.84 0.17
0.69
3 0.7
C4
C 10
D 0.104⊲38⊳ ⊲59.2 ð 10 ⊳
1.8
38
38
38
D 4855 W/m2 Ž C
⊲12.63⊳
Take steam condensing coefficient as 8000 W/m2 Ž C, fouling coefficient 5000 W/m2 Ž C;
butane fouling coefficient, essentially clean, 10,000 W/m2 Ž C.
Tube material will be plain carbon steel, kw D 55 W/mŽ C
30
30 ð 103 ln
1
1
30
1
1
1
25
C
C
C
C
D
Uo
4855 10,000
2 ð 55
25 5000 8000
⊲12.2⊳
Uo D 1341 W/m2 Ž C
Close enough to original estimate of 1000 W/m2 Ž C for the design to stand.
Myers and Katz (Chem. Eng. Prog. Sym. Ser. 49(5) 107 114) give some data on the
boiling of n-butane on banks of tubes. To compare the value estimate with their values
an estimate of the boiling film temperature difference is required:
D
1341
ð 59.1 D 16.3Ž C ⊲29Ž F⊳
4855
Myers data, extrapolated, gives a coefficient of around 3000 Btu/h ft2 Ž F at a 29Ž F temperature difference D 17,100 W/m2 Ž C, so the estimated value of 4855 is certainly on the
safe side.
Check maximum allowable heat flux. Use modified Zuber equation.
Surface tension (estimated) D 9.7 ð 103 N/m
L D 550 kg/m3
273
58
ð
ð 5.84 D 12.6 kg/m3
v D
22.4 ⊲273 C 56⊳
Nt D 52
755
HEAT-TRANSFER EQUIPMENT
For square arrangement Kb D 0.44
qc D 0.44 ð 1.5 ð
326 ð 103
p
[9.7 ð 103 ð 9.81⊲550 12.6⊳12.62 ]0.25 ⊲12.74⊳
52
D 283,224 W/m2
D 280 kW/m2
Applying a factor of 0.7, maximum flux should not exceed 280 ð 0.7 D 196 kW/m2 .
Actual flux of 59.2 kW/m2 is well below maximum allowable.
Layout
From tube sheet layout Db D 420 mm.
Take shell diameter as twice bundle diameter
Ds D 2 ð 420 D 840 mm.
Take liquid level as 500 mm from base,
freeboard D 840 500 D 340 mm, satisfactory.
340
420
500
From sketch, width at liquid level D 0.8 m.
Surface area of liquid D 0.8 ð 2.4 D 1.9 m2 .
1
1
5000
ð
ð
D 0.06 m/s
Vapour velocity at surface D
3600 12.6 1.9
Maximum allowable velocity
uO v D 0.2
550 12.6
12.6
1/2
D 1.3 m/s
⊲12.75⊳
so actual velocity is well below maximum allowable velocity. A smaller shell diameter
could be considered.
756
CHEMICAL ENGINEERING
12.12. PLATE HEAT EXCHANGERS
12.12.1. Gasketed plate heat exchangers
A gasketed plate heat exchanger consists of a stack of closely spaced thin plates clamped
together in a frame. A thin gasket seals the plates round their edges. The plates are
normally between 0.5 and 3 mm thick and the gap between them 1.5 to 5 mm. Plate
surface areas range from 0.03 to 1.5 m2 , with a plate width:length ratio from 2.0 to
3.0. The size of plate heat exchangers can vary from very small, 0.03 m2 , to very large,
1500 m2 . The maximum flow-rate of fluid is limited to around 2500 m3 /h.
The basic layout and flow arrangement for a gasketed plate heat exchanger is shown in
Figure 12.60. Corner ports in the plates direct the flow from plate to plate. The plates are
embossed with a pattern of ridges, which increase the rigidity of the plate and improve
the heat transfer performance.
Plates are available in a wide range of metals and alloys; including stainless steel,
aluminium and titanium. A variety of gasket materials is also used; see Table 12.8.
Selection
The advantages and disadvantages of plate heat exchangers, compared with conventional
shell and tube exchangers are listed below:
Advantages
1. Plates are attractive when material costs are high.
2. Plate heat exchangers are easier to maintain.
Figure 12.60.
Gasketed plate heat exchanger
757
HEAT-TRANSFER EQUIPMENT
Table 12.8.
Typical gasket materials for plated heat exchangers
Material
Approximate temperature
limit, ° C
Fluids
Styrene-butane rubber
Acrylonitrile-butane rubber
85
140
Ethylene-propylene rubber
Fluorocarbon rubber
Compressed asbestos
150
175
250
Aqueous systems
Aqueous system, fats,
aliphatic hydrocarbons
Wide range of chemicals
Oils
General resistance to organic
chemicals
3. Low approach temps can be used, as low as 1 Ž C, compared with 5 to 10 Ž C for
shell and tube exchangers.
4. Plate heat exchangers are more flexible, it is easy to add extra plates.
5. Plate heat exchangers are more suitable for highly viscous materials.
6. The temperature correction factor, Ft , will normally be higher with plate heat
exchangers, as the flow is closer to true counter-current flow.
7. Fouling tends to be significantly less in plate heat exchangers; see Table 12.9.
Disadvantages
1. A plate is not a good shape to resist pressure and plate heat exchangers are not
suitable for pressures greater than about 30 bar.
2. The selection of a suitable gasket is critical; see Table 12.8.
3. The maximum operating temperature is limited to about 250 Ž C, due to the performance of the available gasket materials.
Plate heat exchangers are used extensively in the food and beverage industries, as
they can be readily taken apart for cleaning and inspection. Their use in the chemical
industry will depend on the relative cost for the particular application compared with a
conventional shell and tube exchanger; see Parker (1964) and Trom (1990).
Table 12.9.
Fouling factors (coefficients), typical values for plate heat exchangers
Fluid
Process water
Towns water (soft)
Towns water (hard)
Cooling water (treated)
Sea water
Lubricating oil
Light organics
Process fluids
Coefficient (W/m2 ° C)
Factor (m2 ° C/W)
30,000
15,000
6000
8000
6000
6000
10,000
5000 20,000
0.00003
0.00007
0.00017
0.00012
0.00017
0.00017
0.0001
0.0002 0.00005
Plate heat exchanger design
It is not possible to give exact design methods for plate heat exchangers. They are proprietary designs, and will normally be specified in consultation with the manufacturers.
Information on the performance of the various patterns of plate used is not generally
758
CHEMICAL ENGINEERING
available. Emerson (1967) gives performance data for some proprietary designs, and
Kumar (1984) and Bond (1980) have published design data for APV chevron patterned
plates.
The approximate method given below can be used to size an exchanger for comparison
with a shell and tube exchanger, and to check performance of an existing exchanger for
new duties. More detailed design methods are given by Hewitt et al. (1994) and Cooper
and Usher (1983).
Procedure
The design procedure is similar to that for shell and tube exchangers.
1. Calculate duty, the rate of heat transfer required.
2. If the specification is incomplete, determine the unknown fluid temperature or fluid
flow-rate from a heat balance.
3. Calculate the log mean temperature difference, TLM .
4. Determine the log mean temperature correction factor, Ft ; see method given
below.
5. Calculate the corrected mean temperature difference Tm D Ft ð TLM .
6. Estimate the overall heat transfer coefficient; see Table 12.1.
7. Calculate the surface area required; equation 12.1.
8. Determine the number of plates required D total surface area/area of one plate.
9. Decide the flow arrangement and number of passes.
10. Calculate the film heat transfer coefficients for each stream; see method given
below.
11. Calculate the overall coefficient, allowing for fouling factors.
12. Compare the calculated with the assumed overall coefficient. If satisfactory, say
0% to C 10% error, proceed. If unsatisfactory return to step 8 and increase or
decrease the number of plates.
13. Check the pressure drop for each stream; see method given below.
This design procedure is illustrated in Example 12.13.
Flow arrangements
The stream flows can be arranged in series or parallel, or a combination of series and
parallel, see Figure 12.61. Each stream can be sub-divided into a number of passes;
analogous to the passes used in shell and tube exchangers.
Estimation of the temperature correction factor
For plate heat exchangers it is convenient to express the log mean temperature difference
correction factor, Ft , as a function of the number of transfer units, NTU, and the flow
arrangement (number of passes); see Figure 12.62. The correction will normally be higher
for a plate heat exchanger than for a shell and tube exchanger operating with the same
temperatures. For rough sizing purposes, the factor can be taken as 0.95 for series flow.
HEAT-TRANSFER EQUIPMENT
759
(a) Series flow
(b) Looped ( parallel ) flow
(c)
Figure 12.61.
2 Pass / 2 Pass
5 Channels per pass
19 Thermal plates
21 Plates total
Counter-current flow
Plate heat-exchanger flow arrangements
The number of transfer units is given by:
NTU D ⊲t0 ti ⊳/TLM
where
ti D stream inlet temperature,Ž C,
t0 D stream outlet temperature,Ž C,
TLM D log mean temperature difference,Ž C.
Typically, the NTU will range from 0.5 to 4.0, and for most applications will lie between
2.0 to 3.0.
Heat transfer coefficient
The equation for forced-convective heat transfer in conduits can be used for plate heat
exchangers; equation 12.10.
The values for the constant C and the indices a,b,c will depend on the particular type
of plate being used. Typical values for turbulent flow are given in the equation below,
760
CHEMICAL ENGINEERING
1.00
Correction factor, Ft
0.95
4.4
1.1
0.90
3.3
0.85
2.2
0.80
0
1
2
3
4
5
6
NTU
Figure 12.62.
(1980))
Log mean temperature correction factor for plate heat exchangers (adapted from Raju and Chand
which can be used to make a preliminary estimate of the area required.
hp de
D 0.26Re0.65 Pr 0.4 ⊲/w ⊳0.14
kf
⊲12.77⊳
where hp D plate film coefficient,
Gp de
up de
Re D Reynold number D
D
GP D mass flow rate per unit cross-sectional area D w/Af , kgm2 s1 ,
w D mass flow rate per channel, kg/s,
Af D cross-sectional area for flow, m2 ,
up D channel velocity, m/s,
de D equivalent (hydraulic) diameter, taken as twice the gap between
the plates, m.
The corrugations on the plates will increase the projected plate area, and reduce the
effective gap between the plates. For rough sizing, where the actual plate design is not
known, this increase can be neglected. The channel width equals the plate pitch minus
the plate thickness.
There is no heat transfer across the end plates, so the number of effective plates will
be the total number of plates less two.
761
HEAT-TRANSFER EQUIPMENT
Pressure drop
The plate pressure drop can be estimated using a form of the equation for flow in a
conduit; equation 12.18.
up2
Pp D 8jf ⊲Lp /de ⊳
⊲12.78⊳
2
where LP D the path length and up D Gp /.
The value of the friction factor, jf , will depend on the design of plate used. For
preliminary calculations the following relationship can be used for turbulent flow:
jf D 0.6 Re0.3
The transition from laminar to turbulent flow will normally occur at a Reynolds number of
100 to 400, depending on the plate design. With some designs, turbulence can be achieved
at very low Reynolds numbers, which makes plate heat exchangers very suitable for use
with viscous fluids.
The pressure drop due the contraction and expansion losses through the ports in the
plates must be added to the friction loss. Kumar (1984) suggests adding 1.3 velocity heads
per pass, based on the velocity through the ports.
Ppt D 1.3
where upt
w
Ap
dpt
Np
D
D
D
D
D
2
⊲upt
⊳
2
⊲12.79⊳
Np
the velocity through the ports w/Ap , m/s,
mass flow through the ports, kg/s,
area of the port D ⊲d2pt ⊳/4, m2 ,
port diameter, m,
number of passes.
Example 12.13
Investigate the use of a gasketed plate heat exchanger for the duty set out in Example 12.1:
cooling methanol using brackish water as the coolant. Titanium plates are to be specified,
to resist corrosion by the saline water.
Summary of Example 12.1
Cool 100,000 kg/h of methanol from 95Ž C to 40Ž C, duty 4340 kW. Cooling water inlet
temperature 25Ž C and outlet temperature 40Ž C. Flow-rates: methanol 27.8 kg/s, water
68.9 kg/s.
Physical properties:
Methanol
Water
Density, kg/m3
Viscosity, mN m2 s
Prandtl number
750
3.4
5.1
Logarithmic mean temperature difference 31Ž C.
995
0.8
5.7
762
CHEMICAL ENGINEERING
Solution
NTU, based on the maximum temperature difference
D
95 40
D 1.8
31
Try a 1 : 1 pass arrangement.
From Figure 12.62, Ft D 0.96
From Table 12.2 take the overall coefficient, light organic - water, to be 2000 Wm2Ž C1 .
Then, area required D
4340 ð 103
D 72.92 m2
2000 ð 0.96 ð 31
Select an effective plate area of 0.75 m2 , effective length 1.5 m and width 0.5 m; these
are typical plate dimensions. The actual plate size will be larger to accommodate the
gasket area and ports.
Number of plates D total heat transfer area / effective area of one plate
D 72.92/0.75 D 97
No need to adjust this, 97 will give an even number of channels per pass, allowing for
an end plate.
Number of channels per pass D ⊲97 1⊳/2 D 48
Take plate spacing as 3 mm, a typical value, then:
channel cross-sectional area D 3 ð 103 ð 0.5 D 0.0015 m2
and hydraulic mean diameter D 2 ð 3 ð 103 D 6 ð 103 m
Methanol
Channel velocity D
Re D
27.8
1
1
ð
ð
D 0.51 m/s
750
0.0015 48
750 ð 0.51 ð 6 ð 103
up de
D
D 6750
0.34 ð 103
Nu D 0.26⊲6750⊳0.65 ð 5.10.4 D 153.8
⊲12.77⊳
hp D 153.8⊲0.19/6 ð 103 ⊳ D 4870 Wm2Ž C1
Brackish water
Channel velocity D
Re D
68.9
1
1
ð
ð
D 0.96 m/s
995
0.0015 48
955 ð 0.96 ð 6 ð 103
D 6876
0.8 ð 103
Nu D 0.26⊲6876⊳0.65 ð 5.70.4 D 162.8
3
⊲12.77⊳
2Ž
hp D 162.8⊲0.59/6 ð 10 ⊳ D 16,009 Wm
1
C
763
HEAT-TRANSFER EQUIPMENT
Overall coefficient
From Table 12.9, take the fouling factors (coefficients) as: brackish water (seawater)
6000 Wm2Ž C1 and methanol (light organic) 10,000 Wm2Ž C1 .
Take the plate thickness as 0.75 mm. Thermal conductivity of titanium 21 Wm1Ž C1 .
1
1
0.75 ð 103
1
1
1
D
C
C
C
C
U
4870 10,000
21
16,009 6000
U D 1754 Wm2Ž C1 , too low
Increase the number of channels per pass to 60; giving ⊲2 ð 60⊳ C 1 D 121 plates.
Then, methanol channel velocity D 0.51 ð ⊲48/60⊳ D 0.41 m/s, and Re D 5400.
Cooling water channel velocity D 0.96 ð ⊲48/60⊳ D 0.77 m/s, and Re D 5501.
Giving, hp D 4215 Wm2Ž C1 for methanol, and 13,846 Wm2Ž C1 for water.
Which gives an overall coefficient of 1634 Wm2Ž C1 .
Overall coefficient required 2000 ð 48/60 D 1600 Wm2Ž C1 , so 60 plates per pass
should be satisfactory.
Pressure drops
Methanol
Jf D 0.60⊲5400⊳0.3 D 0.046
Path length D plate length ð number of passes D 1.5 ð 1 D 1.5 m.
1.5
0.412
Pp D 8 ð 0.046
D 5799 N/m2
ð
750
ð
6 ð 103
2
⊲12.78⊳
Port pressure loss, take port diameter as 100 mm, area D 0.00785 m2 .
Velocity through port D ⊲27.8/750⊳/0.00785 D 4.72 m/s.
Ppt D 1.3 ð
750 ð 4.722
D 10,860 N/m2
2
⊲12.79⊳
Total pressure drop D 5799 C 10,860 D 16,659 N/m2 , 0.16 bar.
Water
Jf D 0.6⊲5501⊳0.3 D 0.045
Path length D plate length ð number of passes D 1.5 ð 1 D 1.5 m.
1.5
0.772
Pp D 8 ð 0.045 ð
ð
995
ð
D 26,547 N/m2
6 ð 103
2
⊲12.78⊳
Velocity through port D ⊲68.9/995⊳/0.0078 D 8.88 m/s (rather high)
Ppt D 1.3 ð
995 ð 8.88
D 50,999 N/m2
2
⊲12.79⊳
764
CHEMICAL ENGINEERING
Total pressure drop D 26,547 C 50,999 D 77,546 N/m2 , 0.78 bar
Could increase the port diameter to reduce the pressure drop.
The trial design should be satisfactory, so a plate heat exchanger could be considered
for this duty.
12.12.2. Welded plate
Welded plate heat exchangers use plates similar to those in gasketed plate exchangers but
the plate edges are sealed by welding. This increases the pressure and temperature rating
to up to 80 bar and temperatures in excess of 500Ž C. They retain the advantages of plate
heat exchangers (compact size and good rates of heat transfer) whilst giving security
against leakage. An obvious disadvantage is that the exchangers cannot be dismantled
for cleaning. So, their use is restricted to specialised applications where fouling is not a
problem. The plates are fabricated in a variety of materials.
A combination of gasketed and welded plate construction is also used. An aggressive
process fluid flowing between welded plates and a benign process stream, or service
stream, between gasketed plates.
12.12.3. Plate-fin
Plate-fin exchangers consist essentially of plates separated by corrugated sheets, which
form the fins. They are made up in a block and are often referred to as matrix exchangers;
see Figure 12.63. They are usually constructed of aluminium and joined and sealed by
brazing. The main application of plate-fin exchangers has been in the cryogenics industries, such as air separation plants, where large heat transfer surface areas are needed.
They are now finding wider applications in the chemical processes industry, where large
surface area, compact, exchangers are required. Their compact size and low weight have
lead to some use in off-shore applications. The brazed aluminium construction is limited
to pressures up to around 60 bar and temperatures up to 150Ž C. The units cannot be
mechanically cleaned, so their use is restricted to clean process and service steams. The
Figure 12.63.
Plate-fin exchanger
HEAT-TRANSFER EQUIPMENT
765
construction and design of plate-fin exchangers and their applications are discussed by
Saunders (1988) and Burley (1991), and their use in cryogenic service by Lowe (1987).
12.12.4. Spiral heat exchangers
A spiral heat exchanger can be considered as a plate heat exchanger in which the plates
are formed into a spiral. The fluids flow through the channels formed between the plates.
The exchanger is made up from long sheets, between 150 to 1800 mm wide, formed into
a pair of concentric spiral channels. The channels are closed by gasketed end-plates bolted
to an outer case. Inlet and outlet nozzles are fitted to the case and connect to the channels,
see Figure 12.64. The gap between the sheets varies between 4 to 20 mm; depending on
the size of the exchanger and the application. They can be fabricated in any material that
can be cold-worked and welded.
Figure 12.64.
Spiral heat exchanger
Spiral heat exchangers are compact units: a unit with around 250 m2 area occupying
a volume of approximately 10 m3 . The maximum operating pressure is limited to 20 bar
and the temperature to 400Ž C.
For a given duty, the pressure drop over a spiral heat exchanger will usually be lower
than that for the equivalent shell-and-tube exchanger. Spiral heat exchangers give true
counter-current flow and can be used where the temperature correction factor Ft for a
shell-and-tube exchanger would be too low; see Section 12.6. Because they are easily
cleaned and the turbulence in the channels is high, spiral heat exchangers can be used for
very dirty process fluids and slurries.
The correlations for flow in conduits can be used to estimate the heat transfer coefficient
and pressure drop in the channels; using the hydraulic mean diameter as the characteristic
dimension.
The design of spiral heat exchangers is discussed by Minton (1970)
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CHEMICAL ENGINEERING
12.13. DIRECT-CONTACT HEAT EXCHANGERS
In direct-contact heat exchange the hot and cold streams are brought into contact without
any separating wall, and high rates of heat transfer are achieved.
Applications include: reactor off-gas quenching, vacuum condensers, cooler-condensers,
desuperheating and humidification. Water-cooling towers are a particular example of
direct-contact heat exchange. In direct-contact cooler-condensers the condensed liquid
is frequently used as the coolant, Figure 12.65.
Gas
out
Gas
in
Figure 12.65.
Typical direct-contact cooler (baffle plates)
Direct-contact heat exchangers should be considered whenever the process stream and
coolant are compatible. The equipment used is basically simple and cheap, and is suitable
for use with heavily fouling fluids and with liquids containing solids; spray chambers,
spray columns, and plate and packed columns are used.
There is no general design method for direct contact exchangers. Most applications
will involve the transfer of latent heat as well as sensible heat, and the process is one of
simultaneous heat and mass transfer. When the approach to thermal equilibrium is rapid,
as it will be in many applications, the size of the contacting vessel is not critical and
the design can be based on experience with similar processes. For other situations the
designer must work from first principles, setting up the differential equations for mass
and heat transfer, and using judgement in making the simplifications necessary to achieve
a solution. The design procedures used are analogous to those for gas absorption and
distillation. The rates of heat transfer will be high; with coefficients for packed columns
typically in the range 2000 to 20,000 W/m3Ž C (i.e. per cubic meter of packing).
767
HEAT-TRANSFER EQUIPMENT
The design and application of direct-contact heat exchangers is discussed by Fair (1961,
1972a, 1972b), and Chen-Chia and Fair (1989), they give practical design methods and
data for a range of applications.
The design of water-cooling towers, and humidification, is covered in Volume 1,
Chapter 13. The same basic principles will apply to the design of other direct-contact
exchangers.
12.14. FINNED TUBES
Fins are used to increase the effective surface area of heat-exchanger tubing. Many
different types of fin have been developed, but the plain transverse fin shown in
Figure 12.66 is the most commonly used type for process heat exchangers. Typical fin
dimensions are: pitch 2.0 to 4.0 mm, height 12 to 16 mm; ratio of fin area to bare tube
area 15 : 1 to 20 : 1.
pf
lf
tf
Figure 12.66.
Finned tube
Finned tubes are used when the heat-transfer coefficient on the outside of the tube is
appreciably lower than that on the inside; as in heat transfer from a liquid to a gas, such
as in air-cooled heat exchangers.
The fin surface area will not be as effective as the bare tube surface, as the heat
has to be conducted along the fin. This is allowed for in design by the use of a fin
effectiveness, or fin efficiency, factor. The basic equations describing heat transfer from
a fin are derived in Volume 1, Chapter 9; see also Kern (1950). The fin effectiveness is
a function of the fin dimensions and the thermal conductivity of the fin material. Fins
are therefore usually made from metals with a high thermal conductivity; for copper and
aluminium the effectiveness will typically be between 0.9 to 0.95.
When using finned tubes, the coefficients for the outside of the tube in equation 12.2
are replaced by a term involving fin area and effectiveness:
1
1
1
1
1
Ao
C
D
C
⊲12.80⊳
ho
hod
Ef hf
hdf Af
where hf D heat-transfer coefficient based on the fin area,
768
CHEMICAL ENGINEERING
hdf
Ao
Af
Ef
D
D
D
D
fouling coefficient based on the fin area,
outside area of the bare tube,
fin area,
fin effectiveness.
It is not possible to give a general correlation for the coefficient hf covering all types of
fin and fin dimensions. Design data should be obtained from the tube manufacturers for
the particular type of tube to be used. Some information is given in Volume 1, Chapter 9.
For banks of tubes in cross flow, with plain transverse fins, the correlation given by Briggs
and Young (1963) can be used to make an approximate estimate of the fin coefficient.
pf tf 0.2 pf 0.1134
Nu D 0.134Re0.681 Pr 0.33
⊲12.81⊳
lf
tf
where pf D fin pitch,
lf D fin height,
tf D fin thickness.
The Reynolds number is evaluated for the bare tube (i.e. assuming that no fins exist).
Kern and Kraus (1972) give full details of the use of finned tubes in process heat
exchangers design and design methods.
Low fin tubes
Tubes with low transverse fins, about 1 mm high, can be used with advantage as replacements for plain tubes in many applications. The fins are formed by rolling, and the tube
outside diameters are the same as those for standard plain tubes. Details are given in the
manufacturer’s data books, Wolverine (1984) and an electronic version of their design
manual, www.wlv.com (2001); see also Webber (1960).
12.15. DOUBLE-PIPE HEAT EXCHANGERS
One of the simplest and cheapest types of heat exchanger is the concentric pipe
arrangement shown in Figure 12.67. These can be made up from standard fittings, and are
useful where only a small heat-transfer area is required. Several units can be connected
in series to extend their capacity.
Figure 12.67.
Double-pipe exchanger (constructed for weld fittings)
HEAT-TRANSFER EQUIPMENT
769
The correlation for forced convective heat transfer in conduits (equation 12.10) can be
used to predict the heat transfer coefficient in the annulus, using the appropriate equivalent
diameter:
4⊲d22 d21 ⊳
4 ð cross-sectional area
4 Dd d
de D
D
2
1
wetted perimeter
⊲d2 C d1 ⊳
where d2 is the inside diameter of the outer pipe and d1 the outside diameter of the
inner pipe.
Some designs of double-pipe exchanger use inner tubes fitted with longitudinal fins.
12.16. AIR-COOLED EXCHANGERS
Air-cooled exchangers should be considered when cooling water is in short supply or
expensive. They can also be competitive with water-cooled units even when water is
plentiful. Frank (1978) suggests that in moderate climates air cooling will usually be
the best choice for minimum process temperatures above 65Ž C, and water cooling for
minimum processes temperatures below 50Ž C. Between these temperatures a detailed
economic analysis would be necessary to decide the best coolant. Air-cooled exchangers
are used for cooling and condensing.
Air-cooled exchangers consist of banks of finned tubes over which air is blown or drawn
by fans mounted below or above the tubes (forced or induced draft). Typical units are
shown in Figure 12.68. Air-cooled exchangers are packaged units, and would normally
be selected and specified in consultation with the manufacturers. Some typical overall
coefficients are given in Table 12.1. These can be used to make an approximate estimate
of the area required for a given duty. The equation for finned tubes given in Section 12.14
can also be used.
The design and application of air-cooled exchangers is discussed by Rubin (1960),
Lerner (1972), Brown (1978) and Mukherjee (1997). Design procedures are also given
in the books by Kern (1950), Kern and Kraus (1972), and Kroger (2004). Lerner and
Brown give typical values for the overall coefficient for a range of applications and
provide methods for the preliminary sizing of air-cooled heat exchangers.
Details of the construction features of air-cooled exchangers are given by
Ludwig (1965). The construction features of air-cooled heat exchangers are covered by
the American Petroleum Institute standard, API 661.
12.17. FIRED HEATERS (FURNACES AND BOILERS)
When high temperatures and high flow rates are required, fired-heaters are used. Fired
heaters are directly heated by the products of combustion of a fuel. The capacity of fired
heaters ranges from 3 to 100 MW.
Typical applications of fired heaters are:
1. Process feed-stream heaters; such as the feed heaters for refinery crude columns
(pipe stills); in which up to 60 per cent of the feed may be vaporised.
2. Reboilers for columns, using relatively small size direct-fired units.
770
CHEMICAL ENGINEERING
3. Direct-fired reactors; for example, the pyrolysis of dichloroethane to form vinyl
chloride.
4. Reformers for hydrogen production, giving outlet temperatures of 800 900Ž C.
5. Steam boilers.
Finned
tubes
Hot
fluid in
Air
Fan
Tube supports
Hot
fluid out
Air
Air
Gear
Motor
(a)
Section-support
channels
Hot
fluid in
Tube supports
Air
Hot
fluid out
Fan
Support
Air
Motor
(b)
Figure 12.68.
Air-cooled exchangers
12.17.1. Basic construction
Many different designs and layouts are used, depending on the application, see
Bergman (1979a).
The basic construction consists of a rectangular or cylindrical steel chamber, lined with
refractory bricks. Tubes are arranged around the wall, in either horizontal or vertical banks.
The fluid to be heated flows through the tubes. Typical layouts are shown in Figure 12.69a,
b and c. A more detailed diagram of a pyrolysis furnace is given in Figure 12.70.
Heat transfer to the tubes on the furnace walls is predominantly by radiation. In modern
designs this radiant section is surmounted by a smaller section in which the combustion
HEAT-TRANSFER EQUIPMENT
Figure 12.69.
771
Fired heaters. (a) Vertical-cylindrical, all radiant (b) Vertical-cylindrical, helical coil (c) Verticalcylindrical with convection section
gases flow over banks of tubes and transfer heat by convection. Extended surface tubes,
with fins or pins, are used in the convection section to improve the heat transfer from the
combustion gases. Plain tubes are used in the bottom rows of the convection section to
act as a heat shield from the hot gases in the radiant section. Heat transfer in the shield
section will be by both radiation and convection. The tube sizes used will normally be
between 75 and 150 mm diameter. The tube size and number of passes used depending
on the application and the process-fluid flow-rate. Typical tube velocities will be from
1 to 2 m/s for heaters, with lower rates used for reactors. Carbon steel is used for low
temperature duties; stainless steel and special alloy steels for elevated temperatures. For
high temperatures, a material that resists creep must be used.
The burners are positioned at base or sides of radiant section. Gaseous and liquid fuels
are used. The combustion air may be preheated in tubes in the convection section.
12.17.2. Design
Computer programs for the design of fired heaters are available from commercial organisations; such as HTFS and HTRI, see Section 12.1. Manual calculation methods, suitable
for the preliminary design of fired heaters, are given by Kern (1950), Wimpress (1978)
and Evans (1980). A brief review of the factors to be considered is given in the following
sections.
772
CHEMICAL ENGINEERING
Stock
Root cover flange
for tube coil
removal
A
Inlet
Inlet
Tube
suspension
yoke
Convection
section
Outlet
(optional
at floor)
Explosion
door
Partition
walls
Outlet
Radiant
section
Sight
door
Positioning
guides
Burner
A
Sectional elevation
Figure 12.70.
Section A-A
(Foster Wheeler) Multi-zoned pyrolysis furnace
12.17.3. Heat transfer
Radiant section
Between 50 to 70 per cent of the total heat is transferred in the radiant section.
The gas temperature will depend on the fuel used and the amount of excess air. For
gaseous fuels around 20% excess air is normally used, and 25% for liquid fuels.
Radiant heat transfer from a surface is governed by the Stefan-Boltzman equation, see
Volume 1, Chapter 9.
qr D T4
⊲12.82⊳
where qr D radiant heat flux, W/m2
D Stephen-Boltzman constant, 5.67 ð 108 Wm2 K4
T D temperature of the surface, K.
For the exchange of heat between the combustion gases and the hot tubes the equation
can be written as:
Qr D ⊲˛Acp ⊳F⊲T4g T4t ⊳
⊲12.83⊳
HEAT-TRANSFER EQUIPMENT
773
where Qr D radiant heat transfer rate, W
Acp D the “cold-plane” area of the tubes
D number of tubes ð the exposed length ð tube pitch
˛ D the absorption efficiency factor
F D the radiation exchange factor
Tg D temperature of the hot gases, K
Tt D tube surface temperature, K
Part of the radiation from the hot combustion gases will strike the tubes and be absorbed,
and part will pass through the spaces between the tubes and be radiated back into the
furnace. If the tubes are in front of the wall, some of the radiation from the wall will also be
absorbed by the tubes. This complex situation is allowed for by calculating what is known
as the cold plane area of the tubes Acp , and then applying the absorption efficiency factor ˛
to allow for the fact that the tube area will not be as effective as a plane area. The absorption
efficiency factor is a function of the tube arrangement and will vary from around 0.4 for
widely spaced tubes, to 1.0 for the theoretical situation when the tubes are touching. It will
be around 0.7 to 0.8 when the pitch equals the tube diameter. Values for ˛ are available in
handbooks for a range of tube arrangements; see Perry et al. (1997), and Wimpress (1978).
The radiation exchange factor F depends on the arrangement of the surfaces and their
emissivity and absorptivity. Combustion gases are poor radiators, because only the carbon
dioxide and water vapour, about 20 to 25 per cent of the total, will emit radiation in the
thermal spectrum. For a fired heater the exchange factor will depend on the partial pressure
and emissivity of these gases, and the layout of the heater. The partial pressure is dependent
on the kind of fuel used, liquid or gas, and the amount of excess air. The gas emissivity is
a function of temperature. Methods for estimating the exchange factor for typical furnace
designs are given in the handbooks; see Perry et al. (1997), and Wimpress (1978).
The heat flux to the tubes in the radiant section will lie between 20 to 40 kW/m2 , for
most applications. A value of 30 kW/m2 can be used to make a rough estimate of the
tube area needed in this section.
A small amount of heat will be transferred to the tubes by convection in the radiant
section, but as the superficial velocity of the gases will be low, the heat transfer coefficient
will be low, around 10 Wm2 Ž C1 .
Convection section
The combustion gases flow across the tube banks in the convection section and the correlations for cross-flow in tube banks can be used to estimate the heat transfer coefficient.
The gas side coefficient will be low, and where extended surfaces are used an allowance
must be made for the fin efficiency. Procedures are given in the tube vendors literature,
and in handbooks, see Section 12.14, and Bergman (1978b).
The overall coefficient will depend on the gas velocity and temperature, and the tube
size. Typical values range from 20 to 50 Wm2 Ž C1 .
The lower tubes in the shield bank in the convection section will receive heat by
radiation from the radiant section. This can be allowed for by including the area of the
lower row of tubes with the tubes in the radiant section.
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CHEMICAL ENGINEERING
12.17.4. Pressure drop
Most of the pressure drop will occur in the convection section. The procedures for
estimating the pressure drop across banks of tubes can be used to estimate the pressure
drop in this section, see Section 12.9.4 and Volume 1, Chapter 9.
The pressure drop in the radiant section will be small compared with that across the
convection section and can usually be neglected.
12.17.5. Process-side heat transfer and pressure drop
The tube inside heat transfer coefficients and pressure drop can be calculated using the
conventional methods for flow inside tubes; see Section 12.8, and Volume 1, Chapter 9.
If the unit is being used as a vaporiser the existence of two-phase flow in some of the
tubes must be taken into account. Bergman (1978b) gives a quick method for estimating
two-phase pressure drop in the tubes of fired heaters.
Typical approach temperatures, flue gas to inlet process fluid, are around 100Ž C.
12.17.6. Stack design
Most fired heaters operate with natural draft, and the stack height must be sufficient to
achieve the flow of combustion air required and to remove the combustion products.
It is normal practice to operate with a slight vacuum throughout the heater, so that
air will leak in through sight-boxes and dampers, rather than combustion products leak
out. Typically, the aim would be to maintain a vacuum of around 2 mm water gauge just
below the convection section.
The stack height required will depend on the temperature of the combustion gases
leaving the convection section and the elevation of the site above sea level. The draft
arises from the difference in density of the hot gases and the surrounding air.
The draft in millimetres of water (mm H2 O) can be estimated using the equation:
1
1
Pd D 0.35⊲Ls ⊳⊲p0 ⊳
⊲12.84⊳
Ta
Tga
where Ls
p0
Ta
Tga
D
D
D
D
stack height, m
atmospheric pressure, millibar (N/m2 ð 102 )
ambient temperature, K
average flue-gas temperature, K
Because of heat losses, the temperature at the top of the stack will be around 80Ž C
below the inlet temperature.
The frictional pressure loss in the stack must be added to the loss in the heater when
estimating the stack draft required. This can be calculated using the usual methods for
pressure loss in circular conduits, see Section 12.8. The mass velocity in the stack will be
around 1.5 to 2 kg/m2 . These values can be used to determine the cross-section needed.
An approximate estimate of the pressure losses in the convection section can be made
by multiplying the velocity head (u2 /2g) by factors for each restriction; typical values are
given below:
HEAT-TRANSFER EQUIPMENT
0.2
1.0
0.5
1.0
1.5
775
0.5 for each row of plain tubes
2.0 for each row of finned tubes
for the stack entrance
for the stack exit
for the stack damper
12.17.7. Thermal efficiency
Modern fired heaters operate at thermal efficiencies of between 80 to 90 per cent,
depending on the fuel and the excess air requirement. In some applications additional
excess air may be used to reduce the flame temperature, to avoid overheating of the
tubes.
Where the inlet temperature of the process fluid is such that the outlet temperature from
the convection section would be excessive, giving low thermal efficiency, this excess heat
can be used to preheat the air to the furnace. Tubes would be installed above the process
fluid section in the convection section. Forced draft operation would be needed to drive
the air flow through the preheat section.
Heat losses from the heater casing are normally between 1.5 to 2.5 per cent of the
heat input.
12.18. HEAT TRANSFER TO VESSELS
The simplest way to transfer heat to a process or storage vessel is to fit an external jacket,
or an internal coil.
12.18.1. Jacketed vessels
Conventional jackets
The most commonly used type jacket is that shown in Figure 12.71. It consists of an outer
cylinder which surrounds part of the vessel. The heating or cooling medium circulates in
the annular space between the jacket and vessel walls and the heat is transferred through
the wall of the vessel. Circulation baffles are usually installed in the annular space to
increase the velocity of the liquid flowing through the jacket and improve the heat transfer
coefficient, see Figure 12.72a. The same effect can be obtained by introducing the fluid
through a series of nozzles spaced down the jacket. The momentum of the jets issuing
from the nozzles sets up a swirling motion in the jacket liquid; Figure 12.72d.
The spacing between the jacket and vessel wall will depend on the size of the vessel,
but will typically range from 50 mm for small vessels to 300 mm for large vessels.
Half-pipe jackets
Half-pipe jackets are formed by welding sections of pipe, cut in half along the longitudinal axis, to the vessel wall. The pipe is usually wound round the vessel in a helix;
Figure 12.72c.
776
CHEMICAL ENGINEERING
Figure 12.71.
Figure 12.72.
Jacketed vessel
Jacketed vessels. (a) Spirally baffled jacket (b) Dimple jacket (c) Half-pipe jacket (d) Agitation
nozzle
The pitch of the coils and the area covered can be selected to provide the heat transfer
area required. Standard pipe sizes are used; ranging from 60 to 120 mm outside diameter.
The half-pipe construction makes a strong jacket capable of withstanding pressure better
than the conventional jacket design.
HEAT-TRANSFER EQUIPMENT
777
Dimpled jackets
Dimpled jackets are similar to the conventional jackets but are constructed of thinner
plates. The jacket is strengthened by a regular pattern of hemispherical dimples pressed
into the plate and welded to the vessel wall, Figure 12.72b.
Jacket selection
Factors to consider when selecting the type of jacket to use are listed below:
1. Cost: in terms of cost the designs can be ranked, from cheapest to most expensive,
as:
simple, no baffles
agitation nozzles
spiral baffle
dimple jacket
half-pipe jacket
2. Heat transfer rate required: select a spirally baffled or half-pipe jacket if high rates
are required.
3. Pressure: as a rough guide, the pressure rating of the designs can be taken as:
jackets, up to 10 bar
dimpled jackets, up to 20 bar
half-pipe, up to 70 bar.
So, half-pipe jaclets would be used for high pressure.
Jacket heat transfer and pressure drop
The heat transfer coefficient to the vessel wall can be estimated using the correlations
for forced convection in conduits, such as equation 12.11. The fluid velocity and the path
length can be calculated from the geometry of the jacket arrangement. The hydraulic
mean diameter (equivalent diameter, de ) of the channel or half-pipe should be used as the
characteristic dimension in the Reynolds and Nusselt numbers; see Section 12.8.1.
In dimpled jackets a velocity of 0.6 m can be used to estimate the heat transfer coefficient. A method for calculating the heat transfer coefficient for dimpled jackets is given
by Makovitz (1971).
The coefficients for jackets using agitation nozzles will be similar to that given by using
baffles. A method for calculating the heat transfer coefficient using agitation nozzles is
given by Bolliger (1982).
To increase heat transfer rates, the velocity through a jacket can be increased by recirculating the cooling or heating liquid.
For simple jackets without baffles, heat transfer will be mainly by natural convection
and the heat transfer coefficient will range from 200 to 400 Wm2Ž C1 .
12.18.2. Internal coils
The simplest and cheapest form of heat transfer surface for installation inside a vessel is
a helical coil; see Figure 12.73. The pitch and diameter of the coil can be made to suit the
778
CHEMICAL ENGINEERING
Figure 12.73.
Internal coils
application and the area required. The diameter of the pipe used for the coil is typically
equal to Dv /30, where Dv is the vessel diameter. The coil pitch is usually around twice
the pipe diameter. Small coils can be self supporting, but for large coils some form of
supporting structure will be necessary. Single or multiple turn coils are used.
Coil heat transfer and pressure drop
The heat transfer coefficient at the inside wall and pressure drop through the coil can be
estimated using the correlations for flow through pipes; see Section 12.8 and Volume 1,
Chapters 3 and 9. Correlations for forced convection in coiled pipes are also given in the
Engineering Sciences Data Unit Design Guide, ESDU 78031 (2001).
12.18.3. Agitated vessels
Unless only small rates of heat transfer are required, as when maintaining the temperature
of liquids in storage vessels, some form of agitation will be needed. The various types
of agitator used for mixing and blending described in Chapter 10, Section 10.11.2, are
also used to promote heat transfer in vessels. The correlations used to estimate the heat
transfer coefficient to the vessel wall, or to the surface of coils, have the same form as
those used for forced convection in conduits, equation 12.10. The fluid velocity is replaced
by a function of the agitator diameter and rotational speed, D ð N, and the characteristic
dimension is the agitator diameter.
a
Nu D CRe Pr
b
w
c
⊲12.10⊳
779
HEAT-TRANSFER EQUIPMENT
For agitated vessels:
hv D
DC
kf
where hv
D
N
kf
Cp
D
D
D
D
D
D
D
ND2
a
Cp
kf
b
w
c
⊲12.85⊳
heat transfer coefficient to vessel wall or coil, Wm2 Ž C1
agitator diameter, m
agitator, speed, rps (revolutions per second)
liquid density, kg/m3
liquid thermal conductivity, Wm1 Ž C1
liquid specific heat capacity, J kg1 Ž C1
liquid viscosity, Nm2 s.
The values of constant C and the indices a, b and c depend on the type of agitator,
the use of baffles, and whether the transfer is to the vessel wall or to coils. Some typical
correlations are given below.
Baffles will normally be used in most applications.
1. Flat blade paddle, baffled or unbaffled vessel, transfer to vessel wall, Re < 4000:
0.14
0.67
0.33
⊲12.86a⊳
Nu D 0.36Re Pr
w
2. Flat blade disc turbine, baffled or unbaffled vessel, transfer to vessel wall, Re < 400:
0.14
Nu D 0.54Re0.67 Pr 0.33
⊲12.86b⊳
w
3. Flat blade disc turbine, baffled vessel, transfer to vessel wall, Re > 400:
0.14
⊲12.86c⊳
Nu D 0.74Re0.67 Pr 0.33
w
4. Propeller, 3 blades, transfer to vessel wall, Re > 5000:
0.14
Nu D 0.64Re0.67 Pr 0.33
w
5. Turbine, flat blades, transfer to coil, baffled, Re, 2000 700,000:
0.14
0.62
0.33
Nu D 1.10Re Pr
w
⊲12.86d⊳
⊲12.86e⊳
6. Paddle, flat blades, transfer to coil, baffled,
Nu D 0.87Re
0.62
Pr
0.33
w
0.14
⊲12.86f⊳
More comprehensive design data is given by: Uhl and Gray (1967), Wilkinson and
Edwards (1972), Penny (1983) and Fletcher (1987).
780
CHEMICAL ENGINEERING
Example 12.14
A jacketed, agitated reactor consists of a vertical cylinder 1.5 m diameter, with a
hemispherical base and a flat, flanged, top. The jacket is fitted to the cylindrical section
only and extends to a height of 1 m. The spacing between the jacket and vessel walls is
75 mm. The jacket is fitted with a spiral baffle. The pitch between the spirals is 200 mm.
The jacket is used to cool the reactor contents. The coolant used is chilled water at
10Ž C; flow-rate 32,500 kg/h, exit temperature 20Ž C.
Estimate the heat transfer coefficient at the outside wall of the reactor and the pressure
drop through the jacket.
Solution
The baffle forms a continuous spiral channel, section 75 mm ð 200 mm.
Number of spirals D height of jacket/pitch D
1
ð 103 D 5
200
Length of channel D 5 ð ð 1.5 D 23.6 m
Cross-sectional area of channel D ⊲75 ð 200⊳ ð 106 D 15 ð 103 m
4 ð cross-sectional area
wetted perimeter
4 ð ⊲75 ð 200⊳
D 109 mm
D
2⊲75 C 200⊳
Hydraulic mean diameter, de D
Physical properties at mean temperature of 15Ž C, from steam tables: D 999 kg/m3 ,
D 1.136 mNm2 s, Pr D 7.99, kf D 595 ð 103 Wm1 C1 .
Velocity through channel, u D
Re D
1
1
32,500
ð
ð
D 0.602 m/s
3600
999 15 ð 103
999 ð 0.602 ð 109 ð 103
D 57,705
1.136 ð 103
Chilled water is not viscous so use equation 12.11 with C D 0.023, and neglect the
viscosity correction term.
Nu D 0.023Re0.8 Pr 0.33
hj ð
⊲12.11⊳
3
109 ð 10
D 0.023⊲57,705⊳0.8 ⊲7.99⊳0.33
595 ð 103
hj D 1606 Wm2 Ž C1
Use equation 12.18 for estimating the pressure drop, taking the friction factor from
Figure 12.24. As the hydraulic mean diameter will be large compared to the roughness of
the jacket surface, the relative roughness will be comparable with that for heat exchanger
tubes. The relative roughness of pipes and channels and the effect on the friction factor
is covered in Volume 1, Chapter 3.
HEAT-TRANSFER EQUIPMENT
From Figure 12.24, for Re D 5.8 ð 104 , jf D 3.2 ð 103
2
L
u
P D 8jf
de
2
0.6022
3
3 23.6
ð 10
999 ð
P D 8 ð 3.2 ð 10
109
2
781
⊲12.18⊳
D 1003 N/m2
Example 12.15
The reactor described in Example 12.12 is fitted with a flat blade disc turbine agitator
0.6 m diameter, running at 120 rpm. The vessel is baffled and is constructed of stainless
steel plate 10 mm thick.
The physical properties of the reactor contents are:
D 850 kg/m3 , D 80 mNm2 s, kf D 400 ð 103 Wm1 Ž C1 ,
Cp D 2.65 kJ kg1 Ž C1 .
Estimate the heat transfer coefficient at the vessel wall and the overall coefficient in
the clean condition.
Solution
Agitator speed (revs per sec) D 1200/60 D 2 s1
Re D
Pr D
850 ð 2 ð 0.62
ND2
D 7650
D
80 ð 103
Cp
2.65 ð 103 ð 80 ð 103
D
D 530
kf
400 ð 103
For a flat blade turbine use equation 12.86c:
Nu D 0.74Re
0.67
Pr
0.33
w
0.14
Neglect the viscosity correction term:
h ð 0.6
D 0.74⊲7650⊳0.67 ⊲530⊳0.33
400 ð 103
h D 1564 Wm2 Ž C1
Taking the thermal conductivity of stainless steel as 16 Wm1 Ž C1 and the jacket
coefficient from Example 12.12.
1
1
10 ð 103
1
D
C
C
U
1606
16
1564
U D 530 Wm2 Ž C1
782
CHEMICAL ENGINEERING
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Engineering Sciences Data Unit Reports
ESDU 73031 (1973) Convective heat transfer during crossflow of fluids over plain tube banks.
ESDU 78031 (2001) Internal forced convective heat transfer in coiled pipes.
ESDU 83038 (1984) Baffled shell-and-tube heat exchangers: flow distribution, pressure drop and heat transfer
coefficient on the shellside.
ESDU 84023 (1985) Shell-and-tube exchangers: pressure drop and heat transfer in shellside downflow condensation.
ESDU 87019 (1987) Flow induced vibration in tube bundles with particular reference to shell and tube heat
exchangers.
ESDU 92003 (1993) Forced convection heat transfer in straight tubes. Part 1: turbulent flow.
ESDU 93018 (2001) Forced convection heat transfer in straight tubes. Part 2: laminar and transitional flow.
ESDU 98003 98007 (1998) Design and performance evaluation of heat exchangers: the effectiveness-NTU
method.
ESDU International plc, 27 Corsham Street, London N1 6UA, UK.
American Petroleum Institute Standards
API 661 Air-Cooled Heat Exchangers for General Refinery Service.
Bibliography
AZBEL, D. Heat Transfer Application in Process Engineering (Noyles, 1984).
CHEREMISINOFF, N. P. (ed.) Handbook of Heat and Mass Transfer, 2 vols (Gulf, 1986).
FRAAS, A. P. Heat Exchanger Design, 2nd edn (Wiley, 1989).
GUNN, D. and HORTON, R. Industrial Boilers (Longmans, 1989).
GUPTA, J. P. Fundamentals of Heat Exchanger and Pressure Vessel Technology (Hemisphere, 1986).
KAKAC, S. (ed.) Boilers, Evaporators, and Condensers (Wiley, 1991)
KAKAC, S., BERGLES, A. E. and MAYINGER, F. (eds) Heat Exchangers: thermal-hydraulic fundamentals and
design (Hemisphere, 1981).
McKETTA, J. J. (ed.) Heat Transfer Design Methods (Marcel Dekker, 1990).
PALEN, J. W, (ed.) Heat Exchanger Source Book (Hemisphere, 1986).
PODHORSSKY, M. and KRIPS, H. Heat Exchangers: A Practical Approach to Mechanical Construction, Design,
and Calculations (Begell House, 1998).
SAUNDERS, E. A. D. Heat Exchangers (Longmans, 1988).
786
CHEMICAL ENGINEERING
SCHLUNDER, E. U. (ed.) Heat Exchanger Design Handbook, 5 volumes with supplements (Hemisphere, 1983).
SHAH, R. K. and SEKULIC, D. P. Fundamentals of Heat Exchanger Design (Wiley, 2003).
SHAH, R. K., SUBBARAO, E. C. and MASHELKAR, R. A. (eds) Heat Transfer Equipment Design (Hemisphere,
1988).
SINGH, K. P. Theory and Practice of Heat Exchanger Design (Hemisphere, 1989).
SINGH, K. P. and SOLER, A. I. Mechanical Design of Heat Exchanger and Pressure Vessel Components (Arcturus,
1984).
SMITH, R. A. Vaporisers: selection, design and operation (Longmans, 1986).
WALKER, G. Industrial Heat Exchangers (McGraw-Hill, 1982).
YOKELL, S. A Working Guide to Shell and Tube Heat Exchangers (McGraw-Hill, 1990).
12.20. NOMENCLATURE
Dimensions
in MLTq
A
Acp
Ao
Af
AL
Ao
Ap
As
Asb
Atb
a
Bc
Bb
b
C
Cp
Cpg
CpL
c
cs
ct
D
Db
Ds
Dv
de
di
dpt
do
d1
d2
Ef
F
Fb
F0b
FL
F0L
Fn
Ft
Fw
fc
Heat transfer area
Cold-plane area of tubes
Clearance area between bundle and shell
Fin area
Total leakage area
Outside area of bare tube
Area of a port plate heat exchanger
Cross-flow area between tubes
Shell-to-baffle clearance area
Tube-to-baffle clearance area
Index in equation 12.10
Baffle cut
Bundle cut
Index in equation 12.10
Constant in equation 12.10
Heat capacity at constant pressure
Heat capacity of gas
Heat capacity of liquid phase
Index in equation 12.10
Shell-to-baffle diametrical clearance
Tube-to-baffle diametrical clearance
Agitator diameter
Bundle diameter
Shell diameter
Vessel diameter
Equivalent diameter
Tube inside diameter
Diameter of the ports in the plates of a plate heat exchanger
Tube outside diameter
Outside diameter of inner of concentric tubes
Inside diameter of outer of concentric tubes
Fin efficiency
Radiation exchange factor
Bypass correction factor, heat transfer
Bypass correction factor, pressure drop
Leakage correction factor, heat transfer
Leakage correction factor, pressure drop
Tube row correction factor
Log mean temperature difference correction factor
Window effect correction factor
Two-phase flow factor
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2
L2 T2 q1
L2 T2 q1
L2 T2 q1
L
L
L
L
L
L
L
L
L
L
L
L
HEAT-TRANSFER EQUIPMENT
fm
fs
G
Gp
Gs
Gt
g
Hb
Hc
Hs
Ht
hc
⊲hc ⊳1
⊲hc ⊳b
⊲hc ⊳Nr
⊲hc ⊳v
⊲hc ⊳BK
⊲hc ⊳s
hc0
hcb
hcg
hdf
hf
hfb
0
hfc
hg0
hi
hi0
hid
hnb
0
hnb
ho
hoc
hod
hp
hs
hv
jh
jH
jf
K1
K2
Kb
kf
kL
kv
kw
L0
LP
Ls
lB
lf
N
Nb
Nc
Temperature correction factor for mixtures
Nucleate boiling suppression factor
Total mass flow-rate per unit area
Mass flow-rate per unit cross-sectional area between plates
Shell-side mass flow-rate per unit area
Tube-side mass flow-rate per unit area
Gravitational acceleration
Height from baffle chord to top of tube bundle
Baffle cut height
Sensible heat of stream
Total heat of stream (sensible + latent)
Heat-transfer coefficient in condensation
Mean condensation heat-transfer coefficient for a single tube
Heat-transfer coefficient for condensation on a horizontal tube bundle
Mean condensation heat-transfer coefficient for a tube in a row of tubes
Heat-transfer coefficient for condensation on a vertical tube
Condensation coefficient from Boko-Kruzhilin correlation
Condensation heat transfer coefficient for stratified flow in tubes
Local condensing film coefficient, partial condenser
Convective boiling-heat transfer coefficient
Local effective cooling-condensing heat-transfer coefficient, partial condenser
Fouling coefficient based on fin area
Heat-transfer coefficient based on fin area
Film boiling heat-transfer coefficient
Forced-convection coefficient in equation 12.67
Local sensible-heat-transfer coefficient, partial condenser
Film heat-transfer coefficient inside a tube
Inside film coefficient in Boyko-Kruzhilin correlation
Fouling coefficient on inside of tube
Nucleate boiling-heat-transfer coefficient
Nucleate boiling coefficient in equation 12.67
Heat-transfer coefficient outside a tube
Heat-transfer coefficient for cross flow over an ideal tube bank
Fouling coefficient on outside of tube
Heat-transfer coefficient in a plate heat exchanger
Shell-side heat-transfer coefficient
Heat transfer coefficient to vessel wall or coil
Heat transfer factor defined by equation 12.14
Heat-transfer factor defined by equation 12.15
Friction factor
Constant in equation 12.3, from Table 12.4
Constant in equation 12.61
Constant in equation 12.74
Thermal conductivity of fluid
Thermal conductivity of liquid
Thermal conductivity of vapour
Thermal conductivity of tube wall material
Effective tube length
Path length in a plate heat exchanger
Stack height
Baffle spacing (pitch)
Fin height
Rotational speed
Number of baffles
Number of tubes in cross flow zone
787
ML2 T1
ML2 T1
ML2 T1
ML2 T1
LT2
L
L
ML2 T3
ML2 T3
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MT3 q1
MLT3 q1
MLT3 q1
MLT3 q1
MLT3 q1
L
L
L
L
L
T1
788
N0c
Nc v
Np
Nr
Ns
Nt
Nw
Nw v
P
Pc
Pd
Pc
Pe
Pi
Pp
Ppt
Ps
Pt
Pw
p0
pi
ps
pt
p0t
pw
Q
Qg
Qt
q
q0
qc
qcb
qr
R
Ra
Ra0
Rw
S
T
T
Ta
Tg
Tga
Tr
Ts
Tsat
Tt
Tv
Tw
T1
T2
T
Tlm
Tm
Ts
t
tc
CHEMICAL ENGINEERING
Number of tube rows crossed from end to end of shell
Number of constrictions crossed
Number of passes, plate heat exchanger
Number of tubes in a vertical row
Number of sealing strips
Number of tubes in a tube bundle
Number of tubes in window zone
Number of restrictions for cross flow in window zone
Total pressure
Critical pressure
Stack draft
Pressure drop in cross flow zone⊲1⊳
Pressure drop in end zone⊲1⊳
Pressure drop for cross flow over ideal tube bank⊲1⊳
Pressure drop in a plate heat exchanger⊲1⊳
Pressure loss through the ports in a plate heat exchanger⊲1⊳
Shell-side pressure drop⊲1⊳
Tube-side pressure drop⊲1⊳
Pressure drop in window zone⊲1⊳
Atmospheric pressure
Fin pitch
Saturation vapour pressure
Tube pitch
Vertical tube pitch
Saturation vapour pressure corresponding to wall temperature
Heat transferred in unit time
Sensible-heat-transfer rate from gas phase
Total heat-transfer rate from gas phase
Heat flux (heat-transfer rate per unit area)
Uncorrected value of flux from Figure 12.59
Maximum (critical) flux for a single tube
Maximum flux for a tube bundle
Radiant heat flux
Dimensionless temperature ratio defined by equation 12.6
Ratio of window area to total area
Ratio of bundle cross-sectional area in window zone to total cross-sectional
area of bundle
Ratio number of tubes in window zones to total number
Dimensionless temperature ratio defined by equation 12.7
Shell-side temperature
Temperature of surface
Ambient temperature
Temperature of combustion gases
Average flue-gas temperature
Reduced temperature
Saturation temperature
Saturation temperature
Tube surface temperature
Vapour (gas) temperature
Wall (surface) temperature
Shell-side inlet temperature
Shell-side exit temperature
Temperature difference
Logarithmic mean temperature difference
Mean temperature difference in equation 12.1
Temperature change in vapour (gas) stream
Tube-side temperature
Local coolant temperature
ML1 T2
ML1 T2
L
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
L
ML1 T2
L
L
ML1 T2
ML2 T3
ML2 T3
ML2 T3
MT3
MT3
MT3
MT3
MT3
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
HEAT-TRANSFER EQUIPMENT
Fin thickness
Tube-side inlet temperature
Tube-side exit temperature
Overall heat-transfer coefficient
Uncorrected overall coefficient, equation 12.72
Corrected overall coefficient, equation 12.72
Overall heat-transfer coefficient based on tube outside area
Fluid velocity
Liquid velocity, equation 12.55
Fluid velocity in a plate heat exchanger
Velocity through the ports of a plate heat exchanger
Velocity through channels of a plate heat exchanger
Shell-side fluid velocity
Tube-side fluid velocity
Vapour velocity, equation 12.55
Maximum vapour velocity in kettle reboiler
Velocity in window zone
Geometric mean velocity
Mass flow-rate of fluid
Mass flow through the channels and ports in a plate heat exchanger
Total condensate mass flow-rate
Shell-side fluid mass flow-rate
Lockhart-Martinelli two-phase flow parameter
Mass fraction of vapour
Ratio of change in sensible heat of gas stream to change in total heat of
gas stream (sensible + latent)
˛
Absorption efficiency factor
˛
Factor in equation 12.30
ˇL
Factor in equation 12.31, for heat transfer
ˇL0
Factor in equation 12.31, for pressure drop
b
Angle subtended by baffle chord
Latent heat
Viscosity at bulk fluid temperature
L
Liquid viscosity
v
Vapour viscosity
w
Viscosity at wall temperature
Fluid density
L
Liquid density
v
Vapour density
Stephen-Boltzman constant
Surface tension
Tube loading
h
Condensate loading on a horizontal tube
v
Condensate loading on a vertical tube
Dimensionless numbers
Nu
Nusselt number
Pr
Prandtl number
Prc
Prandtl number for condensate film
Re
Reynolds number
Reynolds number for condensate film
Rec
ReL
Reynolds number for liquid phase
St
Stanton number
tf
t1
t2
U
U0
Uc
Uo
u
uL
up
upt
up
us
ut
uv
uO v
uw
uz
W
w
Wc
Ws
Xtt
x
Z
789
L
q
q
MT3 q1
MT3 q1
MT3 q1
MT3 q1
LT1
LT1
LT1
LT1
LT1
LT1
LT1
LT1
LT1
LT1
LT1
MT1
MT1
MT1
MT1
L2 T2
ML1 T1
ML1 T1
ML1 T1
ML1 T1
ML3
ML3
ML3
MT3 q4
MT2
ML1 T1
ML1 T1
ML1 T1
(1) Note: in Volumes 1 and 2 this symbol is used for pressure difference, and pressure drop (negative pressure
gradient) indicated by a minus sign. In this chapter, as the symbol is only used for pressure drop, the minus
sign has been omitted for convenience.
790
CHEMICAL ENGINEERING
12.21. PROBLEMS
12.1 A solution of sodium hydroxide leaves a dissolver at 80Ž C and is to be cooled
to 40Ž C, using cooling water. The maximum flow-rate of the solution will be
8000 kg/h. The maximum inlet temperature of the cooling water will be 20Ž C
and the temperature rise is limited to 20Ž C.
Design a double-pipe exchanger for this duty, using standard carbon steel pipe and
fittings. Use pipe of 50 mm inside diameter, 55 mm outside diameter for the inner
pipe, and 75 mm inside diameter pipe for the outer. Make each section 5 m long.
The physical properties of the caustic solution are:
temperature, Ž C
specific heat, kJkg1Ž C1
density, kg/m3
thermal conductivity, Wm1Ž C1
viscosity, mN m2 s
40
3.84
992.2
0.63
1.40
80
3.85
971.8
0.67
0.43
12.2. A double-pipe heat exchanger is to be used to heat 6000 kg/h of 22 mol per cent
hydrochloric acid. The exchanger will be constructed from karbate (impervious
carbon) and steel tubing. The acid will flow through the inner, karbate, tube
and saturated steam at 100Ž C will be used for heating. The tube dimensions
will be: karbate tube inside diameter 50 mm, outside diameter 60 mm; steel tube
inside diameter 100 mm. The exchanger will be constructed in sections, with an
effective length of 3 m each.
How many sections will be needed to heat the acid from 15 to 65Ž C?
Physical properties of 22 % HCl at 40Ž C: specific heat 4.93 kJkg1Ž C1 , thermal
conductivity 0.39 Wm1Ž C1 , density 866 kg/m3 .
Viscosity:
temperature
mN m2 s
20
0.68
30
0.55
40
0.44
50
0.36
60
0.33
70Ž C
0.30
Karbate thermal conductivity 480 Wm1Ž C1 .
12.3. In a food processing plant there is a requirement to heat 50,000 kg/h of towns
water from 10 to 70Ž C. Steam at 2.7 bar is available for heating the water.
An existing heat exchanger is available, with the following specification:
Shell inside diameter 337 mm, E type.
Baffles 25 per cent cut, set at a spacing of 106 mm.
Tubes 15 mm inside diameter, 19 mm outside diameter, 4094 mm long.
Tube pitch 24 mm, triangular.
Number of tubes 124, arranged in a single pass.
Would this exchanger be suitable for the specified duty?
12.4. Design a shell and tube exchanger to heat 50,000 kg/h of liquid ethanol from
20Ž C to 80Ž C. Steam at 1.5 bar is available for heating. Assign the ethanol to the
tube-side. The total pressure drop must not exceed 0.7 bar for the alcohol stream.
Plant practice requires the use of carbon steel tubes, 25 mm inside diameter,
29 mm outside diameter, 4 m long.
791
HEAT-TRANSFER EQUIPMENT
Set out your design on a data sheet and make a rough sketch of the heat exchanger.
The physical properties of ethanol can be readily found in the literature.
12.5. 4500 kg/h of ammonia vapour at 6.7 bara pressure is to be cooled from 120Ž C
to 40Ž C, using cooling water. The maximum supply temperature of the cooling
water available is 30Ž C, and the outlet temperature is to be restricted to 40Ž C.
The pressure drops over the exchanger must not exceed 0.5 bar for the ammonia
stream and 1.5 bar for the cooling water.
A contractor has proposed using a shell and tube exchanger with the following
specification for this duty.
Shell: E-type, inside diameter 590 mm.
Baffles: 25 per cent cut, 300 mm spacing.
Tubes: carbon steel, 15 mm inside diameter, 19 mm outside diameter, 2400 mm
long, number 360.
Tube arrangement: 8 passes, triangular tube pitch, pitch 23.75 mm.
Nozzles: shell 150 mm inside diameter, tube headers 75 mm inside diameter.
It is proposed to put the cooling water though the tubes.
Is the proposed design suitable for the duty?
Physical properties of ammonia at the mean temperature of 80Ž C:
specific heat 2.418 kJkg1Ž C1 , thermal conductivity 0.0317 Wm1Ž C1 ,
density 4.03 kg/m3 , viscosity 1.21 ð 105 N m2 s.
12.6. A vaporiser is required to evaporate 10,000 kg/h of a process fluid, at 6 bar. The
liquid is fed to the vaporiser at 20Ž C.
The plant has a spare kettle reboiler available with the following specification.
U-tube bundle, 50 tubes, mean length 4.8 m, end to end.
Carbon steel tubes, inside diameter 25 mm, outside diameter 30 mm, square pitch
45 mm.
Steam at 1.7 bara will be used for heating.
Check if this reboiler would be suitable for the duty specified. Only check the
thermal design. You may take it that the shell will handle the vapour rate.
Take the physical properties of the process fluid as:
liquid: density 535 kg/m3 , specific heat 2.6 kJkg1Ž C1 , thermal conductivity
0.094 Wm1Ž C1 , viscosity 0.12 mN m2 s, surface tension 0.85 N/m, heat of
vaporisation 322 kJ/kg.
Vapour density 14.4 kg/m3 .
Vapour pressure:
temperatureŽ C
pressure bar
50
5.0
60
6.4
70
8.1
80
10.1
90
12.5
100
15.3
110
18.5
120
20.1
12.7. A condenser is required to condense n-propanol vapour leaving the top of a
distillation column. The n-propanol is essentially pure, and is a saturated vapour
at a pressure of 2.1 bara. The condensate needs to be sub-cooled to 45Ž C.
Design a horizontal shell and tube condenser capable of handling a vapour rate
of 30,000 kg/h. Cooling water is available at 30Ž C and the temperature rise is to
be limited to 30Ž C. The pressure drop on the vapour stream is to be less than
50 kN/m2 , and on the water stream less than 70 kN/m2 . The preferred tube size
is 16 mm inside diameter, 19 mm outside diameter, and 2.5 m long.
792
CHEMICAL ENGINEERING
Take the saturation temperature of n-propanol at 2.1 bar as 118Ž C. The other
physical properties required can be found in the literature, or estimated.
12.8. Design a vertical shell and tube condenser for the duty given in question 12.7.
Use the same preferred tube size.
12.9. In the manufacture of methyl ethyl ketone (MEK) from 2-butanol, the reactor
products are precooled and then partially condensed in a shell and tube exchanger.
A typical analysis of the stream entering the condenser is, mol fractions: MEK
0.47, unreacted alcohol 0.06, hydrogen 0.47. Only 85 per cent of the MEK and
alcohol are condensed. The hydrogen is non-condensable.
The vapours enter the condenser at 125Ž C and the condensate and uncondensed
material leave at 27Ž C. The condenser pressure is maintained at 1.1 bara.
Make a preliminary design of this condenser, for a feed rate of 1500 kg/h. Chilled
water will be used as the coolant, at an inlet temperature of 10Ž C and allowable
temperature rise of 30Ž C.
Any of the physical properties of the components not available in Appendix C,
or the general literature, should be estimated.
12.10. A vertical thermosyphon reboiler is required for a column. The liquid at the base
of the column is essentially pure n-butane. A vapour rate of 5 kg/s is required.
The pressure at the base of the column is 20.9 bar. Saturated steam at 5 bar will
be used for heating.
Estimate the number of 25 mm outside diameter, 22 mm inside diameter, 4 m
long, tubes needed.
At 20.9 bar the saturation temperature of n-butane is 117Ž C and the heat of
vaporisation 828 kJ/kg.
12.11. An immersed bundle vaporiser is to be used to supply chlorine vapour to a
chlorination reactor, at a rate of 10,000 kg/h. The chlorine vapour is required at
5 bar pressure. The minimum temperature of the chlorine feed will be 10Ž C. Hot
water at 50Ž C is available for heating. The pressure drop on the water side must
not exceed 0.8 bar.
Design a vaporiser for this duty. Use stainless steel U-tubes, 6 m long, 21 mm
inside diameter, 25 mm outside diameter, on a square pitch of 40 mm.
The physical properties of chlorine at 5 bar are:
saturation temperature 10Ž C, heat of vaporisation 260 kJ/kg, specific heat
0.99 kJkg1Ž C1 , thermal conductivity 0.13 Wm1Ž C1 , density 1440 kg/m3 ,
viscosity 0.3 mN m2 s, surface tension 0.013 N/m, vapour density 16.3 kg/m3 .
The vapour pressure can be estimated from the equation:
Ln⊲P⊳ D 9.34 1978/⊲T C 246⊳;
P bar, TŽ C
12.12. There is a requirement to cool 200,000 kg/h of a dilute solution of potassium
carbonate from 70 to 30Ž C. Cooling water will be used for cooling, with inlet and
outlet temperatures of 20 and 60Ž C. A gasketed-plate heat exchanger is available
with the following specification:
Number of plates 329.
Effective plate dimensions: length 1.5 m, width 0.5 m, thickness 0.75 mm.
HEAT-TRANSFER EQUIPMENT
793
Channel width 3 mm.
Flow arrangement two pass: two pass.
Port diameters 150 mm.
Check if this exchanger is likely to be suitable for the thermal duty required, and
estimate the pressure drop for each stream.
Take the physical properties of the dilute potassium carbonate solution to be the
same as those for water.
CHAPTER 13
Mechanical Design of Process
Equipment
13.1. INTRODUCTION
This chapter covers those aspects of the mechanical design of chemical plant that are
of particular interest to chemical engineers. The main topic considered is the design of
pressure vessels. The design of storage tanks, centrifuges and heat-exchanger tube sheets
are also discussed briefly.
The chemical engineer will not usually be called on to undertake the detailed mechanical
design of a pressure vessel. Vessel design is a specialised subject, and will be carried out
by mechanical engineers who are conversant with the current design codes and practices,
and methods of stress analysis. However, the chemical engineer will be responsible for
developing and specifying the basic design information for a particular vessel, and needs
to have a general appreciation of pressure vessel design to work effectively with the
specialist designer.
The basic data needed by the specialist designer will be:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Vessel function.
Process materials and services.
Operating and design temperature and pressure.
Materials of construction.
Vessel dimensions and orientation.
Type of vessel heads to be used.
Openings and connections required.
Specification of heating and cooling jackets or coils.
Type of agitator.
Specification of internal fittings.
A data sheet for pressure vessel design is given in Appendix G.
There is no strict definition of what constitutes a pressure vessel, but it is generally
accepted that any closed vessel over 150 mm diameter subject to a pressure difference of
more than 0.5 bar should be designed as a pressure vessel.
It is not possible to give a completely comprehensive account of vessel design in one
chapter. The design methods and data given should be sufficient for the preliminary design
of conventional vessels. Sufficient for the chemical engineer to check the feasibility of
a proposed equipment design; to estimate the vessel cost for an economic analysis; and
to determine the vessel’s general proportions and weight for plant layout purposes. For
a more detailed account of pressure vessel design the reader should refer to the books
794
MECHANICAL DESIGN OF PROCESS EQUIPMENT
795
by Singh and Soler (1992), Escoe (1994) and Moss (1987). Other useful books on the
mechanical design of process equipment are listed in the bibliography at the end of this
chapter.
An elementary understanding of the principles of the “Strength of Materials” (Mechanics
of Solids) will be needed to follow this chapter. Readers who are not familiar with the
subject should consult one of the many textbooks available; such as those by Case et al.
(1999), Mott, R. L. (2001), Seed (2001) and Gere and Timoshenko (2000).
13.1.1. Classification of pressure vessels
For the purposes of design and analysis, pressure vessels are sub-divided into two classes
depending on the ratio of the wall thickness to vessel diameter: thin-walled vessels, with
a thickness ratio of less than 1 : 10; and thick-walled above this ratio.
The principal stresses (see Section 13.3.1) acting at a point in the wall of a vessel, due
to a pressure load, are shown in Figure 13.1. If the wall is thin, the radial stress 3 will
be small and can be neglected in comparison with the other stresses, and the longitudinal
and circumferential stresses 1 and 2 can be taken as constant over the wall thickness. In
a thick wall, the magnitude of the radial stress will be significant, and the circumferential
stress will vary across the wall. The majority of the vessels used in the chemical and
allied industries are classified as thin-walled vessels. Thick-walled vessels are used for
high pressures, and are discussed in Section 13.15.
σ3
σ1
σ2
σ2
σ1
σ3
Figure 13.1.
Principal stresses in pressure-vessel wall
13.2. PRESSURE VESSEL CODES AND STANDARDS
In all the major industrialised countries the design and fabrication of thin-walled pressure
vessels is covered by national standards and codes of practice. In most countries the
standards and codes are legally enforceable.
In the United Kingdom all conventional pressure vessels for use in the chemical
and allied industries will invariably be designed and fabricated according to the British
Standard PD 5500 or the European Standard EN 13445; or an equivalent code such as
the American Society of Mechanical Engineers code Section VIII (the ASME code). The
codes and standards cover design, materials of construction, fabrication (manufacture and
796
CHEMICAL ENGINEERING
workmanship), and inspection and testing. They form a basis of agreement between the
manufacturer and customer, and the customer’s insurance company.
In the European Union the design, manufacture and use of pressure systems is also
covered by the Pressure Equipment Directive (Council Directive 97/23/EC) whose use
became mandatory in May 2002.
The current (2003) edition of PD 5500 covers vessels fabricated in carbon and alloy
steels, and aluminium. The design of vessels constructed from reinforced plastics is
covered by BS 4994. The ASME code covers steels, non-ferrous metals, and fibrereinforced plastics.
Where national codes are not available, the British, European or American codes would
be used.
Information and guidance on the pressure vessel codes can be found on the Internet;
www.bsi-global.com.
A comprehensive review of the ASME code is given by Chuse and Carson (1992) and
Yokell (1986); see also Perry et al. (1997).
The national codes and standards dictate the minimum requirements, and give general
guidance for design and construction; any extension beyond the minimum code requirement will be determined by agreement between the manufacturer and customer.
The codes and standards are drawn up by committees of engineers experienced in
vessel design and manufacturing techniques, and are a blend of theory, experiment and
experience. They are periodically reviewed, and revisions issued to keep abreast of developments in design, stress analysis, fabrication and testing. The latest version of the appropriate national code or standard should always be consulted before undertaking the design
of any pressure vessel.
Computer programs to aid in the design of vessels to PD 5500 and the ASME code are
available from several commercial organisations and can be found by making a search of
the World Wide Web.
13.3. FUNDAMENTAL PRINCIPLES AND EQUATIONS
This section has been included to provide a basic understanding of the fundamental
principles that underlie the design equations given in the sections that follow. The
derivation of the equations is given in outline only. A full discussion of the topics covered
can be found in any text on the “Strength of Materials” (Mechanics of Solids).
13.3.1. Principal stresses
The state of stress at a point in a structural member under a complex system of loading is
described by the magnitude and direction of the principal stresses. The principal stresses
are the maximum values of the normal stresses at the point; which act on planes on which
the shear stress is zero. In a two-dimensional stress system, Figure 13.2, the principal
stresses at any point are related to the normal stresses in the x and y directions x and y
and the shear stress xy at the point by the following equation:
Principal stresses, 1 , 2 D 12 ⊲y C x ⊳ š
1
2
2 ]
[⊲y x ⊳2 C 4xy
⊲13.1⊳
MECHANICAL DESIGN OF PROCESS EQUIPMENT
797
σy
τxy
σx
σx
τxy
σy
Figure 13.2.
Two-dimensional stress system
The maximum shear stress at the point is equal to half the algebraic difference between
the principal stresses:
Maximum shear stress D 12 ⊲1 2 ⊳
⊲13.2⊳
Compressive stresses are conventionally taken as negative; tensile as positive.
13.3.2. Theories of failure
The failure of a simple structural element under unidirectional stress (tensile or
compressive) is easy to relate to the tensile strength of the material, as determined in
a standard tensile test, but for components subjected to combined stresses (normal and
shear stress) the position is not so simple, and several theories of failure have been
proposed. The three theories most commonly used are described below:
Maximum principal stress theory: which postulates that a member will fail when one of
the principal stresses reaches the failure value in simple tension, e0 . The failure point in
a simple tension is taken as the yield-point stress, or the tensile strength of the material,
divided by a suitable factor of safety.
Maximum shear stress theory: which postulates that failure will occur in a complex
stress system when the maximum shear stress reaches the value of the shear stress at
failure in simple tension.
For a system of combined stresses there are three shear stresses maxima:
1 2
⊲13.3a⊳
1 D
2
2 3
⊲13.3b⊳
2 D
2
3 1
⊲13.3c⊳
3 D
2
0
In the tensile test,
e D e
⊲13.4⊳
2
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CHEMICAL ENGINEERING
The maximum shear stress will depend on the sign of the principal stresses as well as
their magnitude, and in a two-dimensional stress system, such as that in the wall of a
thin-walled pressure vessel, the maximum value of the shear stress may be that given by
putting 3 D 0 in equations 13.3b and c.
The maximum shear stress theory is often called Tresca’s, or Guest’s, theory.
Maximum strain energy theory: which postulates that failure will occur in a complex
stress system when the total strain energy per unit volume reaches the value at which
failure occurs in simple tension.
The maximum shear-stress theory has been found to be suitable for predicting the
failure of ductile materials under complex loading and is the criterion normally used in
the pressure-vessel design.
13.3.3. Elastic stability
Under certain loading conditions failure of a structure can occur not through gross yielding
or plastic failure, but by buckling, or wrinkling. Buckling results in a gross and sudden
change of shape of the structure; unlike failure by plastic yielding, where the structure
retains the same basic shape. This mode of failure will occur when the structure is
not elastically stable: when it lacks sufficient stiffness, or rigidity, to withstand the
load. The stiffness of a structural member is dependent not on the basic strength of
the material but on its elastic properties (E and v) and the cross-sectional shape of the
member.
The classic example of failure due to elastic instability is the buckling of tall thin
columns (struts), which is described in any elementary text on the “Strength of Materials”.
For a structure that is likely to fail by buckling there will be a certain critical value
of load below which the structure is stable; if this value is exceeded catastrophic failure
through buckling can occur.
The walls of pressure vessels are usually relatively thin compared with the other dimensions and can fail by buckling under compressive loads.
Elastic buckling is the decisive criterion in the design of thin-walled vessels under
external pressure.
13.3.4. Membrane stresses in shells of revolution
A shell of revolution is the form swept out by a line or curve rotated about an axis. (A
solid of revolution is formed by rotating an area about an axis.) Most process vessels are
made up from shells of revolution: cylindrical and conical sections; and hemispherical,
ellipsoidal and torispherical heads; Figure 13.3.
The walls of thin vessels can be considered to be “membranes”; supporting loads
without significant bending or shear stresses; similar to the walls of a balloon.
The analysis of the membrane stresses induced in shells of revolution by internal
pressure gives a basis for determining the minimum wall thickness required for vessel
shells. The actual thickness required will also depend on the stresses arising from the
other loads to which the vessel is subjected.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.3.
799
Typical vessel shapes
Consider the shell of revolution of general shape shown in Figure 13.4, under a loading
that is rotationally symmetric; that is, the load per unit area (pressure) on the shell is
constant round the circumference, but not necessarily the same from top to bottom.
Let P
t
1
2
D
D
D
D
pressure,
thickness of shell,
the meridional (longitudinal) stress, the stress acting along a meridian,
the circumferential or tangential stress, the stress acting along parallel circles
(often called the hoop stress),
r1 D the meridional radius of curvature,
r2 D circumferential radius of curvature.
Note: the vessel has a double curvature; the values of r1 and r2 are determined by
the shape.
Consider the forces acting on the element defined by the points a, b, c, d. Then the
normal component (component acting at right angles to the surface) of the pressure force
on the element
d2
d1
2r2 sin
D P 2r1 sin
2
2
This force is resisted by the normal component of the forces associated with the membrane
stresses in the walls of the vessel (given by, force = stress ð area)
D 22 tdS1 sin
d2
2
C 21 t dS2 sin
d1
2
Equating these forces and simplifying, and noting that in the limit d/2 ! dS/2r, and
sin d ! d, gives:
1
2
P
⊲13.5⊳
C
D
r1
r2
t
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CHEMICAL ENGINEERING
Figure 13.4(a)(b).
Stress in a shell of revolution (c)(d). Forces acting on sides of element abcd
MECHANICAL DESIGN OF PROCESS EQUIPMENT
801
An expression for the meridional stress 1 can be obtained by considering the equilibrium
of the forces acting about any circumferential line, Figure 13.5. The vertical component
of the pressure force
D P⊲r2 sin ⊳2
Figure 13.5.
Meridional stress, force acting at a horizontal plane
This is balanced by the vertical component of the force due to the meridional stress acting
in the ring of the wall of the vessel
D 21 t⊲r2 sin ⊳ sin
Equating these forces gives:
1 D
Pr2
2t
⊲13.6⊳
Equations 13.5 and 13.6 are completely general for any shell of revolution.
Cylinder (Figure 13.6a)
A cylinder is swept out by the rotation of a line parallel to the axis of revolution, so:
r1 D 1
D
r2 D
2
where D is the cylinder diameter.
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CHEMICAL ENGINEERING
Figure 13.6.
Shells of revolution
Substitution in equations 13.5 and 13.6 gives:
2 D
PD
2t
⊲13.7⊳
1 D
PD
4t
⊲13.8⊳
Sphere (Figure 13.6b)
r1 D r2 D
hence:
1 D 2 D
D
2
PD
4t
⊲13.9⊳
MECHANICAL DESIGN OF PROCESS EQUIPMENT
803
Cone (Figure 13.6c)
A cone is swept out by a straight line inclined at an angle ˛ to the axis.
r1 D 1
r
r2 D
cos ˛
substitution in equations 13.5 and 13.6 gives:
Pr
t cos ˛
Pr
1 D
2t cos ˛
2 D
⊲13.10⊳
⊲13.11⊳
The maximum values will occur at r D D2 /2.
Ellipsoid (Figure 13.6d)
For an ellipse with major axis 2a and minor axis 2b, it can be shown that (see any standard
geometry text):
r 3 b2
r1 D 2 4
a
From equations 13.5 and 13.6
Pr2
2t
r22
P
r2
2 D
t
2r1
1 D
(equation 13.6)
⊲13.12⊳
At the crown (top)
r1 D r2 D
a2
b
1 D 2 D
Pa2
2tb
⊲13.13⊳
At the equator (bottom) r2 D a, so r1 D b2 /a
so
Pa
2t
2
P
a2
Pa
1a
2 D
a 2
D
1 2 2
t
2b /a
t
b
1 D
⊲13.13⊳
⊲13.14⊳
It should be noted that if 12 ⊲a/b⊳2 > 1, 2 will be negative (compressive) and the shell
could fail by buckling. This consideration places a limit on the practical proportions of
ellipsoidal heads.
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CHEMICAL ENGINEERING
Torus (Figure 13.6e)
A torus is formed by rotating a circle, radius r2 , about an axis.
Pr2
2t
R0 C r2 sin
R
D
r1 D
sin
sin
Pr2
r2 sin
2 D
1
t
2⊲R0 C r2 sin ⊳
1 D
and
(equation 13.6)
⊲13.15⊳
On the centre line of the torus, point c, D 0 and
2 D
Pr2
t
At the outer edge, point a, D /2, sin D 1 and
Pr2 2R0 C r2
2 D
2t R0 C r2
the minimum value.
At the inner edge, point b, D 3/2, sin D 1 and
Pr2 2R0 r2
2 D
2t R0 r2
⊲13.16⊳
⊲13.17⊳
⊲13.18⊳
the maximum value.
So 2 varies from a maximum at the inner edge to a minimum at the outer edge.
Torispherical heads
A torispherical shape, which is often used as the end closure of cylindrical vessels, is
formed from part of a torus and part of a sphere, Figure 13.7. The shape is close to that
of an ellipse but is easier and cheaper to fabricate.
In Figure 13.7 Rk is the knuckle radius (the radius of the torus) and Rc the crown radius
(the radius of the sphere). For the spherical portion:
1 D 2 D
For the torus:
1 D
PRc
2t
PRk
2t
⊲13.19⊳
⊲13.20⊳
2 depends on the location, and is a function of Rc and Rk ; it can be calculated from
equations 13.15 and 13.9.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.7.
805
Torisphere
The ratio of the knuckle radius to crown radius should be made not less than 6/100 to
avoid buckling. The stress will be higher in the torus section than the spherical section.
13.3.5. Flat plates
Flat plates are used as covers for manholes, as blind flanges, and for the ends of small
diameter and low pressure vessels.
For a uniformly loaded circular plate supported at its edges, the slope at any radius
x is given by:
dw
1 Px 3
C1 x C2
D
D
C
C
⊲13.21⊳
dx
D 16
2
x
(The derivation of this equation can be found in any text on the strength of materials.)
Integration gives the deflection w:
wD
where P
x
D
t
E
D
D
D
D
D
D
Px 4
x2
C1 C2 ln x C C3
64D
4
⊲13.22⊳
intensity of loading (pressure),
radial distance to point of interest,
flexual rigidity of plate D ⊲Et3 ⊳/⊲12⊲1 2 ⊳⊳,
plate thickness,
Poisson’s ratio for the material,
modulus of elasticity of the material (Young’s modulus).
C1 , C2 , C3 are constants of integration which can be obtained from the boundary conditions at the edge of the plate.
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CHEMICAL ENGINEERING
Two limiting situations are possible:
1. When the edge of the plate is rigidly clamped, not free to rotate; which corresponds
to a heavy flange, or a strong joint.
2. When the edge is free to rotate (simply supported); corresponding to a weak joint,
or light flange.
1. Clamped edges (Figure 13.8a)
The edge (boundary) conditions are:
D 0 at x D 0
D 0 at x D a
w D 0 at x D a
where a is the radius of the plate.
Which gives:
C2 D 0,
C1 D
Pa2
,
8D
and C3 D
Pa4
64D
hence
Px 2
⊲a x 2 ⊳
16D
P
wD
⊲x 2 a2 ⊳2
64D
D
and
⊲13.23⊳
⊲13.24⊳
The maximum deflection will occur at the centre of the plate at x D 0
wO D
Pa4
64D
⊲13.25⊳
The bending moments per unit length due to the pressure load are related to the slope
and deflection by:
d
M1 D D
⊲13.26⊳
C
dx
x
d
M2 D D
C
⊲13.27⊳
x
dx
Where M1 is the moment acting along cylindrical sections, and M2 that acting along
diametrical sections.
Substituting for and d/dx in equations 13.26 and 13.27 gives:
P 2
[a ⊲1 C ⊳ x 2 ⊲3 C ⊳]
16
P 2
M2 D
[a ⊲1 C ⊳ x 2 ⊲1 C 3⊳]
16
M1 D
⊲13.28⊳
⊲13.29⊳
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.8.
807
Flat circular plates (a) Clamped edges (b) Simply supported
The maximum values will occur at the edge of the plate, x D a.
O1D
M
Pa2
,
8
O 2 D
M
Pa2
8
The bending stress is given by:
b D
M1
t
ð
I0
2
where I0 D second moment of area per unit length D t3 /12, hence
O b D
2
O1
6M
3 Pa
D
4 t2
t2
⊲13.30⊳
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CHEMICAL ENGINEERING
2. Simply supported plate (Figure 13.8b)
The edge (boundary) conditions are:
D 0 at x D 0
w D 0 at x D a
M1 D 0 at x D a (free to rotate)
which gives C2 and C3 D 0.
Hence
D
1 Px 3
C1 x
C
D 16
2
and
C1
1 3Px 2
d
C
D
dx
D 16
2
Substituting these values in equation 13.26, and equating to zero at x D a, gives:
C1 D
Pa2 ⊲3 C ⊳
8D ⊲1 C ⊳
and hence
M1 D
P
⊲3 C ⊳⊲a2 x 2 ⊳
16
⊲13.31⊳
The maximum bending moment will occur at the centre, where M1 D M2
so
and
O1DM
O2D
M
O b D
P⊲3 C ⊳a2
16
O1
Pa2
6M
3
D
⊲3
C
⊳
8
t2
t2
⊲13.32⊳
⊲13.33⊳
General equation for flat plates
A general equation for the thickness of a flat plate required to resist a given pressure load
can be written in the form:
P
t D CD
⊲13.34⊳
f
where f D the maximum allowable stress (the design stress),
D D the effective plate diameter,
C D a constant, which depends on the edge support.
The limiting value of C can be obtained from equations 13.30 and 13.33. Taking Poisson’s
ratio as 0.3, a typical value for steels, then if the edge can be taken as completely rigid
C D 0.43, and if it is essentially free to rotate C D 0.56.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
809
13.3.6. Dilation of vessels
Under internal pressure a vessel will expand slightly. The radial growth can be calculated
from the elastic strain in the radial direction. The principal strains in a two-dimensional
system are related to the principal stresses by:
1
⊲1 2 ⊳
E
1
ε2 D ⊲2 1 ⊳
E
ε1 D
⊲13.35⊳
⊲13.36⊳
The radial (diametrical strain) will be the same as the circumferential strain ε2 . For any
shell of revolution the dilation can be found by substituting the appropriate expressions
for the circumferential and meridional stresses in equation 13.36.
The diametrical dilation D Dε1 .
For a cylinder
PD
4t
PD
2 D
2t
1 D
substitution in equation 13.36 gives:
c D
PD2
⊲2 ⊳
4tE
⊲13.37⊳
For a sphere (or hemisphere)
1 D 2 D
and
s D
PD
4t
PD2
⊲1 ⊳
4tE
⊲13.38⊳
So for a cylinder closed by a hemispherical head of the same thickness the difference in
dilation of the two sections, if they were free to expand separately, would be:
c s D
PD2
4tE
13.3.7. Secondary stresses
In the stress analysis of pressure vessels and pressure vessel components stresses are
classified as primary or secondary. Primary stresses can be defined as those stresses
that are necessary to satisfy the conditions of static equilibrium. The membrane stresses
induced by the applied pressure and the bending stresses due to wind loads are examples
of primary stresses. Primary stresses are not self-limiting; if they exceed the yield point
of the material, gross distortion, and in the extreme situation, failure of the vessel
will occur.
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CHEMICAL ENGINEERING
Secondary stresses are those stresses that arise from the constraint of adjacent parts
of the vessel. Secondary stresses are self-limiting; local yielding or slight distortion will
satisfy the conditions causing the stress, and failure would not be expected to occur in
one application of the loading. The “thermal stress” set up by the differential expansion
of parts of the vessel, due to different temperatures or the use of different materials,
is an example of a secondary stress. The discontinuity that occurs between the head
and the cylindrical section of a vessel is a major source of secondary stress. If free,
the dilation of the head would be different from that of the cylindrical section (see
Section 13.3.6); they are constrained to the same dilation by the welded joint between
the two parts. The induced bending moment and shear force due to the constraint give
rise to secondary bending and shear stresses at the junction. The magnitude of these
discontinuity stresses can be estimated by analogy with the behaviour of beams on
elastic foundations; see Hetenyi (1958) and Harvey (1974). The estimation of the stresses
arising from discontinuities is covered in the books by Bednar (1990), and Jawad and
Farr (1989).
Other sources of secondary stresses are the constraints arising at flanges, supports, and
the change of section due to reinforcement at a nozzle or opening (see Section 13.6).
Though secondary stresses do not affect the “bursting strength” of the vessel, they are
an important consideration when the vessel is subject to repeated pressure loading. If local
yielding has occurred, residual stress will remain when the pressure load is removed, and
repeated pressure cycling can lead to fatigue failure.
13.4. GENERAL DESIGN CONSIDERATIONS: PRESSURE
VESSELS
13.4.1. Design pressure
A vessel must be designed to withstand the maximum pressure to which it is likely to be
subjected in operation.
For vessels under internal pressure, the design pressure is normally taken as the pressure
at which the relief device is set. This will normally be 5 to 10 per cent above the normal
working pressure, to avoid spurious operation during minor process upsets. When deciding
the design pressure, the hydrostatic pressure in the base of the column should be added
to the operating pressure, if significant.
Vessels subject to external pressure should be designed to resist the maximum differential pressure that is likely to occur in service. Vessels likely to be subjected to vacuum
should be designed for a full negative pressure of 1 bar, unless fitted with an effective,
and reliable, vacuum breaker.
13.4.2. Design temperature
The strength of metals decreases with increasing temperature (see Chapter 7) so the
maximum allowable design stress will depend on the material temperature. The design
temperature at which the design stress is evaluated should be taken as the maximum
working temperature of the material, with due allowance for any uncertainty involved in
predicting vessel wall temperatures.
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MECHANICAL DESIGN OF PROCESS EQUIPMENT
13.4.3. Materials
Pressure vessels are constructed from plain carbon steels, low and high alloy steels, other
alloys, clad plate, and reinforced plastics.
Selection of a suitable material must take into account the suitability of the material
for fabrication (particularly welding) as well as the compatibility of the material with the
process environment.
The pressure vessel design codes and standards include lists of acceptable materials;
in accordance with the appropriate material standards.
13.4.4. Design stress (nominal design strength)
For design purposes it is necessary to decide a value for the maximum allowable stress
(nominal design strength) that can be accepted in the material of construction.
This is determined by applying a suitable “design stress factor” (factor of safety) to the
maximum stress that the material could be expected to withstand without failure under
standard test conditions. The design stress factor allows for any uncertainty in the design
methods, the loading, the quality of the materials, and the workmanship.
For materials not subject to high temperatures the design stress is based on the yield
stress (or proof stress), or the tensile strength (ultimate tensile stress) of the material at
the design temperature.
For materials subject to conditions at which the creep is likely to be a consideration,
the design stress is based on the creep characteristics of the material: the average stress to
produce rupture after 105 hours, or the average stress to produce a 1 per cent strain after
105 hours, at the design temperature. Typical design stress factors for pressure components
are shown in Table 13.1.
Table 13.1.
Design stress factors
Property
Minimum yield
stress or 0.2 per
cent proof stress,
at the design
temperature
Minimum tensile
strength, at room
temperature
Mean stress to
produce rupture
at 105 h at the
design temperature
Material
Carbon
Carbon-manganese,
low alloy steels
Austenitic
stainless
steels
Non-ferrous
metals
1.5
1.5
1.5
2.35
2.5
4.0
1.5
1.5
1.0
In the British Standard, PD 5500, the nominal design strengths (allowable design
stresses), for use with the design methods given, are listed in the standard, for the range
812
CHEMICAL ENGINEERING
of materials covered by the standard. The standard should be consulted for the principles
and design stress factors used in determining the nominal design strengths.
Typical design stress values for some common materials are shown in Table 13.2. These
may be used for preliminary designs. The standards and codes should be consulted for
the values to be used for detailed vessel design.
Table 13.2. Typical design stresses for plate
(The appropriate material standards should be consulted for particular grades and plate thicknesses)
Material
Carbon steel
(semi-killed or
silicon killed)
Carbon-manganese steel
(semi-killed or
silicon killed)
Carbon-molybdenum
steel, 0.5
per cent Mo
Low alloy steel
(Ni, Cr, Mo, V)
Stainless steel
18Cr/8Ni
unstabilised (304)
Stainless steel
18Cr/8Ni
Ti stabilised (321)
Stainless steel
18Cr/8Ni
Mo 2 21 per cent
(316)
Design stress at temperature ° C (N/mm2 )
Tensile
strength
(N/mm2 )
0 to 50
100
150
200
250
300
350
400
360
135
125
115
105
95
85
80
70
460
180
170
150
140
130
115
105
100
450
180
170
145
140
130
120
110
110
550
240
240
240
240
240
235
230
510
165
145
130
115
110
105
540
165
150
140
135
130
520
175
150
135
120
115
450
500
220
190
170
100
100
95
90
130
125
120
120
115
110
105
105
100
95
13.4.5. Welded joint efficiency, and construction categories
The strength of a welded joint will depend on the type of joint and the quality of the
welding.
The soundness of welds is checked by visual inspection and by non-destructive testing
(radiography).
The possible lower strength of a welded joint compared with the virgin plate is usually
allowed for in design by multiplying the allowable design stress for the material by a
“welded joint factor” J. The value of the joint factor used in design will depend on the
type of joint and amount of radiography required by the design code. Typical values are
shown in Table 13.3. Taking the factor as 1.0 implies that the joint is equally as strong
as the virgin plate; this is achieved by radiographing the complete weld length, and
cutting out and remaking any defects. The use of lower joint factors in design, though
saving costs on radiography, will result in a thicker, heavier, vessel, and the designer
must balance any cost savings on inspection and fabrication against the increased cost of
materials.
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MECHANICAL DESIGN OF PROCESS EQUIPMENT
Table 13.3.
Maximum allowable joint efficiency
Type of joint
Double-welded butt
or equivalent
Single-weld butt
joint with bonding strips
Degree of radiography
100
per cent
spot
none
1.0
0.85
0.7
0.9
0.80
0.65
The national codes and standards divide vessel construction into different categories,
depending on the amount of non-destructive testing required. The higher categories require
100 per cent radiography of the welds, and allow the use of highest values for the weldjoint factors. The lower-quality categories require less radiography, but allow only lower
joint-efficiency factors, and place restrictions on the plate thickness and type of materials
that can be used. The highest category will invariably be specified for process-plant
pressure vessels.
The standards should be consulted to determine the limitations and requirements of
the construction categories specified. Welded joint efficiency factors are not used, as
such, in the design equations given in BS PD 5500; instead limitations are placed on the
values of the nominal design strength (allowable design stress) for materials in the lower
construction category. The standard specifies three construction categories:
Category 1: the highest class, requires 100 per cent non-destructive testing (NDT) of
the welds; and allows the use of all materials covered by the standard, with no restriction
on the plate thickness.
Category 2: requires less non-destructive testing but places some limitations on the
materials which can be used and the maximum plate thickness.
Category 3: the lowest class, requires only visual inspection of the welds, but is
restricted to carbon and carbon-manganese steels, and austenitic stainless steel; and limits
are placed on the plate thickness and the nominal design stress. For carbon and carbonmanganese steels the plate thickness is restricted to less than 13 mm and the design
stress is about half that allowed for categories 1 and 2. For stainless steel the thickness
is restricted to less than 25 mm and the allowable design stress is around 80 per cent of
that for the other categories.
13.4.6. Corrosion allowance
The “corrosion allowance” is the additional thickness of metal added to allow for material
lost by corrosion and erosion, or scaling (see Chapter 7). The allowance to be used should
be agreed between the customer and manufacturer. Corrosion is a complex phenomenon,
and it is not possible to give specific rules for the estimation of the corrosion allowance
required for all circumstances. The allowance should be based on experience with the
material of construction under similar service conditions to those for the proposed design.
For carbon and low-alloy steels, where severe corrosion is not expected, a minimum
allowance of 2.0 mm should be used; where more severe conditions are anticipated this
should be increased to 4.0 mm. Most design codes and standards specify a minimum
allowance of 1.0 mm.
814
CHEMICAL ENGINEERING
13.4.7. Design loads
A structure must be designed to resist gross plastic deformation and collapse under all
the conditions of loading. The loads to which a process vessel will be subject in service
are listed below. They can be classified as major loads, that must always be considered in
vessel design, and subsidiary loads. Formal stress analysis to determine the effect of the
subsidiary loads is only required in the codes and standards where it is not possible to
demonstrate the adequacy of the proposed design by other means; such as by comparison
with the known behaviour of existing vessels.
Major loads
1.
2.
3.
4.
5.
6.
Design pressure: including any significant static head of liquid.
Maximum weight of the vessel and contents, under operating conditions.
Maximum weight of the vessel and contents under the hydraulic test conditions.
Wind loads.
Earthquake (seismic) loads.
Loads supported by, or reacting on, the vessel.
Subsidiary loads
1. Local stresses caused by supports, internal structures and connecting pipes.
2. Shock loads caused by water hammer, or by surging of the vessel contents.
3. Bending moments caused by eccentricity of the centre of the working pressure
relative to the neutral axis of the vessel.
4. Stresses due to temperature differences and differences in the coefficient expansion
of materials.
5. Loads caused by fluctuations in temperature and pressure.
A vessel will not be subject to all these loads simultaneously. The designer must determine
what combination of possible loads gives the worst situation, and design for that loading
condition.
13.4.8. Minimum practical wall thickness
There will be a minimum wall thickness required to ensure that any vessel is sufficiently
rigid to withstand its own weight, and any incidental loads. As a general guide the wall
thickness of any vessel should not be less than the values given below; the values include
a corrosion allowance of 2 mm:
Vessel diameter (m)
Minimum thickness (mm)
1
to
to
to
to
5
7
9
10
12
1
2
2.5
3.0
2
2.5
3.0
3.5
815
MECHANICAL DESIGN OF PROCESS EQUIPMENT
13.5. THE DESIGN OF THIN-WALLED VESSELS UNDER
INTERNAL PRESSURE
13.5.1. Cylinders and spherical shells
For a cylindrical shell the minimum thickness required to resist internal pressure can
be determined from equation 13.7; the cylindrical stress will be the greater of the two
principal stresses.
If Di is internal diameter and e the minimum thickness required, the mean diameter
will be ⊲Di C e⊳; substituting this for D in equation 13.7 gives:
eD
Pi ⊲Di C e⊳
2f
where f is the design stress and Pi the internal pressure. Rearranging gives:
eD
Pi Di
2f Pi
⊲13.39⊳
This is the form of the equation given in the British Standard PD 5500.
An equation for the minimum thickness of a sphere can be obtained from equation 13.9:
eD
Pi Di
4f Pi
⊲13.40⊳
The equation for a sphere given in BS 5500 is:
eD
Pi Di
4f 1.2Pi
⊲13.41⊳
The equation given in the British Standard PD 5500 differs slightly from equation 13.40,
as it is derived from the formula for thick-walled vessels; see Section 13.15.
If a welded joint factor is used equations 13.39 and 13.40 are written:
eD
eD
and
Pi Di
2Jf Pi
Pi Di
4Jf 1.2Pi
⊲13.39a⊳
⊲13.40b⊳
where J is the joint factor.
Any consistent set of units can be used for equations 13.39a to 13.40b.
13.5.2. Heads and closures
The ends of a cylindrical vessel are closed by heads of various shapes. The principal
types used are:
1.
2.
3.
4.
Flat plates and formed flat heads; Figure 13.9.
Hemispherical heads; Figure 13.10a.
Ellipsoidal heads; Figure 13.10b.
Torispherical heads; Figure 13.10c.
816
Figure 13.9.
CHEMICAL ENGINEERING
Flat-end closures (a) Flanged plate (b) Welded plate (c) Welded plate (d) Bolted cover
(e) Bolted cover
Hemispherical, ellipsoidal and torispherical heads are collectively referred to as domed
heads. They are formed by pressing or spinning; large diameters are fabricated from
formed sections. Torispherical heads are often referred to as dished ends.
The preferred proportions of domed heads are given in the standards and codes.
Choice of closure
Flat plates are used as covers for manways, and as the channel covers of heat exchangers.
Formed flat ends, known as “flange-only” ends, are manufactured by turning over a flange
with a small radius on a flat plate, Figure 13.9a. The corner radius reduces the abrupt
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.10.
817
Domed heads (a) Hemispherical (b) Ellipsoidal (c) Torispherical
change of shape, at the junction with the cylindrical section; which reduces the local
stresses to some extent: “Flange-only” heads are the cheapest type of formed head to
manufacture, but their use is limited to low-pressure and small-diameter vessels.
Standard torispherical heads (dished ends) are the most commonly used end closure for
vessels up to operating pressures of 15 bar. They can be used for higher pressures, but
above 10 bar their cost should be compared with that of an equivalent ellipsoidal head.
Above 15 bar an ellipsoidal head will usually prove to be the most economical closure
to use.
A hemispherical head is the strongest shape; capable of resisting about twice the
pressure of a torispherical head of the same thickness. The cost of forming a hemispherical
head will, however, be higher than that for a shallow torispherical head. Hemispherical
heads are used for high pressures.
13.5.3. Design of flat ends
Though the fabrication cost is low, flat ends are not a structurally efficient form, and very
thick plates would be required for high pressures or large diameters.
The design equations used to determine the thickness of flat ends are based on the
analysis of stresses in flat plates; Section 13.3.5.
818
CHEMICAL ENGINEERING
The thickness required will depend on the degree of constraint at the plate periphery.
The minimum thickness required is given by:
e D C p De
Pi
f
⊲13.42⊳
where Cp D a design constant, dependent on the edge constraint,
De D nominal plate diameter,
f D design stress.
Any consistent set of units can be used.
Values for the design constant Cp and the nominal plate diameter De are given in the
design codes and standards for various arrangements of flat end closures.
The values of the design constant and nominal diameter for the typical designs shown
in Figure 13.9 are given below:
(a)
Flanged-only end, for diameters less than 0.6 m and corner radii at least equal to
0.25e, Cp can be taken as 0.45; De is equal to Di .
(b, c) Plates welded to the end of the shell with a fillet weld, angle of fillet 45Ž and depth
equal to the plate thickness, take Cp as 0.55 and De D Di .
(d) Bolted cover with a full face gasket (see Section 13.10), take Cp D 0.4 and De
equal to the bolt circle diameter.
(e)
Bolted end cover with a narrow-face gasket, take Cp D 0.55 and De equal to the
mean diameter of the gasket.
13.5.4. Design of domed ends
Design equations and charts for the various types of domed heads are given in the codes
and standards and should be used for detailed design. The codes and standards cover both
unpierced and pierced heads. Pierced heads are those with openings or connections. The
head thickness must be increased to compensate for the weakening effect of the holes
where the opening or branch is not locally reinforced (see Section 13.6).
For convenience, simplified design equations are given in this section. These are
suitable for the preliminary sizing of unpierced heads and for heads with fully compensated openings or branches.
Hemispherical heads
It can be seen by examination of equations 13.7 and 13.9, that for equal stress in the
cylindrical section and hemispherical head of a vessel the thickness of the head need
only be half that of the cylinder. However, as the dilation of the two parts would then be
different, discontinuity stresses would be set up at the head and cylinder junction. For no
difference in dilation between the two parts (equal diametrical strain) it can be shown that
for steels (Poisson’s ratio D 0.3) the ratio of the hemispherical head thickness to cylinder
819
MECHANICAL DESIGN OF PROCESS EQUIPMENT
thickness should be 7/17. However, the stress in the head would then be greater than that
in the cylindrical section; and the optimum thickness ratio is normally taken as 0.6; see
Brownell and Young (1959).
Ellipsoidal heads
Most standard ellipsoidal heads are manufactured with a major and minor axis ratio of
2 : 1. For this ratio, the following equation can be used to calculate the minimum thickness
required:
Pi Di
⊲13.43⊳
eD
2Jf 0.2Pi
Torispherical heads
There are two junctions in a torispherical end closure: that between the cylindrical section
and the head, and that at the junction of the crown and the knuckle radii. The bending
and shear stresses caused by the differential dilation that will occur at these points must
be taken into account in the design of the heads. One approach taken is to use the basic
equation for a hemisphere and to introduce a stress concentration, or shape, factor to
allow for the increased stress due to the discontinuity. The stress concentration factor is
a function of the knuckle and crown radii.
eD
Pi Rc Cs
2fJ C Pi ⊲Cs 0.2⊳
where Cs D stress concentration factor for torispherical heads D 41 ⊲3 C
Rc D crown radius,
Rk D knuckle radius.
⊲13.44⊳
Rc /Rk ⊳,
The ratio of the knuckle to crown radii should not be less than 0.06, to avoid buckling;
and the crown radius should not be greater than the diameter of the cylindrical section.
Any consistent set of units can be used with equations 13.43 and 13.44. For formed heads
(no joints in the head) the joint factor J is taken as 1.0.
Flanges (skirts) on domed heads
Formed domed heads are made with a short straight cylindrical section, called a flange or
skirt; Figure 13.10. This ensures that the weld line is away from the point of discontinuity
between the head and the cylindrical section of the vessel.
13.5.5. Conical sections and end closures
Conical sections (reducers) are used to make a gradual reduction in diameter from one
cylindrical section to another of smaller diameter.
Conical ends are used to facilitate the smooth flow and removal of solids from process
equipment; such as, hoppers, spray-dryers and crystallisers.
820
CHEMICAL ENGINEERING
From equation 13.10 it can be seen that the thickness required at any point on a cone
is related to the diameter by the following expression:
eD
Pi Dc
1
.
2fJ Pi cos ˛
⊲13.45⊳
where Dc is the diameter of the cone at the point,
˛ D half the cone apex angle.
This equation will only apply at points away from the cone to cylinder junction. Bending
and shear stresses will be caused by the different dilation of the conical and cylindrical
sections. This can be allowed for by introducing a stress concentration factor, in a similar
manner to the method used for torispherical heads,
eD
Cc Pi Dc
2fJ Pi
⊲13.46⊳
The design factor Cc is a function of the half apex angle ˛:
˛
Cc
20Ž
1.00
30Ž
1.35
45Ž
2.05
60Ž
3.20
A formed section would normally be used for the transition between a cylindrical
section and conical section; except for vessels operating at low pressures, or under
hydrostatic pressure only. The transition section would be made thicker than the conical
or cylindrical section and formed with a knuckle radius to reduce the stress concentration at the transition, Figure 13.11. The thickness at the knuckle can be calculated
using equation 13.46, and that for the conical section away from the transition from
equation 13.45.
Di
14° max
ek
Knuckle radius
Lk
Dc
ec
Figure 13.11.
α
Conical transition section
821
MECHANICAL DESIGN OF PROCESS EQUIPMENT
The length of the thicker section Lk depends on the cone angle and is given by:
Lk D
Di e k
4 cos ˛
⊲13.47⊳
where ek is the thickness at the knuckle.
Design procedures for conical sections are given in the codes and standards.
Example 13.1
2m
Estimate the thickness required for the component parts of the vessel shown in the
diagram. The vessel is to operate at a pressure of 14 bar (absolute) and temperature
of 300Ž C. The material of construction will be plain carbon steel. Welds will be fully
radiographed. A corrosion allowance of 2 mm should be used.
1.5 m
Nominal
dimensions
Solution
Design pressure, take as 10 per cent above operating pressure,
D ⊲14 1⊳ ð 1.1
D 14.3 bar
D 1.43 N/mm2
Design temperature 300Ž C.
From Table 13.2, typical design stress D 85 N/mm2 .
Cylindrical section
eD
1.43 ð 1.5 ð 103
D 12.7 mm
2 ð 85 1.43
add corrosion allowance 12.7 C 2 D 14.7
say 15 mm plate
⊲13.39⊳
822
CHEMICAL ENGINEERING
Domed head
(i) Try a standard dished head (torisphere):
crown radius Rc D Di D 1.5 m
knuckle radius D 6 per cent Rc D 0.09 m
A head of this size would be formed by pressing: no joints, so J D 1.
Rc
1.5
1
Cs D 4 3 C
D 1.77
D 41 3 C
Rk
0.09
eD
1.43 ð 1.5 ð 103 ð 1.77
D 22.0 mm
2 ð 85 C 1.43⊲1.77 0.2⊳
⊲13.44⊳
⊲13.44⊳
(ii) Try a “standard” ellipsoidal head, ratio major : minor axes D 2 : 1
1.43 ð 1.5 ð 103
2 ð 85 0.2 ð 1.43
D 12.7 mm
eD
⊲13.43⊳
So an ellipsoidal head would probably be the most economical. Take as same thickness
as wall 15 mm.
Flat head
Use a full face gasket Cp D 0.4
De D bolt circle diameter, take as approx. 1.7 m.
e D 0.4 ð 1.7 ð 103
1.43
D 88.4 mm
85
⊲13.42⊳
Add corrosion allowance and round-off to 90 mm.
This shows the inefficiency of a flat cover. It would be better to use a flanged
domed head.
13.6. COMPENSATION FOR OPENINGS AND BRANCHES
All process vessels will have openings for connections, manways, and instrument fittings.
The presence of an opening weakens the shell, and gives rise to stress concentrations.
The stress at the edge of a hole will be considerably higher than the average stress in
the surrounding plate. To compensate for the effect of an opening, the wall thickness is
increased in the region adjacent to the opening. Sufficient reinforcement must be provided
to compensate for the weakening effect of the opening without significantly altering the
general dilation pattern of the vessel at the opening. Over-reinforcement will reduce the
flexibility of the wall, causing a “hard spot”, and giving rise to secondary stresses; typical
arrangements are shown in Figure 13.12.
y
;
;
y
;
y
y;y;y;y;y;y;y;y;y;y;y;
MECHANICAL DESIGN OF PROCESS EQUIPMENT
823
(a)
(b)
(c)
Figure 13.12.
Types of compensation for openings (a) Welded pad (b) Inset nozzle (c) Forged ring
The simplest method of providing compensation is to weld a pad or collar around the
opening, Figure 13.12a. The outer diameter of the pad is usually between 1 12 to 2 times the
diameter of the hole or branch. This method, however, does not give the best disposition
of the reinforcing material about the opening, and in some circumstances high thermal
stress can arise due to the poor thermal conductivity of the pad to shell junction.
At a branch, the reinforcement required can be provided, with or without a pad, by
allowing the branch, to protrude into the vessel, Figure 13.12b. This arrangement should
be used with caution for process vessels, as the protrusion will act as a trap for crud,
and local corrosion can occur. Forged reinforcing rings, Figure 13.12c, provide the most
effective method of compensation, but are expensive. They would be used for any large
openings and branches in vessels operating under severe conditions.
Calculation of reinforcement required
The “equal area method” is the simplest method used for calculating the amount of
reinforcement required, and is allowed in most design codes and standards. The principle
used is to provide reinforcement local to the opening, equal in cross-sectional area to the
area removed in forming the opening, Figure 13.13. If the actual thickness of the vessel
;
;
;;;;;
CHEMICAL ENGINEERING
@;y;@y;@y@;y@;y@;y@;y@;y@;y@;y@;y@;y
824
dr
dh
A1 = Area removed
A2 = reinforcement area
A 2 = A1
d r = 1.5 to 2.0 x dh
Figure 13.13.
Equal-area method of compensation
Max. allowed h0 and hi D 0.64
⊲dh C tn ⊳tn
All dimensions shown are in the fully corroded condition (i.e. less corrosion allowance)
Figure 13.14.
Branch compensation
MECHANICAL DESIGN OF PROCESS EQUIPMENT
825
wall is greater than the minimum required to resist the loading, the excess thickness can
be taken into account when estimating the area of reinforcement required. Similarly with
a branch connection, if the wall thickness of the branch or nozzle is greater than the
minimum required, the excess material in the branch can be taken into account. Any
corrosion allowance must be deducted when determining the excess thickness available
as compensation. The standards and codes differ in the areas of the branch and shell
considered to be effective for reinforcement, and should be consulted to determine the
actual area allowed and the disposition of the various types of reinforcement. Figure 13.14
can be used for preliminary calculations. For branch connections of small diameter the
reinforcement area can usually be provided by increasing the wall thickness of the branch
pipe. Some design codes and standards do not require compensation for connections below
89 mm (3 in.) diameter.
If anything, the equal area method tends to over-estimate the compensation required
and in some instances the additional material can reduce the fatigue life of the vessel. More
sophisticated methods for determining the compensation required have been introduced
into the latest editions of the codes and standards.
The equal-area method is generally used for estimating the increase in thickness
required to compensate for multiple openings.
13.7. DESIGN OF VESSELS SUBJECT TO
EXTERNAL PRESSURE
13.7.1. Cylindrical shells
Two types of process vessel are likely to be subjected to external pressure: those operated
under vacuum, where the maximum pressure will be 1 bar (atm); and jacketed vessels,
where the inner vessel will be under the jacket pressure. For jacketed vessels, the maximum
pressure difference should be taken as the full jacket pressure, as a situation may arise
in which the pressure in the inner vessel is lost. Thin-walled vessels subject to external
pressure are liable to failure through elastic instability (buckling) and it is this mode of
failure that determines the wall thickness required.
For an open-ended cylinder, the critical pressure to cause buckling Pc is given by the
following expression; see Windenburg and Trilling (1934):
3
t
2Et/D0
2n2 1 v
2E
C
Pc D 31 n2 1 C
2
2
2
⊲1 v ⊳ D0
2L
2L 2
n2
1
2
2
C1
⊲n 1⊳ n
D0
D0
⊲13.48⊳
where L D the unsupported length of the vessel, the effective length,
D0 D external diameter,
t D wall thickness,
E D Young’s modulus,
v D Poisson’s ratio,
n D the number of lobes formed at buckling.
826
CHEMICAL ENGINEERING
For long tubes and cylindrical vessels this expression can be simplified by neglecting
terms with the group ⊲2L/D0 ⊳2 in the denominator; the equation then becomes:
3
2E
t
⊲13.49⊳
Pc D 31 ⊲n2 1⊳
⊲1 v2 ⊳
D0
The minimum value of the critical pressure will occur when the number of lobes is 2,
and substituting this value into equation 13.49 gives:
3
2E
t
Pc D
⊲13.50⊳
1 v2 D0
For most pressure-vessel materials Poisson’s ratio can be taken as 0.3; substituting this
in equation 13.50 gives:
3
t
Pc D 2.2E
⊲13.51⊳
D0
For short closed vessels, and long vessels with stiffening rings, the critical buckling
pressure will be higher than that predicted by equation 13.51. The effect of stiffening can
be taken into account by introducing a “collapse coefficient”, Kc , into equation 13.51.
3
t
Pc D Kc E
⊲13.52⊳
D0
where Kc is a function of the diameter and thickness of the vessel, and the effective length
L 0 between the ends or stiffening rings; and is obtained from Figure 13.16. The effective
length for some typical arrangements is shown in Figure 13.15.
It can be shown (see Southwell, 1913) that the critical distance between stiffeners, Lc ,
beyond which stiffening will not be effective is given by:
p
4 6D0
D0 1/2
Lc D
⊲1 v2 ⊳1/4
⊲13.53⊳
27
t
Substituting v D 0.3 gives:
Lc D 1.11D0
D0
t
1/2
⊲13.54⊳
Any stiffening rings used must be spaced closer than Lc . Equation 13.52 can be used to
determine the critical buckling pressure and hence the thickness required to resist a given
external pressure; see Example 13.2. A factor of safety of at least 3 should be applied to
the values predicted using equation 13.52.
The design methods and design curves given in the standards and codes should be
used for the detailed design of vessels subject to external pressure.
Out of roundness
Any out-of-roundness in a shell after fabrication will significantly reduce the ability of
the vessel to resist external pressure. A deviation from a true circular cross-section equal
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.15.
827
Effective length, vessel under external pressure (a) Plain vessel (b) With stiffeners (use smaller
of L0 and Ls ) (c) I section stiffening rings (d) Jacketed vessel
to the shell thickness will reduce the critical buckling pressure by about 50 per cent. The
ovality (out-of-roundness) of a cylinder is measured by:
Ovality D
2⊲Dmax Dmin ⊳
ð 100, per cent
⊲Dmax C Dmin ⊳
For vessels under external pressure this should not normally exceed 1.5 per cent.
828
CHEMICAL ENGINEERING
Figure 13.16.
Collapse coefficients for cylindrical shells (after Brownell and Young, 1959)
13.7.2. Design of stiffness rings
The usual procedure is to design stiffening rings to carry the pressure load for a distance
of 21 Ls on each side of the ring, where Ls is the spacing between the rings. So, the load
per unit length on a ring Fr will be given by:
Fr D Pe Ls
⊲13.55⊳
where Pe is the external pressure.
The critical load to cause buckling in a ring under a uniform radial load Fc is given
by the following expression
24EIr
⊲13.56⊳
Fc D
Dr3
where Ir D second moment of area of the ring cross-section,
Dr D diameter of the ring (approximately equal to the shell outside diameter).
Combining equations 13.55 and 13.56 will give an equation from which the required
dimensions of the ring can be determined:
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Pe Ls 6>
24EIr
ł ⊲factor of safety⊳
Dr3
829
⊲13.57⊳
In calculating the second moment of area of the ring some allowance is normally made
for the vessel wall; the use of Ir calculated for the ring alone will give an added factor
of safety.
In vacuum distillation columns, the plate-support rings will act as stiffening rings and
strengthen the vessel; see Example 13.2.
13.7.3. Vessel heads
The critical buckling pressure for a sphere subject to external pressure is given by (see
Timoshenko, 1936):
2Et2
Pc D
⊲13.58⊳
Rs2 3⊲1 v2 ⊳
where Rs is the outside radius of the sphere. Taking Poisson’s ratio as 0.3 gives:
2
t
⊲13.59⊳
Pc D 1.21E
Rs
This equation gives the critical pressure required to cause general buckling; local buckling
can occur at a lower pressure. Karman and Tsien (1939) have shown that the pressure
to cause a “dimple” to form is about one-quarter of that given by equation 13.59, and is
given by:
2
t
⊲13.60⊳
Pc0 D 0.365E
Rs
A generous factor of safety is needed when applying equation 13.60 to the design of
heads under external pressure. A value of 6 is typically used, which gives the following
equation for the minimum thickness:
Pe
e D 4Rs
⊲13.61⊳
E
Any consistent system of units can be used with equation 13.61.
Torispherical and ellipsoidal heads can be designed as equivalent hemispheres. For a
torispherical head the radius Rs is taken as equivalent to the crown radius Rc . For an
ellipsoidal head the radius can be taken as the maximum radius of curvature; that at the
top, given by:
a2
Rs D
⊲13.62⊳
b
where 2a D major axis D D0 (shell o.d.),
2b D minor axis D 2h,
h D height of the head from the tangent line.
Because the radius of curvature of an ellipse is not constant the use of the maximum
radius will over-size the thickness required.
830
CHEMICAL ENGINEERING
Design methods for heads under external pressure are given in the standards and
codes.
Example 13.2
A vacuum distillation column is to operate under a top pressure of 50 mmHg. The plates
are supported on rings 75 mm wide, 10 mm deep. The column diameter is 1 m and the
plate spacing 0.5 m. Check if the support rings will act as effective stiffening rings. The
material of construction is carbon steel and the maximum operating temperature 50Ž C. If
the vessel thickness is 10 mm, check if this is sufficient.
Solution
10 mm
10 mm
75 mm
0.5 m
Take the design pressure as 1 bar external.
From equation 13.55 the load on each ring D 0.5 ð 105 N/m.
Taking E for steel at 50Ž C as 200,000 N/mm2 D 2 ð 1011 N/m2 , and using a factor
of safety of 6, the second moment of area of the ring to avoid buckling is given by:
equation 13.57
0.5 ð 105 D
24 ð 2 ð 1011 ð Ir
13 ð 6
Ir D 6.25 ð 108 m4
For a rectangular section, the second moment of area is given by
breadth ð depth3
12
10 ð ⊲75⊳3 ð 1012
so Ir for the support rings D
12
D 3.5 ð 107 m4
ID
MECHANICAL DESIGN OF PROCESS EQUIPMENT
831
and the support ring is of an adequate size to be considered as a stiffening ring.
0.5
L0
D
D 0.5
D0
1
D0
1000
D
D 100
t
10
From Figure 13.16 Kc D 75
From equation 13.52
Pc D 75 ð 2 ð 1011
1
100
3
D 15 ð 106 N/m2
which is well above the maximum design pressure of 105 N/m2 .
13.8. DESIGN OF VESSELS SUBJECT TO COMBINED LOADING
Pressure vessels are subjected to other loads in addition to pressure (see Section 13.4.7)
and must be designed to withstand the worst combination of loading without failure It is
not practical to give an explicit relationship for the vessel thickness to resist combined
loads. A trial thickness must be assumed (based on that calculated for pressure alone)
and the resultant stress from all loads determined to ensure that the maximum allowable
stress intensity is not exceeded at any point.
The main sources of load to consider are:
1.
2.
3.
4.
5.
Pressure.
Dead weight of vessel and contents.
Wind.
Earthquake (seismic).
External loads imposed by piping and attached equipment.
The primary stresses arising from these loads are considered in the following paragraphs,
for cylindrical vessels; Figure 13.17.
Primary stresses
1. The longitudinal and circumferential stresses due to pressure (internal or external),
given by:
PDi
⊲13.63⊳
2t
PDi
L D
⊲13.64⊳
4t
2. The direct stress w due to the weight of the vessel, its contents, and any attachments.
The stress will be tensile (positive) for points below the plane of the vessel supports,
and compressive (negative) for points above the supports, see Figure 13.18. The
dead-weight stress will normally only be significant, compared to the magnitude of
the other stresses, in tall vessels.
h D
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CHEMICAL ENGINEERING
W
M
σz
σh
σh
t
Di
σz
DO
T
Figure 13.17.
Stresses in a cylindrical shell under combined loading
w D
W
⊲Di C t⊳t
⊲13.65⊳
where W is the total weight which is supported by the vessel wall at the plane
considered, see Section 13.8.1.
3. Bending stresses resulting from the bending moments to which the vessel is
subjected. Bending moments will be caused by the following loading conditions:
(a) The wind loads on tall self-supported vessels (Section 13.8.2).
(b) Seismic (earthquake) loads on tall vessels (Section 13.8.3).
(c) The dead weight and wind loads on piping and equipment which is attached to
the vessel, but offset from the vessel centre line (Section 13.8.4).
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.18.
833
Stresses due to dead-weight loads
(d) For horizontal vessels with saddle supports, from the disposition of dead-weight
load (see Section 13.9.1).
The bending stresses will be compressive or tensile, depending on location, and are
given by:
M Di
Ct
⊲13.66⊳
b D š
Iv 2
where Mv is the total bending moment at the plane being considered and Iv the
second moment of area of the vessel about the plane of bending.
Iv D
4
⊲D Di4 ⊳
64 0
⊲13.67⊳
4. Torsional shear stresses resulting from torque caused by loads offset from the
vessel axis. These loads will normally be small, and need not be considered in
preliminary vessel designs.
The torsional shear stress is given by:
T Di
D
Ct
⊲13.68⊳
Ip 2
where T D the applied torque,
Ip D polar second moment of area D ⊲/32⊳⊲D04 Di4 ⊳
Principal stresses
The principal stresses will be given by:
1 D 21 [h C z C
⊲h z ⊳2 C 4 2 ]
⊲13.69⊳
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CHEMICAL ENGINEERING
2 D 21 [h C z
⊲h z ⊳2 C 4 2 ]
⊲13.70⊳
where z D total longitudinal stress
D L C w š b
w should be counted as positive if tension and negative if compressive.
is not usually significant.
The third principal stress, that in the radial direction 3 , will usually be negligible for
thin-walled vessels (see Section 13.1.1). As an approximation it can be taken as equal to
one-half the pressure loading
⊲13.71⊳
3 D 0.5P
3 will be compressive (negative).
Allowable stress intensity
The maximum intensity of stress allowed will depend on the particular theory of failure
adopted in the design method (see Section 13.3.2). The maximum shear-stress theory is
normally used for pressure vessel design.
Using this criterion the maximum stress intensity at any point is taken for design
purposes as the numerically greatest value of the following:
⊲1 2 ⊳
⊲1 3 ⊳
⊲2 3 ⊳
The vessel wall thickness must be sufficient to ensure the maximum stress intensity does
not exceed the design stress (nominal design strength) for the material of construction, at
any point.
Compressive stresses and elastic stability
Under conditions where the resultant axial stress z due to the combined loading is
compressive, the vessel may fail by elastic instability (buckling) (see Section 13.3.3).
Failure can occur in a thin-walled process column under an axial compressive load by
buckling of the complete vessel, as with a strut (Euler buckling); or by local buckling, or
wrinkling, of the shell plates. Local buckling will normally occur at a stress lower than
that required to buckle the complete vessel. A column design must be checked to ensure
that the maximum value of the resultant axial stress does not exceed the critical value at
which buckling will occur.
For a curved plate subjected to an axial compressive load the critical buckling stress
c is given by (see Timoshenko, 1936):
E
t
c D
⊲13.72⊳
2
3⊲1 v ⊳ Rp
where Rp is the radius of curvature.
835
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Taking Poisson’s ratio as 0.3 gives:
c D 0.60E
t
Rp
⊲13.73⊳
By applying a suitable factor of safety, equation 13.72 can be used to predict the
maximum allowable compressive stress to avoid failure by buckling. A large factor of
safety is required, as experimental work has shown that cylindrical vessels will buckle
at values well below that given by equation 13.72. For steels at ambient temperature
E D 200,000 N/mm2 , and equation 13.72 with a factor of safety of 12 gives:
t
4
N/mm2
⊲13.74⊳
c D 2 ð 10
Do
The maximum compressive stress in a vessel wall should not exceed that given by
equation 13.74; or the maximum allowable design stress for the material, whichever is
the least.
Stiffening
As with vessels under external pressure, the resistance to failure buckling can be increased
significantly by the use of stiffening rings, or longitudinal strips. Methods for estimating
the critical buckling stress for stiffened vessels are given in the standards and codes.
Loading
The loads to which a vessel may be subjected will not all occur at the same time. For
example, it is the usual practice to assume that the maximum wind load will not occur
simultaneously with a major earthquake.
The vessel must be designed to withstand the worst combination of the loads likely to
occur in the following situations:
1.
2.
3.
4.
During erection (or dismantling) of the vessel.
With the vessel erected but not operating.
During testing (the hydraulic pressure test).
During normal operation.
13.8.1. Weight loads
The major sources of dead weight loads are:
1.
2.
3.
4.
5.
6.
The vessel shell.
The vessel fittings: manways, nozzles.
Internal fittings: plates (plus the fluid on the plates); heating and cooling coils.
External fittings: ladders, platforms, piping.
Auxiliary equipment which is not self-supported; condensers, agitators.
Insulation.
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CHEMICAL ENGINEERING
7. The weight of liquid to fill the vessel. The vessel will be filled with water for the
hydraulic pressure test; and may fill with process liquid due to misoperation.
Note: for vessels on a skirt support (see Section 13.9.2), the weight of the liquid to fill
the vessel will be transferred directly to the skirt.
The weight of the vessel and fittings can be calculated from the preliminary design
sketches. The weights of standard vessel components: heads, shell plates, manways,
branches and nozzles, are given in various handbooks; Megyesy (2001) and Brownell
and Young (1959).
For preliminary calculations the approximate weight of a cylindrical vessel with domed
ends, and uniform wall thickness, can be estimated from the following equation:
Wv D Cv m Dm g⊲Hv C 0.8Dm ⊳t ð 103
⊲13.75⊳
where Wv D total weight of the shell, excluding internal fittings, such as plates, N,
Cv D a factor to account for the weight of nozzles, manways, internal supports,
etc; which can be taken as
D 1.08 for vessels with only a few internal fittings,
D 1.15 for distillation columns, or similar vessels, with several manways,
and with plate support rings, or equivalent fittings,
Hv D height, or length, between tangent lines (the length of the cylindrical
section), m,
g D gravitational acceleration, 9.81 m/s2 ,
t D wall thickness, mm
m D density of vessel material, kg/m3 ,
Dm D mean diameter of vessel D ⊲Di C t ð 103 ⊳, m.
For a steel vessel, equation 13.75 reduces to:
Wv D 240Cv Dm ⊲Hv C 0.8Dm ⊳t
⊲13.76⊳
The following values can be used as a rough guide to the weight of fittings; see
Nelson (1963):
(a)
(b)
(c)
(d)
caged ladders, steel, 360 N/m length,
plain ladders, steel, 150 N/m length,
platforms, steel, for vertical columns, 1.7 kN/m2 area,
contacting plates, steel, including typical liquid loading, 1.2 kN/m2 plate area.
Typical values for the density of insulating materials are (all kg/m3 ):
Foam glass
Mineral wool
Fibreglass
Calcium silicate
150
130
100
200
These densities should be doubled to allow for attachment fittings, sealing, and moisture
absorption.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
837
13.8.2. Wind loads (tall vessels)
Figure 13.19.
;
;
;
;
;;;;;
;
;;;;;
;
;;;;
;;
Bending moment diagram
Wind load, W N / m
Wind loading will only be important on tall columns installed in the open. Columns and
chimney-stacks are usually free standing, mounted on skirt supports, and not attached
to structural steel work. Under these conditions the vessel under wind loading acts as a
cantilever beam, Figure 13.19. For a uniformly loaded cantilever the bending moment at
any plane is given by:
wx 2
⊲13.77⊳
Mx D
2
where x is the distance measured from the free end and w the load per unit length (Newtons
per metre run).
Wind loading on a tall column
So the bending moment, and hence the bending stress, will vary parabolically from zero
at the top of the column to a maximum value at the base. For tall columns the bending
stress due to wind loading will often be greater than direct stress due to pressure, and will
determine the plate thickness required. The most economical design will be one in which
the plate thickness is progressively increased from the top to the base of the column. The
thickness at the top being sufficient for the pressure load, and that at the base sufficient
for the pressure plus the maximum bending moment.
Any local increase in the column area presented to the wind will give rise to a local,
concentrated, load, Figure 13.20. The bending moment at the column base caused by a
concentrated load is given by:
Mp D Fp Hp
⊲13.78⊳
where Fp D local, concentrated, load,
Hp D the height of the concentrated load above the column base.
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CHEMICAL ENGINEERING
Fp
Hp
Figure 13.20.
Local wind loading
Dynamic wind pressure
The load imposed on any structure by the action of the wind will depend on the shape of
the structure and the wind velocity.
Pw D 21 Cd a uw2
where Pw
Cd
a
uw
D
D
D
D
⊲13.79⊳
wind pressure (load per unit area),
drag coefficient (shape factor),
density of air,
wind velocity.
The drag coefficient is a function of the shape of the structure and the wind velocity
(Reynolds number).
For a smooth cylindrical column or stack the following semi-empirical equation can be
used to estimate the wind pressure:
Pw D 0.05uw2
⊲13.79a⊳
where Pw D wind pressure, N/m2 ,
uw D wind speed, km/h.
If the column outline is broken up by attachments, such as ladders or pipe work, the factor
of 0.05 in equation 13.79a should be increased to 0.07, to allow for the increased drag.
A column must be designed to withstand the highest wind speed that is likely to be
encountered at the site during the life of the plant. The probability of a given wind speed
occurring can be predicted by studying meteorological records for the site location.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
839
Data and design methods for wind loading are given in the Engineering Sciences Data
Unit (ESDU) Wind Engineering Series (www.ihsedsu.com).
Design loadings for locations in the United States are given by Moss (2003), Megyesy
(2001) and Escoe (1994).
A wind speed of 160 km/h (100 mph) can be used for preliminary design studies;
equivalent to a wind pressure of 1280 N/m2 (25 lb/ft2 ).
At any site, the wind velocity near the ground will be lower than that higher up (due to
the boundary layer), and in some design methods a lower wind pressure is used at heights
below about 20 m; typically taken as one-half of the pressure above this height.
The loading per unit length of the column can be obtained from the wind pressure by
multiplying by the effective column diameter: the outside diameter plus an allowance for
the thermal insulation and attachments, such as pipes and ladders.
Fw D Pw Deff
⊲13.80⊳
An allowance of 0.4 m should be added for a caged ladder. The calculation of the wind
load on a tall column, and the induced bending stresses, is illustrated in Example 13.3.
Further examples of the design of tall columns are given by Brownell (1963), Henry
(1973), Bednar (1990), Escoe (1994) and Jawad and Farr (1989).
Deflection of tall columns
Tall columns sway in the wind. The allowable deflection will normally be specified as
less than 150 mm per 30 metres of height (6 in. per 100 ft).
For a column with a uniform cross-section, the deflection can be calculated using the
formula for the deflection of a uniformly loaded cantilever. A method for calculating the
deflection of a column where the wall thickness is not constant is given by Tang (1968).
Wind-induced vibrations
Vortex shedding from tall thin columns and stacks can induce vibrations which, if the
frequency of shedding of eddies matches the natural frequency of the column, can be
severe enough to cause premature failure of the vessel by fatigue. The effect of vortex
shedding should be investigated for free standing columns with height to diameter ratios
greater than 10. Methods for estimating the natural frequency of columns are given by
Freese (1959) and DeGhetto and Long (1966).
Helical strakes (strips) are fitted to the tops of tall smooth chimneys to change the
pattern of vortex shedding and so prevent resonant oscillation. The same effect will be
achieved on a tall column by distributing any attachments (ladders, pipes and platforms)
around the column.
13.8.3. Earthquake loading
The movement of the earth’s surface during an earthquake produces horizontal shear
forces on tall self-supported vessels, the magnitude of which increases from the base
upward. The total shear force on the vessel will be given by:
W
⊲13.81⊳
Fs D ae
g
840
CHEMICAL ENGINEERING
where ae D the acceleration of the vessel due to the earthquake,
g D the acceleration due to gravity,
W D total weight of the vessel.
The term (ae /g) is called the seismic constant Ce , and is a function of the natural period of
vibration of the vessel and the severity of the earthquake. Values of the seismic constant
have been determined empirically from studies of the damage caused by earthquakes, and
are available for those geographical locations which are subject to earthquake activity.
Values for sites in the United States, and procedures for determining the stresses induced
in tall columns are given by Megyesy (2001), Escoe (1994) and Moss (2003).
A seismic stress analysis is not made as a routine procedure in the design of vessels
for sites in the United Kingdom, except for nuclear installations, as the probability of
an earthquake occurring of sufficient severity to cause significant damage is negligible.
However, the possibility of earthquake damage may be considered if the site is a Major
Hazards installation, see Chapter 9, Section 9.9.
13.8.4. Eccentric loads (tall vessels)
Ancillary equipment attached to a tall vessel will subject the vessel to a bending moment
if the centre of gravity of the equipment does not coincide with the centre line of the
vessel (Figure 13.21). The moment produced by small fittings, such as ladders, pipes and
manways, will be small and can be neglected. That produced by heavy equipment, such
as reflux condensers and side platforms, can be significant and should be considered. The
moment is given by:
Me D We Lo
⊲13.82⊳
where We D dead weight of the equipment,
Lo D distance between the centre of gravity of the equipment and the column
centre line.
Figure 13.21.
Bending moment due to offset equipment
MECHANICAL DESIGN OF PROCESS EQUIPMENT
841
13.8.5. Torque
Any horizontal force imposed on the vessel by ancillary equipment, the line of thrust
of which does not pass through the centre line of the vessel, will produce a torque on
the vessel. Such loads can arise through wind pressure on piping and other attachments.
However, the torque will normally be small and usually can be disregarded. The pipe work
and the connections for any ancillary equipment will be designed so as not to impose a
significant load on the vessel.
Example 13.3
Make a preliminary estimate of the plate thickness required for the distillation column
specified below:
Height, between tangent lines
50 m
Diameter
2m
Skirt support, height
3m
100 sieve plates, equally spaced
Insulation, mineral wool
75 mm thick
Material of construction, stainless steel, design stress 135 N/mm2 at design temperature 200Ž C
Operating pressure 10 bar (absolute)
Vessel to be fully radiographed (joint factor 1).
Solution
Design pressure; take as 10 per cent above operating pressure
D ⊲10 1⊳ ð 1.1 D 9.9 bar, say 10 bar
D 1.0 N/mm2
Minimum thickness required for pressure loading
D
1 ð 2 ð 103
D 7.4 mm
2 ð 135 1
⊲13.39⊳
A much thicker wall will be needed at the column base to withstand the wind and dead
weight loads.
As a first trial, divide the column into five sections (courses), with the thickness
increasing by 2 mm per section. Try 10, 12, 14, 16, 18 mm.
Dead weight of vessel
Though equation 13.76 only applies strictly to vessels with uniform thickness, it can be
used to get a rough estimate of the weight of this vessel by using the average thickness
in the equation, 14 mm.
Take Cv D 1.15, vessel with plates,
Dm D 2 C 14 ð 103 D 2.014 m,
842
CHEMICAL ENGINEERING
Hv D 50 m,
t D 14 mm
Wv D 240 ð 1.15 ð 2.014⊲50 C 0.8 ð 2.014⊳14
D 401643 N
D 402 kN
⊲13.76⊳
Weight of plates:
plate area D /4 ð 22 D 3.14 m2
weight of a plate (see page 761) D 1.2 ð 3.14 D 3.8 kN
100 plates D 100 ð 3.8 D 380 kN
Weight of insulation:
mineral wool density D 130 kg/m3
approximate volume of insulation D ð 2 ð 50 ð 75 ð 103
D 23.6 m3
weight D 23.6 ð 130 ð 9.81 D 30,049 N
double this to allow for fittings, etc. D 60 kN
Total weight:
shell
plates
insulation
402
380
60
842 kN
Wind loading
Take dynamic wind pressure as 1280 N/m2 .
Mean diameter, including insulation D 2 C 2⊲14 C 75⊳ ð 103
D 2.18 m
Loading (per linear metre) Fw D 1280 ð 2.18 D 2790 N/m
(13.80)
Bending moment at bottom tangent line:
Mx D
2790
ð 502 D 3,487,500 Nm
2
⊲13.77⊳
L D
1.0 ð 2 ð 103
D 27.8 N/mm2
4 ð 18
⊲13.64⊳
Analysis of stresses
At bottom tangent line
Pressure stresses:
h D
1 ð 2 ð 103
D 55.6 N/mm2
2 ð 18
⊲13.63⊳
MECHANICAL DESIGN OF PROCESS EQUIPMENT
843
Dead weight stress:
Wv
842 ð 103
D
⊲Di C t⊳t
⊲2000 C 18⊳18
w D
⊲13.65⊳
D 7.4 N/mm2 (compressive)
Bending stresses:
Do D 2000 C 2 ð 18 D 2036 mm
Iv D
⊲20364 20004 ⊳ D 5.81 ð 1010 mm4
64
3,487,500 ð 103 2000
b D š
C 18
5.81 ð 1010
2
⊲13.67⊳
⊲13.66⊳
D š61.1 N/mm2
The resultant longitudinal stress is:
z D L C w š b
w is compressive and therefore negative.
z (upwind) D 27.8 7.4 C 61.1 D C81.5 N/mm2 .
z (downwind) D 27.8 7.4 61.1 D 40.7 N/mm2 .
As there is no torsional shear stress, the principal stresses will be z and h .
The radial stress is negligible, ' ⊲Pi /2⊳ D 0.5 N/mm2 .
40.7
81.5
55.6
55.6
Down − wind
Up − wind
The greatest difference between the principal stresses will be on the down-wind side
⊲55.6 ⊲40.7⊳⊳ D 96.5 N/mm2 ,
well below the maximum allowable design stress
Check elastic stability (buckling)
Critical buckling stress:
4
c D 2 ð 10
18
2036
D 176.8 N/mm2
⊲13.74⊳
844
CHEMICAL ENGINEERING
The maximum compressive stress will occur when the vessel is not under pressure D
7.4 C 61.1 D 68.5, well below the critical buckling stress.
So design is satisfactory. Could reduce the plate thickness and recalculate.
13.9. VESSEL SUPPORTS
The method used to support a vessel will depend on the size, shape, and weight of the
vessel; the design temperature and pressure; the vessel location and arrangement; and
the internal and external fittings and attachments. Horizontal vessels are usually mounted
on two saddle supports; Figure 13.22. Skirt supports are used for tall, vertical columns;
Figure 13.23. Brackets, or lugs, are used for all types of vessel; Figure 13.24. The supports
must be designed to carry the weight of the vessel and contents, and any superimposed
loads, such as wind loads. Supports will impose localised loads on the vessel wall, and
the design must be checked to ensure that the resulting stress concentrations are below
the maximum allowable design stress. Supports should be designed to allow easy access
to the vessel and fittings for inspection and maintenance.
Figure 13.22.
Horizontal cylindrical vessel on saddle supports
13.9.1. Saddle supports
Though saddles are the most commonly used support for horizontal cylindrical vessels,
legs can be used for small vessels. A horizontal vessel will normally be supported at
two cross-sections; if more than two saddles are used the distribution of the loading is
uncertain.
A vessel supported on two saddles can be considered as a simply supported beam, with
an essentially uniform load, and the distribution of longitudinal axial bending moment
will be as shown in Figure 13.22. Maxima occur at the supports and at mid-span. The
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Typical skirt-support designs (a) Straight skirt (b) Conical skirt
y
;
;
y
y;y;y;y;
Figure 13.23.
845
(b)
(a)
Figure 13.24.
Bracket supports (a) Supported on legs (b) Supported from steel-work
theoretical optimum position of the supports to give the least maximum bending moment
will be the position at which the maxima at the supports and at mid-span are equal in
magnitude. For a uniformly loaded beam the position will be at 21 per cent of the span,
in from each end. The saddle supports for a vessel will usually be located nearer the ends
than this value, to make use of the stiffening effect of the ends.
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CHEMICAL ENGINEERING
Stress in the vessel wall
The longitudinal bending stress at the mid-span of the vessel is given by:
b1 D
where ML1
Ih
D
t
D
D
D
D
D
ML1
4ML1
ð '
Ih
2
D2 t
⊲13.83⊳
longitudinal bending stress at the mid-span,
second moment of area of the shell,
shell diameter,
shell thickness.
The resultant axial stress due to bending and pressure will be given by:
z D
PD 4ML1
š
4t
D2 t
⊲13.84⊳
The magnitude of the longitudinal bending stress at the supports will depend on the local
stiffness of the shell; if the shell does not remain circular under load a portion of the upper
part of the cross-section is ineffective against longitudinal bending; see Figure 13.25. The
stress is given by:
4ML2
b2 D
⊲13.85⊳
Ch D2 t
where ML2 D longitudinal bending moment at the supports,
Ch D an empirical constant; varying from 1.0 for a completely stiff shell to
about 0.1 for a thin, unstiffened, shell.
;;;;;;;;;;
; ;;
Figure 13.25.
Saddle supports: shaded area is ineffective against longitudinal bending in an unstiffened shell
The ends of the vessels will stiffen the shell if the position of the saddles is less than
D/4 from the ends. Ring stiffeners, located at the supports, are used to stiffen the shells
of long thin vessels. The rings may be fitted inside or outside the vessel.
In addition to the longitudinal bending stress, a vessel supported on saddles will
be subjected to tangential shear stresses, which transfer the load from the unsupported
sections of the vessel to the supports; and to circumferential bending stresses. All these
stresses need to be considered in the design of large, thin-walled, vessels, to ensure that
the resultant stress does not exceed the maximum allowable design stress or the critical
buckling stress for the material. A detailed stress analysis is beyond the scope of this
847
MECHANICAL DESIGN OF PROCESS EQUIPMENT
book. A complete analysis of the stress induced in the shell by the supports is given by
Zick (1951). Zick’s method forms the basis of the design methods given in the national
codes and standards. The method is also given by Brownell and Young (1959), Escoe
(1994) and Megyesy (2001).
Design of saddles
The saddles must be designed to withstand the load imposed by the weight of the vessel
and contents. They are constructed of bricks or concrete, or are fabricated from steel
plate. The contact angle should not be less than 120Ž , and will not normally be greater
than 150Ž . Wear plates are often welded to the shell wall to reinforce the wall over the
area of contact with the saddle.
The dimensions of typical “standard” saddle designs are given in Figure 13.26. To take
up any thermal expansion of the vessel, such as that in heat exchangers, the anchor bolt
holes in one saddle can be slotted.
Procedures for the design of saddle supports are given by Brownell and Young (1959),
Megyesy (2001), Escoe (1994) and Moss (2003).
Dimensions (m)
mm
Vessel
diam.
(m)
Maximum
weight
(kN)
V
Y
C
E
J
G
t2
t1
Bolt
diam.
Bolt
holes
0.6
0.8
0.9
1.0
1.2
35
50
65
90
180
0.48
0.58
0.63
0.68
0.78
0.15
0.15
0.15
0.15
0.20
0.55
0.70
0.81
0.91
1.09
0.24
0.29
0.34
0.39
0.45
0.190
0.225
0.275
0.310
0.360
0.095
0.095
0.095
0.095
0.140
6
8
10
11
12
5
5
6
8
10
20
20
20
20
24
25
25
25
25
30
All contacting edges fillet welded
(a)
Figure 13.26.
Standard steel saddles (adapted from Bhattacharyya, 1976). (a) for vessels up to 1.2 m
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CHEMICAL ENGINEERING
Dimensions (m)
mm
Vessel
diam.
(m)
Maximum
weight
(kN)
V
Y
C
E
J
G
t2
t1
Bolt
diam.
Bolt
holes
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.6
230
330
380
460
750
900
1000
1350
1750
2000
2500
0.88
0.98
1.08
1.18
1.28
1.38
1.48
1.58
1.68
1.78
1.98
0.20
0.20
0.20
0.20
0.225
0.225
0.225
0.25
0.25
0.25
0.25
1.24
1.41
1.59
1.77
1.95
2.13
2.30
2.50
2.64
2.82
3.20
0.53
0.62
0.71
0.80
0.89
0.98
1.03
1.10
1.18
1.26
1.40
0.305
0.350
0.405
0.450
0.520
0.565
0.590
0.625
0.665
0.730
0.815
0.140
0.140
0.140
0.140
0.150
0.150
0.150
0.150
0.150
0.150
0.150
12
12
12
12
16
16
16
16
16
16
16
10
10
10
10
12
12
12
12
12
12
12
24
24
24
24
24
27
27
27
27
27
27
30
30
30
30
30
33
33
33
33
33
33
All contacting edges fillet welded
(b)
Figure 13.26.
(b) for vessels greater than 1.2 m
13.9.2. Skirt supports
A skirt support consists of a cylindrical or conical shell welded to the base of the vessel.
A flange at the bottom of the skirt transmits the load to the foundations. Typical designs
are shown in Figure 13.23. Openings must be provided in the skirt for access and for any
connecting pipes; the openings are normally reinforced. The skirt may be welded to the
bottom head of the vessel. Figure 13.27a; or welded flush with the shell, Figure 13.27b;
or welded to the outside of the vessel shell, Figure 13.27c. The arrangement shown in
Figure 13.27b is usually preferred.
Skirt supports are recommended for vertical vessels as they do not impose concentrated
loads on the vessel shell; they are particularly suitable for use with tall columns subject
to wind loading.
Skirt thickness
The skirt thickness must be sufficient to withstand the dead-weight loads and bending
moments imposed on it by the vessel; it will not be under the vessel pressure.
;
y
;
y
;
y
y;y;y;y;y;
y; y;y;y;
y;y;
849
MECHANICAL DESIGN OF PROCESS EQUIPMENT
(a)
(b)
Figure 13.27.
(c)
Skirt-support welds
The resultant stresses in the skirt will be:
s (tensile) D bs ws
⊲13.86⊳
s (compressive) D bs C ws
⊲13.87⊳
and
where bs D bending stress in the skirt
D
4Ms
,
⊲Ds C ts ⊳ts Ds
(13.88)
ws D the dead weight stress in the skirt,
D
W
⊲Ds C ts ⊳ts
(13.89)
where Ms D maximum bending moment, evaluated at the base of the skirt (due to
wind, seismic and eccentric loads, see Section 13.8),
W D total weight of the vessel and contents (see Section 13.8),
Ds D inside diameter of the skirt, at the base,
ts D skirt thickness.
The skirt thickness should be such that under the worst combination of wind and
dead-weight loading the following design criteria are not exceeded:
s (tensile) 6> fs J sin s
ts
s (compressive) 6> 0.125E
sin s
Ds
⊲13.90⊳
⊲13.91⊳
where fs D maximum allowable design stress for the skirt material, normally taken at
ambient temperature, 20Ž C,
850
CHEMICAL ENGINEERING
J D weld joint factor, if applicable,
s D base angle of a conical skirt, normally 80Ž to 90Ž .
;
;;;;;;
;
The minimum thickness should be not less than 6 mm.
Where the vessel wall will be at a significantly higher temperature than the skirt,
discontinuity stresses will be set up due to differences in thermal expansion. Methods for
calculating the thermal stresses in skirt supports are given by Weil and Murphy (1960)
and Bergman (1963).
Base ring and anchor bolt design
;
;;;;;;
The loads carried by the skirt are transmitted to the foundation slab by the skirt base
ring (bearing plate). The moment produced by wind and other lateral loads will tend to
overturn the vessel; this will be opposed by the couple set up by the weight of the vessel
and the tensile load in the anchor bolts. A variety of base ring designs is used with skirt
supports. The simplest types, suitable for small vessels, are the rolled angle and plain
flange rings shown in Figure 13.28a and b. For larger columns a double ring stiffened
by gussets, Figure 13.18c, or chair supports, Figure 13.30, are used. Design methods for
base rings, and methods for sizing the anchor bolts, are given by Brownell and Young
(1959). For preliminary design, the short-cut method and nomographs given by Scheiman
(1963) can be used. Scheiman’s method is based on a more detailed procedure for the
design of base rings and foundations for columns and stacks given by Marshall (1958).
Scheiman’s method is outlined below and illustrated in Example 13.4.
Gusset
;;;;
;
(a)
(b)
(c)
Figure 13.28.
Flange ring designs (a) Rolled-angle (b) Single plate with gusset (c) Double plate with gusset
MECHANICAL DESIGN OF PROCESS EQUIPMENT
851
The anchor bolts are assumed to share the overturning load equally, and the bolt area
required is given by:
1
4Ms
Ab D
W
⊲13.92⊳
Nb fb Db
where Ab D area of one bolt at the root of the thread, mm2 ,
Nb D number of bolts,
fb D maximum allowable bolt stress, N/mm2 ;
typical design value 125 N/mm2 (18,000 psi),
Ms D bending (overturning) moment at the base, Nm,
W D weight of the vessel, N,
Db D bolt circle diameter, m.
Scheiman gives the following guide rules which can be used for the selection of the
anchor bolts:
1.
2.
3.
4.
Bolts smaller than 25 mm (1 in.) diameter should not be used.
Minimum number of bolts 8.
Use multiples of 4 bolts.
Bolt pitch should not be less than 600 mm (2 ft).
If the minimum bolt pitch cannot be accommodated with a cylindrical skirt, a conical
skirt should be used.
The base ring must be sufficiently wide to distribute the load to the foundation. The
total compressive load on the base ring is given by:
W
4Ms
Fb D
C
⊲13.93⊳
Ds2
Ds
where Fb D the compressive load on the base ring, Newtons per linear metre,
Ds D skirt diameter, m.
The minimum width of the base ring is given by:
Lb D
Fb
1
ð 3
fc
10
⊲13.94⊳
where Lb D base ring width, mm (Figure 13.29),
fc D the maximum allowable bearing pressure on the concrete foundation pad,
which will depend on the mix used, and will typically range from 3.5 to
7 N/mm2 (500 to 1000 psi).
The required thickness for the base ring is found by treating the ring as a cantilever beam.
The minimum thickness is given by:
3f0c
tb D L r
⊲13.95⊳
fr
852
y
;
;
y
y; y;
y;;yy;y;y;y;
CHEMICAL ENGINEERING
Figure 13.29.
Flange ring dimensions
A
B
F
E
D
50
min
G
305 mm
12.5
12.5
tb
C
All contacting edges fillet welded
Dimensions mm
Bolt
size
Root
area
M24
M30
M36
M42
M48
M56
M64
70
76
353
561
817
1120
1470
2030
2680
A
B
C
D
E
F
G
45
50
57
60
67
75
83
89
95
76
76
102
102
127
150
152
178
178
64
64
76
76
89
102
102
127
127
13
13
16
16
19
25
25
32
32
19
25
32
32
38
45
50
64
64
30
36
42
48
54
60
70
76
83
36
42
48
54
60
66
76
83
89
Bolt size = Nominal dia. (BS 4190: 1967)
Figure 13.30.
Anchor bolt chair design
where Lr D the distance from the edge of the skirt to the outer edge of the ring, mm;
Figure 13.29,
tb D base ring thickness, mm,
f0c D actual bearing pressure on base, N/mm2 ,
fr D allowable design stress in the ring material, typically 140 N/mm2 .
MECHANICAL DESIGN OF PROCESS EQUIPMENT
853
Standard designs will normally be used for the bolting chairs. The design shown in
Figure 13.30 has been adapted from that given by Scheiman.
Example 13.4
Design a skirt support for the column specified in Example 13.3.
Solution
Try a straight cylindrical skirt (s D 90Ž ) of plain carbon steel, design stress 135 N/mm2
and Young’s modulus 200,000 N/mm2 at ambient temperature.
The maximum dead weight load on the skirt will occur when the vessel is full of water.
ð 22 ð 50 1000 ð 9.81
Approximate weight D
4
D 1,540,951 N
D 1541 kN
Weight of vessel, from Example 13.3 D 842 kN
Total weight D 1541 C 842 D 2383 kN
Wind loading, from Example 13.4 D 2.79 kN/m
532
2
D 3919 kNm
Bending moment at base of skirt D 2.79 ð
⊲13.77⊳
As a first trial, take the skirt thickness as the same as that of the bottom section of the
vessel, 18 mm.
bs D
4 ð 3919 ð 103 ð 103
⊲2000 C 18⊳2000 ð 18
⊲13.88⊳
D 68.7 N/mm2
ws (test) D
ws (operating) D
1543 ð 103
D 13.5 N/mm2
⊲2000 C 18⊳18
⊲13.89⊳
842 ð 103
D 7.4 N/mm2
⊲2000 C 18⊳18
⊲13.89⊳
Note: the “test” condition is with the vessel full of water for the hydraulic test. In
estimating total weight, the weight of liquid on the plates has been counted twice. The
weight has not been adjusted to allow for this as the error is small, and on the “safe side”.
Maximum O s (compressive) D 68.7 C 13.5 D 82.2 N/mm2
Maximum O s (tensile) D 68.7 7.4 D 61.3 N/mm2
Take the joint factor J as 0.85.
⊲13.87⊳
⊲13.86⊳
854
CHEMICAL ENGINEERING
Criteria for design:
O s (tensile) 6> fs J sin
⊲13.90⊳
61.3 6> 0.85 ð 135 sin 90
61.3 6> 115
ts
O s (compressive) 6> 0.125E
Ds
sin
82.2 6> 0.125 ð 200,000
18
2000
⊲13.91⊳
sin 90
82.2 6> 225
Both criteria are satisfied, add 2 mm for corrosion, gives a design thickness of 20 mm
Base ring and anchor bolts
Approximate pitch circle dia., say, 2.2 m
Circumference of bolt circle D 2200
Number of bolts required, at minimum recommended bolt spacing
D
2200
D 11.5
600
Closest multiple of 4 D 12 bolts
Take bolt design stress D 125 N/mm2
Ms D 3919 kN m
Take W D operating value D 842 kN.
Ab D
4 ð 3919 ð 103
1
842 ð 103
12 ð 125
2.2
⊲13.92⊳
D 4190 mm2
Bolt root dia. D
4190 ð 4
D 73 mm, looks too large.
Total compressive load on the base ring per unit length
842 ð 103
4 ð 3919 ð 103
C
Fb D
ð 2.02
ð 2.0
⊲13.93⊳
D 1381 ð 103 N/m
Taking the bearing pressure as 5 N/mm2
Lb D
Rather large
1381 ð 103
D 276 mm
5 ð 103
consider a flared skirt.
⊲13.94⊳
855
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Take the skirt bottom dia. as 3 m
Skirt base angle s D tan1
1
⊲3
2
3
D 80.5Ž
2⊳
Keep the skirt thickness the same as that calculated for the cylindrical skirt. Highest
stresses will occur at the top of the skirt; where the values will be close to those calculated
for the cylindrical skirt. Sin 80.5Ž D 0.99, so this term has little effect on the design
criteria.
Assume bolt circle dia. D 3.2 m.
Take number of bolts as 16.
ð 3.2 ð 103
D 628 mm satisfactory.
16
1
4 ð 3919 ð 103
3
Ab D
842 ð 10
16 ð 125
3.2
Bolt spacing D
D 2029 mm2
Use M56 bolts (BS 4190:1967) root area D 2030 mm2 ,
Fb D
842 ð 103
4 ð 3919 ð 103
C
ð 3.02
ð 3.0
D 644 kN/m.
Lb D
644 ð 103
D 129 mm
5 ð 103
This is the minimum width required; actual width will depend on the chair design.
Actual width required (Figure 13.30):
D Lr C ts C 50 mm
D 150 C 20 C 50 D 220 mm
Actual bearing pressure on concrete foundation:
f0c D
644 ð 103
D 2.93 N/mm2
220 ð 103
3 ð 2.93
D 37.6 mm
140
round off to 40 mm
tb D 150
Chair dimensions from Figure 13.30 for bolt size M56.
Skirt to be welded flush with outer diameter of column shell.
⊲13.95⊳
856
50
305
75
45
;
;
;
;
;
;
;
;;;; ;
CHEMICAL ENGINEERING
40
170
All dimensions mm
13.9.3. Bracket supports
Brackets, or lugs, can be used to support vertical vessels. The bracket may rest on the
building structural steel work, or the vessel may be supported on legs; Figure 13.24.
The main load carried by the brackets will be the weight of the vessel and contents; in
addition the bracket must be designed to resist the load due to any bending moment due
to wind, or other loads. If the bending moment is likely to be significant skirt supports
should be considered in preference to bracket supports.
As the reaction on the bracket is eccentric, Figure 13.31, the bracket will impose a
bending moment on the vessel wall. The point of support, at which the reaction acts,
should be made as close to the vessel wall as possible; allowing for the thickness of any
insulation. Methods for estimating the magnitude of the stresses induced in the vessel
Bending
moment
Backing
plate
Reaction
Figure 13.31.
Loads on a bracket support
857
MECHANICAL DESIGN OF PROCESS EQUIPMENT
;;;;;
;;
;;;
;;
;;;
;;;
;;
;;
;;;;;;; ; ;
;;;;; ;;;;;;;;;;;;;;;
;;;;; ;;;; ;;;;;;;;;;
;; ;;;;;;; ;;;; ;;
;;;;; ;;;;;;;;;;;;;;;;;;;;;;
;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;
;;
wall by bracket supports are given by Brownell and Young (1959) and by Wolosewick
(1951). Backing plates are often used to carry the bending loads.
The brackets, and supporting steel work, can be designed using the usual methods for
structural steelwork. Suitable methods are given by Bednar (1986) and Moss (2003).
A quick method for sizing vessel reinforcing rings (backing plates) for bracket supports
is given by Mahajan (1977).
Typical bracket designs are shown in Figures 13.32a and b. The loads which steel
brackets with these proportions will support are given by the following formula:
1.5 L c
Fillet welds
all round
Throat
= 0.7 t c
Leg = t c
tc
1.5 L c
Lc
1.5 L c
;;;
;;; ;
;;;;;;;;; ;;;;;;;;;;;;;;;;;;
;;
(a)
2 Lc
tc
Lc
(b)
Figure 13.32.
Bracket designs (a) Single gusset plate (b) Double gusset plate
Single-gusset plate design, Figure 13.32a:
Fbs D 60Lc tc
⊲13.96⊳
858
CHEMICAL ENGINEERING
Double-gusset plate design, Figure 13.32b:
Fbs D 120Lc tc
⊲13.97⊳
where Fbs D maximum design load per bracket, N,
Lc D the characteristic dimension of bracket (depth), mm,
tc D thickness of plate, mm.
13.10. BOLTED FLANGED JOINTS
Flanged joints are used for connecting pipes and instruments to vessels, for manhole
covers, and for removable vessel heads when ease of access is required. Flanges may
also be used on the vessel body, when it is necessary to divide the vessel into sections
for transport or maintenance. Flanged joints are also used to connect pipes to other
equipment, such as pumps and valves. Screwed joints are often used for small-diameter
pipe connections, below 40 mm. Flanged joints are also used for connecting pipe sections
where ease of assembly and dismantling is required for maintenance, but pipework will
normally be welded to reduce costs.
Flanges range in size from a few millimetres diameter for small pipes, to several metres
diameter for those used as body or head flanges on vessels.
13.10.1. Types of flange, and selection
Several different types of flange are used for various applications. The principal types
used in the process industries are:
1.
2.
3.
4.
5.
Welding-neck flanges.
Slip-on flanges, hub and plate types.
Lap-joint flanges.
Screwed flanges.
Blank, or blind, flanges.
Welding-neck flanges, Figure 13.33a: have a long tapered hub between the flange
ring and the welded joint. This gradual transition of the section reduces the discontinuity stresses between the flange and branch, and increases the strength of the flange
assembly. Welding-neck flanges are suitable for extreme service conditions; where the
flange is likely to be subjected to temperature, shear and vibration loads. They will
normally be specified for the connections and nozzles on process vessels and process
equipment.
Slip-on flanges, Figure 13.33b: slip over the pipe or nozzle and are welded externally,
and usually also internally. The end of the pipe is set back from 0 to 2.0 mm. The
strength of a slip-on flange is from one-third to two-thirds that of the corresponding
standard welding-neck flange. Slip-on flanges are cheaper than welding-neck flanges and
are easier to align, but have poor resistance to shock and vibration loads. Slip-on flanges
are generally used for pipe work. Figure 13.33b shows a forged flange with a hub; for
light duties slip-on flanges can be cut from plate.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.33.
859
Flange types (a) Welding-neck (b) Slip-on (c) Lap-joint (d) Screwed
Lap-joint flanges, Figure 13.33c: are used for piped work. They are economical when
used with expensive alloy pipe, such as stainless steel, as the flange can be made from
inexpensive carbon steel. Usually a short lapped nozzle is welded to the pipe, but with
some schedules of pipe the lap can be formed on the pipe itself, and this will give a cheap
method of pipe assembly.
Lap-joint flanges are sometimes known as “Van-stone flanges”.
Screwed flanges, Figure 13.33d: are used to connect screwed fittings to flanges. They
are also sometimes used for alloy pipe which is difficult to weld satisfactorily.
Blind flanges (blank flanges): are flat plates, used to blank off flange connections, and
as covers for manholes and inspection ports.
13.10.2. Gaskets
Gaskets are used to make a leak-tight joint between two surfaces. It is impractical
to machine flanges to the degree of surface finish that would be required to make a
satisfactory seal under pressure without a gasket. Gaskets are made from “semi-plastic”
materials; which will deform and flow under load to fill the surface irregularities between
the flange faces, yet retain sufficient elasticity to take up the changes in the flange
alignment that occur under load.
860
CHEMICAL ENGINEERING
Table 13.4. Gasket materials
(Based on a similar table in BS 5500: 1991; see BS PD 5500 2003)
Gasket material
Rubber without fabric or a high percentage of
asbestos fibre; hardness:
below 75° IRH
75° IRH or higher
3.2 mm thick
Asbestos with a suitable binder
for the operating conditions
1.6 mm thick
0.8 mm thick
Rubber with cotton fabric insertion
3-ply
Rubber with asbestos fabric
insertion, with or without wire
reinforcement
2-ply
1-ply
Vegetable fibre
Spiral-wound metal, asbestos
filled
Corrugated metal,
asbestos inserted
or
Corrugated metal,
jacketed asbestos filled
Corrugated metal
Flat metal jacketed
asbestos filled
Grooved metal
Carbon
Stainless or
monel
Soft aluminium
Soft copper or brass
Iron or soft steel
Monel or 4 to 6
per cent chrome
Stainless steels
Soft aluminium
Soft copper or brass
Iron or soft steel
Monel or 4 to 6
per cent chrome
Stainless steels
Soft aluminium
Soft copper or brass
Iron or soft steel
Monel
4 to 6 per cent
chrome
Stainless steels
Soft aluminium
Soft copper or brass
Iron or soft steel
Monel or 4 to 6
per cent chrome
Stainless steels
Soft aluminium
Soft copper or brass
Gasket
factor
m
Min.
design
seating
stress
y(N/mm2 )
0.50
1.00
2.00
2.75
3.50
1.25
2.25
0
1.4
11.0
25.5
44.8
2.8
15.2
10
2.50
20.0
10
2.75
1.75
2.50
3.00
25.5
7.6
20.0
31.0
2.50
2.75
3.00
20.0
25.5
31.0
10
3.25
3.50
2.75
3.00
3.25
37.9
44.8
25.5
31.0
37.9
10
3.50
3.75
3.25
3.50
3.75
3.50
44.8
52.4
37.9
44.8
52.4
55.1
10
3.75
3.75
3.25
3.50
3.75
62.0
62.0
37.9
44.8
52.4
10
3.75
4.25
4.00
4.75
62.0
69.5
60.6
89.5
Sketches
Minimum
gasket
width
(mm)
10
10
10
10
861
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Table 13.4.
(continued)
Gasket
factor
m
Gasket material
Solid flat metal
Ring joint
Iron or soft steel
Monel or 4 to 6
per cent chrome
Stainless steels
Iron or soft steel
Monel or 4 to 6
per cent chrome
Stainless steels
Min.
design
seating
stress
y(N/mm2 )
5.50
124
6.00
6.50
5.50
150
179
124
6.00
6.50
150
179
Sketches
Minimum
gasket
width
(mm)
6
6
A great variety of proprietary gasket materials is used, and reference should be made
to the manufacturers’ catalogues and technical manuals when selecting gaskets for a
particular application. Design data for some of the more commonly used gasket materials
are given in Table 13.4. Further data can be found in the pressure vessel codes and
standards and in various handbooks; Perry et al. (1997). The minimum seating stress y is
the force per unit area (pressure) on the gasket that is required to cause the material to
flow and fill the surface irregularities in the gasket face.
The gasket factor m is the ratio of the gasket stress (pressure) under the operating
conditions to the internal pressure in the vessel or pipe. The internal pressure will force
the flanges’ faces apart, so the pressure on the gasket under operating conditions will
be lower than the initial tightening-up pressure. The gasket factor gives the minimum
pressure that must be maintained on the gasket to ensure a satisfactory seal.
The following factors must be considered when selecting a gasket material:
1. The process conditions: pressure, temperature, corrosive nature of the process fluid.
2. Whether repeated assembly and disassembly of the joint is required.
3. The type of flange and flange face (see Section 13.10.3).
Up to pressures of 20 bar, the operating temperature and corrosiveness of the process
fluid will be the controlling factor in gasket selection. Vegetable fibre and synthetic rubber
gaskets can be used at temperatures of up to 100Ž C. Solid polyfluorocarbon (Teflon) and
compressed asbestos gaskets can be used to a maximum temperature of about 260Ž C.
Metal-reinforced gaskets can be used up to around 450Ž C. Plain soft metal gaskets are
normally used for higher temperatures.
13.10.3. Flange faces
Flanges are also classified according to the type of flange face used. There are two basic
types:
1. Full-faced flanges, Figure 13.34a: where the face contact area extends outside the
circle of bolts; over the full face of the flange.
862
Figure 13.34.
CHEMICAL ENGINEERING
Flange types and faces (a) Full-face (b) Gasket within bolt circle (c) Spigot and socket (d) Ring
type joint
2. Narrow-faced flanges, Figure 13.34b, c, d: where the face contact area is located
within the circle of bolts.
Full face, wide-faced, flanges are simple and inexpensive, but are only suitable for low
pressures. The gasket area is large, and an excessively high bolt tension would be needed
to achieve sufficient gasket pressure to maintain a good seal at high operating pressures.
The raised face, narrow-faced, flange shown in Figure 13.34b is probably the most
commonly used type of flange for process equipment.
Where the flange has a plain face, as in Figure 13.34b, the gasket is held in place by
friction between the gasket and flange surface. In the spigot and socket, and tongue and
grooved faces, Figure 13.34c, the gasket is confined in a groove, which prevents failure by
“blow-out”. Matched pairs of flanges are required, which increases the cost, but this type
is suitable for high pressure and high vacuum service. Ring joint flanges, Figure 13.34d,
are used for high temperatures and high pressure services.
13.10.4. Flange design
Standard flanges will be specified for most applications (see Section 13.10.5). Special
designs would be used only if no suitable standard flange were available; or for large
MECHANICAL DESIGN OF PROCESS EQUIPMENT
863
flanges, such as the body flanges of vessels, where it may be cheaper to size a flange
specifically for the duty required rather than to accept the nearest standard flange, which
of necessity would be over-sized.
Figure 13.35 shows the forces acting on a flanged joint. The bolts hold the faces
together, resisting the forces due to the internal pressure and the gasket sealing pressure.
As these forces are offset the flange is subjected to a bending moment. It can be considered
as a cantilever beam with a concentrated load. A flange assembly must be sized so as
to have sufficient strength and rigidity to resist this bending moment. A flange that lacks
sufficient rigidity will rotate slightly, and the joint will leak; Figure 13.36. The principles
of flange design are discussed by Singh and Soler (1992), and Azbel and Cheremisinoff
(1982). Singh and Soler give a computer programme for flange design.
Design procedures and work sheets for non-standard flanges are given in the national
codes and standards.
Figure 13.35.
Figure 13.36.
Forces acting on an integral flange
Deflection of a weak flange (exaggerated)
864
CHEMICAL ENGINEERING
For design purposes, flanges are classified as integral or loose flanges.
Integral flanges are those in which the construction is such that the flange obtains
support from its hub and the connecting nozzle (or pipe). The flange assembly and nozzle
neck form an “integral” structure. A welding-neck flange would be classified as an integral
flange.
Loose flanges are attached to the nozzle (or pipe) in such a way that they obtain no
significant support from the nozzle neck and cannot be classified as an integral attachment.
Screwed and lap-joint flanges are typical examples of loose flanges.
The design procedures given in the codes and standards can be illustrated by considering
the forces and moments which act on an integral flange, Figure 13.35.
The total moment Mop acting on the flange is given by:
Mop D Hd hd C Ht ht C Hg hg
Where Hg
Ht
H
Hd
G
B
2b
b
⊲13.98⊳
D gasket reaction (pressure force), = G⊲2b⊳mPi
D pressure force on the flange face = H Hd ,
D total pressure force = ⊲/4⊳G2 Pi ,
D pressure force on the area inside the flange = ⊲/4⊳B2 Pi ,
D mean diameter of the gasket,
D inside diameter of the flange,
D effective gasket pressure width,
D effective gasket sealing width,
hd , hg and ht are defined in Figure 13.35.
The minimum required bolt load under the operating conditions is given by:
Wm1 D H C Hg
⊲13.99⊳
The forces and moments on the flange must also be checked under the bolting-up conditions.
The moment Matm is given by:
Matm D Wm2 hg
⊲13.100⊳
where Wm2 is the bolt load required to seat the gasket, given by:
Wm2 D yGb
⊲13.101⊳
where y is the gasket seating pressure (stress).
The flange stresses are given by:
longitudinal hub stress,
hb D F1 M
⊲13.102⊳
radial flange stress,
rd D F2 M
⊲13.103⊳
tangential flange stress,
tg D F3 M F4 rd
⊲13.104⊳
where M is taken as Mop or Matm , whichever is the greater; and the factors F1 to F4 are
functions of the flange type and dimensions, and are obtained from equations and graphs
given in the codes and standards (BS 5500, clause 3.8).
MECHANICAL DESIGN OF PROCESS EQUIPMENT
865
The flange must be sized so that the stresses given by equations 13.102 to 13.104
satisfy the following criteria:
hb 6> 1.5ff0
⊲13.105⊳
rd 6> ff0
⊲13.106⊳
1
2 ⊲hb
C rd ⊳ 6> ff0
⊲13.107⊳
1
2 ⊲hb
C tg ⊳ 6> ff0
⊲13.108⊳
where ff0 is the maximum allowable design stress for the flange material at the operating
conditions.
The minimum bolt area required Abf will be given by:
Abf D
Wm
fb
⊲13.109⊳
where Wm is the greater value of Wm1 or Wm2 , and fb the maximum allowable bolt
stress. Standard size bolts should be chosen, sufficient to give the required area. The
bolt size will not normally be less than 12 mm, as smaller sizes can be sheared off by
over-tightening.
The bolt spacing must be selected to give a uniform compression of the gasket. It will
not normally be less than 2.5 times the bolt diameter, to give sufficient clearance for
tightening with a wrench or spanner. The following formula can be used to determine the
maximum bolt spacing:
6tf
pb D 2db C
⊲13.110⊳
⊲m C 0.5⊳
where pb
db
tf
m
D
D
D
D
bolt pitch (spacing), mm,
bolt diameter, mm,
flange thickness, mm,
gasket factor.
13.10.5. Standard flanges
Standard flanges are available in a range of types, sizes and materials; and are used
extensively for pipes, nozzles and other attachments to pressure vessels.
The proportions of standard flanges are set out in various codes and standards. A typical
example of a standard flange design is shown in Figure 13.37. This was taken from BS
4504, which has now been superseded by the European standard BS EN 1092. The design
of standard flanges is also specified in BS 1560.
In the United States, flanges are covered by the standards issued by the American
National Standards Institute (ANSI). An abstract of the American standards is given by
Perry et al. (1997).
Standard flanges are designated by class numbers, or rating numbers, which correspond
to the primary service (pressure) rating of the flange at room temperature.
866
CHEMICAL ENGINEERING
STEEL SLIP-ON BOSS FLANGE FOR WELDING
Nominal pressure 6 bar
Nom.
size
10
15
20
25
32
40
50
65
80
100
125
150
200
250
300
Pipe
o.d.
d1
³
17.2
21.3
26.9
33.7
42.4
48.3
60.3
76.1
88.9
114.3
139.7
168.3
219.1
273
323.9
Flange
Raised face
D
b
h
d4
f
75
80
90
100
120
130
140
160
190
210
240
265
320
375
440
12
12
14
14
14
14
14
14
16
16
18
18
20
22
22
20
20
24
24
26
26
28
32
34
40
44
44
44
44
44
35
40
50
60
70
80
90
110
128
148
178
202
258
312
365
2
2
2
2
2
3
3
3
3
3
3
3
3
3
4
Figure 13.37.
Bolting
M10
M10
M10
M10
M12
M12
M12
M12
M16
M16
M16
M16
M16
M16
M20
Drilling
Boss
No.
d2
k
d3
4
4
4
4
4
4
4
4
4
4
8
8
8
12
12
11
11
11
11
14
14
14
14
18
18
18
18
18
18
22
50
55
65
75
90
100
110
130
150
170
200
225
280
335
395
25
30
40
50
60
70
80
100
110
130
160
185
240
295
355
Typical standard flange design (All dimensions mm)
The flange class number required for a particular application will depend on the design
pressure and temperature, and the material of construction. The reduction in strength
at elevated temperatures is allowed for by selecting a flange with a higher rating than
the design pressure. For example, for a design pressure of 10 bar (150 psi) a BS 1560
carbon steel flange class 150 flange would be selected for a service temperature below
300Ž C; whereas for a service temperature of, say, 300Ž C a 300 pound flange would be
specified. A typical pressure temperature relationship for carbon steel flanges is shown
in Table 13.5. Pressure temperature ratings for a full range of materials can be obtained
from the standards.
Typical designs, dimensioned, for welding-neck flanges over a range of pressure ratings
are given in Appendix E. These can be used for preliminary designs. The current standards
and suppliers’ catalogues should be consulted before firming up the design.
867
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Table 13.5.
Nominal
pressure
(bar)
2.5
6
10
16
25
40
Typical pressure-temperature ratings for carbon steel flanges, BS 4504.
Design pressure at temperature, ° C (bar)
up to
120
150
200
250
300
350
400
2.5
6.0
10
16
25
40
2.3
5.4
9.0
14.4
2.5
36.0
2.0
4.8
8.0
12.8
20.0
32.0
1.8
4.2
7.0
11.2
17.5
28.0
1.5
3.6
6.0
9.6
15.0
24.0
1.3
3.0
5.0
8.0
12.5
20.0
0.9
2.1
3.5
5.6
8.8
14.0
13.11. HEAT-EXCHANGER TUBE-PLATES
The tube-plates (tube-sheets) in shell and tube heat exchangers support the tubes, and
separate the shell and tube side fluids (see Chapter 12). One side is subject to the shellside pressure and the other the tube-side pressure. The plates must be designed to support
the maximum differential pressure that is likely to occur. Radial and tangential bending
stresses will be induced in the plate by the pressure load and, for fixed-head exchangers,
by the load due to the differential expansion of the shell and tubes.
A tube-plate is essentially a perforated plate with an unperforated rim, supported at its
periphery. The tube holes weaken the plate and reduce its flexual rigidity. The equations
developed for the stress analysis of unperforated plates (Section 13.3.5) can be used for
perforated plates by substituting “virtual” (effective) values for the elastic constants E
and v, in place of the normal values for the plate material. The virtual elastic constants
E0 and v0 are functions of the plate ligament efficiency, Figure 13.38; see O’Donnell and
Langer (1962). The ligament efficiency of a perforated plate is defined as:
D
ph dh
ph
⊲13.111⊳
where ph D hole pitch,
dh D hole diameter.
The “ligament” is the material between the holes (that which holds the holes together). In
a tube-plate the presence of the tubes strengthens the plate, and this is taken into account
when calculating the ligament efficiency by using the inside diameter of the tubes in place
of the hole diameter in equation 13.111.
Design procedures for tube-plates are given in BS PD 5500, and in the TEMA heat
exchanger standards (see Chapter 12). The tube-plate must be thick enough to resist the
bending and shear stresses caused by the pressure load and any differential expansion of
the shell and tubes. The minimum plate thickness to resist bending can be estimated using
an equation of similar form to that for plate end closures (Section 13.5.3).
P0
tp D Cph Dp
⊲13.112⊳
fp
868
CHEMICAL ENGINEERING
Figure 13.38.
where tp
P0
fp
Cph
Dp
D
D
D
D
D
D
Virtual elastic constants
the minimum plate thickness,
the effective tube plate design pressure,
ligament efficiency,
maximum allowable design stress for the plate,
a design factor,
plate diameter.
The value of the design factor Cph will depend on the type of head, the edge support
(clamped or simply supported), the plate dimensions, and the elastic constants for the
plate and tube material.
The tube-sheet design pressure P0 depends on the type of exchanger. For an exchanger
with confined heads or U-tubes it is taken as the maximum difference between the shellside and tube-side operating pressures; with due consideration being given to the possible
loss of pressure on either side. For exchangers with unconfined heads (plates fixed to the
shell) the load on the tube-sheets due to differential expansion of the shell and tubes must
be added to that due to the differential pressure.
The shear stress in the tube-plate can be calculated by equating the pressure force on
the plate to the shear force in the material at the plate periphery. The minimum plate
thickness to resist shear is given by:
tp D
0.155Dp P0
p
⊲13.113⊳
MECHANICAL DESIGN OF PROCESS EQUIPMENT
869
where p D the maximum allowable shear stress, taken as half the maximum allowable
design stress for the material (see Section 13.3.2).
The design plate thickness is taken as the greater of the values obtained from
equations 13.112 and 13.113 and must be greater than the minimum thickness given
below:
Tube o.d. (mm)
Minimum plate thickness (mm)
25
25 30
30 40
40 50
0.75 ð tube o.d.
22
25
30
For exchangers with fixed tube-plates the longitudinal stresses in the tubes and shell
must be checked to ensure that the maximum allowable design stresses for the materials
are not exceeded. Methods for calculating these stresses are given in the standards.
A detailed account of the methods used for the stresses analysis of tube sheets is given
by Jawad and Farr (1989), and Singh and Soler (1992). Singh and Soler give computer
programs for the design of the principal types of tube-plate.
13.12. WELDED JOINT DESIGN
Process vessels are built up from preformed parts: cylinders, heads, and fittings, joined
by fusion welding. Riveted construction was used extensively in the past (prior to the
1940s) but is now rarely seen.
Cylindrical sections are usually made up from plate sections rolled to the required
curvature. The sections (strakes) are made as large as is practicable to reduce the number
of welds required. The longitudinal welded seams are offset to avoid a conjunction of
welds at the corners of the plates.
Many different forms of welded joint are needed in the construction of a pressure
vessel. Some typical forms are shown in Figures 13.39 to 13.41.
The design of a welded joint should satisfy the following basic requirements:
1.
2.
3.
4.
Give good accessibility for welding and inspection.
Require the minimum amount of weld metal.
Give good penetration of the weld metal; from both sides of the joint, if practicable.
Incorporate sufficient flexibility to avoid cracking due to differential thermal
expansion.
The preferred types of joint, and recommended designs and profiles, are given in the
codes and standards.
The correct form to use for a given joint will depend on the material, the method of
welding (machine or hand), the plate thickness, and the service conditions. Double-sided
V- or U-sections are used for thick plates, and single V- or U-profiles for thin plates.
A backing strip is used where it is not possible to weld from both sides. Lap joints
are seldom used for pressure vessels construction, but are used for atmospheric pressure
storage tanks.
870
;;;;
;;;
;
CHEMICAL ENGINEERING
(a)
70°
(b)
(c)
10˚
(e)
(d)
Figure 13.39.
Weld profiles; (b to e) butt welds (a) Lap joint (b) Single ‘V’ (c) Backing strip (d) Single ‘U’
(e) Double ‘U’
(a)
(c)
Figure 13.40.
Typical weld profiles
(b)
(d)
Branches (a), (b) Set-on branches (c), (d) Set-in branches
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Figure 13.41.
Figure 13.42.
871
Typical construction methods for welded jackets
Transition between plates of unequal thickness
Where butt joints are made between plates of different thickness, the thicker plate is
reduced in thickness with a slope of not greater than 1 in 4 (14Ž ) (Figure 13.42).
The local heating, and consequent expansion, that occurs during welding can leave the
joint in a state of stress. These stresses are relieved by post-welding heat treatment. Not
all vessels will be stress relieved. Guidance on the need for post-welding heat treatment is
given in the codes and standards, and will depend on the service and conditions, materials
of construction, and plate thickness.
872
CHEMICAL ENGINEERING
To ensure that a satisfactory quality of welding is maintained, welding-machine
operators and welders working on the pressure parts of vessels are required to pass welder
approval tests; which are designed to test their competence to make sound welds.
13.13. FATIGUE ASSESSMENT OF VESSELS
During operation the shell, or components of the vessel, may be subjected to cyclic
stresses. Stress cycling can arise from the following causes:
1.
2.
3.
4.
5.
Periodic fluctuations in operating pressure.
Temperature cycling.
Vibration.
“Water hammer”.
Periodic fluctuation of external loads.
A detailed fatigue analysis is required if any of these conditions is likely to occur to
any significant extent. Fatigue failure will occur during the service life of the vessel if the
endurance limit (number of cycles for failure) at the particular value of the cyclic stress
is exceeded. The codes and standards should be consulted to determine when a detailed
fatigue analysis must be undertaken.
13.14. PRESSURE TESTS
The national pressure vessel codes and standards require that all pressure vessels be
subjected to a pressure test to prove the integrity of the finished vessel. A hydraulic
test is normally carried out, but a pneumatic test can be substituted under circumstances
where the use of a liquid for testing is not practical. Hydraulic tests are safer because
only a small amount of energy is stored in the compressed liquid. A standard pressure
test is used when the required thickness of the vessel parts can be calculated in accordance with the particular code or standard. The vessel is tested at a pressure above the
design pressure, typically 25 to 30 per cent. The test pressure is adjusted to allow for the
difference in strength of the vessel material at the test temperature compared with the
design temperature, and for any corrosion allowance.
Formulae for determining the appropriate test pressure are given in the codes and
standards; such as that given below:
t
fa
⊲13.114⊳
ð
Test pressure D 1.25 Pd
fn
⊲t c⊳
where Pd
fa
fn
c
t
D
D
D
D
D
design pressure, N/mm2 ,
nominal design strength (design stress) at the test temperature, N/mm2 ,
nominal design strength at the design temperature, N/mm2 ,
corrosion allowance, mm,
actual plate thickness, mm.
When the required thickness of the vessel component parts cannot be determined by
calculation in accordance with the methods given, the codes and standards require that
a hydraulic proof test be carried out. In a proof test the stresses induced in the vessel
873
MECHANICAL DESIGN OF PROCESS EQUIPMENT
during the test are monitored using strain gauges, or similar techniques. The requirements
for the proof testing of vessels are set out in the codes and standards.
13.15. HIGH-PRESSURE VESSELS
High pressures are required for many commercial chemical processes. For example, the
synthesis of ammonia is carried out at reactor pressures of up to 1000 bar, and high-density
polyethylene processes operate up to 1500 bar.
Only a brief discussion of the design of vessels for operation at high pressures will
be given in this section; sufficient to show the fundamental limitations of single-wall
(monobloc) vessels, and the construction techniques that are used to overcome this
limitation. A full discussion of the design and construction of high-pressure vessels and
ancillary equipment (pumps, compressors, valves and fittings) is given in the books by
Fryer and Harvey (1997) and Jawad and Farr (1989); see also the relevant ASME code,
ASME (2004).
13.15.1. Fundamental equations
Thick walls are required to contain high pressures, and the assumptions made in the earlier
sections of this chapter to develop the design equations for “thin-walled” vessels will not
be valid. The radial stress will not be negligible and the tangential (hoop) stress will vary
across the wall.
Consider the forces acting on the elemental section of the wall of the cylinder shown
in Figure 13.43. The cylinder is under an internal pressure Pi and an external pressure
Pe . The conditions for static equilibrium, with the forces resolved radially, give:
r rυ 2t υr sin
υ
⊲r C υr ⊳⊲r C υr⊳υ D 0
2
δφ
σ δ
σ + δσ
′
σ
′
δφ
′
δ
′
σ
δ
δ
δφ
−
σ
δφ
′
Figure 13.43.
Thick cylinder
′
+ δ δφ
874
CHEMICAL ENGINEERING
multiplying out taking the limit gives:
t C r
dr
C r D 0
dr
⊲13.115⊳
A second equation relating the radial and tangential stresses can be written if the
longitudinal strain εL and stress L are taken to be constant across the wall; that is, that
there is no distortion of plane sections, which will be true for sections away from the
ends. The longitudinal strain is given by:
εL D
1
[L ⊲t r ⊳v]
E
⊲13.116⊳
If εL and L are constant, then the term (t r ) must also be constant, and can be
written as:
⊲t r ⊳ D 2A
⊲13.117⊳
where A is an arbitrary constant.
Substituting for t in equation 13.115 gives:
2r C r
dr
D 2A
dr
and integrating
r D A C
B0
r2
⊲13.118⊳
where B0 is the constant of integration.
In terms of the cylinder diameter, the equations can be written as:
B
d2
B
t D A C 2
d
r D A C
⊲13.119⊳
⊲13.120⊳
These are the fundamental equations for the design of thick cylinders and are often referred
to as Lamé’s equations, as they were first derived by Lamé and Clapeyron (1833). The
constants A and B are determined from the boundary conditions for the particular loading
condition.
Most high-pressure process vessels will be under internal pressure only, the atmospheric
pressure outside a vessel will be negligible compared with the internal pressure. The
boundary conditions for this loading condition will be:
r D Pi at d D Di
r D 0 at d D Do
Substituting these values in equation 13.119 gives
Pi D A C
B
Di2
MECHANICAL DESIGN OF PROCESS EQUIPMENT
0 D A C
and
875
B
Do2
subtracting gives
1
1
2
Pi D B
2
Do
Di
hence
B D Pi
A D Pi
and
⊲Di2 Do2 ⊳
⊲Do2 Di2 ⊳
Di2
⊲Do2 Di2 ⊳
Substituting in equations 13.119 and 13.120 gives:
2 2
Di ⊲Do d2 ⊳
r D Pi 2 2
d ⊲Do Di2 ⊳
2 2
Di ⊲Do C d2 ⊳
t D Pi 2 2
d ⊲Do Di2 ⊳
⊲13.121⊳
⊲13.122⊳
The stress distribution across the vessel wall is shown plotted in Figure 13.44. The
maximum values will occur at the inside surface, at d D Di .
2
σt
0
σr
Compression
Stress
2
Do+ Di
Do2 - Di2
Tension
σ
ˆ t = Pi
σ̂r
= Pi
D1
Do
d
Figure 13.44.
Stress distribution in wall of a monobloc cylinder
Putting K D Do /Di , the maximum values are given by:
O r D Pi (compressive)
⊲13.123⊳
876
CHEMICAL ENGINEERING
O t D Pi
K2 C 1
K2 1
⊲13.124⊳
An expression for the longitudinal stress can be obtained by equating forces in the axial
direction:
D2
L ⊲Do2 Di2 ⊳ D Pi i
4
4
hence
L D
Pi Di2
Pi
D
2
2
2
⊲K 1⊳
⊲Do Di ⊳
⊲13.125⊳
The maximum shear stress will be given by (see Section 13.3.1):
O D 12 ⊲O t C O r ⊳ D
Pi K2
⊲K2 1⊳
⊲13.126⊳
Theoretical maximum pressure
If the maximum shear stress theory is taken as the criterion of failure (Section 13.3.2),
then the maximum pressure that a monobloc vessel can be designed to withstand without
failure is given by:
Pi K2
e0
D
2
⊲K2 1⊳
e0 K2 1
PO i D
2
K2
O D
hence
⊲13.127⊳
where e0 is the elastic limit stress for the material of construction divided by a suitable
factor of safety. As the wall thickness is increased the term ⊲K2 1⊳/K2 tends to 1,
and
PO i D
e0
2
⊲13.128⊳
which sets an upper limit on the pressure that can be contained in a monobloc cylinder.
Manning (1947) has shown that the maximum shear strain energy theory of failure
(due to Mises (1913)) gives a closer fit to experimentally determined failure pressures for
monobloc cylinders than the maximum shear stress theory. This criterion of failure gives:
0
PO i D pe
3
⊲13.129⊳
From Figure (13.44) it can be seen that the stress falls off rapidly across the wall and
that the material in the outer part of the wall is not being used effectively. The material
can be used more efficiently by prestressing the wall. This will give a more uniform
stress distribution under pressure. Several different “prestressing” techniques are used;
the principal methods are described briefly in the following sections.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
877
13.15.2. Compound vessels
Shrink-fitted cylinders
Compound vessels are made by shrinking one cylinder over another. The inside diameter
of the outer cylinder is made slightly smaller than the outer diameter of the inner cylinder,
and is expanded by heating to fit over the inner. On cooling the outer cylinder contracts and
places the inner under compression. The stress distribution in a two-cylinder compound
vessel is shown in Figure 13.45; more than two cylinders may be used.
Di
σ t, tangential stress
(a)
(b)
(c)
Figure 13.45.
Stress distribution in a shrink-fitted compound cylinder (a) Due to shrinkage (b) Due to pressure
(c) Combined (a C b)
Shrink-fitted compound cylinders are used for small-diameter vessels, such as
compressor cylinder barrels. The design of shrink-fitted compound cylinders is discussed
by Manning (1947) and Jawad and Farr (1989).
Multilayer vessels
Multilayer vessels are made by wrapping several layers of relatively thin plate round a
central tube. The plates are heated, tightened and welded, and this gives the desired stress
distribution in the compound wall. The vessel is closed with forged heads. A typical
878
CHEMICAL ENGINEERING
Figure 13.46.
Multilayer construction
design is shown in Figure 13.46. This construction technique is discussed by Jasper and
Scudder (1941) and Jawad and Farr (1989).
Wound vessels
Cylindrical vessels can be reinforced by winding on wire or thin ribbons. Winding on
the wire under tension places the cylinder under compression. For high-pressure vessels
special interlocking strips are used, such as those shown in Figure 13.47. The interlocking
gives strength in the longitudinal direction and a more uniform stress distribution. The
strips may be wound on hot to increase the prestressing. This type of construction is
described by Birchall and Lake (1947). Wire winding was used extensively for the barrels
of large guns.
Interlocking
strips
Figure 13.47.
Inner cylinder
Strip wound vessel
13.15.3. Autofrettage
Autofrettage is a technique used to prestress the inner part of the wall of a monobloc
vessel, to give a similar stress distribution to that obtained in a shrink-fitted compound
cylinder. The finished vessel is deliberately over pressurised by hydraulic pressure. During
this process the inner part of the wall will be more highly stressed than the outer part
and will undergo plastic strain. On release of the “autofrettage” pressure the inner part,
which is now over-size, will be placed under compression by the elastic contraction of the
outer part, which gives a residual stress distribution similar to that obtained in a two-layer
shrink-fitted compound cylinder. After straining the vessel is annealed at a relatively low
temperature, approximately 300Ž C. The straining also work-hardens the inner part of the
MECHANICAL DESIGN OF PROCESS EQUIPMENT
879
wall. The vessel can be used at pressures up to the “autofrettage” pressure without further
permanent distortion.
The autofrettage technique is discussed by Manning (1950) and Jawad and Farr (1989).
13.16. LIQUID STORAGE TANKS
Vertical cylindrical tanks, with flat bases and conical roofs, are universally used for the
bulk storage of liquids at atmospheric pressure. Tank sizes vary from a few hundred
gallons (tens of cubic metres) to several thousand gallons (several hundred cubic metres).
The main load to be considered in the design of these tanks is the hydrostatic pressure
of the liquid, but the tanks must also be designed to withstand wind loading and, for some
locations, the weight of snow on the tank roof.
The minimum wall thickness required to resist the hydrostatic pressure can be calculated
from the equations for the membrane stresses in thin cylinders (Section 13.3.4):
es D
where es
HL
L
J
g
ft
Dt
D
D
D
D
D
D
D
L HLg Dt
2ft J 103
⊲13.130⊳
tank thickness required at depth HL , mm,
liquid depth, m,
liquid density, kg/m3 ,
joint factor (if applicable),
gravitational acceleration, 9.81 m/s2 ,
design stress for tank material, N/mm2 ,
tank diameter, m.
The liquid density should be taken as that of water (1000 kg/m3 ), unless the process liquid
has a greater density.
For small tanks a constant wall thickness would normally be used, calculated at the
maximum liquid depth.
With large tanks, it is economical to take account of the variation in hydrostatic pressure
with depth, by increasing the plate thickness progressively from the top to bottom of the
tank. Plate widths of 2 m (6 ft) are typically used in tank construction.
The roofs of large tanks need to be supported by a steel framework; supported on
columns in very large-diameter tanks.
The design and construction of atmospheric storage tanks for the petroleum industry
are covered by British Standard BS 2654, and the American Petroleum Industry standards
API 650 (2003) and 620 (2002). The design of storage tanks is covered in the books by
Myers (1997), and Jawad and Farr (1989). See also the papers by Debham et al. (1968)
and Zick and McGarth (1968).
13.17. MECHANICAL DESIGN OF CENTRIFUGES
13.17.1. Centrifugal pressure
The fluid in a rotating centrifuge exerts pressure on the walls of the bowl or basket. The
minimum wall thickness required to contain this pressure load can be determined in a
880
CHEMICAL ENGINEERING
similar manner to that used for determining the wall thickness of a pressure vessel under
internal pressure. If the bowl contains a single homogeneous liquid, Figure 13.48a, the
fluid pressure is given by:
Pf D 21 L ω2 ⊲R12 R22 ⊳
⊲13.131⊳
where Pf
L
ω
R1
R2
D
D
D
D
D
centrifugal pressure, N/m2 ,
liquid density, kg/m3 ,
rotational speed of the centrifuge, radians/s,
inside radius of the bowl, m,
radius of the liquid surface, m.
Figure 13.48.
Centrifugal fluid pressure (a) Single fluid (b) Two fluids
For design, the maximum fluid pressure will occur when the bowl is full, R2 D 0.
If the centrifuge is separating two immiscible liquids, Figure 13.48b, the pressure will
be given by:
Pf D 12 ω2 [L1 ⊲R12 Ri2 ⊳ C L2 ⊲Ri2 R22 ⊳]
⊲13.132⊳
where L1 D density of the heavier liquid, kg/m3 ,
L2 D density of the lighter liquid, kg/m3 ,
Ri D radius of the interface between the two liquids, m.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
881
If the machine is separating a solid-liquid mixture, the mean density of the slurry in the
bowl should be used in equation 13.131.
The shell of an empty centrifuge bowl will be under stress due to the rotation of the
bowl’s own mass; this “self-pressure” Pm is given by:
Pm D 12 ω2 m [⊲R1 C t⊳2 R12 ]
⊲13.133⊳
where m D density of the bowl material, kg/m3 ,
t D bowl wall thickness, m.
The minimum wall thickness required can be estimated using the equations for
membrane stress derived in Section 13.3.4. For a solid bowl
ec D
Pt R1
fm ð 103
⊲13.134⊳
where Pt D the total (maximum) pressure (fluid C self-pressure), N/m2 ,
fm D maximum allowable design stress for the bowl material, N/mm2 ,
ec D wall thickness, mm.
With a perforated basket the presence of the holes will weaken the wall. This
can be allowed for by introducing a “ligament efficiency” into equation 13.134 (see
Section 13.11)
Pt R1
ec D
⊲13.135⊳
fm ð 103
where D ligament efficiency D ⊲ph dh ⊳/⊲ph ⊳,
ph D hole pitch,
dh D hole diameter.
Equations 13.134 and 13.135 can also be used to estimate the maximum safe load (or
speed) for an existing centrifuge, if the service is to be changed.
In deriving these equations no account was taken of the strengthening effect of the
bottom and top rings of the bowl or basket; so the equations will give estimates that are
on the safe side. Strengthening hoops or bands are used on some basket designs.
13.17.2. Bowl and spindle motion: critical speed
Centrifuges are classified according to the form of mounting used: fixed or free spindle.
With fixed-spindle machines, the bearings are rigidly mounted; whereas, in a free spindle,
or self-balancing, machine a degree of “free-play” is allowed in the spindle mounting. The
amount of movement of the spindle is restrained by some device, such as a rubber buffer.
This arrangement allows the centrifuge to operate with a certain amount of out-of-balance
loading without imposing an undue load on the bearings. Self-balancing centrifuges can
be under or over-driven; that is, with the drive mounted below or above the bowl.
Severe vibration can occur in the operation of fixed-spindle centrifuges and these are
often suspended on rods, supported from columns mounted on an independent base, to
prevent the vibration being transmitted to the building structure.
882
CHEMICAL ENGINEERING
Critical speed
If the centre of gravity of the rotating load does not coincide with the axis of rotation
of the bowl an uneven force will be exerted on the machine spindle. In a self-balancing
machine (or a suspended fixed-spindle machine) this will cause the spindle to deflect from
the vertical position and the bowl will develop a whirling vibration. The phenomenon is
analogous with the whirling of the shafts in other rotating machinery; such as compressors,
pumps, and agitators; which is considered under the general heading of the “whirling of
shafts” in standard texts on the “Theory of Machines”.
The simple analysis given below is based on that used to determine the whirling
speed of a shaft with a single concentrated mass. Figure 13.49 shows the position of
the centre of gravity of a rotating mass mc with an initial displacement hc . Let xc
be the additional displacement caused by the action of centrifugal force, and s the
restoring force, assumed to be proportional to the displacement. The radial outward
centrifugal force due to the displacement of the centre of the gravity from the axis of
rotation will be D mc ω2 ⊲x C hc ⊳. This is balanced by the inward action of the restoring
force D sxc .
Figure 13.49.
Displacement of centre of gravity of a centrifuge bowl
Equating the two forces:
mc ω2 ⊲xc C hc ⊳ D sxc
from which
xc
D
hc
1
s
1
mc ω 2
⊲13.136⊳
It can be seen by inspection of equation 13.136 that the deflection (the ratio xc /hc )
will become indefinitely large when the term s/mc ω2 D 1; the corresponding value of ω
is known as the critical, or whirling, speed. Above the critical speed the term s/mc ω2
becomes negative, and xc /hc tends to a limiting value of 1 at high speeds. This shows
that if the centrifuge is run at speeds in excess of the critical speed the tendency is for the
spindle to deflect so that the axis of rotation passes through the centre of gravity of the
system. The sequence of events as a self-balancing centrifuge run up to speed is shown
MECHANICAL DESIGN OF PROCESS EQUIPMENT
883
in Figure 13.50. In practice, a centrifuge is accelerated rapidly to get through the critical
speed range quickly, and the observed deflections are not great.
It can be seen from equation 13.136 that the critical speed of a centrifuge will depend
on the mass of the bowl and the magnitude of the restoring force; it will also depend
on the dimensions of the machine and the length of the spindle. The critical speed of a
simple system can be calculated, but for a complex system, such as loaded centrifuges, the
critical speed must be determined by experiment. It can be shown that the critical speed
of a rotating system corresponds with the natural frequency of vibration of the system.
A low critical speed is desired, as less time is then spent accelerating the bowl through
the critical range. Suspended fixed-spindle centrifuges generally have a low critical speed.
Precession
In addition to the whirling vibration due to an out-of-balance force, another type of motion
can occur in a free-spindle machine. When the bowl or basket is tilted the spindle may
move in a circle. This slow gyratory motion is known as “precession”, and is similar to
the “precession” of a gyroscope. It is usually most pronounced at high speeds, above the
critical speed.
A complete analysis of the motion of centrifuges is given by Alliott (1924, 1926).
Figure 13.50.
Diagram of action of self-balancing centrifuge, showing motion of centre of gravity and
unbalanced load with increasing speed
13.18. REFERENCES
ALLIOT, E. A. (1924) Trans. Inst. Chem. Eng. 2, 39. Self-balancing centrifugals.
ALLIOT, E. A. (1926) Centrifugal dryers and separators (Benn).
API 620 (2002) The design and construction of large, welded, low pressure storage tanks, 10th edn (American
Petroleum Institute).
API 650 (2003) Welded steel tanks for oil storage, 10th edn (American Petroleum Institute).
884
CHEMICAL ENGINEERING
AZBEL, D. S. and CHEREMISINOFF, N. P. (1982) Chemical and Process Equipment Design: vessel design and
selection (Ann Arbor Science).
BEDNAR, H. H. (1990) Pressure Vessel Design Handbook, 2nd edn (Krieger).
BHATTACHARYYA, B. C. (1976) Introduction to Chemical Equipment Design, Mechanical Aspects (Indian Institute
of Technology).
BERGMAN, D. J. (1963) Trans. Am. Soc. Mech. Eng. (J. Eng. for Ind.) 85, 219. Temperature gradients for skirt
supports of hot vessels.
BIRCHALL, H. and LAKE, G. F. (1947) Proc. Inst. Mech. Eng. 56, 349. An alternative form of pressure vessel
of novel construction.
BROWNELL, L. E. (1963) Hyd. Proc. and Pet. Ref. 42 (June) 109. Mechanical design of tall towers.
BROWNELL, L. E. and YOUNG, E. H. (1959) Process Equipment Design: Vessel design (Wiley).
CASE, J., CHILVER, A. H. and ROSS, C. (1999) Strength of Materials and Structures (Butterworth-Heinemann).
CHUSE, R. and CARSON, B. E. (1992) Pressure Vessels: the ASME code simplified, 7th edn (McGraw-Hill).
DEBHAM, J. B., RUSSEL, J. and WIILS, C. M. R. (1968) Hyd. Proc. 47 (May) 137. How to design a 600,000
b.b.l. tank.
DeGHETTO, K. and LONG, W. (1966) Hyd. Proc. and Pet. Ref. 45 (Feb.) 143. Check towers for dynamic stability.
ESCOE, A. K. (1994) Mechanical Design of Process Equipment, Vol. 1. 2nd edn Piping and Pressure Vessels
(Gulf).
FREESE, C. E. (1959) Trans. Am. Soc. Mech. E. (J. Eng. Ind.) 81, 77. Vibrations of vertical pressure vessels.
FRYER, D. M. and HARVEY, J. F. (1997) High Pressure Vessels (Kluwer).
GERE, J. M. and TIMOSHENKO, S. P. (2000) Mechanics of Materials (Brooks Cole).
HARVEY, J. F. (1974) Theory and Design of Modern Pressure Vessels, 2nd ed. (Van Nostrand-Reinhold).
HENRY, B. D. (1973) Aust. Chem. Eng. 14 (Mar.) 13. The design of vertical, free standing process vessels.
HETENYI, M. (1958) Beams on Elastic Foundations (University of Michigan Press).
HIGH PRESS. TECH. ASSOC. (1975) High Pressure Safety Code (High Pressure Technology Association, London).
JASPER, MCL, T. and SCUDDER, C. M. (1941) Trans. Am. Inst. Chem. Eng. 37, 885. Multi-layer construction of
thick wall pressure vessels.
I. WELD. (1952) Handbook for Welded Structural Steel Work, 4th ed. (The Institute of Welding).
JAWAD, M. H. and FARR, J. R. (1989) Structural Design of Process Equipment, 2nd edn (Wiley).
KARMAN, VON T. and, TSIEN, H-S. (1939) J. Aeronautical Sciences 7 (Dec.) 43. The buckling of spherical shells
by external pressure.
LAMÉ, G. and CLAPEYRON, B. P. E. (1833) Mém presinteś par Divers Savart 4, Paris.
MAHAJAN, K. K. (1977) Hyd. Proc. 56 (4) 207. Size vessel stiffners quickly.
MANNING, W. R. D. (1947) Engineering 163 (May 2nd) 349. The design of compound cylinders for high
pressure service.
MANNING, W. R. D. (1950) Engineering 169 (April 28th) 479, (May 5th) 509, (May 15th) 562, in three parts.
The design of cylinders by autofrettage.
MARSHALL, V. O. (1958) Pet. Ref. 37 (May) (supplement). Foundation design handbook for stacks and towers.
MEGYESY, E. F. (2001) Pressure Vessel Hand Book, 12th edn (Pressure Vessel Hand Book Publishers).
MISES VON R. (1913) Math. Phys. Kl., 582. Göttinger nachrichten.
MOSS, D. R. (2003) Pressure Vessel Design Manual (Elsevier/Butterworth-Heinemann).
MOTT, R. L. (2001) Applied Strength of Materials (Prentice Hall).
MYERS, P. E. (1997) Above Ground Storage Tanks (McGraw-Hill).
NELSON, J. G. (1963) Hyd. Proc. and Pet. Ref. 42 (June) 119. Use calculation form for tower design.
O’DONNELL, W. J. and LANGER, B. F. (1962) Trans. Am. Soc. Mech. Eng. (J. Eng. Ind.) 84, 307. Design of
perforated plates.
PERRY, R. H., GREEN, D. W. and MALONEY, J. O. (eds) (1997) Perry’s Chemical Engineers’ Handbook, 7th
edn. (McGraw-Hill)
SCHEIMAN, A. D. (1963) Hyd. Proc. and Pet. Ref. 42 (June) 130. Short cuts to anchor bolting and base ring
sizing.
SEED, G. M. (2001) Strength of Materials: An Undergraduate Text (Paul & Co. Publishing Consortium).
SINGH, K. P. and SOLER, A. I. (1992) Mechanical Design of Heat Exchangers and Pressure Vessel Components
(Springer-Verlag).
SOUTHWELL, R. V. (1913) Phil. Trans. 213A, 187. On the general theory of elastic stability.
TANG, S. S. (1968) Hyd. Proc. 47 (Nov.) 230. Shortcut methods for calculating tower deflections.
TIMOSHENKO, S. (1936) Theory of Elastic Stability (McGraw-Hill).
WEIL, N. A. and MURPHY, J. J. (1960) Trans. Am. Soc. Mech. Eng. (J. Eng. Ind.) 82 (Jan.) 1. Design and
analysis of welded pressure vessel skirt supports.
WINDENBURG, D. F. and TRILLING, D. C. (1934) Trans. Am. Soc. Mech. Eng. 56, 819. Collapse by instability
of thin cylindrical shells under external pressure.
WOLOSEWICK, F. E. (1951) Pet. Ref. 30 (July) 137, (Aug.) 101, (Oct.) 143, (Dec.) 151, in four parts. Supports
for vertical pressure vessels.
MECHANICAL DESIGN OF PROCESS EQUIPMENT
885
YOKELL, S. (1986) Chem. Eng., NY 93 (May 12th) 75. Understanding pressure vessel codes.
ZICK, L. P. (1951) Welding J. Research Supplement 30, 435. Stresses in large horizontal cylindrical pressure
vessels on two saddle supports.
ZICK, L. P. and MCGRATH, R. V. (1968) Hyd. Proc. 47 (May) 143. New design approach for large storage
tanks.
Bibliography
Useful references on pressure vessel design.
AZBEL, D. S. and CHEREMISINOFF, N. P. Chemical and Process Equipment Design: vessel design and selection
(Ann Arbor Science, 1982).
BEDNAR, H. H. Pressure Vessel Design Handbook, 2nd edn (Van Nostrand Reinhold, 1986).
CHUSE, R. Pressure Vessels: the ASME code simplified, 6th edn (McGraw-Hill, 1984).
ESCOE, A. K. Mechanical Design of Process Equipment, Vol. 1. Piping and Pressure Vessels. Vol. 2. Shell-andtube Heat Exchangers, Rotating Equipment, Bins, Silos and Stacks (Gulf, 1986).
FARR, J. R. and JAWAD, M. H. Guidebook for the Design of ASME Section VIII, Pressure Vessels, 2nd edn
(American Society of Mechanical Engineers, 2001).
GUPTA, J. P. Fundamentals of Heat Exchanger and Pressure Vessel Technology (Hemisphere, 1986).
JAWAD, M. H. and FARR, J. R. Structural Design of Process Equipment, 2nd edn (Wiley, 1989).
MEGYESY, E. F. Pressure Vessel Hand Book, 7th edn (Pressure Vessel Hand Book Publishers, 1986).
MOSS, D. R. Pressure Vessel Design Manual (Hemisphere, 1987).
ROAKE, R. J., YOUNG, W. C. and BUDYNAS, R. G. Formulas for Stress and Strain (McGraw-Hill, 2001).
SINGH, K. P. and SOLER, A. I. Mechanical Design of Heat Exchangers and Pressure Vessel Components
(Arcturus, 1984).
Standards
American Petroleum Institute, Washington DC, USA
API 620 (2002) Design and construction of large, welded, low pressure storage tanks, 10th edn.
API 650 (2002) Welded steel tanks for oil storage, 10th edn.
British Standards Institute, London, UK
BS 2654 (1989) Specification for the manufacture of welded non-refrigerated storage tanks for the petroleum
industry.
BS 4494 (1987) Specification for vessels and tanks in reinforced plastics.
BS CP 5500 (2003) Specification for unfired fusion welded pressure vessels.
BS EN 13445, Unfired pressure vessels
American Society of Mechanical Engineers, New York, USA
ASME Boiler and pressure vessel code (2204)
13.19. NOMENCLATURE
Dimensions
in MLT
A
Abf
A1
A2
a
2a
ae
Arbitrary constant in equation 13.117
Total bolt area required for a flange
Area removed in forming hole
Area of compensation
Diameter of flat plate
Major axis of ellipse
Acceleration due to an earthquake
ML1 T2
L2
L2
L2
L
L
LT2
886
B
B
B0
b
2b
C
Cc
Cd
Ce
Ch
Cp
Cph
Cs
c
D
D
Db
Dc
De
Deff
Di
Dm
Do
Dp
Dr
Ds
Dt
d
db
dh
dr
E
e
ec
ek
em
es
Fb
Fbs
Fc
Fp
Fr
Fs
Fw
F1
F2
F3
F4
f
fa
fb
fc
f0c
ff
fm
fn
fp
fr
fs
CHEMICAL ENGINEERING
Inside diameter of flange
Arbitrary constant in equation 13.120
Constant of integration in equation 13.118
Effective sealing width of gasket
Minor axis of ellipse
Constant in equation 13.34
Design factor in equation 13.46
Drag coefficient in equation 13.79
Seismic constant
Constant in equation 13.85
Constant in equation 13.34
Design factor in equation 13.112
Design factor in equation 13.44
Corrosion allowance
Diameter
Flexual rigidity
Bolt circle diameter
Diameter of cone at point of interest
Nominal diameter of flat end
Effective diameter of column for wind loading
Internal diameter
Mean diameter
Outside diameter
Plate diameter, tube-sheet
Diameter of stiffening ring
Skirt internal diameter
Tank diameter
Diameter at point of interest, thick cylinder
Bolt diameter
Hole diameter
Diameter of reinforcement pad
Young’s modulus
Minimum plate thickness
Minimum thickness of conical section
Minimum thickness of conical transition section
Minimum wall thickness, centrifuge
Minimum thickness of tank
Compressive load on base ring, per unit length
Load supported by bracket
Critical buckling load for a ring, per unit length
Local, concentrated, wind load
Load on stiffening ring, per unit length
Shear force due an earthquake
Loading due to wind pressure, per unit length
Factor in equation 13.102
Factor in equation 13.103
Factor in equation 13.104
Factor in equation 13.104
Maximum allowable stress (design stress)
Nominal design strength at test temperature
Maximum allowable bolt stress
Maximum allowable bearing pressure
Actual bearing pressure
Maximum allowable design stress for flange material
Maximum allowable stress for centrifuge material
Nominal design strength at design temperature
Maximum allowable design stress for plate
Maximum allowable design stress for ring material
Maximum allowable design stress for skirt material
L
MLT2
MLT2
L
L
L
L
ML2 T2
L
L
L
L
L
L
L
L
L
L
L
L
L
L
L
ML1 T2
L
L
L
L
L
MT2
MLT2
MT2
MLT2
MT2
MLT2
MT2
L3
L3
L3
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
MECHANICAL DESIGN OF PROCESS EQUIPMENT
ft
G
g
H
Hd
Hg
HL
Hp
Ht
Hv
h
hc
hd
hg
hi
ho
ht
I
I0
Ih
Ip
Ir
Iv
J
K
Kc
L
L0
Lc
Lk
Lo
Lr
M
Matm
Me
ML1
ML2
Mop
Ms
Mv
Mx
M1
M2
mc
Nb
n
P
Pc
Pc0
Pd
Pe
Pf
Pi
Pm
Pt
Pw
P0
pb
Maximum allowable design stress for tank material
Mean diameter of gasket
Gravitational acceleration
Total pressure force on flange
Pressure force on area inside flange
Gasket reaction
Liquid depth
Height of local load above base
Pressure force on flange face
Height (length) of cylindrical section between tangent lines
Height of domed head from tangent line
Initial displacement of shaft
Moment arm of force Hd
Moment arm of force Hg
Internal height of branch allowed as compensation
External height of branch allowed as compensation
Moment arm of force Ht
Second moment of area (moment of inertia)
Second moment of area per unit length
Second moment of area of shell, horizontal vessel
Polar second moment of area
Second moment of area of ring
Second moment of area of vessel
Joint factor, welded joint
Ratio of diameters of thick cylinder D Do /Di
Collapse coefficient in equation 13.52
Unsupported length of vessel
Effective length between stiffening rings
Critical distance between stiffening rings
Length of conical transition section
Distance between centre line of equipment and column
Distance between edge of skirt to outer edge of flange
Bending moment
Moment acting on flange during bolting up
Bending moment due to offset equipment
Longitudinal bending moment at mid-span
Longitudinal bending moment at saddle support
Total moment acting on flange
Bending moment at base of skirt
Bending moment acting on vessel
Bending moment at point x from free end of column
Bending moment acting along cylindrical sections
Bending moment acting along diametrical sections
Displaced mass, centrifuge
Number of bolts
Number of lobes
Pressure
Critical buckling pressure
Critical pressure to cause local buckling in a spherical shell
Design pressure
External pressure
Centrifugal pressure
Internal pressure
Self-pressure, centrifuge
Total pressure acting on centrifuge wall
Wind pressure loading
Effective tube-plate design pressure difference
Bolt pitch
887
ML1 T2
L
LT2
MLT2
MLT2
MLT2
L
L
MLT2
L
L
L
L
L
L
L
L
L4
L3
L4
L4
L4
L4
L
L
L
L
L
L
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
ML2 T2
M
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
L
888
ph
Rc
Rk
Ri
Ro
Rp
Rs
R1
R2
r
r1
r2
s
T
t
tb
tc
tf
tn
tp
ts
uw
W
We
Wm
Wm1
Wm2
Wv
w
w
x
x
xc
y
˛
c
s
ε
ε1 , ε2
s
m
a
L
L1
L2
b
b1
b2
e
e0
h
hb
L
r
CHEMICAL ENGINEERING
Hole pitch
Crown radius
Knuckle radius
Radius of interface
Major radius of torus
Radius of curvature of plate
Outside radius of sphere
Inside radius of centrifuge bowl
Radius of liquid surface
Radius
Meridional radius of curvature
Circumferential radius of curvature
Resisting force per unit displacement
Torque
Thickness of plate (shell)
Thickness of base ring
Thickness of bracket plate
Thickness of flange
Actual thickness of branch
Tube-plate thickness
Skirt thickness
Wind velocity
Total weight of vessel and contents
Weight of ancillary equipment
Greater value of Wm1 and Wm2 in equation 13.109
Minimum bolt load required under operating conditions
Minimum bolt load required to seal gasket
Weight of vessel
Deflection of flat plate
Loading per unit length
Radius from centre of flat plate to point of interest
Distance from free end of cantilever beam
Displacement caused by centrifugal force
Minimum seating pressure for gasket
Cone half cone apex angle
Dilation
Dilation of cylinder
Dilation of sphere
Strain
Principal strains
Angle
Base angle of conical section
Ligament efficiency
Poisson’s ratio
Density of vessel material
Density of air
Liquid density
Density of heavier liquid
Density of lighter liquid
Normal stress
Bending stress
Bending stress at mid-span
Bending stress at saddle supports
Stress at elastic limit of material
Elastic limit stress divided by factor of safety
Circumferential (hoop) stress
Longitudinal hub stress
Longitudinal stress
Radial stress
L
L
L
L
L
L
L
L
L
L
L
L
MT2
ML2 T2
L
L
L
L
L
L
L
LT1
MLT2
MLT2
MLT2
MLT2
MLT2
MLT2
L
MT2
L
L
L
ML1 T2
L
L
L
ML3
ML3
ML3
ML3
ML3
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
889
MECHANICAL DESIGN OF PROCESS EQUIPMENT
Radial flange stress
Stress in skirt support
Tangential (hoop) stress
Tangential flange stress
Stress in skirt due to weight of vessel
Normal stress in x direction
Normal stress in y direction
Axial stresses in vessel
Principal stresses
Torsional shear stress
Shear stress
Shear stress maxima
Slope of flat plate
Angle
Rotational speed
rd
s
t
tg
ws
x
y
z
1 , 2 , 3
xy
1 , 2 , 3
ω
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
ML1 T2
T1
Superscript
^
Maximum
13.20. PROBLEMS
13.1. Calculate the maximum membrane stress in the wall of shells having the shapes
listed below. The vessel walls are 2 mm thick and subject to an internal pressure
of 5 bar.
1.
2.
3.
4.
An infinitely long cylinder, inside diameter 2 m.
A sphere, inside diameter 2 m.
An ellipsoid, major axis 2 m, minor axis 1.6 m.
A torus, mean diameter 2 m, diameter of cylinder 0.3 m.
13.2. Compare the thickness required for a 2 m diameter flat plate, designed to resist
a uniform distributed load of 10 kN/m2 , if the plate edge is:
(a) completely rigid,
(b) free to rotate.
Take the allowable design stress for the material as 100 MN/m2 and Poisson’s
ratio for the material as 0.3.
13.3. A horizontal, cylindrical, tank, with hemispherical ends, is used to store liquid
chlorine at 10 bar. The vessel is 4 m internal diameter and 20 m long. Estimate
the minimum wall thickness required to resist this pressure, for the cylindrical
section and the heads. Take the design pressure as 12 bar and the allowable
design stress for the material as 110 MN/m2 .
13.4. The thermal design of a heat exchanger to recover heat from a kerosene stream
by transfer to a crude oil stream was carried in Chapter 12, Example 12.2. Make
a preliminary mechanical design for this exchanger. Base your design on the
specification obtained from the CAD design procedure used in the example. All
material of construction to be carbon steel (semi-killed or silicon killed). Your
design should cover:
(a) choice of design pressure and temperature,
(b) choice of the required corrosion allowances,
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CHEMICAL ENGINEERING
(c)
(d)
(e)
(f)
(g)
(h)
choice of the type of end covers,
determination of the minimum wall thickness for the shell, headers and ends,
a check on the pressure rating of the tubes,
a suggested thickness for the tube sheets detailed stressing is not required,
selection the flange types and dimensions use standard flanges,
design of the exchanger supports.
13.5. Make a preliminary mechanical design for the vertical thermosyphon reboiler for
which the thermal design was done as Example 12.9 in Chapter 12. The inlet
liquid nozzle and the steam connections will be 50 mm inside diameter. Flat
plate end closures will be used on both headers. The reboiler will be hung from
four bracket supports, positioned 0.5 m down from the top tube plate. The shell
and tubes will be of semi-killed carbon steel.
Your design should cover:
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
choice of design pressure and temperature,
choice of the required corrosion allowances,
selection of the header dimensions.
determination of the minimum wall thickness for the shell, headers and ends,
a check on the pressure rating of the tubes,
a suggested thickness for the tube sheets detailed stressing is not required,
selection the flanges types and dimensions use standard flanges,
reinforcement at the nozzles, if required,
design of the exchanger support brackets.
13.6. The specification for of a sieve plate column is given below. Make a preliminary
mechanical design for the column. You design should include:
(a)
(b)
(c)
(d)
(e)
column wall thickness,
selection and sizing of vessel heads,
reinforcement, if any, of openings,
the nozzles and flanges (use standard flanges),
column supporting skirt and base ring/flange.
You need not design the plates or plate supports.
You should consider the following design loads:
(a) internal pressure,
(b) wind loading,
(c) dead weight of vessel and contents (vessel full of water).
There will be no significant loading from piping and external equipment. Earthquake loading need not be considered.
Column specification:
Length of cylindrical section 37 m
Internal diameter 1.5 m
Heads, standard ellipsoidal
50 sieve plates
Nozzles: feed, at mid-point, 50 mm inside diameter,
vapour out, 0.7 m below top of cylindrical section, 250 mm
MECHANICAL DESIGN OF PROCESS EQUIPMENT
891
inside diameter
bottom product, centre of vessel head, 50 mm inside diameter
reflux return, 1.0 m below top of cylindrical section, 50 mm
inside diameter
Two 0.6 m diameter access ports (manholes) situated 1.0 m above the
bottom and 1.5 m below the top of the column
Support skirt height 2.5 m
Access ladder with platforms
Insulation, mineral wool, 50 mm thick
Materials of construction: vessel stainless steel, unstabilised (304)
nozzles as vessel
skirt carbon steel, silicon killed
Design pressure 1200 kN/m2
Design temperature 150 Ž C
Corrosion allowance 2 mm.
Make a dimensioned sketch of your design and fill out the column specification
sheet given in Appendix G.
13.7. A jacketed vessel is to be used as a reactor. The vessel has an internal diameter
of 2 m and is fitted with a jacket over a straight section 1.5 m long. Both the
vessel and jacket walls are 25 mm thick. The spacing between the vessel and
jacket is 75 mm.
The vessel and jacket are made of carbon steel. The vessel will operate at
atmospheric pressure and the jacket will be supplied with steam at 20 bar. Check
if the thickness of the vessel and jacket is adequate for this duty.
Take the allowable design stress as 100 N/mm2 and the value of Young’s modulus
at the operating temperature as 180,000 N/mm2 .
13.8. A high pressure steam pipe is 150 mm inside diameter and 200 mm outside
diameter. If the steam pressure is 200 bar, what will be the maximum shear
stress in the pipe wall?
13.9. A storage tank for concentrated nitric acid will be constructed from aluminium
to resist corrosion. The tank is to have an inside diameter of 6 m and a height of
17 m. The maximum liquid level in the tank will be at 16 m. Estimate the plate
thickness required at the base of the tank. Take the allowable design stress for
aluminium as 90 N/mm2 .
CHAPTER 14
General Site Considerations
14.1. INTRODUCTION
In the discussion of process and equipment design given in the previous chapters no
reference was made to the plant site. A suitable site must be found for a new project, and
the site and equipment layout planned. Provision must be made for the ancillary buildings
and services needed for plant operation; and for the environmentally acceptable disposal
of effluent. These subjects are discussed briefly in this chapter.
14.2. PLANT LOCATION AND SITE SELECTION
The location of the plant can have a crucial effect on the profitability of a project,
and the scope for future expansion. Many factors must be considered when selecting
a suitable site, and only a brief review of the principal factors will be given in this
section. Site selection for chemical process plants is discussed in more detail by Merims
(1966) and Mecklenburgh (1985); see also AIChemE (2003). The principal factors to
consider are:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Location, with respect to the marketing area.
Raw material supply.
Transport facilities.
Availability of labour.
Availability of utilities: water, fuel, power.
Availability of suitable land.
Environmental impact, and effluent disposal.
Local community considerations.
Climate.
Political and strategic considerations.
Marketing area
For materials that are produced in bulk quantities; such as cement, mineral acids, and
fertilisers, where the cost of the product per tonne is relatively low and the cost of
transport a significant fraction of the sales price, the plant should be located close to the
primary market. This consideration will be less important for low volume production,
high-priced products; such as pharmaceuticals.
892
GENERAL SITE CONSIDERATIONS
893
In an international market, there may be an advantage to be gained by locating the plant
within an area with preferential tariff agreements; such as the European Community (EC).
Raw materials
The availability and price of suitable raw materials will often determine the site location.
Plants producing bulk chemicals are best located close to the source of the major raw
material; where this is also close to the marketing area.
Transport
The transport of materials and products to and from the plant will be an overriding
consideration in site selection.
If practicable, a site should be selected that is close to at least two major forms of
transport: road, rail, waterway (canal or river), or a sea port. Road transport is being
increasingly used, and is suitable for local distribution from a central warehouse. Rail
transport will be cheaper for the long-distance transport of bulk chemicals.
Air transport is convenient and efficient for the movement of personnel and essential
equipment and supplies, and the proximity of the site to a major airport should be
considered.
Availability of labour
Labour will be needed for construction of the plant and its operation. Skilled construction
workers will usually be brought in from outside the site area, but there should be an
adequate pool of unskilled labour available locally; and labour suitable for training to
operate the plant. Skilled tradesmen will be needed for plant maintenance. Local trade
union customs and restrictive practices will have to be considered when assessing the
availability and suitability of the local labour for recruitment and training.
Utilities (services)
Chemical processes invariably require large quantities of water for cooling and general
process use, and the plant must be located near a source of water of suitable quality.
Process water may be drawn from a river, from wells, or purchased from a local authority.
At some sites, the cooling water required can be taken from a river or lake, or from
the sea; at other locations cooling towers will be needed.
Electrical power will be needed at all sites. Electrochemical processes that require large
quantities of power; for example, aluminium smelters, need to be located close to a cheap
source of power.
A competitively priced fuel must be available on site for steam and power generation.
Environmental impact, and effluent disposal
All industrial processes produce waste products, and full consideration must be given to
the difficulties and cost of their disposal. The disposal of toxic and harmful effluents will
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CHEMICAL ENGINEERING
be covered by local regulations, and the appropriate authorities must be consulted during
the initial site survey to determine the standards that must be met.
An environmental impact assessment should be made for each new project, or major
modification or addition to an existing process, see Section 14.6.5.
Local community considerations
The proposed plant must fit in with and be acceptable to the local community. Full
consideration must be given to the safe location of the plant so that it does not impose a
significant additional risk to the community.
On a new site, the local community must be able to provide adequate facilities for the
plant personnel: schools, banks, housing, and recreational and cultural facilities.
Land (site considerations)
Sufficient suitable land must be available for the proposed plant and for future expansion.
The land should ideally be flat, well drained and have suitable load-bearing characteristics.
A full site evaluation should be made to determine the need for piling or other special
foundations.
Climate
Adverse climatic conditions at a site will increase costs. Abnormally low temperatures
will require the provision of additional insulation and special heating for equipment
and pipe runs. Stronger structures will be needed at locations subject to high winds
(cyclone/hurricane areas) or earthquakes.
Political and strategic considerations
Capital grants, tax concessions, and other inducements are often given by governments to
direct new investment to preferred locations; such as areas of high unemployment. The
availability of such grants can be the overriding consideration in site selection.
14.3. SITE LAYOUT
The process units and ancillary buildings should be laid out to give the most economical
flow of materials and personnel around the site. Hazardous processes must be located
at a safe distance from other buildings. Consideration must also be given to the future
expansion of the site. The ancillary buildings and services required on a site, in addition
to the main processing units (buildings), will include:
1.
2.
3.
4.
5.
6.
Storages for raw materials and products: tank farms and warehouses.
Maintenance workshops.
Stores, for maintenance and operating supplies.
Laboratories for process control.
Fire stations and other emergency services.
Utilities: steam boilers, compressed air, power generation, refrigeration, transformer
stations.
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GENERAL SITE CONSIDERATIONS
7.
8.
9.
10.
Effluent disposal plant.
Offices for general administration.
Canteens and other amenity buildings, such as medical centres.
Car parks.
;
;;;; ;
; ;;;;;;;
When roughing out the preliminary site layout, the process units will normally be sited
first and arranged to give a smooth flow of materials through the various processing steps,
from raw material to final product storage. Process units are normally spaced at least 30 m
apart; greater spacing may be needed for hazardous processes.
The location of the principal ancillary buildings should then be decided. They should
be arranged so as to minimise the time spent by personnel in travelling between buildings.
Administration offices and laboratories, in which a relatively large number of people will
be working, should be located well away from potentially hazardous processes. Control
rooms will normally be located adjacent to the processing units, but with potentially
hazardous processes may have to be sited at a safer distance.
The siting of the main process units will determine the layout of the plant roads, pipe
alleys and drains. Access roads will be needed to each building for construction, and for
operation and maintenance.
Utility buildings should be sited to give the most economical run of pipes to and from
the process units.
Cooling towers should be sited so that under the prevailing wind the plume of
condensate spray drifts away from the plant area and adjacent properties.
The main storage areas should be placed between the loading and unloading facilities
and the process units they serve. Storage tanks containing hazardous materials should be
sited at least 70 m (200 ft) from the site boundary.
A typical plot plan is shown in Figure 14.1.
;;;;
Rail siding
Emergency
water
Fire station
Tank farm
Expansion
Pipe bridge
Plant area
1
Plant area
2
Plant
utilities
Workshops
Stores
Laboratory
Canteen
Change house
Expansion
Roads
Figure 14.1.
A typical site plan
Offices
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CHEMICAL ENGINEERING
A comprehensive discussion of site layout is given by Mecklenburgh (1985); see also
House (1969), Kaess (1970) and Meissner and Shelton (1992).
14.4. PLANT LAYOUT
The economic construction and efficient operation of a process unit will depend on how
well the plant and equipment specified on the process flow-sheet is laid out.
A detailed account of plant layout techniques cannot be given in this short section. A
fuller discussion can be found in the book edited by Mecklenburgh (1985) and in articles
by Kern (1977, 1978), Meissner and Shelton (1992), Brandt et al. (1992), and Russo and
Tortorella (1992).
The principal factors to be considered are:
1.
2.
3.
4.
5.
6.
7.
Economic considerations: construction and operating costs.
The process requirements.
Convenience of operation.
Convenience of maintenance.
Safety.
Future expansion.
Modular construction.
Costs
The cost of construction can be minimised by adopting a layout that gives the shortest
run of connecting pipe between equipment, and the least amount of structural steel work.
However, this will not necessarily be the best arrangement for operation and maintenance.
Process requirements
An example of the need to take into account process considerations is the need to elevate
the base of columns to provide the necessary net positive suction head to a pump (see
Chapter 5) or the operating head for a thermosyphon reboiler (see Chapter 12).
Operation
Equipment that needs to have frequent operator attention should be located convenient to
the control room. Valves, sample points, and instruments should be located at convenient
positions and heights. Sufficient working space and headroom must be provided to allow
easy access to equipment.
Maintenance
Heat exchangers need to be sited so that the tube bundles can be easily withdrawn for
cleaning and tube replacement. Vessels that require frequent replacement of catalyst or
packing should be located on the outside of buildings. Equipment that requires dismantling for maintenance, such as compressors and large pumps, should be placed under
cover.
GENERAL SITE CONSIDERATIONS
897
Safety
Blast walls may be needed to isolate potentially hazardous equipment, and confine the
effects of an explosion.
At least two escape routes for operators must be provided from each level in process
buildings.
Plant expansion
Equipment should be located so that it can be conveniently tied in with any future
expansion of the process.
Space should be left on pipe alleys for future needs, and service pipes over-sized to
allow for future requirements.
Modular construction
In recent years there has been a move to assemble sections of plant at the plant
manufacturer’s site. These modules will include the equipment, structural steel, piping
and instrumentation. The modules are then transported to the plant site, by road or sea.
The advantages of modular construction are:
1.
2.
3.
4.
Improved quality control.
Reduced construction cost.
Less need for skilled labour on site.
Less need for skilled personnel on overseas sites.
Some of the disadvantages are:
1.
2.
3.
4.
Higher design costs.
More structural steel work.
More flanged connections.
Possible problems with assembly, on site.
A fuller discussion of techniques and applications of modular construction is given by
Shelley (1990), Hesler (1990), and Whitaker (1984).
General considerations
Open, structural steelwork, buildings are normally used for process equipment; closed
buildings are only used for process operations that require protection from the weather.
The arrangement of the major items of equipment will usually follow the sequence
given on the process flow-sheet: with the columns and vessels arranged in rows and the
ancillary equipment, such as heat exchangers and pumps, positioned along the outside. A
typical preliminary layout is shown in Figure 14.2.
14.4.1. Techniques used in site and plant layout
Cardboard cut-outs of the equipment outlines can be used to make trial plant layouts.
Simple models, made up from rectangular and cylindrical blocks, can be used to study
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CHEMICAL ENGINEERING
Compressor house
Control room
C2
E7
P12
V3
P9
E6
P8
P7
F1
C4
P5
P4
E5
E3
C1
P2
Road Process equipment Pumps
pipe alley
over
Figure 14.2.
A typical plant layout
alternative layouts in plan and elevation. Cut-outs and simple block models can also be
used for site layout studies. Once the layout of the major pieces of equipment has been
decided, the plan and elevation drawings can be made and the design of the structural
steel-work and foundations undertaken.
Large-scale models, to a scale of at least 1 : 30, are normally made for major projects.
These models are used for piping design and to decide the detailed arrangement of small
items of equipment, such as valves, instruments and sample points. Piping isometric
diagrams are taken from the finished models. The models are also useful on the
construction site, and for operator training. Proprietary kits of parts are available for
the construction of plant models.
Computers are being increasingly used for plant layout studies, and computer models
are complementing, if not yet replacing, physical models. Several proprietary programs
are available for the generation of 3-dimensional models of plant layout and piping.
Present systems allow designers to zoom in on a section of plant and view it from
various angles. Developments of computer technology will soon enable engineers to
GENERAL SITE CONSIDERATIONS
Figure 14.3.
899
Computer generated layout “model” (Courtesy: Babcock Construction Ltd.)
virtually walk through the plant. A typical computer generated model is shown in
Figure 14.3.
Some of the advantages of computer graphics modelling compared with actual scale
models are:
1. The ease of electronic transfer of information. Piping drawings can be generated
directly from the layout model. Bills of quantities: materials, valves, instruments,
are generated automatically.
2. The computer model can be part of an integrated project information system,
covering all aspects of the project from conception to operation.
3. It is easy to detect interference between pipe runs, and pipes and structural steel:
occupying same space.
4. A physical model of a major plant construction can occupy several hundred
square metres. The computer model is contained on a few discs.
5. The physical model has to be transported to the plant site for use in the plant
construction and operator training. A computer model can be instantly available
in the design office, the customer’s offices, and at the plant site.
6. Expert systems and optimisation programs can be incorporated in the package
to assist the designer to find the best practical layout; see Madden et al. (1990).
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CHEMICAL ENGINEERING
14.5. UTILITIES
The word “Utilities” is now generally used for the ancillary services needed in the
operation of any production process. These services will normally be supplied from a
central site facility; and will include:
1.
2.
3.
4.
5.
6.
7.
8.
9.
Electricity.
Steam, for process heating.
Cooling water.
Water for general use.
Demineralised water.
Compressed air.
Inert-gas supplies.
Refrigeration.
Effluent disposal facilities.
Electricity
The power required for electrochemical processes; motor drives, lighting, and general
use, may be generated on site, but will more usually be purchased from the local supply
company (the national grid system in the UK). The economics of power generation on
site are discussed by Caudle (1975).
The voltage at which the supply is taken or generated will depend on the demand. For
a large site the supply will be taken at a very high voltage, typically 11,000 or 33,000 V.
Transformers will be used to step down the supply voltage to the voltages used on the
site. In the United Kingdom a three-phase 415-V system is used for general industrial
purposes, and 240-V single-phase for lighting and other low-power requirements. If a
number of large motors is used, a supply at an intermediate high voltage will also be
provided, typically 6000 or 11,000 V.
A detailed account of the factors to be considered when designing electrical distribution
systems for chemical process plants, and the equipment used (transformers, switch gear
and cables), is given by Silverman (1964).
Steam
The steam for process heating is usually generated in water tube boilers; using the most
economical fuel available. The process temperatures required can usually be obtained
with low-pressure steam, typically 2.5 bar (25 psig), and steam is distributed at a
relatively low mains pressure, typically around 8 bar (100 psig). Higher steam pressures,
or proprietary heat-transfer fluids, such as Dowtherm (see Conant and Seifert, 1963),
will be needed for high process temperatures. The generation, distribution and utilisation
of steam for process heating in the manufacturing industries is discussed in detail by
Lyle (1963).
Combined heat and power (co-generation)
The energy costs on a large site can be reduced if the electrical power required is generated
on site and the exhaust steam from the turbines used for process heating. The overall
GENERAL SITE CONSIDERATIONS
901
thermal efficiency of such systems can be in the range 70 to 80 per cent; compared with
the 30 to 40 per cent obtained from a conventional power station, where the heat in the
exhaust steam is wasted in the condenser. Whether a combined heat and power system
scheme is worth considering for a particular site will depend on the size of the site, the
cost of fuel, the balance between the power and heating demands; and particularly on the
availability of, and cost of, standby supplies and the price paid for any surplus power
electricity generated. The economics of combined heat and power schemes for chemical
process plant sites in the United Kingdom is discussed by Grant (1979).
On any site it is always worth while considering driving large compressors or pumps
with steam turbines and using the exhaust steam for local process heating.
Cooling water
Natural and forced-draft cooling towers are generally used to provide the cooling water
required on a site; unless water can be drawn from a convenient river or lake in sufficient
quantity. Sea water, or brackish water, can be used at coastal sites, but if used directly
will necessitate the use of more expensive materials of construction for heat exchangers
(see Chapter 7).
Water for general use
The water required for general purposes on a site will usually be taken from the local
mains supply, unless a cheaper source of suitable quality water is available from a river,
lake or well.
Demineralised water
Demineralised water, from which all the minerals have been removed by ion-exchange,
is used where pure water is needed for process use, and as boiler feed-water. Mixed and
multiple-bed ion-exchange units are used; one resin converting the cations to hydrogen
and the other removing the acid radicals. Water with less than 1 part per million of
dissolved solids can be produced.
Refrigeration
Refrigeration will be needed for processes that require temperatures below those that can
be economically obtained with cooling water. For temperatures down to around 10Ž C
chilled water can be used. For lower temperatures, down to 30Ž C, salt brines (NaCl and
CaCl2 ) are used to distribute the “refrigeration” round the site from a central refrigeration
machine. Vapour compression machines are normally used.
Compressed air
Compressed air will be needed for general use, and for the pneumatic controllers that
are usually used for chemical process plant control. Air is normally distributed at a
mains pressure of 6 bar (100 psig). Rotary and reciprocating single-stage or two-stage
compressors are used. Instrument air must be dry and clean (free from oil).
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CHEMICAL ENGINEERING
Inert gases
Where large quantities of inert gas are required for the inert blanketing of tanks and for
purging (see Chapter 9) this will usually be supplied from a central facility. Nitrogen is
normally used, and is manufactured on site in an air liquefaction plant, or purchased as
liquid in tankers.
Effluent disposal
Facilities will be required at all sites for the disposal of waste materials without creating
a public nuisance; see Section 14.6.1.
14.6. ENVIRONMENTAL CONSIDERATIONS
All individuals and companies have a duty of care to their neighbours, and to the
environment in general. In the United Kingdom this is embodied in the Common Law. In
addition to this moral duty, stringent controls over the environment are being introduced
in the United Kingdom, the European Union, the United States, and in other industrialised
countries and developing countries.
Vigilance is required in both the design and operation of process plant to ensure that
legal standards are met and that no harm is done to the environment.
Consideration must be given to:
1.
2.
3.
4.
5.
6.
7.
All emissions to land, air, water.
Waste management.
Smells.
Noise.
The visual impact.
Any other nuisances.
The environmental friendliness of the products.
14.6.1. Waste management
Waste arises mainly as byproducts or unused reactants from the process, or as offspecification product produced through mis-operation. There will also be fugitive
emissions from leaking seals and flanges, and inadvertent spills and discharges through
mis-operation. In emergency situations, material may be discharged to the atmosphere
through vents normally protected by bursting discs and relief values.
The designer must consider all possible sources of pollution and, where practicable,
select processes that will eliminate or reduce (minimise) waste generation. The Institution
of Chemical Engineers has published a guide to waste minimisation, IChemE (1997).
Unused reactants can be recycled and off-specification product reprocessed. Integrated
processes can be selected: the waste from one process becoming the raw material for
another. For example, the otherwise waste hydrogen chloride produced in a chlorination
process can be used for chlorination using a different reaction; as in the balanced,
chlorination-oxyhydrochlorination process for vinyl chloride production. It may be
GENERAL SITE CONSIDERATIONS
903
possible to sell waste to another company, for use as raw material in their manufacturing
processes. For example, the use of off-specification and recycled plastics in the production
of lower grade products, such as the ubiquitous black plastics bucket.
Processes and equipment should be designed to reduce the chances of mis-operation; by
providing tight control systems, alarms and interlocks. Sample points, process equipment
drains, and pumps should be sited so that any leaks flow into the plant effluent collection
system, not directly to sewers. Hold-up systems, tanks and ponds, should be provided to
retain spills for treatment. Flanged joints should be kept to the minimum needed for the
assembly and maintenance of equipment.
When waste is produced, processes must be incorporated in the design for its treatment
and safe disposal. The following techniques can be considered:
1.
2.
3.
4.
5.
6.
7.
8.
Dilution and dispersion.
Discharge to foul water sewer (with the agreement of the appropriate authority).
Physical treatments: scrubbing, settling, absorption and adsorption.
Chemical treatment: precipitation (for example, of heavy metals), neutralisation.
Biological treatment: activated sludge and other processes.
Incineration on land, or at sea.
Landfill at controlled sites.
Sea dumping (now subject to tight international control).
A British Standard has been published to assist with the management of waste systems,
BS EN ISO 14401 (1996).
The sources of air pollution and their control are covered in several books: Walk (1997),
Heumann (1997), Davies (2000), and Cooper and Ally (2002).
Gaseous wastes
Gaseous effluents which contain toxic or noxious substances will need treatment before
discharge into the atmosphere. The practice of relying on dispersion from tall stacks is
seldom entirely satisfactory. Witness the problems with acid rain in Scandinavian countries
attributed to discharges from power stations in the United Kingdom. Gaseous pollutants
can be removed by absorption or adsorption. Finely dispersed solids can be removed by
scrubbing, or using electrostatic precipitators; see Chapter 10. Flammable gases can be
burnt. The subject of air pollution is covered by Strauss and Mainwarring (1984).
Liquid wastes
The waste liquids from a chemical process, other than aqueous effluent, will usually be
flammable and can be disposed of by burning in suitably designed incinerators. Care must
be taken to ensure that the temperatures attained in the incinerator are high enough to
completely destroy any harmful compounds that may be formed; such as the possible
formation of dioxins when burning chlorinated compounds. The gases leaving an incinerator may be scrubbed, and acid gases neutralised. A typical incinerator for burning
gaseous or liquid wastes is shown in Chapter 3, Figure 3.16. The design of incinerators
for hazardous waste and the problems inherent in the disposal of waste by incineration
are discussed by Butcher (1990) and Baker-Counsell (1987).
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CHEMICAL ENGINEERING
In the past, small quantities of liquid waste, in drums, has been disposed of by dumping
at sea or in land-fill sites. This is not an environmentally acceptable method and is now
subject to stringent controls.
Solid wastes
Solid waste can be burnt in suitable incinerators or disposed by burial at licensed land-fill
sites. As for liquid wastes, the dumping of toxic solid waste at sea is now not acceptable.
Aqueous wastes
The principal factors which determine the nature of an aqueous industrial effluent and on
which strict controls will be placed by the responsible authority are:
1.
2.
3.
4.
pH.
Suspended solids.
Toxicity.
Biological oxygen demand.
The pH can be adjusted by the addition of acid or alkali. Lime is frequently used to
neutralise acidic effluents.
Suspended solids can be removed by settling, using clarifiers (see Chapter 10).
For some effluents it will be possible to reduce the toxicity to acceptable levels by
dilution. Other effluents will need chemical treatment.
The oxygen concentration in a water course must be maintained at a level sufficient
to support aquatic life. For this reason, the biological oxygen demand of an effluent is
of utmost importance. It is measured by a standard test: the BOD5 (five-day biological
oxygen demand). This test measures the quantity of oxygen which a given volume of the
effluent (when diluted with water containing suitable bacteria, essential inorganic salts,
and saturated with oxygen) will absorb in 5 days, at a constant temperature of 20Ž C.
The results are reported as parts of oxygen absorbed per million parts effluent (ppm).
The BOD5 test is a rough measure of the strength of the effluent: the organic matter
present. It does not measure the total oxygen demand, as any nitrogen compounds present
will not be completely oxidised in 5 days. The Ultimate Oxygen Demand (UOD) can be
determined by conducting the test over a longer period, up to 90 days. If the chemical
composition of the effluent is known, or can be predicted from the process flow-sheet, the
UOD can be estimated by assuming complete oxidation of the carbon present to carbon
dioxide, and the nitrogen present to nitrate:
UOD D 2.67C C 4.57N
where C and N are the concentrations of carbon and nitrogen in ppm.
Activated sludge processes are frequently used to reduce the biological oxygen demand
of an aqueous effluent before discharge.
A full discussion of aqueous effluent treatment is given by Eckenfelder et al. (1985);
see also Eckenfelder (1999).
GENERAL SITE CONSIDERATIONS
905
Where waste water is discharged into the sewers with the agreement of the local water
authorities, a charge will normally be made according to the BOD value, and any treatment
required. Where treated effluent is discharged to water courses, with the agreement of the
appropriate regulatory authority, the BOD5 limit will typically be set at 20 ppm.
14.6.2. Noise
Noise can cause a serious nuisance in the neighbourhood of a process plant. Care needs to
be taken when selecting and specifying equipment such as compressors, air-cooler fans,
induced and forced draught fans for furnaces, and other noisy plant. Excessive noise can
also be generated when venting through steam and other relief valves, and from flare
stacks. Such equipment should be fitted with silencers. Vendors’ specifications should
be checked to ensure that equipment complies with statutory noise levels; both for the
protection of employees (see Chapter 9), as well as for noise pollution considerations.
Noisy equipment should, as far as practicable, be sited well away from the site boundary.
Earth banks and screens of trees can be used to reduce the noise level perceived outside
the site.
14.6.3. Visual impact
The appearance of the plant should be considered at the design stage. Few people object
to the fairyland appearance of a process plant illuminated at night, but it is a different
scene in daylight. There is little that can be done to change the appearance of a modern
style plant, where most of the equipment and piping will be outside and in full view,
but some steps can be taken to minimise the visual impact. Large equipment, such as
storage tanks, can be painted to blend in with, or even contrast with, the surroundings.
Landscaping and screening by belts of trees can also help improve the overall appearance
of the site.
14.6.4. Legislation
It is not feasible to review the growing body of legislation covering environmental control
in this short chapter.
Stricter legislation and tighter control of discharges into the environment are being
introduced in most countries. The specialist texts brought out by publishers catering
for management topics, and by the government departments, should be consulted for
up-to-date information on environmental legislation.
Legislation and control procedures in the United Kingdom are increasingly being derived
from regulations promulgated by the European Union (EU).
Kiely (1996) gives a comprehensive summary of EU and US environmental legislation.
All the legislation embodies the concept of Best Practicable Means (BPM). This
requires the designer to use the most appropriate treatment to comply with the regulation,
whilst taking into account: local conditions, current technology and cost. The concept of
BPM also applies to the installation, maintenance and operation of the plant.
906
CHEMICAL ENGINEERING
14.6.5. Environmental auditing
An environmental audit is a systematic examination of how a business operation affects
the environment. It will include all emissions to air, land, and water; and cover the legal
constraints, the effect on community, the landscape, and the ecology. Products will be
considered, as well as processes.
When applied at the design stage of a new development it is more correctly called an
environmental impact assessment.
The aim of the audit or assessment is to:
1. Identify environmental problems associated with manufacturing process and the use
of the products, before they become liabilities.
2. To develop standards for good working practices.
3. To provide a basis for company policy.
4. To ensure compliance with environmental legislation.
5. To satisfy requirements of insurers.
6. To be seen to be concerned with environmental questions: important for public
relations.
7. To minimise the production of waste: an economic factor.
Environmental auditing is discussed by Grayson (1992). His booklet is a good source
of references for commentary on the subject, and to government bulletins.
14.7. REFERENCES
A.I.CHEM.E (2003) Guidelines for Facility Siting and Layout (American Institute of Chemical Engineers).
BAKER-COUNSELL, J. (1987) Process Eng. (April) 26. Hazardous wastes: the future for incineration.
BRANDT, D., GEORGE, W., HATHAWAY C. and MCCLINTOCK, N. (1992) Chem. Eng., NY, 99 (April) 97. Plant
layout, Part 2: The impact of codes, standards and regulations.
BS EN ISO 14001 (1996) Environmental Management Systems: specification with guidance for use (British
Standards Institute)
BUTCHER, C. (1990) Chem. Engr., London No. 471 (April 12th) 27. Incinerating hazardous waste.
CAUDLE, P. G. (1975) Chemistry & Industry (Sept. 6th) 717 The comparative economics of self generated and
purchased power.
CONANT, A. R. and SEIFERT, W. F. (1963) Chem. Eng. Prog. 59 (May) 46. High temperature heating media:
Dowtherm.
COOPER, C. D. and ALLY, F. C. (2002) Air Pollution Control, 3rd edn (Waveland Press)
DAVIES W. T. (ed.) (2000) Air Pollution Engineering Manual (Wiley International).
ECKENFELDER, W. W., PATOCZKA, J. and WATKIN, A. T. (1985) Chem. Eng., NY, 92 (Sept.) 60. Wastewater
treatment.
ECKENFELDER, W. W. (1999) Industrial Water Pollution Control, 2nd edn (McGraw-Hill).
GRAYSON, L. (ed.) (1992) Environmental Auditing (Technical Communications, UK).
HESLER, W. E. (1990) Chem. Eng. Prog. 86 (10) 76. Modular design: where it fits.
HEUMANN, W. L. (1997) Industrial Air Pollution Control Systems (McGraw-Hill).
HOUSE, F. F. (1969) Chem. Eng., NY 76 (July 28) 120. Engineers guide to plant layout.
ICHEME (1997) Waste Minimisation, a practical guide (Institution of Chemical Engineers), London.
KAESS, D. (1970) Chem. Eng., NY 77 (June 1st) 122. Guide to trouble free plant layouts.
KERN, R. (1977) Chem. Eng., NY 84:
(May 23rd) 130. How to manage plant design to obtain minimum costs.
(July 4th) 123. Specifications are the key to successful plant design.
(Aug. 15th) 153. Layout arrangements for distillation columns.
(Sept. 12th) 169. How to find optimum layout for heat exchangers.
(Nov. 7th) 93. Arrangement of process and storage vessels.
(Dec. 5th) 131. How to get the best process-plant layouts for pumps and compressors.
GENERAL SITE CONSIDERATIONS
907
KERN, R. (1978) Chem. Eng., NY 85:
(Jan. 30th) 105. Pipework design for process plants.
(Feb. 27th) 117. Space requirements and layout for process furnaces.
(April 10th) 127. Instrument arrangements for ease of maintenance and convenient operation.
(May 8th) 191. How to arrange plot plans for process plants.
(July 17th) 123. Arranging the housed chemical process plant.
(Aug. 14th) 141. Controlling the cost factor in plant design.
KIELY, G. (1996) Environmental Engineering (McGraw-Hill)
LYLE, O. (1963) The Efficient Use of Steam (HMSO).
MADDEN, J., PULFORD, C. and SHADBOLT, N. (1990) Chem. Engr., London No. 474 (May 24th) 32. Plant
layout untouched by human hand?
MECKLENBURGH, J. C. (ed.) (1985) Process Plant Layout (Godwin/Longmans).
MEISSNER, R. E. and SHELTON, D. C. (1992) Chem. Eng., NY, 99 (April) 97. Plant layout, Part 1: Minimizing
problems in plant layout.
MERIMS, R. (1966) Plant location and site considerations, in The Chemical Plant, Landau, R. (ed.) (Reinhold).
RUSSO, T. J. and TORTORELLA, A. J. (1992) Chem. Eng., NY 99 (April) 97. Plant layout, Part 3: The contribution
of CAD.
SILVERMAN, D. (1964) Chem. Eng., NY 71 (May 25th) 131, (June 22nd) 133, (July 6th) 121, (July 20th), 161,
in four parts. Electrical design.
SHELLEY, S. (1990) Chem. Eng. NY, 97 (Aug.) 30. Making inroads with modular construction.
WALK, K. (1997) Air Pollution: Its Origin and Control, 3rd edn (1997).
WHITTAKER, R. (1984) Chem. Eng. NY, 92 (May 28th) 80. Onshore modular construction.
APPENDIX A
Graphical Symbols for Piping Systems
and Plant
BASED ON BS 1553: PART 1: 1977
Scope
This part of BS 1553 specifies graphical symbols for use in flow and piping diagrams for
process plant.
Symbols (or elements of symbols) for use in conjunction with other
symbols
Access point
Mechanical linkage
Equipment branch:
general symbol
Note. The upper representation does not
necessarily imply a
flange, merely the termination point. Where a
breakable connection is
required the branch/pipe
would be as shown in the
lower symbol
Weight device
Electrical device
Vibratory or loading
device (any type)
Equipment penetration
(fixed)
Spray device
Equipment penetration
(removable)
Rotary movement
Boundary line
Stirring device
Point of change
Fan
Discharge to atmosphere
908
APPENDIX A
Basic and developed symbols for plant and equipment
Heat transfer equipment
Heat exchanger (basic symbols)
Alternative:
Shell and tube: fixed tube sheet
Shell and tube: U tube or floating head
Shell and tube: kettle reboiler
Air - blown cooler
Plate type
Double pipe type
Heating / cooling coil (basic symbol)
Fired heater / boiler (basic symbol)
909
910
CHEMICAL ENGINEERING
Upshot heater
Detail A
Where complex burners are employed
the ‘‘burner block’’ may be detailed
elsewhere on the drawing, thus
Detail A
Vessels and tanks
Drum or simple pressure vessel
(basic symbol)
Knock-out drum (with demister pad)
Tray column (basic symbol)
Tray column
Trays should be numbered from the
bottom; at least the first and the last
should be shown. Intermediate trays
should be included and numbered where
they are significant.
30
14
APPENDIX A
Fluid contacting vessel (basic symbol)
Fluid contacting vessel
Support grids and distribution details
may be shown
Reaction or absorption vessel
(basic symbol)
Reaction or absorption vessel
Where it is necessary to show more than
one layer of material alternative
hatching should be used
Autoclave (basic symbol)
Autoclave
911
912
CHEMICAL ENGINEERING
Open tank (basic symbol)
Open tank
Clarifier or settling tank
Sealed tank
Covered tank
Tank with fixed roof (with draw-off
sump)
Tank with floating roof (with roof drain)
Storage sphere
Gas holder (basic symbol for all types)
APPENDIX A
Pumps and compressors
Rotary pump, fan or simple compressor
(basic symbol)
Centrifugal pump or centrifugal fan
Centrifugal pump (submerged suction)
Positive displacement rotary pump or rotary
compressor
Positive displacement pump (reciprocating)
Axial flow fan
Compressor: centrifugal / axial flow ( basic
symbol )
Compressor: centrifugal / axial flow
Compressor: reciprocating ( basic symbol )
Ejector / injector ( basic symbol )
913
914
CHEMICAL ENGINEERING
Solids handling
Size reduction
Breaker gyratory
Roll crusher
Pulverizer : ball mill
Mixing (basic symbol)
Kneader
Ribbon blender
Double cone blender
Filter (basic symbol, simple batch)
Filter press (basic symbol)
Rotary filter, film drier or flaker
APPENDIX A
Cyclone and hydroclone (basic symbol)
Cyclone and hydroclone
Centrifuge (basic symbol)
Centrifuge: horizontal peeler type
Centrifuge: disc bowl type
Drying
Drying oven
Belt drier (basic symbol)
Rotary drier (basic symbol)
Rotary kiln
915
916
CHEMICAL ENGINEERING
Spray drier
Materials handling
Belt conveyor
Screw conveyor
Elevator (basic symbol)
Prime movers
Electric motor (basic
symbol)
Turbine (basic symbol)
APPENDIX B
Corrosion Chart
An R indicates that the material is resistant to the named chemical up to the temperature
shown, subject to the limitations given in the notes. The notes are given at the end of the
table.
A blank indicates that the material is unsuitable. ND indicates that no data was available
for the particular combination of material and chemical.
This chart is reproduced with the permission of IPC Industrial Press Ltd.
NOTE
This appendix should be used as a guide only
before a material is used its suitability should be
cross-checked with the manufacturer.
917
918
CHEMICAL ENGINEERING
Centigrade
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R82
R
R
R
R
R
R
R
R
R
R24 R
R R
R11 R
R
R
R
R
R2
R1
R
Alum
Aluminium chloride
Ammonia, anhydrous
Ammonia, aqueous
Ammonium chloride
R
R11
R
R
R84
R
ND
R
R
R
R
ND
R
R
R
R R R
R20 R20
R R R
Amyl acetate
Aniline
Antimony trichloride
Aqua regia
Aromatic solvents
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Beer
Benzoic acid
Boric acid
Brines, saturated
Bromine
R
R
R
R
R11
R
R
R
R
R
R
R
R
R
R
R
R20
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Calcium chloride
Carbon disulphide
Carbonic acid
Carbon tetrachloride
Caustic soda & potash
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Chlorates of Na, K, Ba
Chlorine, dry
Chlorine, wet
Chlorides of Na, K, Mg
Chloroacetic acids
R11 R
R R
R
R
R
R
R
R
R
R
R
Chlorobenzene
Chloroform
Chlorosulphonic acid
Chromic acid (80%)
Citric acid
R ND ND
R1 R R
R R R
R R R
R20 R20 R20
R
R
Fluorine, dry
Fluorine, wet
Fluosilicic acid
Formaldehyde (40%)
Formic acid
R R
R R
R R
R R
No data
R
R
R
R
R
R
Acetylene
Acid fumes
Alcohols (most fatty)
Aliphatic esters
Alkyl chlorides
Ether
Fatty acids (> C6 )
Ferric chloride
Ferrous sulphate
Fluorinated refrigerants,
aerosols, e.g. Freon
Nickel (cast)
Mild Steel
BSS 15
Lead
High Si Iron
(14% Si) (c)
Gunmetal and
Bronze (d)
Copper
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Acetaldehyde
R
Acetic acid (10%)
R
Acetic acid (glac. & anh.) R1
Acetic anhydride
R1
Acetone
R
Other ketones
R
Copper salts (most)
Cresylic acids (50%)
Cyclohexane
Detergents, synthetic
Emulsifiers (all conc.)
Cast Iron (c)
Brass (b)
Aluminium
Bronze
Aluminium (a)
METALS
R2 R2 R2
R R R
R R R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R1 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R83
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R18 R10
R4,10
R R R62
R R
R R
R
R
R
R
R
R R
R R
R11 R
R
R
R
R4 ND ND
R R
R4 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R4
R R R
ND
R R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R R4
R R
R4 R4,22
R
R
R
R
R
R
R
R
No data
R R
No data
R R
R R
R11 R
R
R
R
R
R
R
R R
No data
No data
R
R R20
No data
R
No data
R R
R
R
R
R
R
R
R
R
R R
No data
R
R
R
R
R
R
R
R11
R
R
R
R
R
R
R
R
R4
R
R
R R
R R
R R
R R
No data
R16 R R
R R R
R R R
No data
No data
R16 R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R11 R
R
R
R
R
R
R
R
R
R
R
No data
No data
R11 R
R R
R
R
R
R
R
R
R11 R
R11 R
R
R
R25
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R4 R
R4
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R4 R
R R ND
R R R58
No data
R30 R36
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R62
R
R
R
R
R
R
R
R
R
No data
No data
R
R
R4
R R
R R
R24
R
R20
R
R
R
R
R R
No data
R11
R
R R
No data
R R
R R
R R R
R
R
R R
R R
No data
R
R
R11
R
R
R
R20
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R20 R20 R20
R
R
R
R
R
ND
R
R
R
R2
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R11
No data
R
R11 R
R R
R
R
R
R
R
R
R
R
R
R
R11 ND ND
No data
R
R
R
ND
ND
ND
R
R
R
R
R
R
R
R
R
R11 R
R
R
R
R
R
R
R
R
R
84
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R R
No data
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
No data
R
R
R
R
R
R
R
R11 R
R R
R11 R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
No data
No data
R
R
R
R58
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R20 R
R
R
R R
R R
R
R
R
R
R
R
R
R
R
R R
R11 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R R
No data
R
R
R
R
R
R
R
R
R11 ND ND
R
R
R
R
No data
R
R
R20
R
R
R
R
R
R
R
R
R
R
R
R
919
APPENDIX B
Zirconium
Titanium
Tin (g)
Tantalum
Austenitic Ferricr
Stainless Steel (x)
Molybdenum
Stainless
Steel 18/8 (f)
Stainless Steel
18/8 (f)
Silver
Platinum
Ni Resist
(High Ni
Iron) (c)
Nickel-Copper
Alloys (e)
METALS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R2
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R80
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16 R
R R
R R
R
R
R
R
R2
R
R
R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R30
R73
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R84
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R2
R
R
R11
R
R
R
R
R
R
R
R
R
R
R R13
R84
R R R
R R R
R84
R
R84
R
R
R84
R
R
R
R
R
R R
R R
R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R102
R
R
R
R
R102
R
R
R
R
R102
R
R
R
R
R5
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R44 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R57
R R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R R R
R R R
R11 R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R11 R
R
R
R
R
R
R
R
R
R
R
R25
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R11 R R
R
R R
R20 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R R
R42
R
R
R
R R
R R
R R
R42
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R11
R
ND
R
R
R13
R42
R
R
R11
R
ND
R
R
R13
R
R
R
R103
R R
R R
R R
R103
R
R
R
R
R
R
R
R
R
R70
R
R
R
R
R
R
R
R
R
R
R
R16 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R30
R
R
R
R
R
R
R
R
R
R
R
ND
R
R11 R
R11 R
R84
R
R
R
R
R
R
R
R
R
R
R11 R
R11 R
R
R
R
R
R30
R
R13 R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R30
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16
R
R
R
R
R16
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R11 R
R
R11 R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R R
R R
No data
R
R
R R R
ND ND ND
R
R
R
R
R
R
R
R
R
R
ND ND
R R
No data
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
No data
R32 R32 ND
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R84
R
R
R
R
R84 R
R R
R R
No data
R R R
R56 R56
R R R
R R
R R
No data
R
ND ND
R
R
ND ND
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R2
R93
R
R
ND
R2
R93
R
R
ND
R2
R93
R
R
R
R2
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R
ND
R
R
R
R
R
R
R
R90
R
R
R
R
R
R
R
R
R
R
R
R
R90
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R19
R
R
R
R
R15
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R79 R79 R79
R
R57 R
R
R
R
R
R
R
R
R
R
R
R
R
R2
R
R
R2
No data
R ND
R
R
R
R19
27
R R
ND ND
R R
R ND
No data
R R
R R
No data
R25 R25 R25
R91 R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R19
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R5
R
R
R
R
R
R
R
R
R
R
R
R
R R
R67
R
69
R
R10
20
920
CHEMICAL ENGINEERING
Centigrade
Fruit juices
Gelatine
Glycerine
Glycols
Hexamine
R
R
R
R
Hydrofluoric acid (40%)
Hydrofluoric acid (75%)
Hydrogen peroxide (30%) R
(30 90%) R
Hydrogen sulphide
R
Hypochlorites
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Nickel (cast)
Mild Steel
BSS 15
Lead
High Si Iron
(14% Si) (c)
R
R
R
R
R
No data
ND ND
R
R
R
R
R
R
R
R
R
R
No data
R
R62
R20 R20 R20
R
R
R
R
R
R
R
R
R
R
R
R
R11
R
R
R
R
R
R
R
R
R
R
No data
R R R
No data
R R R
Mercuric chloride
Mercury
Milk & its products
Moist air
Molasses
R
R
R
R
R
R
R
R
R
R R R
R R R
R30 R30 R30
R
R30 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
ND
R
R
R
R R
No data
No data
R R R
R11
R
R
R
R
R11
R
R
No data
No data
R
No data
ND
R
R
R
R4,11
R R
R R
No data
No data
R73 R73 R73
R
R
R
R
R
R
R
R
R R
R R
No data
R R R
R
Oils, vegetable & animal
Oxalic acid
Ozone
Paraffin wax
Perchloric acid
R R
R50
R R
R R
R
R
R
Phenol
Phosphoric acid (25%)
Phosphoric acid (50%)
Phosphoric acid (95%)
Phosphorus chlorides
R
R
R
R
R
R
R
R
R11
Phosphorus pentoxide
Phthalic acid
Picric acid
Pyridine
Sea water
R11
R
R
R
R
ND
R
ND
R
R
ND
R
ND
R
R
No data
R R R
Silicic acid
Silicone fluids
Silver nitrate
Sodium carbonate
Sodium peroxide
R
R
R
R
R
R
R
R
R
R
R
R11
R
R
R
R
R11
No data
R R
R
R
R
R
R4 R4
R
R
R
R R
No data
R
R
R
R
R R
R4,34,76
R
R
R
ND
R
R
R R
No data
R
R
R
R
R R
R R
No data
R11 R R
R R
R30 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
No data
No data
R R R
No data
R
R
R
R
R
R
R
ND ND
R R
R
R
R
R
R
R
R
R
R
R
R
R4
R
R
No data
R R
R
R
R R
R ND
No data
R11 R
4
R
R
No data
R
R R
No data
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R R
R4
No data
R R
R
R
R
R11 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R11
R4
R
R
R
R
R R
R84
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R11
R10
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R
R
R
R
R ND
No data
R R R
R R R
R10 R10 R10
R
R
R
R R
R R
No data
R R R
R
R
R
R
R
R
R
R
R
No data
R R R
R R R
R R R
R
R R
No data
No data
R
R R
R R
No data
R R R
R
R
R
R
R R
No data
R R R
R R R
R
R
R
R
R
R
R
R
R
11
R
R
No data
R62 R
R
R
R R
R R
R30 R
R
R
R
R
R
R
ND ND
R
R
R
R R
No data
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R R
R4
R R
R R
R
R4
R
R
R11 R
R
R20
R
R
R
R
No data
R
R42 R
R
R
R11
R
R11
R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R62
R62
Lactic acid (100%)
Lead acetate
Lime (CaO)
Maleic acid
Meat juices
Nitric acid (50%)
Nitric acid (95%)
Nitric acid, fuming
Oils, essential
Oils, mineral
Gunmetal and
Bronze (d)
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Hydrazine
R
Hydrobromic acid (50%)
Hydrochloric acid (10%)
Hydrochloric acid (conc.)
Hydrocyanic acid
R
Naphtha
Naphthalene
Nickel salts
Nitrates of Na, K, NH3
Nitric acid (<25%)
Copper
Cast Iron (c)
Brass (b)
Aluminium
Bronze
Aluminium (a)
METALS
R R
R R
R R
R R
No data
R27
R
R
R
R
R
R
R
R
R
R
R
R
R R
R40 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
11
R
R
R19
R
R4
R
R
R
R
R
R
R
R
R
No data
R11 R
R
R11 R R
No data
No data
R
No data
No data
R
R
R
No data
R R
R
R
R
R
R
R
No data
R R R
11
R
R R R
R ND ND
R
R
R
R
ND
R
R
R
R
R
R
R
921
APPENDIX B
Zirconium
Titanium
Tin (g)
Tantalum
Austenitic Ferricr
Stainless Steel (x)
Molybdenum
Stainless
Steel 18/8 (f)
Stainless Steel
18/8 (f)
Silver
Platinum
Ni Resist
(High Ni
Iron) (c)
Nickel-Copper
Alloys (e)
METALS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
ND
No data
R
R
R
R
R
R
R
R87
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R7
R
R
R R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R R
R R R
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R19
R
R70
R70
R
R
R
R
R
R
R
R
R
R
R
R
R
R87
R87
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R45
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R13
R
R R
R R
R13 R13
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R86 R
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R30
R
R
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R16
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R87
R
R
R R
R63
R R
R
R
R
R
R
R
R
R80
R R
R R
R
R
R
R
R
R
R
R
R
R
No data
R R
R R
R R
R R
R R R
R R
R11 R11 R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R99
R
R
R
R
R
R
R
R
R
R
R104
R
R
R
R104
R
R
R
R104
R
R
R
R39
R
R
R48
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R98 R
R
R
R
R
R94
R16
R
R
R
R
R
R
ND
R R
R R
R
R
R
R
R
R
R20
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R11
R
R
R
R
R
R
R
R
R
R
R
R
R R
R13
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R70
R
R
R
R
R
R
R
R
R
R
R
R R11
No data
R R R
R R R
R57
R R11
No data
R R R
R R R
R57
R R
No data
R R R
R R R
R R R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R R
No data
ND ND ND
R R R
R10 R10 R10
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R ND
R ND
R ND
No data
R
R
R
R
R
R
R
R30
R
R92
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R R
R R
R92 R92
No data
R
R
R
R
R
R
R
R
R R
ND ND
No data
R R R
No data
R R
No data
R R R
R R R
R R R
R R7
R ND
No data
R R R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R ND
R R31
32
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R R ND
R23
No data
R R R
R R ND
R
R
R
R
R
R49
78
R49
78
R11
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
No data
R ND ND
No data
R R ND
R R R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R20 R
R R
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R R
R R
R11 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R8
R9
R
R
No data
R R ND
R R49
R
78
R78 R78 ND
No data
R
R
R
R
R11 ND ND
R
R13
R
R
R
R
R
R
R R
R
R
R57 R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
No data
R R R
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R49
78
R
R11 ND
No data
R R R
19
R R19 ND
R R R
No data
R
R
R R
R R
No data
R R R
R32 R R
R
R
R
R
R
R
No data
ND ND
No data
R R R
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
922
CHEMICAL ENGINEERING
Centigrade
Nickel (cast)
Mild Steel
BSS 15
Lead
High Si Iron
(14% Si) (c)
Gunmetal and
Bronze (d)
Copper
Cast Iron (c)
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Sodium silicate
Sodium sulphide
Stannic chloride
Starch
Sugar, syrups, jams
R
Sulphamic acid
Sulphates (Na, K, Mg, Ca)
Sulphites
Sulphonic acids
Sulphur
R50
R R R
R R R
No data
R R R
Sulphur dioxide, dry
Sulphur dioxide, wet
Sulphur trioxide
Sulphuric acid (< 50%)
Sulphuric acid (70%)
R R
R4 R
Sulphuric acid (95%)
Sulphuric acid, fuming
Sulphur chlorides
Tallow
Tannic acid (10%)
Brass (b)
Aluminium
Bronze
Aluminium (a)
METALS
R
R
R
R
R
R
R
R
R
R11
R R
R R
R
R
R
R
R
R
R
R
No data
R R
R R
No data
R
R
R11
R
R
R
R
R
R
R62
R
R
R
R
R
R
R
R
R
No data
R R
R
R
No data
R
R
R
R11 R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R38 R
R11
R R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
No data
R
R
R
R
R
R11 R
R R
R
R
R11 R
R
R
R62
R4
R
R R
R11
R R
R
R
R
R
R
R
R
R
R
R
R
R
Tartaric acid
Trichlorethylene
Vinegar
Water, distilled
Water, soft
R
R
R
R
R43
R
R
R
R
R
R
R
R
R
R
R
R
R
R53
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Water, hard
Yeast
Zinc chloride
R43 R
R R
R
R
R
R R
No data
R R R
R
R R
No data
R
R
R
R
R
No data
R R
R
R
R11
R
R
R
R
R
R
R
R R
ND
R
R R
R R
R
R
R38
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R53 R
R R
R
R53 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R
R
R
R R
R R
No data
R R R
R R R
R R
R4 R
R
R
R
R
R
R
R
R
R
No data
No data
R
R
R
R
R
R
R
No data
No data
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R4
R
R
R
R
No data
R R
R R
No data
R R R
R
R
R
R
R
R
R
R
No data
R R
R
R
R
R
R
R11 R
R
R
R
R
R
R
R
R
4
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R4 R
R R
R
R53 R
R
R
R
R
R
R
R
R
R
R11 R
R R
No data
R R
4
R53 R
R53 R
R
R
R
R R
No data
No data
No data
ND ND
R20
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R20 R
R
R
R
923
APPENDIX B
Zirconium
Titanium
Tin (g)
Tantalum
Austenitic Ferricr
Stainless Steel (x)
Molybdenum
Stainless
Steel 18/8 (f)
Stainless Steel
18/8 (f)
Silver
Platinum
Ni Resist
(High Ni
Iron) (c)
Nickel-Copper
Alloys (e)
METALS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
R
R R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R20
R R R
R38 R R
No data
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R20
R
R
R
R
R
R
R
R
R
R
ND
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R94 R
R
R
R
R
R
R
R
R
R R
R R
R R
No data
R11 R R
R44
R R R
R R R
No data
R R R
R
R
R
R
R
R
R
R
R
R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
No data
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R48 R
R R
R R
R
R
R
R
R
R
R
R R
R
No data
R R R
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R37
R R
R R
No data
R R R
R
R
R
R
R R
R R
No data
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R11 R
R10
R R R
R R
R11 R11 R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R80
R
R
R
R
R
R
R
R
R
R
R
R
R70
R
R
R
R
R
R
R
R
R
R
R11
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R11
R
R
R84
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R80 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R15
R
R ND
ND R10
R15 R15
R ND
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R20
R11
R
R
R
R
R
R
R
R
R
R
R
R84 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R57 R
R R
R
R
R
R15
R
R
No data
R R
R R
R R
R R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R19
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
No data
R R52
R
R
R
R
R
R
R
R
R
R
R
R49
R
78
R
R
R
R15
R
R
R R
ND R734
No data
R R R
R49
R
78
R
R
No data
R R R
R R R
R
R
R15
R
R
R
R
R
R
R
R
R
R
R
No data
R R
R R
R
R
R
R
R
924
CHEMICAL ENGINEERING
Centigrade
Alum
Aluminium chloride
Ammonia, anhydrous
Ammonia, aqueous
Ammonium chloride
Amyl acetate
Aniline
Antimony trichloride
Aqua regia
Aromatic solvents
R
No data
R68
R
R68
R
R
R4
R
68
R
R
ND ND
R R50 ND
R50
R
R
R
R
R
R
No data
R R
R ND ND
No data
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
No data
R R
R
R ND
R46 ND ND
R
R
R
R
R R R
R43 R R
No data
R R ND
R R R
R
R
R
R
R
R
ND
ND
ND
ND
R
R
R
R
R
R
R
R
R ND ND
R50
R50 ND ND
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
50
R
ND
ND
ND
ND
R50 R
R
R
R
R50
ND ND
R
R
R
R
R
R
R
R
R
R
R
R50
R
R
R50
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R R
R R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R R
R R
R33
R
R
R107
R107
R
R
R
R107
R107
R
R
R
R107
R107
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R14
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R80
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R107
R
R
R
R
R107
R
ND
R
R
R107
R
R
R
R R
R14
R R
R
R
R
R
R
R
R
No data
No data
No data
R
R
No data
R
Calcium chloride
Carbon disulphide
Carbonic acid
Carbon tetrachloride
Caustic soda & potash
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
ND
R
ND
ND
ND
ND
R
R
R
R
R
R
R
ND
R
R
R50
R50
R
R
R
R
R
R
R
R43 R
R ND
No data
R R R
R R R
R
R
R
R
R
R14
R
Chlorates of Na, K, Ba
Chlorine, dry
Chlorine, wet
Chlorides of Na, K, Mg
Chloroacetic acids
R R68
ND
R4
R R
No data
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R2
R
R
R
R
R2
R
R
R
R
R2
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R R
Fluorine, dry
Fluorine, wet
Fluosilicic acid
Formaldehyde (40%)
Formic acid
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
ND ND
R68 R
R
R
R
R
R31
48
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R R
R ND
R43
R R
R
R
R
R
R
R
ND
R
R
No data
R
R
R
R
R
R
No data
No data
No data
No data
R ND
10
R
43
No data
50
R
R
R
R
R
R
R
R
ND
R
R
R14
R14
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R50
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R ND ND
R ND ND
R30,50
R R
R
R
R
R
R
R
R14 R
R
R
R
R
R
R
R
R
R
R48 R R
No data
No data
R R R
R R R
R
R
R
R
R
ND ND
R43 R
R R
R32 R10
R
R50 R50
No data
R
R
R
R
R
R
R
R
R
R
R R
R R
No data
R R R
R50 R R
R R
R50
R R
R R
R
No data
data
data
data
data
data
R
R
R R
No data
R43 R R
R R R
R
No
No
No
No
No
R
R ND
No data
R R R
R14 R
R
R
R
R
R
R
ND
ND
R
R
R
R
R
R6
R R
R50
R
R
R
R
R106
R
ND
R68
R
Ether
Fatty acids (>C6 )
Ferric chloride
Ferrous sulphate
Fluorinated refrigerants,
aerosols, e.g. Freon
R
No data
R R
R R
R
R
R
R
R
R
R
R
R
R
Copper salts (most)
Cresylic acids (50%)
Cyclohexane
Detergents, synthetic
Emulsifiers (all conc.)
R
50
R ND
R R
R R50
R
R37
R37
Beer
Benzoic acid
Boric acid
Brines, saturated
Bromine
Chlorobenzene
Chloroform
Chlorosulphonic acid
Chromic acid (80%)
Citric acid
Plasticised
PVC
Rigid
Unplasticised
PVC
PVDF (y)
PTFE (n)
PCTFE
Nylon 66
Plastics (m)
Nylon 66
Fibre (m)
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Acetaldehyde
Acetic acid (10%)
R R50
Acetic acid (glac. & anh.)
Acetic anhydride
R50
Acetone
Other ketones
Acetylene
Acid fumes
Alcohols (most fatty)
Aliphatic esters
Alkyl chlorides
Acrylonitrile
Butadiene
Styrene
Resins (l)
Acrylic Sheet
(e.g. Perspex)
THERMOPLASTIC
RESINS
R
R
R
R
R
No data
R R ND
R
R
No data
No data
R
R
No data
ND
R19 R19
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
No data
R
R
R
R
R
R
R
No data
R R
R15 R
R R30
R
R
No data
R
No data
925
APPENDIX B
20° 60° 100°
R27
R
R
R27
ND
R
R56
R56
R
R
R56
R80
R
R50,56
R50
R
R
R
R
R56
R
R
R
R
R
R
R
R
ND ND
No data
46
R
ND ND
ND
R
No data
R2 R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
ND ND
ND
R
R
R
R
R
R
R50 R
R50 R
R
R
27
R
No data
R
R
R
R
R
R
No data
R80
R
R
R
R
R
R
R
R
R
R1
R
R
R
R
R
R
R
R
R
R
R
R
R50
R
R
R
R
R19 R
R
R
R
R
R80
R
R
No data
R50
R
R
R
R
80
R
R
R
R
R
R50
R56 R
R
R
No data
R
R
R56 R
R13
R50
R56
R56
R
R50
R
R
No data
R
R
R56
R56
R
R
R50
56
R
R
R
56
R50
R3
R
R
R3
R
R
H.D. Polyethylene is suitab’e for a number of applications at 100° C for limited periods, depending on the environment.
No data
No data
R
R
R
ND
No data
ND ND
20° 60° 100°
20° 60° 100°
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R
R
R
No data
R2 R
R
R33
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
ND ND
R
R
R
R
R
R
R
R
R
R
R
ND ND
R7
No data
R
R
ND
R
R
R
R
R
R
R
R
R
ND
R
R
No data
ND
ND
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND ND
R
ND
R
ND
R
R
R
R
R
ND
ND
R
R
R
ND
R50
R
R
R
R
R
R
R
ND
ND
R
R
R6 R
R56 R
R56 R
ND
ND
ND
R
R
R32 R32
R
R
R
ND ND ND
ND ND ND
R
R
R
R
R
R
R
R
R
R
ND ND
R
ND
ND ND
R
ND ND
R
R
R
R
R
R
R10
R
No data
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
ND
No data
R
R
R
R
No data
R
R
R
No data
R
ND
R
ND
ND ND
R430 ND
R2
R50
R50
R30
71
No data
R30
R30,71
R30,71
R
R
R
R
R
ND ND
ND ND
R
R30
R
R
R4,30
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R30
R
R
R
R
R
R30 R65
R30 R65
R
R
ND ND
No data
R
ND
R
R
R
R
No data
R
R30
R
R
R
R
R
R
R
R
R
R
R30
R
ND
R
R19
R
R
R30
R13
No data
R
R
R
ND ND
R
R4,30
R
R
R
ND ND
30
R
R
ND
R44
30
30
R
R
R
R
R
R
R
R
R
R30 R65
R
R30
R30
R30
R
R
R
R
R
R
No data
R
R
R
R
No data
R
ND ND
No data
R
No data
No data
R
R
No data
No data
R30 ND
R30 ND
R68 ND
R
R
R
No data
No data
No data
R
R
R
R
No data
R
R
R
ND
R30 ND
No data
R
R
R
R
R
ND ND
R
R
R
ND ND
R
R
No data
R
ND
R
ND
R
ND
R
R
R
Polyester
Resins
No data
R
R23
30
R
R
R
R
R
R
Phenol Formaldehyde
Resins (r)
20° 60° 100°
R
R
R
R
20° 60° 100°
R
R
R
R
R
R
R
ND
ND
ND
R
R
No data
R
R
R
No data
R
R30 R65
R
R30
R
R30
R
R30 R65
R30
R
R
ND ND
R
R
R
R
R
R
R68 R68
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
No data
R62 R62
No data
ND
R
ND
ND
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
ND ND
R
R
No data
No data
R
ND
R
ND
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
No data
No data
R
R
R
20° 60° 100°
R
R
R30
R68
R
R
No data
R
Epoxy
Resins (p)
Furane
Resin
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
ND
ND ND
No data
No data
R
R
R
R
R
R
No data
R
R
R
R
R
ND
R
ND
R
R
No data
R
R98 R98
ND
R50
20° 60° 100°
R
R
R
R
ND
R
ND ND
ND
ND ND
No data
R
R
R
ND
ND ND
R4
R
R
R
R
R
R
56
R
R
R
20° 60° 100°
No data
ND
ND
ND
7
Melamine
Resins (o)
Polystyrene
Polycarbonate
Resins
Polyethylene
High Density
Polyethylene
Low Density
20° 60° 100°
No data
20° 60° 100°
THERMOSETTING
RESINS
Polypropylene
THERMOPLASTIC
RESINS
No data
R
ND
R
R
R
R
ND
R
ND
ND
ND
R4,30
R
R
R
R
R
R
R30 R
R30 R4,30
R4,30
R4,30
R10
R
R
R30
R
R30
R30
R30 R65
R30 R65
No data
No data
No data
R15
R30 R
R15
926
CHEMICAL ENGINEERING
Centigrade
Fruit juices
Gelatine
Glycerine
Glycols
Hexamine
R68
R
R
R
R
R
R
ND
No data
R
R
R
R
R
R
No data
R
R R
R
R10 R10
Hydrofluoric acid (40%)
Hydrofluoric acid (75%)
Hydrogen peroxide (30%)
(30 90%)
Hydrogen sulphide
R ND
Hypochlorites
R34 ND
R
R68
R
R
R
R
R
R
R
R
R
Mercuric chloride
Mercury
Milk & its products
Moist air
Molasses
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
Naphtha
Naphthalene
Nickel salts
Nitrates of Na, K, NH3
Nitric acid (<25%)
R4
R
R
R
Phenol
Phosphoric acid (25%)
Phosphoric acid (50%)
Phosphoric acid (95%)
Phosphorus chlorides
Phosphorus pentoxide
Phthalic acid
Picric acid
Pyridine
Sea water
Silicic acid
Silicone fluids
Silver nitrate
Sodium carbonate
Sodium peroxide
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R50
No data
R
R
R
R
50
R
ND
R50 ND
No data
R
R
R
R
R
R
R
R
R
R
No data
Plasticised
PVC
Rigid
Unplasticised
PVC
PVDF (y)
PTFE (n)
PCTFE
R
ND
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R107
R
R
R
R
R
R107
R
R
R
R
R
R107
R30
R19
R
R
R
R50
R
R30
R
R
ND
ND
ND
R
R
ND
No data
R R
R
R R
ND
R R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R15
R
R
R
R
R
R
R
R37
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R37
R
R
R
R
R
ND
R
R
R
R
R
ND
No data
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R30
R
ND
R
R
R
R
R
R
R62 R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R52
R
R
R
R
R
R
R
R
R
ND
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R55 R
No data
R
ND
No data
R R
ND
R R
R
R
R
R
R
No data
R R
R R
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R43 R
R
R R
R
43
R R
R
No data
R50
R
R50
R
R43
R
R
R
R
R50
R
R
R
R
R
R
R
R
R
R
ND
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R
R
R68
R
R68
R
R
R
R10
R
R
R
R
R43
R
Lactic acid (100%)
Lead acetate
Lime (CaO)
Maleic acid
Meat juices
Oils, vegetable & animal
Oxalic acid
Ozone
Paraffin wax
Perchloric acid
Nylon 66
Plastics (m)
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Hydrazine
No data
Hydrobromic acid (50%) R R
Hydrochloric acid (10%) R R
Hydrochloric acid (conc.) R R50
Hydrocyanic acid
Nitric acid (50%)
Nitric acid (95%)
Nitric acid, fuming
Oils, essential
Oils, mineral
Nylon 66
Fibre (m)
Acrylonitrile
Butadiene
Styrene
Resins (l)
Acrylic Sheet
(e.g. Perspex)
THERMOPLASTIC
RESINS
R
R
No data
31
R R
R
No data
43
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R50
R
ND
R
R
R
R
R
No data
ND ND
No data
R R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R62 R62
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
No data
R
R
R
No data
No data
No data
No data
No data
No data
No data
R
R R
R R
R4
R
R
R
R
ND ND
No data
R R
R
R
R
R
R
R
R
R
R50
R50
R
R
ND
ND
R
R
ND
ND
R
R
R
R
R68 R
No data
R68
No data
R R
R430
R
R
R
R
R
R
No data
R R64
R R
R ND
No data
No data
No data
No data
R R
R
R R
R
R R
ND
R
R50
R ND ND
R R
R
R
R
R
R
No data
R ND ND
R ND ND
R ND ND
ND
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R32
R
R3
R
R
R
R
R
No data
R
R
R3
R
No data
R
No data
No data
R
R
R
No data
R
R
ND
No data
R
R
R
R
No data
R
R
No data
No data
R
R
No data
R
No data
66
R
R
R
R
R
R10
R68
R
R
No data
No data
No data
R
R
No data
ND
ND
R
R
No data
No data
No data
R
ND
R
R105 ND
No data
R
R
R
No data
R
R
R
R
R
R
No data
No data
No data
R
ND
R
R
R
927
APPENDIX B
R
No data
R
R
R
R
No data
R
R
R56
R56
R56
R
R
R
R
R
No data
R
R
R
R
R56
R
R
R14
R
R
R
R
R14
R
R
R
R
R
R13
R
R80
R80
R
R56
R
R
R19
R
R56
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R80
R80
ND
R
R
R
R50
R80
R50
R50 R
R50
R50 R
R50
R
R
R62
R56 R
ND ND
R10 R10
R
R
R
R
50
R
R
R
R
R
No data
R13
R
R
R50
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R50
R
R50
R66
R
R
R
R
R
R
R
R
R
R
R
R80
R
R
R56
R
R
R13
R
R56
R
R
ND
R50
These results at 20° C refer to low stress moulded parts made from Makrolon. The chemical resistance of this material may be affected by mechanical stresses and high temperatures. The polymer
may however be used at relatively high temperatures for a thermoplastic: it has good heat resistance up to 135° C. Makrolon is the polycarbonic acid ester of 4,40 -dihydroxydipheny-2 20 -propane.
R
R
R30
R
R
ND
ND
R
R13
R56
R
R
R
R
ND
R
ND
R
ND
R
R30
R
ND
No data
ND
R27
R
R
R
ND
R27
R50
R13
No data
R
R
R
R
No data
No data
No data
R
R
ND
R
ND ND
R56 ND
R
R
R
R
ND
R
R
R
ND
R
R7
R711
R
R
R
R
R
R
R
ND
ND
R
R
ND
R
R
R
R
6
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
ND
ND
ND
ND
R77,75
R
R30
R
R
R7
R
ND
R
R
R
R
ND
R
R30
ND
R
ND
ND
R
R
R30
R
ND
ND
R
R
R
R
R
R
R
ND
R
R
R
ND
ND
ND
R
R
R
R
ND
ND
R
R
ND
R
R
R
R
R
R
R
R
R
R
R4,30
R
R
R
R4,30
No data
ND ND
R
R
R
R
R
R4,30
R4,30
R4,30
No data
No data
R
No data
R
R
R
R
R
R10
ND ND
R
ND
ND ND
R
R
R
No data
R
R
R34 R34 ND
R
R
No data
R
R
ND
R
R
R
R
R
R
R
R
R
R
ND
ND
R
ND
ND
ND
R10
R
R
R
R
No data
No data
R
R
R
R
R
R
R
R
ND
R
ND
ND
ND
ND
R
No data
No data
No data
R
R
R
R
R
ND
R
ND
R
ND
R
ND
No data
R
ND ND
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R50
R
R
R
R
R
R
R
R
R
R
No data
R23 R
10
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
No data
R
R
R
R
R
R
R10
R
ND
No data
R
R
R
R
R
R
No data
No data
R
ND ND
R
R
R
No data
R
R
R
R
R
R
No data
R
R
R
R
No data
R
R
No data
ND ND
No data
R
R
R
No data
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
ND
R
R
ND
ND ND
R
R
R
R
R
ND
No data
R
R
R
No data
R
R
No data
R
R
R
No data
R
R
R
No data
R30
R30
R
R4,30
Polyester
Resins
Phenol Formaldehyde
Resins (r)
Epoxy
Resins (p)
R
R
R
R
R
R
R
R
60° 100° 20° 60° 100° 20° 60° 100°
No data
No data
R
R
R
R
R
R
ND ND ND
ND ND
No data
R32
ND
R
R
ND
ND
R7,34
R
R
R
ND
R
Furane
Resin
60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20°
R
ND
R
R
ND
R
R
R
R
ND
Melamine
Resins (o)
Polystyrene
Polycarbonate
Resins
Polyethylene
High Density
Polyethylene
Low Density
20° 60° 100° 20° 60° 100° 20°
THERMOSETTING
RESINS
Polypropylene
THERMOPLASTIC
RESINS
No data
No data
ND ND
ND ND
R30
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R65
No data
R
R
R65
R
ND ND
No data
R
R
R
R
No data
ND ND
R
R
ND ND
No data
No data
No data
R30 R
R65
R
ND ND
R10
R
ND ND
R
R
ND ND
R
R
No data
R4,30
R
R
R
R30
R30
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R30
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R75
R
R
R
R
R
R
R
R
R30
R30
R
R65
R30 R65
R
R
R
R
R
R
R
R
R
ND
No data
R
R
R
R
R
ND ND
No data
R
R
R30
R
R44,30
R44,30
R
R30
R4,30
4,30
R
No data
R30
R
R
R
R65
ND
No data
R
R
R
R
R
ND ND
No data
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
No data
ND ND
ND ND
R30
R
R
R
R
R30
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
No data
R
R
R
R
R
R
R
R
R
R65
R30 ND
13
R
R
No data
R30
R
R
R
No data
R
R
R
R
R
R
R30
No data
R
R
R
R10
R
R
R
R65
R30 R65
No data
No data
No data
R
R
R65
R10 ND ND
R
R
R
No data
No data
R
R30 R65
R
R
No data
928
CHEMICAL ENGINEERING
Centigrade
Sodium silicate
Sodium sulphide
Stannic chloride
Starch
Sugar, syrups, jams
Sulphuric acid (95%)
Sulphuric acid, fuming
Sulphur chlorides
Tallow
Tannic acid (10%)
Plasticised
PVC
Rigid
Unplasticised
PVC
PVDF (y)
PTFE (n)
PCTFE
Nylon 66
Plastics (m)
Nylon 66
Fibre (m)
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
R
R
R68
R
R
R
R68
R
R
R
Sulphamic acid
No data
Sulphates (Na, K, Mg, Ca) R R
Sulphites
R R
Sulphonic acids
No data
Sulphur
R R68
Sulphur dioxide, dry
Sulphur dioxide, wet
Sulphur trioxide
Sulphuric acid (<50%)
Sulphuric acid (70%)
Acrylonitrile
Butadiene
Styrene
Resins (l)
Acrylic Sheet
(e.g. Perspex)
THERMOPLASTIC
RESINS
R68
R68
No data
R25 R32
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
ND
R
R
R
R
R
R
R
R
R50
R
R
R
ND
ND
R
R
R
ND
ND
R
R
R43 R R
R R R
No data
R
No data
R
No data
No data
R ND ND
R50
No data
R R
No data
ND ND
R
No data
R R
No data
Tartaric acid
Trichlorethylene
Vinegar
Water, distilled
Water, soft
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Water, hard
Yeast
Zinc chloride
R
R
R
R
R68
R68
R
R
R
R
68
R
R
No data
ND
No data
R68 R
R ND
R
R
R
R
R
R
R R
ND ND
R
R
ND ND
R R
R
R
R
R
R
R
R R
R R
R43 R
R
R
R
No data
R ND ND
R ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R
R R
No data
R R R
R
R
R
R
R
R
R R
R R
No data
R R R
R R R
R
R
R
R
R
R
R
R
R
R
R
R
R R
R R
No data
R R R
R R ND
R
R
R30
R
R
R
R
R50
R
R
R50
R
ND
R50
R50
ND
R50
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R14
R
R
R
R
R
R50 R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R
R R
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R13
R
R
R
R50
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R50
No data
R R R
R R R
ND
R R
R R
No data
R ND
R ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
ND
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
ND
R
No data
R
R
R50
R
R
R
R
R
R
R
R
R
R
No data
No data
R
No data
No data
No data
R R
ND
No data
R ND
No data
No data
929
APPENDIX B
Polyester
Resins
Phenol Formaldehyde
Resins (r)
Epoxy
Resins (p)
Furane
Resin
Melamine
Resins (o)
Polystyrene
Polycarbonate
Resins
Polyethylene
High Density
Polyethylene
Low Density
THERMOSETTING
RESINS
Polypropylene
THERMOPLASTIC
RESINS
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
20° 60° 100°
R
R
R
R
R
R
R
R
R
R
ND
R
R
R7
R
R
No data
No data
1
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R68
R
R
R
R
R
R
R
R
ND ND
R
R
No data
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
ND
R
R
R
R
R
R
R
R
R
R10
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R34
No data
R
R
R
R
R
R
R
No data
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R50
R
R
R
R50
R50
ND ND
R
R
R
R
R10
R50 R80
R60
No data
R50 ND ND
56
R
R
R
R
R
R
R
R
R
R50
R
R
R
R
R
R
R
ND
R
R
R
R
R
No data
No data
R
ND
R
No data
R
ND
No data
No data
No data
R
R
R
No data
ND
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
ND
R
ND
R
ND
No data
R
R
ND
R
R
ND
No data
R
R
R
R
R
No data
R
R
No data
No data
R
R
R
R
R
R
ND
No data
No data
R
R
R
R
R
R
R
R
No data
R30
R
R44
R
R
R
R
11
R
R
R30
R30
No data
R
ND ND
R
R
R
R
R
R
R
R
No data
R
R
R
No data
No data
R
R
R
R
ND
ND
ND
R
ND
ND
ND
R
R
R
R
R30
R30
R30
R30
R
R65
R
R65
No data
No data
No data
No data
R30 R65
R30 R65
No data
No data
ND ND
ND ND
ND ND
R
R
R56
R60
R
ND
ND
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
ND
R
R
R
No data
R
ND
R
ND
R
ND
No data
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R
R
R
No data
No data
R
R
No data
R
R30
R
R
R
ND ND
R
R
R
R
No data
No data
R
R
R
No data
R
R
No data
R
R
R
R
R
R
R
R30
R
R
R
4
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
No data
R
ND ND
R
R
R
R
No data
R
R
R
R
R
R
R30
30
R
R
R30
R
R30
R
R30
No data
R
R30 R65
930
CHEMICAL ENGINEERING
Silicone
Rubbers (k)
Polyurethane
Rubber (v)
Chlorosulphonated
Polyethylene
Nitrile Rubber
Neoprene (i)
Soft Natural
Rubber (h)
Hard Rubber
(Ebonite) (h)
Butyl Rubber
and Halo-Butyl
Rubber
Ethylene Propylene
Rubber (q)
RUBBERS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Acetaldehyde
R
Acetic acid (10%)
R14
Acetic acid (glac. & anh.) R14
Acetic anhydride
R80
Acetone
R
Other ketones
R13
R
R
R
R
R
R
Acetylene
Acid fumes
Alcohols (most fatty)
Aliphatic esters
Alkyl chlorides
R
R2
R
Alum
Aluminium chloride
Ammonia, anhydrous
Ammonia, aqueous
Ammonium chloride
R
R
R
R
R
R
R
R
R80 R80 ND
R
R
R60 R
R30
R
60
R80 R
R2 R
R30
R
60
R
R
R
R2 R
R60 R
R
R
R
R
R
R
R
R
R
R
R
R
R80
R
R
R R
ND
R R14 ND
R14 R14 ND
No data
R60 R60
R60 R60
R
R
R
R
R
R13
80
R80
R
R
R
No data
R2 R2 R2
R60 R60
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
Amyl acetate
Aniline
Antimony trichloride
Aqua regia
Aromatic solvents
R80
R R
R R
ND
R
Beer
Benzoic acid
Boric acid
Brines, saturated
Bromine
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Calcium chloride
Carbon disulphide
Carbonic acid
Carbon tetrachloride
Caustic soda & potash
R
R
R
R
R
R
R
R
R
R
R
R
Chlorates of Na, K, Ba
Chlorine, dry
Chlorine, wet
Chlorides of Na, K, Mg
Chloroacetic acids
R
R50
R80
R
R10
R
R
R
R
R
R
R
R
R
R50
R50
R
R
R50
R50
R
13
13
Chlorobenzene
Chloroform
Chlorosulphonic acid
Chromic acid (80%)
Citric acid
Copper salts (most)
Cresylic acids (50%)
Cyclohexane
Detergents, synthetic
Emulsifiers (all conc.)
Ether
Fatty acids (>C6 )
Ferric chloride
Ferrous sulphate
Fluorinated refrigerants,
aerosols, e.g. Freon
Fluorine, dry
Fluorine, wet
Fluosilicic acid
Formaldehyde (40%)
Formic acid
ND
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
No data
R
R
R
R14
R30
R
R
R
R
R
R
R
R
R
R R
R95
R R
R
R14
ND ND
R80 R80
R80
R
R4
R
R R
ND
R85
R R
ND
R15 ND ND
R14 R
R
R2,80 R2 R
R
R R
R14
No data
R
R2
R
ND ND
R
R
R14 R
R R
R R
R
R2
R
ND ND
R2 R2
R4 R4
R
R
R
R
R80
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
ND
R
R
R
R
R80
R30
R
R
ND
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
No data
R
R
ND
R
R
R R
R50
R
R
R
R80
R
ND ND
R62 R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R13
R
R50
R50
R
R
R30
R13
R
R2
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R21 R
R R
R R
R
R4
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R21
R
R
R
R
R
R
R
R
R
R
R30
No data
R
R
R
R
R
R
R30
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R80
R
R
R
R
R
R
R21 R
R
R
R
R
R
ND
No data
R
R
R
R30
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R2
R
R30
R21
R
R
R
R
R
R
R86 R
R
No data
R R
R
R R
R
R
R
R
R
No data
R
R
R17
R
R17
R17
R
R
R
R
R
R
R
R
No data
R3 ND ND
R R
R
R
R30 R30
R
R
R
R
R80
R21 R
13
13
R
R
R
R
R
R
R
R
R
R
R4
R
R
R
R13 R
R R
R1
R
R
R
R
R80 R
R
R
R
R
R4
ND ND
R80
R80
R
R80
R13
ND ND
ND ND
R
R
R
R
13
R
R
ND
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R13 R13 R13
No data
R
R
R80 R80
R R
R
R R
R
No data
No data
R80 R13
80
R R R
R R R
R80
R80
R
R80
R14
R13
R13
R
R
R
ND ND
ND ND
R
R
R14
R
R4
R
R4
No data
R13
R13
R
R30
R80
ND
ND
R
R
R
R80 R80 R
No data
80
R
R
R
R
R
R
No data
R R
R14
R80
R
No data
R30 R
ND
R R
R
R
ND
R
R
R
R
R
R
R
ND ND
R R
R30 R
R
R
R30 R30
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R R
R30 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R4
R
R
ND
R30 R
R
R
R
R30 R
No data
No data
R R
R
R ND ND
R R
R
No data
R
R
30
No data
R19 R
R
R R
R
R
R21
R21
R
R
R
R
ND
R
R
R
R
ND
R
R
R80
R
R
ND
ND
R
R
R
R
R
R
R
R
R
R30 ND ND
R430
R
R
ND
ND
No data
No data
R R
R
R
R R
R
R
R
ND ND
80
R
R80
R
R
R
R
R
R
R4,21
R
R
R
R
ND ND
931
APPENDIX B
NOTES
Wood (z)
Viterous
Enamel (w)
Porcelain and
Stoneware
Graphite (u)
Glass (t)
Concrete (s)
MISCELLANEOUS
Explanatory notes at lower temperatures may be taken to apply also at
higher temperatures unless otherwise
shown.
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
No data
No data
R
R
R
R
No data
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
ND
R
R
R
R5
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R511
R
R
R
R
R
R
R
R
R
ND
R
R
ND
R
R
R
R30
No data
R
R
R50
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R35
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R44
R
R50
R
R72
R
R
R
R
ND
ND
ND
R
R
ND
ND
R
R
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
R
R
R
R
R
R
R
R
R
R
R10
R
R
No data
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
No data
R13 R30
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
No data
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R12 R
R
R
R
R
R
R
R
R
R
R
R
R81 R
R
No data
R
R
R
R
R
R
No data
No data
R
R
R
80
R
R
R
R
R
R
R
R
R
R51 R
R
R
R
R
R
R
R
R
R
No data
R
R
ND
ND
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
ND
R
R
ND
ND
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
ND
R
ND
No data
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
No data
R
R
R
ND ND
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R39 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
ND
R
R
R
R
R
R
R
R14
R14
No data
R
ND
No data
No data
No data
No data
R
R
R
R
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
Not anhydrous
Depending on the acid
35%
Fair resistance
Not HF fumes
Up to 40%
Saturated solution
Pineapple and grapefruit juices 20° C
Photographic emulsions up to 20° C
10%
Anhydrous
Not Mg
Depending on concentration
Discoloration and/or swelling and softening
Up to 25%
Not chloride/not if chloride ions present
Not fluorinated silicone rubbers
Up to 60%
Up to 50%
Not aerated solutions
Fluorinated silicone rubbers only
ND for Mg
5%
Pure only
Up to 30%
If no iron salts or free chlorine
May crack under stressed conditions
45%
55%
Depending upon composition
Chloride
20%
Depending on alcohol
Data for sodium
Fresh
Over 85%
Some attack at high temperature
Neutral
Attacked by fluoride ions
Sulphate and nitrate
Softening point
In strong solutions only when inhibited
Depending on water conditions
Dilute
Up to 15%
Not methyl
Drawn wire
Some attack, but protective coating forms
Using anodic passivation techniques
Some attack/absorption/slow erosion
Not sulphate
70%
In absence of dissolved O2 and CO2
75%
80%
May cause stress cracking
Pitting possible in stagnant solutions
In presence of H2 SO4
Not ethyl
May discolour liquid
The material can cause decomposition
Depending on type
95%
Slight plating will occur
Not recommended under certain conditions of
temperature, etc.
65%
Aerated solution
Estimated effect
Up to 90%
Not oxidising conditions
Not lower members of series
Not high alumina cement concrete
932
CHEMICAL ENGINEERING
Silicone
Rubbers (k)
Polyurethane
Rubber (v)
Chlorosulphonated
Polyethylene
Nitrile Rubber
Neoprene (i)
Soft Natural
Rubber (h)
Hard Rubber
(Ebonite) (h)
Butyl Rubber
and Halo-Butyl
Rubber
Ethylene Propylene
Rubber (q)
RUBBERS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Fruit juices
Gelatine
Glycerine
Glycols
Hexamine
R80
R
R
R
R
R80
R
R
R
R
R
R
R
ND
Hydrazine
Hydrobromic acid (50%)
Hydrochloric acid (10%)
Hydrochloric acid (conc.)
Hydrocyanic acid
R
R
R
R4
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
Hydrofluoric acid (40%)
Hydrofluoric acid (75%)
Hydrogen peroxide (30%)
(30 90%)
Hydrogen sulphide
Hypochlorites
R30 R
R
R80
R80
R
R30
R
R87
R
R80
R
ND
R
R
R30 R30 ND
R30 ND ND
R80 ND ND
Lactic acid (100%)
Lead acetate
Lime (CaO)
Maleic acid
Meat juices
R
R
R
R
R
R
R
R
R
R
Mercuric chloride
Mercury
Milk & its products
Moist air
Molasses
R
R
R80
R
R
R
R
R
R
R
Naphtha
Naphthalene
Nickel salts
Nitrates of Na, K, NH3
Nitric acid (<25%)
Nitric acid (50%)
Nitric acid (95%)
Nitric acid, fuming
Oils, essential
Oils, mineral
Oils, vegetable & animal
Oxalic acid
Ozone
Paraffin wax
Perchloric acid
R
R
R
R
R
ND
R
R
R4
R
ND
ND
R
R80
R
R65
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R37
R
R37
R
R37
R
R37
R
R65
R
R
R
R
R
R80
R R
R
R30 R30
R30 R
R
R
R
R
ND
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R14,80
R80 R
R R
R R
R13 R
R
R
R
R
R
R
R
R
R
R
R
R80
R
R
R
R
R80
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R14
R R
R
R R
80
R60
R
R R
R R
No data
R80
R87
R R
R30
R
13
R R R
R R R
R23 R23 R23
R14 R
R60
R
R
R
R
R
R
R
R
R
R
R
R R
R R
R101 R
R60 ND ND
R80 R80 R80
R14
R14 R14
No data
R R
R R ND
R
R80
R
R
R
R
R
R
Phenol
Phosphoric acid (25%)
Phosphoric acid (50%)
Phosphoric acid (95%)
Phosphorus chlorides
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
Phosphorus pentoxide
Phthalic acid
Picric acid
Pyridine
Sea water
R
R13
R80
R4
R
R
R
R
ND
R
R
R R ND
R13 R13 ND
No data
R
R
R
Silicic acid
Silicone fluids
Silver nitrate
Sodium carbonate
Sodium peroxide
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R R
No data
R60 R60
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R R R60
R R R60
R36 R R60
No data
R14 R
R80 R
R
R
R14
R
R
R
R
R37
R
R
R
R
R
R
R
R
R
R44
R
R
R
R
ND
ND
R
R95
R
ND
ND
R
ND
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
ND ND
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R61
R
R13
R
R
R
R
R
R
R
R
R
R80
R
R
R
R
R
R
R80
R
R80
R
R
R
R
R
R
R
R
R
R97
R
ND
R
R
R4
ND
R R
R R
R R
R R
No data
No data
R R R
R30
No data
ND
ND
R
R
R
R
R
R
R
R30
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R86
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R21
R21
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R38
R
R
ND
R
R
R
ND ND
R15 R15
80
R
R
R
R
R
R
R23
R
R
R
R
R
R
R
R
R
R
R87
R87
ND
R
R
R
R
R
ND
R23
R
R
R
R
R
R
R
R
R
R
R
No data
No data
R
ND
R
R
R
ND
R
R
R
R
ND
R
R
No data
R R
R
No data
R R
R
R
R
R
R
30
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R30 ND
R14
R
R
R
ND
R
R
R
R4
R
R
R
R
R
R
R R R
R30 R R
No data
R R R
R4
R
R
R60
R
ND
R
R
R87
R87
R
R
R14 ND ND
R ND ND
R R
R80 R80 R80
R R30 R
30
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R R
R R
R R
R R4
No data
R
R R R60
R R R60
R36 R R60
No data
R R
R R
R R
No data
R
R R
R R
R101
No data
R13
80
80
R R
R80,76
13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R21
R
R R
R
R89
R30
R30
R
R
R
R
R30 R
R30 R
R30
R ND ND
R R
R
R R
R
No data
R
ND
R
R
ND
R
ND
R
R
ND
R
R
R
R
R R
R R
R R
R R
No data
R
R
R
R
R
R
R
R
R
R30
R30
R R
R R
R R
R R
No data
R
R
R
R
R
R
ND ND
R
ND ND
R13
No data
No data
R R
R
ND ND
R
ND
ND ND
R
R
R
R
R
R
R
R
R R
R R
No data
No data
R R R
R
R
R
R
ND
ND
R
R
R
R
R
R
13
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
ND
R
R
ND
R
R21
30
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
933
APPENDIX B
Wood (z)
Vitreous
Enamel (w)
Porcelain and
Stoneware
Graphite (u)
Glass (t)
Concrete (s)
MISCELLANEOUS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
R
R
R
No data
No data
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R50
R50
R50
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R37
R
R
R
R
R
R37
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
No data
No data
R
R
No data
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R72 R
R
R
R35 R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R73 R
R
R
R
R
R
R
No data
No data
R
R
R
R
ND ND
R
R
R50
R
R
R
R
R
R
R
R
R
R
R50
R50
R50
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R15 R10
R
R
R
R
R
ND
R
R
R
ND
ND
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R4
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R74 R
R
No data
R72 R
R
R72 R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
No data
R
R
R
R
R
ND
R
ND ND
R
R
R
R
R
R
No data
No data
R
R
R
R
R
No data
R
ND
R
R
R
R
R
R
R
R
R
R
No data
R
ND ND
R
R
R
R
R
ND
R
R
ND
ND
ND
R
R
R
R
R
R
No data
R
R
R
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
R
R14
R
R
R
R
R
R
R
R
R
R
R
R14
R
R
R
R
R
R
14
R
R14
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R
R
R
R
R
R
R
ND
R
ND
No data
No data
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
No data
R
R
No data
R14
R
R
R
R
R
R
R
R
R
R
R
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
Not ammonium
Not chlorsilanes
Data for ammonium
Data for calcium
Data for potassium
In presence of heavy metal ions
ND for Ba
Limited service
Except those containing sulphate
Provided less than 70% copper
Water less than 150 ppm
May cause some localised pitting
60% in one month
Low taste and odour
Catalyses decomp. of H2 O2
65%
1 2 days
Wet gas
Less than 0 005% water
In absence of heavy metal ions oxidising agents
Stress corrosion in MeOH and halides (not in other alcohols)
When free of SO2
50% swell in 28 days
60% swell in 3 days
Could be dangerous in black loaded compounds
Not alkaline
Ozone 2% Oxygen 98%
This is the softening point
Nitric acid less than 5% concentration
Acid fumes dry. Attack might occur if moisture present and
concentrated condensate built up
Stainless steels not normally recommended for caustic applications
In the absence of impurities
10% w/w in alcohol
Swelling with some ketones
Some stress cracking at high pH
(a) Aluminium: In many cases where the chart indicates that
aluminium is a suitable material there is some attack, but the
corrosion is slight enough to allow aluminium to be used
economically.
(b) Brass: Some types of brass have less corrosion resistance than is
shown on the chart, others have more, e.g. Al brass.
(c) Cast iron: This is considered to be resistant if the material
corrodes at a rate of less than 0.25 mm per annum. When
choosing cast iron, Ni-Resist or high Si iron for a particular
application the very different physical properties of these
materials must be taken into account.
(d) Gunmetal: The data refer only to high tin gunmetals.
(e) Nickel-copper alloys: The physical properties are for annealed
material. Both the tensile strength and hardness can vary with
form and heat treatment condition.
(f) Stainless steels: Less expensive 13% chromium steels may be
used for some applications instead of 18/8 steels. Under certain
conditions the addition of titanium increases the corrosion
resistance of 18/8 steels. Also, it produces materials which can be
welded without the need for subsequent heat treatment. These
steels are, however, inferior in corrosion resistance to the more
expensive 18/8/Mo steels.
(g) Tin: Data refer to pure or lightly alloyed tin; not to discontinuous tin coatings.
(h) Soft natural rubber and ebonite: Performance at higher
temperatures depends on method of compounding.
(i) Neoprene: Brush or spray applied 1.5 mm thick, and properly
cured.
(k) Silicone rubbers: Withstand temperatures ranging from
90° C to above 250° C and are resistant to many oils and
chemicals. In some cases particularly good resistance is
shown by the fluorinated type.
934
CHEMICAL ENGINEERING
Silicone
Rubbers (k)
Polyurethane
Rubber (v)
Chlorosulphonated
Polyethylene
Nitrile Rubber
Neoprene (i)
Soft Natural
Rubber (h)
Hard Rubber
(Ebonite) (h)
Butyl Rubber
and Halo-Butyl
Rubber
Ethylene Propylene
Rubber (q)
RUBBERS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
Sodium silicate
Sodium sulphide
Stannic chloride
Starch
Sugar, syrups, jams
R
R
R
R
R
R
R
R
R
R60
R
R
R
R
R60
R
R
R
R
R60
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
Sulphamic acid
No data
Sulphates (Na, K, Mg, Ca) R R R
Sulphites
R R R
Sulphonic acids
R13 R
Sulphur
R R R
R
R
R
R13
R
R
R
R
R13
R
ND
R
R
R13
R
R13
R
R
R2
R
R
R
R
R2
R
R
R
R2
R
Sulphur dioxide, dry
Sulphur dioxide, wet
Sulphur trioxide
Sulphuric acid (<50%)
Sulphuric acid (70%)
R
R
R
R
R
R
R
R
R
R
R
R4
Sulphuric acid (95%)
Sulphuric acid, fuming
Sulphur chlorides
Tallow
Tannic acid (10%)
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R13
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
R R R
80
R R80
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
No data
R R R
R R R
ND
R30 R R
R
R
R
R
R
R
R
R
R
R
R
R
ND
ND
R
R
R
R
R
R
R
R R
No data
R R
R R
R R
R
R
R
R
R
R
ND
R
R
R
R
R
R
ND
ND
R
R
R R
R80
R
R R
R66
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R4
R
R
ND ND
ND ND
R
R
R
R
R
R25 R25
80
R
R
R
R
R
R
ND
R
R30 R
R R
R
R
R
No data
R
R
R
R
R
R
No data
R R
R R
No data
R R R
R
R
R ND
R ND
R R
R R
No data
R
R
R
R
R
R4
R
R
R
R4
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
Tartaric acid
Trichlorethylene
Vinegar
Water, distilled
Water, soft
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R14
R R
R R
Water, hard
Yeast
Zinc chloride
R
R
R
R
R
R
R
R
R
R
R R
No data
R R R
No data
R R
R
R
R
No data
R R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R80 R
R30 R
R R
R
R
R
R
R
R
R
R
R
R
R
R
R65
R
R
R
R
R R
R30 R
R R
R37 R
R R
R R
R
R
R
R
R
R
R
R
R
R80 R80
R R
R R
R
R21
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R R
ND ND
R ND
R
R
R
R
R
R
R
R
R
R R
ND ND
R R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
935
APPENDIX B
Wood (z)
Vitreous
Enamel (w)
Porcelain and
Stoneware
Graphite (u)
Glass (t)
Concrete (s)
MISCELLANEOUS
20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100° 20° 60° 100°
R
R
R
R
R
R
No data
R
R
R
No data
No data
R80
R
R
R
R50 R
R50 R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
No data
No data
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND
ND
R
R
R
R
R
R
R
No data
R
ND
R
R
R
ND
R
R
(l) Acrylonitrile butadiene styrene resins: The information refers
to a general purpose moulding grade material.
R
R
R
R
R
R
R
R
R
R
No data
R
R
(n) P.T.F.E.: Is attacked by alkali metals (molten or in solution)
and by certain rare fluorinated gases at high temperatures and
pressures. Some organic and halogenated solvents can cause
swelling and slight dimensional changes but the effects are
physical and reversible.
(o) Melamine resins: The information refers mainly to laminates
surfaced with melamine resins, Melamine coating resins are
always used in conjunction with alkyd resins and the specifications will depend on the alkyd resin used.
(p) Epoxy resins: Data are for cold curing systems.
R10
(q) The information given is based on compounds made from
ethylene propylene terpolymer rubber.
R
R
R
R
R
R
No data
R
R
R
R2
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND ND
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
ND
R
R
R
R
R
R
R
R
R
(m) Nylon: Prolonged heating may cause oxidation and embrittle
ment. Data on nylon 66 plastics refer to Maranyl products.
Other nylons, such as types 6 and 610, can behave differently,
e.g. towards aqueous solutions of salts.
(r) Phenol formaldehyde resins: These are of several types and care
should be taken that the right type is chosen.
No data
R
R
R
R
R
R
(s) Concrete: Usually made from Portland cement, but if made
from Ciment Fondu or gypsum slag cement might have
superior resistance in particular applications.
(t) Glass: The information refers to heat-resistant borosilicate
glass.
(u) Graphite: Data refer to resin-impregnated graphite. Other
specially treated graphites have improved corrosion resistance to many chemicals.
(v) Chemical resistance of polyurethanes is dependent on the
particular structure of the material and is not necessarily
applicable to all polyurethanes. Specially designed polyurethanes can be used at higher temperatures than 60° C
but chemical resistance is temperature dependent.
(w) Vitreous enamel: Special enamels may be required to
withstand particular reagents.
(x) Data is based on Ferralium alloy 255.
(y) Data is based on Solef.
(z) Wood: The behaviour of wood depends both on the species
used and on the physical conditions of service. Aqueous
solutions of some chemicals may cause more rapid degradation. Organic solvents may dissolve out resins, etc. Hydrogen peroxide (over 50% w/w) produces a fire risk.
APPENDIX C
Physical Property Data Bank
Inorganic compounds are listed in alphabetical order of the principal element in the
empirical formula.
Organic compounds with the same number of carbon atoms are grouped together, and
arranged in order of the number of hydrogen atoms, with other atoms in alphabetical order.
NO
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
VISA, VISB
D
D
D
D
D
D
D
D
D
D
D
Number in list
Molecular weight
Normal freezing point, deg C
Normal boiling point, deg C
Critical temperature, deg K
Critical pressure, bar
Critical volume, cubic metre/mol
Liquid density, kg/cubic metre
Reference temperature for liquid density, deg C
Heat of vaporisation at normal boiling point, J/mol
Constants in the liquid viscosity equation:
LOG[viscosity] D [VISA] Ł [(1/T) (1/VISB)], viscosity mNs/sq.m, T deg K.
DELHF D Standard enthalpy of formation of vapour at 298 K, kJ/mol.
DELGF D Standard Gibbs energy of formation of vapour at 298 K, kJ/mol.
CPVAPA, CPVAPB, CPVAPC, CPVAPD = Constants in the ideal gas heat capacity
equation:
Cp D CPVAPA + (CPVAPB) Ł T C (CPVAPC) Ł T
Cp J/mol K, T deg K.
ŁŁ
2 + (CPVAPD) Ł T
ŁŁ
3,
ANTA, ANTB, ANTC D Constants in the Antione equation:
Ln (vapour pressure) D ANTA ANTB/ (T + ANTC), vap. press. mmHg, T deg K.
To convert mmHg to N/sq.m multiply by 133.32.
To convert degrees Celsius to Kelvin add 273.15.
TMN D Minimum temperature for Antoine constant, deg C
TMX D Maximum temperature for Antoine constant, deg C
Most of the values in this data bank were taken, with the permission of the publishers,
from: The Properties of Gases and Liquids, by Reid, R. C., Sherwood, T. K. and
Prausnitz, J. M., 3rd edn, McGraw-Hill.
937
FORMULA
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
AR
BCL3
BF3
BR2
CLNO
CL2
CL3P
CL4SI
D2
D2O
F2
F3N
F4SI
F6S
HBR
HCL
HF
HI
H2
H2O
H2S
H3N
H3P
H4N2
H4SI
HE(4)
I2
KR
NO
NO2
N2
N2O
NE
O2
O2S
O3
O3S
XE
ARGON
BORON TRICHLORIDE
BORON TRIFLUORIDE
BROMINE
NITROSYL CHLORIDE
CHLORINE
PHOSPHORUS TRICHLORIDE
SILICON TETRACHLORIDE
DEUTERIUM
DEUTERIUM OXIDE
FLUORINE
NITROGEN TRIFLUORIDE
SILICON TETRAFLUORIDE
SULPHUR HEXAFLUORIDE
HYDROGEN BROMIDE
HYDROGEN CHLORIDE
HYDROGEN FLUORIDE
HYDROGEN IODIDE
HYDROGEN
WATER
HYDROGEN SULPHIDE
AMMONIA
PHOSPHINE
HYDRAZINE
SILANE
HELIUM4
IODINE
KRYPTON
NITRIC OXIDE
NITROGEN DIOXIDE
NITROGEN
NITROUS OXIDE
NEON
OXYGEN
SULPHUR DIOXIDE
OZONE
SULPHUR TRIOXIDE
XENON
COMPOUND NAME
39.948
117.169
67.805
159.808
65.459
70.906
137.333
169.898
4.032
20.031
37.997
71.002
104.080
146.050
80.912
36.461
20.006
127.912
2.016
18.015
34.080
17.031
33.998
32.045
32.112
4.003
253.808
83.800
30.006
46.006
28.013
44.013
20.183
31.999
64.063
47.998
80.058
131.300
189.9
107.3
126.7
7.2
59.7
101.0
112.2
68.9
254.5
3.8
219.7
206.8
90.2
50.7
86.1
114.2
83.2
50.8
259.2
0.0
85.6
77.8
133.8
1.5
185.0
150.8
452.0
260.8
584.0
440.0
417.0
563.0
507.0
38.4
644.0
144.3
234.0
259.0
318.7
363.2
324.6
461.0
424.0
33.2
647.3
373.2
405.6
324.8
653.0
269.7
5.2
819.0
209.4
180.0
431.4
126.2
309.6
44.4
154.6
430.8
261.0
491.0
289.7
48.7
38.7
49.9
103.4
91.2
77.0
0.075
1373
1350
183
11
6531
3119
1420
1563
1574
1480
165
1105
1510
1537
1660
1830
2160
1193
967
2803
71
998
993
639
20
12
34
21
20
250
20
188
129
95
50
57
85
20
36
253
20
60
0
30,187
25,707
20,432
37.5
16.6
216.6
52.2
45.3
37.2
37.6
85.5
83.1
64.8
83.1
13.0
220.5
89.4
112.8
62.7
146.9
48.4
2.3
116.5
55.0
64.8
101.3
33.9
72.4
27.6
50.5
78.8
55.7
82.1
58.4
0.127
0.139
0.124
0.260
0.326
0.060
0.056
0.066
0.057
0.155
0.091
0.058
0.170
0.090
0.097
0.042
0.073
0.122
0.089
0.130
0.118
1008
680
123
3740
2420
1280
1447
805
1226
1204
1149
1455
1356
1780
3060
CBRF3
CCLF3
CCL2F2
CCL2O
CCL3F
CCL4
CF4
CO
COS
CO2
CS2
CHBR3
TRIFLUOROBROMOMETHANE
CHLOROTRIFLUOROMETHANE
DICHLORODIFLUOROMETHANE
PHOSGENE
TRICHLOROFLUOROMETHANE
CARBON TETRACHLORIDE
CARBON TETRAFLUORIDE
CARBON MONOXIDE
CARBONYL SULPHIDE
CARBON DIOXIDE
CARBON DISULPHIDE
BROMOFORM
148.910
104.459
120.914
98.916
137.368
153.823
88.005
28.010
60.070
44.010
76.131
94.940
340.2
302.0
385.0
455.0
471.2
556.4
227.6
132.9
375.0
304.2
552.0
464.0
39.7
39.2
41.2
56.7
44.1
45.6
37.4
35.0
58.8
73.8
79.0
66.1
0.200
0.180
0.217
0.190
0.248
0.276
0.140
0.093
0.140
0.094
0.170
0.162
20
88
269
180
153
152
20
195
90
246
183
10
112
45
108
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
185.9
12.5
99.9
58.7
5.5
34.5
75.8
57.2
249.5
101.4
188.2
129.1
86.2
63.9
67.1
85.1
19.5
35.6
252.8
100.0
60.4
33.5
87.5
113.5
112.2
269.0
184.3
153.4
151.8
21.1
195.8
88.5
246.2
183.0
10.2
111.9
44.8
108.2
113.6
157.4
163.7
11.3
209.9
90.9
248.7
218.8
75.5
192.7
16.8
111.9
181.2
157.8
128.2
111.2
23.2
186.8
205.1
138.9
56.6
111.9
178.3
59.2
81.5
29.8
7.6
23.8
76.5
128.0
191.5
50.3
78.5
46.2
3.5
0.198
0.100
0.081
0.069
0.131
0.065
0.056
0.099
0.073
0.113
0.096
1750
1361
115
20
1584
25
803
1274
777
1293
1733
192
99
20
0
0
27,549
1223
41,366
6531
,
17,668
16,161
6699
19,778
904
40,683
18,673
23,362
14,725
44,799
92
41,868
9667
13,816
19,071
5581
16,559
1842
6824
24,932
11,179
40,679
13,013
15,516
19,979
24,409
24,786
30,019
11,974
6046
17,166
26,754
24,241
39
40
41
42
43
44
45
46
47
48
49
50
CHEMICAL ENGINEERING
MOLWT
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
938
NO
VISA
VISB
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
107.57
58.76
387.82
292.79
52.63
191.96
172.35
19.67
757.92
84.20
8.38
304.58
52.52
251.29
88.08
372.78
438.74
155.15
13.82
658.25
342.79
349.02
180.75
166.32
277.74
199.62
285.43
5.39
283.16
165.54
169.63
524.98
290.88
559.62
520.55
406.20
90.30
85.68
397.85
313.79
1372.80
215.09
230.21
46.14
51.50
208.42
120.34
315.99
165.55
540.15
290.84
94.06
48.90
578.08
274.08
185.24
200.22
DELGF
66.99
249.41
234.80
124.68
127.19
1221.71
36.26
92.36
271.30
26.38
1117.88
53.30
95.33
273.40
1.59
242.00
20.18
45.72
229.44
95.25
32.66
228.77
33.08
16.16
90.43
33.87
86.75
52.00
81.60
103.71
297.05
142.77
395.53
300.36
162.91
370.62
649.37
695.01
481.48
221.06
284.70
100.48
933.66
110.62
138.50
393.77
117.15
36.34
623.00
654.40
442.54
206.91
245.51
58.28
889.03
137.37
165.76
394.65
66.95
158.64
54.93
CPVAPA
CPVAPB
CPVAPC
20.804
3.211E-05
51.665E-09
CPVAPD
33.859
34.097
26.929
11.254E-03
44.715E-03
33.838E-03
1.192E-05
3.340E-05
3.869E-05
45.343E-10
10.149E-09
15.470E-09
30.250
6.406E-03
11.698E-06
3.684E-09
23.216
36.568E-03
3.462E-05
12.041E-09
30.647
30.291
29.061
31.158
27.143
32.243
31.941
27.315
23.228
9.768
11.179
9.462E-03
7.201E-03
66.110E-05
1.428E-02
92.738E-04
19.238E-04
14.365E-04
23.831E-03
44.003E-03
18.945E-02
12.200E-02
17.224E-06
12.460E-06
2.032E-06
29.722E-06
1.381E-05
10.555E-06
24.321E-06
17.074E-06
13.029E-06
1.657E-04
5.548E-05
6.238E-09
3.898E-09
25.037E-10
1.353E-08
76.451E-10
3.596E-09
1.176E-08
1.185E-08
1.593E-08
60.248E-09
68.412E-10
35.592
65.147E-04
6.988E-06
28.345E-10
29.345
24.233
31.150
21.621
20.786
28.106
23.852
20.545
16.370
9.378E-04
48.358E-03
1.357E-02
72.808E-03
97.469E-07
2.081E-05
26.796E-06
5.778E-05
4.187E-09
29.308E-11
1.168E-08
18.301E-09
3.680E-06
66.989E-03
80.093E-03
14.591E-02
17.459E-06
4.961E-05
6.243E-05
1.120E-04
1.065E-08
13.281E-09
16.973E-09
32.423E-09
22.814
31.598
28.089
40.985
40.717
13.980
30.869
23.567
19.795
27.444
19.113E-02
17.823E-02
13.607E-02
16.308E-02
20.486E-02
20.256E-02
1.285E-02
79.842E-03
73.436E-03
81.266E-03
1.576E-04
1.509E-04
1.374E-04
1.416E-04
2.270E-04
1.625E-04
27.892E-06
7.017E-05
5.602E-05
7.666E-05
44.589E-09
43.417E-09
50.702E-09
41.462E-09
88.425E-09
45.134E-09
1.272E-08
24.535E-09
17.153E-09
26.729E-09
ANTA
ANTB
ANTC
TMN
TMX
NO
15.2330
700.51
5.84
192
179
15.8441
16.9505
15.9610
2582.32
2520.70
1978.32
51.56
23.46
27.01
14
63
101
81
12
9
15.8019
13.2954
2634.16
157.89
43.15
35
254
91
248
15.6700
15.6107
714.10
1155.69
6.00
15.37
214
170
182
118
19.3785
14.4687
16.5040
17.6958
12.9149
13.6333
18.3036
16.1040
16.9481
2524.78
1242.53
1714.25
3404.49
957.96
164.90
3816.44
1768.69
2132.50
11.16
47.86
14.45
15.06
85.06
3.19
46.13
26.06
32.98
114
89
136
67
58
259
11
83
94
53
52
73
40
17
248
168
43
12
17.9899
16.3424
12.2514
16.1597
15.2677
20.1314
20.5324
14.9542
16.1271
14.0099
15.4075
16.7680
15.7427
20.8403
15.2958
3877.65
1629.99
33.73
3709.23
958.75
1572.52
4141.29
588.72
1506.49
180.47
734.55
2302.35
1272.18
3995.70
1303.92
45.15
5.35
1.79
68.16
8.71
4.88
3.65
6.60
25.99
2.61
6.45
35.97
22.16
36.66
14.50
15
111
269
110
160
178
43
219
129
249
210
78
164
17
115
70
179
269
214
144
133
47
183
73
244
173
7
99
59
95
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
15.7565
15.8516
15.8742
16.0543
14.3686
2167.31
2401.61
2808.19
1244.55
530.22
43.15
36.30
45.99
13.06
13.15
60
33
20
180
210
68
27
101
125
165
22.5898
15.9844
15.7078
3103.39
2690.85
3163.17
0.16
31.62
72.18
119
45
101
69
69
30
39
40
41
42
43
44
45
46
47
48
49
50
939
39
40
41
42
43
44
45
46
47
48
49
50
DELHF
APPENDIX C
NO
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
CHCLF2
CHCL2F
CHCL3
CHN
CH2BR2
CH2CL2
CH2O
CH2O2
CH3BR
CH3CL
CH3F
CH3I
CH3NO2
CH4
CH4O
CH4S
CH5N
CH6N2
CH6SI
CHLORODIFLUOROMETHANE
DICHLOROFLUOROMETHANE
CHLOROFORM
HYDROGEN CYANIDE
DIBROMOMETHANE
DICHLOROMETHANE
FORMALDEHYDE
FORMIC ACID
METHYL BROMIDE
METHYL CHLORIDE
METHYL FLUORIDE
METHYL IODIDE
NITROMETHANE
METHANE
METHANOL
METHYL MERCAPTAN
METHYL AMINE
METHYL HYDRAZINE
METHYL SILANE
COMPOUND NAME
86.469
102.923
119.378
27.026
173.835
84.993
30.026
46.025
94.939
50.488
34.033
141.939
61.041
16.043
32.042
48.107
31.058
46.072
46.145
160.2
135.2
63.6
13.3
52.6
95.1
117.2
8.3
93.7
97.8
141.8
66.5
28.6
182.5
97.7
123.2
93.5
369.2
451.6
536.4
456.8
583.0
510.0
408.0
580.0
464.0
416.3
317.8
528.0
588.0
190.6
512.6
470.0
430.0
567.0
352.5
49.8
51.7
54.7
53.9
71.9
60.8
65.9
0.165
0.197
0.239
0.139
1230
1380
1489
688
2500
1317
815
1226
1737
915
843
2279
1138
425
791
866
703
16
9
20
20
20
25
20
15
5
20
60
20
20
161
20
20
14
20,205
24,953
29,726
25,234
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
C2CLF5
C2CL2F4
C2CL2F4
C2CL3F3
C2CL4
C2CL4F2
C2F4
C2F6
C2N2
C2HCL3
C2HF3O2
C2H2
C2H2F2
C2H2O
C2H3CL
C2H3CLF2
C2H3CLO
C2H3CL3
C2H3F
C2H3F3
C2H3N
C2H3NO
C2H4
C2H4CL2
C2H4CL2
C2H4F2
C2H4O
C2H4O
C2H4O2
C2H4O2
C2H5BR
CHLOROPENTAFLUOROETHANE
1;1-DICHLORO-1;2;2;2-TETRAFLUOROETHANE
1;2-DICHLORO-1;1;2;2-TETRAFLUOROETHANE
1;2-DICHLORO-1;1;2;2-TETRAFLUOROETHANE
TETRACHLOROETHYLENE
1;1;2;2-TETRACHLORO-1;2-DIFLUOROETHANE
TETRAFLUOROETHYLENE
HEXAFLUOROETHANE
CYANOGEN
TRICHLOROETHYLENE
TRIFLUROROACETIC ACID
ACETYLENE
1;1-DIFLUOROETHYLENE
KETENE
VINYL CHLORIDE
1-CHLORO-1;1-DIFLUOROETHANE
ACETYL CHLORIDE
1;1;2-TRICHLOROETHANE
VINYL FLUORIDE
1;1;1-TRIFLUOROETHANE
ACETONITRILE
METHYL ISOCYANATE
ETHYLENE
1;1-DICHLOROETHANE
1;2-DICHLOROETHANE
1;1-DIFLUOROETHANE
ACETALDEHYDE
ETHYLENE OXIDE
ACETIC ACID
METHYL FORMATE
ETHYL BROMIDE
154.467
170.992
170.922
187.380
165.834
203.831
100.016
138.012
52.035
131.389
114.024
26.038
64.035
42.038
62.499
100.490
78.498
133.400
46.044
84.041
41.053
57.052
28.054
98.960
98.960
66.051
44.054
44.054
60.052
60.052
108.966
106.2
94.2
93.9
35.0
22.2
24.8
142.5
100.8
27.9
116.4
15.3
80.8
40.8
8.8
61.1
25.7
96.8
39.8
19.2
100.6
3.5
24.3
78.4
42.4
101.2
161.5
64.6
5.9
6.4
90.8
57.6
1455
1480
1580
1620
1645
1519
1590
25
4
16
20
25
76
78
1462
1535
615
20
0
84
969
1100
1104
1441
14
30
20
20
782
958
577
1168
1250
20
20
110
25
16
778
899
1049
974
1451
20
0
20
20
25
156.5
135.2
153.8
131.2
113.0
36.7
143.2
111.3
43.9
169.2
97.0
35.7
117.0
123.0
112.2
16.6
99.0
118.6
39.2
3.8
3.7
47.5
121.1
91.5
75.7
78.3
20.7
87.2
72.4
84.0
41.2
13.4
9.8
50.7
113.7
37.7
47.7
81.6
38.8
103.8
57.2
83.4
24.8
20.4
10.3
117.9
31.7
38.3
353.2
418.6
418.9
487.2
620.0
551.0
306.4
292.8
400.0
571.0
491.3
308.3
302.8
380.0
429.7
410.2
508.0
602.0
327.8
346.2
548.0
491.0
282.4
523.0
561.0
386.6
461.0
469.0
594.4
487.2
503.8
0.193
86.1
66.8
58.8
65.9
63.1
46.0
81.0
72.3
74.6
80.4
0.139
0.124
0.190
0.173
0.099
0.118
0.145
0.140
0.271
31.6
33.0
32.6
34.1
44.6
0.252
0.294
0.293
0.304
0.290
39.4
0.175
0.224
59.8
49.1
32.6
61.4
44.6
64.8
56.0
41.2
58.8
41.5
52.4
37.6
48.3
55.7
50.4
50.7
53.7
45.0
55.7
71.9
57.9
60.0
62.3
0.256
0.113
0.154
0.145
0.169
0.231
0.204
0.294
0.144
0.221
0.173
0.129
0.240
0.220
0.181
0.154
0.140
0.171
0.172
0.215
28,010
23,027
21,939
23,928
21,436
27,214
34,436
8185
35,278
24,577
26,000
19,469
23,279
27,507
34,750
16,161
31,401
16,957
20,641
20,641
28,680
33,327
19,176
31,401
29,601
13,553
28,721
32,029
21,353
25,749
25,623
23,697
28,219
26,502
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
CHEMICAL ENGINEERING
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
FORMULA
940
NO
NO
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
VISB
394.81
194.70
428.91
359.55
319.83
729.35
298.15
426.45
246.50
145.31
294.57
225.13
171.35
325.72
211.15
193.56
336.19
452.80
114.14
555.30
229.95
261.21
57.60
260.64
311.80
176.30
392.58
145.67
281.82
196.60
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
470.89
268.37
68.58
120.20
5.61
68.91
109.99
351.23
28.18
62.93
210.14
15.66
6.95
50.87
162.62
9.92
32.28
177.98
17.300
23.664
24.003
21.863
16.182E-02
15.814E-02
18.933E-02
60.625E-03
1.170E-04
1.200E-04
1.841E-04
4.961E-05
30.585E-09
32.636E-09
66.570E-09
18.154E-09
15.5602
1704.80
41.30
48
33
15.9732
16.5138
2696.79
2585.80
46.16
37.15
13
39
97
57
12.954
23.475
11.715
14.428
13.875
13.825
10.806
7.423
19.251
21.152
13.268
11.476
16.232E-02
31.568E-03
13.578E-02
10.911E-02
10.140E-02
86.164E-03
13.892E-02
19.778E-02
52.126E-03
70.924E-03
14.566E-02
14.273E-02
1.302E-04
29.852E-06
8.411E-05
5.401E-05
3.889E-05
2.071E-05
1.041E-04
1.081E-04
11.974E-06
25.870E-06
8.545E-05
5.334E-05
42.077E-09
2.300E-08
20.168E-09
95.836E-10
25.665E-10
1.985E-09
34.855E-09
20.850E-09
1.132E-08
2.852E-08
20.750E-09
47.520E-10
16.3029
16.4775
16.9882
16.0252
16.1052
16.3428
16.0905
16.2193
15.2243
18.5875
16.1909
17.2622
15.1424
2622.44
2204.13
3599.58
2271.71
2077.97
1704.41
2629.55
2972.64
597.84
3626.55
2338.38
2484.83
2319.84
41.70
30.15
26.09
34.83
29.55
19.27
36.50
64.15
7.16
34.29
34.44
32.92
91.70
44
88
2
58
93
132
13
5
180
16
73
61
3
59
2
136
53
7
64
52
136
153
91
27
38
127
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
34.918E-02
32.783E-02
34.399E-02
28.742E-02
22.554E-02
2.891E-04
2.752E-04
2.950E-04
2.420E-04
2.294E-04
81.391E-09
78.209E-09
85.076E-09
69.040E-09
83.820E-09
15.7343
1848.90
30.88
98
43
22.61
27.834
40.453
38.778
61.140
45.971
15.8424
16.1642
2532.61
3259.29
45.67
52.15
23
34
87
187
659.00
1343.96
309.15
5.86
624.13
1258.22
297.39
19.89
29.010
26.816
35.935
30.174
22.772E-02
34.579E-02
92.528E-03
22.868E-02
2.037E-04
2.869E-04
8.223E-05
2.229E-04
67.784E-09
81.350E-09
29.496E-09
82.438E-09
15.8800
15.6422
1574.60
1512.94
27.22
26.94
133
103
63
73
16.1827
3028.13
43.15
13
127
226.88
345.41
61.13
35.17
209.34
321.71
60.33
51.54
26.821
3.073
6.385
5.949
16.818
25.020
6.322
75.781E-03
24.447E-02
16.383E-02
20.193E-02
27.566E-02
17.107E-02
34.307E-02
5.007E-05
2.099E-04
1.084E-04
1.536E-04
1.992E-04
9.856E-05
2.958E-04
14.122E-09
70.213E-09
26.984E-09
47.730E-09
53.047E-09
22.190E-09
97.929E-09
16.3481
1637.14
19.77
79
71
16.0197
14.9601
1849.21
1803.84
35.15
43.15
103
88
18
17
15.7514
16.0381
2447.33
3110.79
55.53
56.16
36
29
82
155
5.744
20.482
35.764
3.806
12.472
20.486
8.675
7.716
7.519
4.840
1.432
6.657
31.409E-02
10.831E-02
10.396E-02
15.659E-02
26.959E-02
23.103E-02
23.957E-02
18.225E-02
22.224E-02
25.485E-02
27.001E-02
23.480E-02
2.597E-04
4.492E-05
5.820E-06
8.348E-05
2.050E-04
1.438E-04
1.457E-04
1.007E-04
1.256E-04
1.753E-04
1.949E-04
1.472E-04
84.155E-09
32.029E-10
1.687E-08
17.551E-09
63.011E-09
33.888E-09
33.942E-09
23.802E-09
25.916E-09
49.488E-09
57.024E-09
38.041E-09
15.8965
16.2874
16.3258
15.5368
16.0842
16.1764
16.1871
16.2418
16.7400
16.8080
16.5104
15.9338
1814.91
2945.47
2480.37
1347.01
2697.29
2927.17
2095.35
2465.15
2567.61
3405.57
2590.87
2511.68
29.92
49.15
56.31
18.15
45.03
50.22
29.16
37.15
29.01
56.34
42.60
41.44
3
13
43
153
31
33
35
63
73
17
48
47
27
117
67
91
79
100
0
47
37
157
51
60
898.49
745.67
12.14
276.90
167.04
346.72
304.43
244.09
138.58
206.37
77.54
334.91
616.78
168.98
412.27
473.95
319.27
368.70
341.88
600.94
363.19
369.80
210.05
227.47
93.94
239.10
277.98
186.56
192.82
194.22
306.21
212.70
220.68
746.09
87.92
90.02
52.33
130.00
129.79
494.04
166.47
52.67
435.13
350.02
64.06
679.22
105.67
68.16
73.14
73.90
436.52
133.39
13.10
376.94
297.39
26.33
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
941
DELHF
502.00
298.94
101.32
130.63
4.19
95.46
115.97
378.86
37.68
86.37
234.04
13.98
74.78
74.86
201.30
22.99
23.03
85.41
APPENDIX C
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
VISA
ETHYL CHLORIDE
ETHYL FLUORIDE
ETHYLENE IMIDE
NITROETHANE
ETHANE
DIMETHYL ETHER
ETHANOL
ETHYLENE GLYCOL
ETHYL MERCAPTAN
DIMETHYL SULPHIDE
ETHYL AMINE
DIMETHYL AMIDE
MONOETHANOLAMINE
ETHYLENEDIAMINE
COMPOUND NAME
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
C3H3N
C3H4
C3H4
C3H4O
C3H4O2
C3H4O2
C3H5CL
C3H5CL3
C3H5N
C3H6
C3H6
C3H6CL2
C3H6O
C3H6O
C3H6O
C3H6O
C3H6O
C3H6O2
C3H6O2
C3H6O2
C3H7CL
C3H7CL
C3H8
C3H8O
C3H8O
C3H8O
C3H8O2
C3H8O2
C3H8O2
C3H8O3
C3H8S
C3H9N
C3H9N
C3H9N
ACRYLONITRILE
PROPADIENE
METHYL ACETYLENE
ACROLEIN
ACRYLIC ACID
VINYL FORMATE
ALLYL CHLORIDE
1;2;3-TRICHLOROPROPANE
PROPIONITRILE
CYCLOPROPANE
PROPYLENE
1;2-DICHLOROPROPANE
ACETONE
ALLYL ALCOHOL
PROPIONALDEHYDE
PROPYLENE OXIDE
VINYL METHYL ETHER
PROPIONIC ACID
ETHYL FORMATE
METHYL ACETATE
PROPYL CHLORIDE
ISOPROPYL CHLORIDE
PROPANE
N-PROPYL ALCOHOL
ISOPROPYL ALCOHOL
METHYL ETHYL ETHER
METHYLAL
1;2-PROPANEDIOL
1;3-PROPANEDIOL
GLYCEROL
METHYL ETHYL SULPHIDE
N-PROPYL AMINE
ISOPROPYL AMINE
TRIMETHYL AMINE
149
150
C4H2O3
C4H4
MALEIC ANHYDRIDE
VINYL ACETYLENE
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
64.515
48.060
43.069
75.068
30.070
46.069
46.069
62.069
62.134
62.130
45.085
45.085
61.084
60.099
136.4
143.3
78.2
89.2
183.3
141.5
114.1
13.0
147.9
98.3
81.2
92.2
10.3
10.8
12.2
37.8
56.6
114.0
88.7
24.9
78.3
197.2
35.0
37.3
16.5
6.8
170.3
117.2
460.4
375.3
52.7
50.3
0.199
0.169
896
20
24,702
595.0
305.4
400.0
516.2
645.0
499.0
503.0
456.0
437.6
614.0
593.0
48.5
48.8
53.7
63.8
77.0
54.9
55.3
56.2
53.1
44.6
62.8
0.228
0.148
0.178
0.167
0.186
0.207
0.201
0.178
0.187
0.196
0.206
833
1047
548
667
789
1114
839
848
683
656
1016
896
25
20
90
20
20
20
20
20
20
20
20
20
32,071
35,994
14,717
21,520
38,770
52,544
26,796
26,963
28,052
26,502
50,242
41,868
101
102
103
104
105
106
107
108
109
110
111
112
113
114
53.064
40.065
40.065
56.064
72.064
72.064
76.526
147.432
55.080
42.081
42.081
112.987
58.080
58.080
58.080
58.080
58.080
74.080
74.080
74.080
78.542
78.452
44.097
60.096
60.096
60.096
76.096
76.096
76.096
92.095
76.157
59.112
59.112
59.112
83.7
136.3
102.7
87.2
11.8
57.7
134.5
14.7
92.7
127.5
185.3
100.5
95.0
129.2
80.2
112.2
121.7
20.7
79.4
98.2
122.8
117.2
187.7
126.3
88.5
139.2
105.2
60.2
26.8
17.8
106.0
83.2
95.3
117.2
77.3
34.5
23.2
52.8
140.8
46.4
45.1
155.8
97.3
32.8
47.8
96.3
56.2
96.8
47.8
34.3
4.8
140.8
54.2
56.9
46.4
35.7
42.1
97.2
82.2
7.3
41.8
187.3
214.4
289.8
66.6
48.6
32.4
2.9
536.0
393.0
402.4
506.0
615.0
475.0
514.0
651.0
564.4
397.8
365.0
577.0
508.1
545.0
496.0
482.2
436.0
612.0
508.4
506.8
503.0
485.0
369.8
536.7
508.3
437.8
497.0
625.0
658.0
726.0
533.0
497.0
476.0
433.2
35.5
54.7
56.2
51.7
56.7
57.8
47.6
39.5
41.8
54.9
46.2
44.6
47.0
57.1
47.6
49.2
47.6
53.7
47.4
46.9
45.8
47.2
42.5
51.7
47.6
44.0
0.210
0.162
0.164
0.233
0.229
0.254
20
35
50
20
20
20
20
20
20
15
50
20
20
15
20
20
20
20
16
20
20
20
42
20
20
20
18
20
20
20
20
20
20
20
32,657
18,631
22,148
28,345
46,055
32,155
27,110
38,435
32,280
20,055
18,422
31,401
29,140
39,984
28,303
27,005
19,050
32,238
30,145
30,145
27,256
26,293
18,786
41,784
39,858
24,702
60.8
59.8
66.9
42.6
47.4
50.7
40.7
806
658
706
839
1051
963
937
1389
782
563
612
1150
790
855
797
829
750
993
927
934
891
862
582
804
786
700
888
1036
1053
1261
837
717
688
633
199.6
4.9
455.0
49.6
0.202
1310
710
60
0
98.058
52.076
52.8
45.6
0.210
0.210
0.234
0.348
0.230
0.170
0.181
0.226
0.209
0.203
0.223
0.186
0.205
0.230
0.229
0.228
0.254
0.230
0.203
0.219
0.220
0.221
0.237
0.241
0.255
54,177
56,522
61,127
29,517
29,726
27,214
24,116
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
24,493
149
150
CHEMICAL ENGINEERING
FORMULA
C2H5CL
C2H5F
C2H5N
C2H5NO2
C2H6
C2H6O
C2H6O
C2H6O2
C2H6S
C2H6S
C2H7N
C2H7N
C2H7NO
C2H8N2
942
NO
101
102
103
104
105
106
107
108
109
110
111
112
113
114
VISB
DELHF
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
320.94
190.83
60.04
209.67
178.11
0.553
4.346
20.771
26.063E-02
21.801E-02
30.225E-02
1.840E-04
1.166E-04
2.063E-04
55.475E-09
24.103E-09
56.480E-09
156.60
95.57
686.64
1365.00
419.60
267.34
340.54
300.88
402.41
206.21
184.24
192.44
32.95
113.00
168.39
304.67
4.69
6.95
37.30
68.04
1984.10
839.76
367.03
316.41
111.79
261.67
123.51
101.32
84.74
184.18
234.96
389.58
46.14
37.56
46.05
18.84
201.72
5.409
17.015
9.014
35.697
14.922
24.304
3.693
0.172
9.311
38.297
17.811E-02
17.907E-02
21.407E-02
24.832E-02
23.509E-02
18.748E-02
27.516E-02
26.955E-02
30.095E-02
24.070E-02
37
21
86
21
74
8
96
221
57
58
43
37
204
152
101
102
103
104
105
106
107
108
109
110
111
112
113
114
388.17
733.02
428.40
368.27
818.63
366.77
217.14
307.15
224.83
210.61
342.88
225.86
185.06
192.26
185.56
70.92
336.45
195.44
202.52
194.56
65.19
286.25
273.84
514.36
367.25
793.52
343.44
377.43
318.41
535.04
400.91
408.62
374.77
306.25
222.67
951.04
1139.70
303.82
131.63
281.03
209.68
307.26
219.33
213.36
180.98
299.32
226.23
224.03
215.00
212.24
133.41
327.83
323.44
171.66
0.63
185.89
50.66
53.34
20.43
165.80
217.71
132.09
192.17
92.82
43.63
97.85
96.21
104.46
62.76
83.15
153.15
71.30
130.54
25.79
455.44
371.54
409.72
130.21
146.54
103.92
256.57
272.60
216.58
369.57
10.693
9.906
14.708
11.970
1.742
27.813
2.529
26.883
15.403
35.240
3.710
10.450
6.301
1.105
11.723
8.457
15.629
5.669
24.673
16.550
3.345
1.842
4.224
2.470
32.427
18.669
22.077E-02
19.774E-02
18.644E-02
21.055E-02
31.908E-02
18.388E-02
30.467E-02
36.220E-02
22.454E-02
38.133E-02
23.454E-02
36.547E-02
26.059E-02
31.464E-02
26.142E-02
32.569E-02
23.413E-02
36.890E-02
23.161E-02
22.454E-02
36.258E-02
34.876E-02
30.626E-02
33.252E-02
18.862E-02
26.854E-02
1.565E-04
1.182E-04
1.174E-04
1.071E-04
2.352E-04
3.560E-05
2.278E-04
2.787E-04
1.100E-04
2.881E-04
1.160E-04
2.604E-04
1.253E-04
2.032E-04
1.300E-04
1.989E-04
9.697E-05
2.865E-04
2.120E-05
4.342E-05
2.508E-04
2.244E-04
1.586E-04
1.855E-04
64.058E-06
1.025E-04
46.013E-09
27.821E-09
32.243E-09
19.058E-09
69.752E-09
2.335E-07
72.934E-09
87.881E-09
19.540E-09
90.351E-09
22.048E-09
77.414E-09
20.377E-09
53.214E-09
21.261E-09
48.232E-09
10.622E-09
98.767E-09
5.359E-08
29.144E-09
74.483E-09
58.615E-09
32.146E-09
42.957E-09
9.261E-08
89.514E-10
1404.20
1813.00
3337.10
426.74
406.96
406.00
433.64
228.46
42.119E-02
36.756E-02
44.422E-02
28.906E-02
34.985E-02
41.755E-02
39.716E-02
89.514E-09
50.535E-09
93.784E-09
12.866E-09
35.864E-09
83.485E-09
46.222E-09
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
48.399E-09
74.609E-09
16.2747
16.0100
3765.65
2203.57
18
99
90
38
42
33
43
42
3
93
113
15
32
13
38
48
83
42
33
28
43
48
109
12
0
68
3
84
107
167
23
38
34
58
112
16
6
87
177
77
77
197
132
28
33
135
77
127
77
67
42
177
87
87
77
67
24
127
111
37
42
210
252
327
87
77
64
32
365.81
2.981E-04
2.162E-04
3.159E-04
1.209E-04
1.822E-04
2.826E-04
2.189E-04
2782.21
1054.72
1850.66
2606.53
3319.18
2569.68
2531.92
3417.27
2940.86
1971.04
1807.53
2985.07
2940.46
2928.20
2659.02
2107.58
1980.22
3723.42
2603.30
2601.92
2581.48
2490.48
1872.46
3166.38
3640.20
1161.63
2415.92
6091.95
3888.84
4487.04
2722.95
2551.72
2582.35
2230.51
952.48
0.632
8.269
8.424
19.527
6.691
7.486
8.206
15.9253
13.1563
15.6227
15.9057
16.5617
16.6531
15.9772
16.1246
15.9571
15.8599
15.7027
16.0385
16.6513
16.9066
16.2315
15.3227
14.4602
17.3789
16.1611
16.1295
15.9594
16.0384
15.7260
17.5439
18.6929
13.5435
15.8237
20.5324
17.2917
17.2392
15.9765
15.9957
16.3637
16.0499
36.48
27.00
63.15
31.96
17.16
17.10
41.68
28.25
41.77
42.35
37.30
35.15
86.93
72.15
73
103
25
114
143
94
3
91
49
47
58
55
71
19
210.42
87.127E-10
1.918E-09
13.733E-10
30.103E-09
31.619E-09
40.989E-10
38.083E-09
23.392E-09
46.557E-09
3.948E-08
2332.01
1966.89
2610.44
3848.24
1511.42
2361.44
3803.98
6022.18
2497.23
2511.56
2616.73
2358.77
3988.33
3108.49
343.31
6.938E-05
5.233E-05
8.390E-05
1.497E-04
1.369E-04
6.875E-05
1.583E-04
1.329E-04
1.818E-04
4.338E-05
15.9800
16.0686
16.4227
17.4716
15.6637
16.8467
18.9119
20.2501
16.0077
16.0001
17.0073
16.2653
17.8174
16.4082
243
32
149
150
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
50.70
62.55
23.49
161.90
173.50
117.73
424.25
409.09
585.31
59.66
72.43
83.82
23.86
11.43
39.82
304.80
306.18
98.98
13.075
6.757
34.847E-02
28.407E-02
2.184E-04
2.265E-04
51.15
77.08
44.07
45.15
80.15
63.15
47.15
69.15
55.15
26.65
26.15
52.16
35.93
85.15
44.15
64.87
25.15
67.48
54.15
56.15
42.95
43.15
25.16
80.15
53.54
112.40
52.58
22.46
123.20
140.20
48.37
49.15
40.15
39.15
82.15
43.15
79
73
943
VISA
APPENDIX C
NO
101
102
103
104
105
106
107
108
109
110
111
112
113
114
C4H4O
C4H4S
C4H5CL
C4H5CL
C4H5N
C4H5N
C4H6
C4H6
C4H6
C4H6
C4H6O2
C4H6O3
C4H6O4
C4H6O4
C4H7N
C4H7O2
C4H8
C4H8
C4H8
C4H8
C4H8
C4H8O
C4H8O
C4H8O
C4H8O
C4H8O
C4H8O2
C4H8O2
C4H8O2
C4H8O2
C4H8O2
C4H8O2
C4H9CL
C4H9CL
C4H9CL
C4H9N
C4H9NO
C4H10
C4H10
C4H10O
C4H10O
C4H10O
C4H10O
C4H10O
C4H10O2
C4H10O3
C4H10S
C4H10S2
C4H11N
C4H11N
COMPOUND NAME
FURAN
THIOPHENE
CHLOROPRENE
CHLOROBUTADIENE
ALLYL CYANIDE
PYRROLE
ETHYLACETYLENE
DIMETHYL ACETYLENE
1;2-BUTADIENE
1;3-BUTADIENE
VINYL ACETATE
ACETIC ANHYDRIDE
DIMETHYL OXALATE
SUCCINIC ACID
BUTYRONITRILE
METHYL ACRYLATE
1-BUTENE
CIS-2-BUTENE
TRANS-2-BUTENE
CYCLOBUTANE
ISOBUTYLENE
N-BUTYRALDEHYDE
ISOBUTYRALDEHYDE
MERTYL ETHYL KETONE
TETRAHYDROFURAN
VINYL ETHYL ETHER
N-BUTYRIC ACID
1;4-DIOXANE
ETHYL ACETATE
ISOBUTYRIC ACID
METYL PROPIONATE
N-PROPYL FORMATE
1-CHLOROBUTANE
2-CHLOROBUTANE
2-CHLORO-2-METHYL PROPANE
PYRROLIDINE
MORPHOLINE
N-BUTANE
ISOBUTANE
N-BUTANOL
2-BUTANOL
ISOBUTANOL
2-METHYL-2-PROPANOL
ETHYL ETHER
1;2-DIMETHOXYETHANE
DIETHYLENE GLYCOL
DIMETHYL SULPHIDE
DIETHYL DISULPHIDE
N-BUTYL AMINE
ISOBUTYL AMINE
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
68.075
84.136
88.537
88.537
67.091
67.091
54.092
54.092
54.092
54.092
86.091
102.089
118.090
118.090
69.107
86.091
56.108
56.108
56.108
56.108
56.108
72.107
72.107
72.107
72.107
72.107
88.107
88.107
88.107
88.107
88.107
88.107
92.569
92.569
92.569
71.123
87.122
58.124
58.124
74.123
74.123
74.123
74.123
74.123
90.123
106.122
90.184
122.244
73.139
73.139
85.7
38.3
31.3
84.1
59.4
67.8
118.8
129.8
8.0
27.0
10.8
4.5
72.8
138.8
163.4
234.8
117.8
80.3
6.3
3.7
0.8
12.5
6.9
74.8
63.8
79.6
65.9
35.6
163.2
101.3
77.1
154.7
79.8
80.5
78.4
68.2
50.8
86.5
128.2
0.5
11.9
117.7
99.5
107.8
82.4
34.5
85.4
245.8
92.1
154.0
77.4
67.4
490.2
579.4
511.2
527.2
585.0
640.0
463.7
488.6
443.7
425.0
525.0
569.0
628.0
55.0
56.9
42.5
39.5
39.5
0.218
0.219
0.266
0.265
0.265
0.220
0.221
0.219
0.221
0.265
0.290
20
16
20
20
20
21
16
20
20
20
20
20
15
27,105
31,485
29,658
29,038
34,332
47.1
50.9
45.0
43.3
43.6
46.8
39.8
938
1071
958
963
835
967
650
691
652
621
932
1087
1150
37.9
42.6
37.2
42.0
41.0
49.9
40.0
40.5
41.5
41.5
51.9
40.7
52.7
52.1
38.3
40.5
40.0
40.6
36.9
39.5
39.5
56.1
54.7
38.0
36.5
44.2
41.9
43.0
39.7
36.4
38.7
46.6
39.6
0.285
0.265
0.240
0.234
0.238
0.210
0.239
0.278
0.274
0.267
0.224
0.260
0.292
0.238
0.286
0.292
0.282
0.285
0.312
0.305
0.295
0.249
0.253
0.255
0.263
0.274
0.268
0.273
0.275
0.280
0.271
0.316
0.318
41.5
42.6
0.288
0.284
792
956
595
621
604
694
594
802
789
805
889
793
958
1033
901
968
915
911
886
873
842
852
1000
579
557
810
807
802
787
713
867
1116
837
998
739
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
16
20
20
20
22
20
20
20
20
20
20
20
20
20
20
20
20
20
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
60.0
86.5
125.8
32.3
136.2
108.9
100.2
74.2
53.8
182.8
112.2
76.5
185.4
138.9
105.6
90.8
140.4
96.4
65.0
86.7
108.5
115.3
5.3
11.8
83.6
46.0
87.5
92.9
123.1
131.4
25.4
4.8
138.4
159.6
89.3
114.7
108.0
25.6
116.3
71.2
8.2
104.0
101.5
49.1
85.2
582.2
536.0
419.6
435.6
428.6
459.9
417.9
524.0
513.0
535.6
540.2
475.0
628.0
587.0
523.2
609.0
530.6
538.0
542.0
520.6
507.0
568.6
618.0
425.2
408.1
562.9
536.0
547.7
506.2
466.7
536.0
681.0
557.0
642.0
524.0
516.0
24,995
26,670
24,283
22,483
41,240
34,415
32,029
21,930
23,362
22,772
24,200
22,131
31,527
31,401
31,234
29,601
26,502
42,035
36,383
32,238
41,156
32,573
32,490
30,019
29,224
27,424
37,681
22,408
21,311
43,124
40,821
42,077
39,063
26,712
31,443
57,234
31,778
37,723
32,113
30,982
CHEMICAL ENGINEERING
FORMULA
944
NO
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
VISB
DELHF
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
389.40
498.60
222.70
264.90
34.71
115.81
65.86
79.97
0.88
126.86
35.529
30.606
43.208E-02
44.799E-02
3.455E-04
3.772E-04
10.743E-08
12.527E-08
16.0612
16.0243
14.4844
244.70
2869.07
1938.59
45.41
51.80
85.36
35
13
27
90
107
84
521.30
252.03
21.700
25.715E-02
1.192E-04
12.292E-09
12.548
15.927
11.200
1.687
15.160
23.128
27.436E-02
23.815E-02
27.235E-02
34.185E-02
27.951E-02
50.870E-02
1.545E-04
1.070E-04
1.468E-04
2.340E-04
8.805E-05
3.580E-04
34.499E-09
17.534E-09
30.890E-09
63.346E-09
1.660E-08
98.348E-09
16.0019
16.7966
16.0605
16.2821
16.1039
15.7727
16.1003
16.3982
3128.75
3457.47
2271.42
2536.78
2397.26
2142.66
2744.68
3287.56
58.15
62.73
40.30
37.34
30.88
34.30
56.15
75.11
127
57
73
33
28
58
18
35
157
167
27
47
32
17
106
164
15.211
15.165
2.994
0.440
18.317
50.254
16.052
14.080
24.463
10.944
19.104
17.279
11.740
53.574
7.235
9.814
18.204
15.072E+00
32.058E-02
27.959E-02
35.320E-02
29.534E-02
25.636E-02
50.242E-02
28.043E-02
34.570E-02
33.557E-02
35.592E-02
51.623E-02
32.360E-02
41.370E-02
59.871E-02
40.717E-02
46.683E-02
31.397E-02
46.892E-03
1.638E-04
8.805E-05
1.982E-04
1.018E-04
7.013E-05
3.558E-04
1.091E-04
1.723E-04
2.057E-04
1.900E-04
4.132E-04
1.471E-04
2.430E-04
4.085E-04
2.092E-04
3.720E-04
9.353E-05
3.143E-04
29.823E-09
1.660E-08
44.631E-09
6.155E-10
8.989E-09
10.471E-08
90.979E-10
28.872E-09
63.681E-09
39.197E-09
14.541E-08
21.495E-09
55.308E-09
10.622E-08
28.546E-09
13.502E-08
1.828E-08
2.613
3.433
3.931
51.531
42.802
9.487
1.390
3.266
5.753
7.708
48.613
21.424
32.234
73.060
13.595
26.896
5.079
9.491
44.966E-02
45.594E-02
46.515E-02
53.382E-02
53.884E-02
33.130E-02
38.473E-02
41.801E-02
42.454E-02
46.892E-02
71.720E-02
33.587E-02
35.672E-02
34.441E-02
39.595E-02
46.013E-02
44.757E-02
44.296E-02
2.937E-04
2.981E-04
2.886E-04
3.240E-04
2.666E-04
1.108E-04
1.846E-04
2.242E-04
2.328E-04
2.884E-04
7.084E-04
1.035E-04
1.336E-04
1.468E-04
1.780E-04
2.710E-04
2.407E-04
2.110E-04
80.805E-09
82.564E-09
78.712E-09
75.279E-09
41.994E-09
2.822E-09
28.952E-09
46.850E-09
47.730E-09
72.306E-09
29.199E-08
9.357E-09
83.987E-10
18.464E-09
26.490E-09
59.704E-09
75.990E-09
23.329E-09
16.2092
16.1088
15.7564
15.8171
15.8177
15.9254
15.7528
16.1668
15.9888
16.5986
16.1069
15.8911
17.9240
16.1327
16.1516
16.7792
16.1693
15.7671
15.9750
15.9907
15.8121
15.9444
16.2364
15.6782
15.5381
17.2160
17.2102
16.8712
16.8548
16.0828
16.0241
17.0326
15.9531
16.0607
16.6085
16.1419
3202.21
2788.43
2132.42
2210.71
2212.32
2359.09
2125.75
2839.09
2676.98
3150.42
2768.38
2449.26
4130.93
2966.88
2790.50
3385.49
2804.06
2593.95
2826.26
2753.43
2567.15
2717.03
3171.35
2154.90
2032.73
3137.02
3026.03
2874.73
2658.29
2511.29
2869.79
4122.52
2896.27
3421.57
3012.70
2704.16
56.16
59.15
33.15
36.15
33.15
31.78
33.15
50.15
51.15
36.65
46.90
44.15
70.55
62.15
57.15
94.15
58.92
69.69
49.05
47.15
44.15
67.90
71.15
34.42
33.15
94.43
86.65
100.30
95.50
41.95
53.15
122.50
54.49
64.19
48.96
56.15
34
13
83
73
73
73
83
18
26
16
3
48
62
2
13
57
13
7
18
23
38
27
27
78
86
15
25
20
20
48
11
129
13
39
14
22
160
117
22
32
27
17
17
107
97
103
97
67
197
137
112
192
112
87
112
102
87
127
167
17
7
131
120
115
103
67
120
287
117
182
100
100
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
300.59
457.89
502.33
163.12
235.35
286.04
0.00
438.04
451.02
256.30
268.94
259.01
256.84
245.30
151.86
155.34
153.30
472.31
464.06
423.84
419.79
349.95
640.42
660.36
427.38
588.65
442.88
452.97
783.72
480.77
543.41
233.42
253.64
231.67
244.46
189.02
321.13
308.77
235.98
311.24
238.39
246.09
260.03
237.30
253.35
914.14
265.84
302.51
984.54
1441.70
1199.10
972.10
353.14
332.75
160.20
170.20
341.12
331.50
343.85
363.38
190.58
1943.00
407.59
385.24
233.32
472.06
243.98
108.35
165.29
146.41
162.32
110.24
316.10
576.10
477.00
34.08
108.73
0.13
6.99
11.18
26.67
16.91
205.15
215.87
238.52
184.34
140.26
476.16
315.27
443.21
484.25
71.34
65.90
63.01
110.11
58.11
114.84
121.42
146.16
202.22
185.56
198.58
150.77
180.91
327.62
147.38
161.61
183.38
3.60
38.81
53.51
64.14
114.76
126.23
134.61
274.86
292.82
283.40
312.63
252.38
17.17
20.89
150.89
167.72
167.43
177.77
122.42
571.50
83.53
74.69
92.11
17.79
22.27
49.24
945
VISA
APPENDIX C
NO
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
C4H11N
C4H12SI
DIETHYL AMINE
TETRAMETHYLSILANE
COMPOUND NAME
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
73.139
88.225
49.8
102.2
55.4
27.6
496.6
448.6
37.1
28.2
0.301
0.362
707
646
20
20
27,842
24,685
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
C5H4O2
C5H5N
C5H8
C5H8
C5H8
C5H8
C5H8
C5H8
C5H8
C5H8O
C5H8O2
C5H10
C5H10
C5H10
C5H10
C5H10
C5H10
C5H10
C5H10O
C5H10O
C5H10O
C5H10O
C5H10O2
C5H10O2
C5H10O2
C5H10O2
C5H10O2
C5H10O2
C5H11N
C5H12
C5H12
C5H12
C5H12O
C5H12O
C5H12O
C5H12O
C5H12O
C5H12O
C5H12O
C5H12O
FURFURAL
PYRIDINE
CYCLOPENTENE
1;2-PENTADIENE
1-TRANS-3-PENTADIENE
1;4-PENTADIENE
1-PENTYNE
2-METHYL-1;3-BUTADIENE
3-METHYL-1;2-BUTADIENE
CYCLOPENTONE
ETHYL ACRYLATE
CYCLOPENTANE
1-PENTENE
CIS-2-PENTENE
TRANS-2-PENTENE
2-METHYL-1-BUTENE
2-METHYL-2-BUTENE
3-METHYL-1-BUTENE
VALERALDEHYDE
METHYL N-PROPYL KETONE
METHYL ISOPROPYL KETONE
DIETHYL KETONE
N-VALERIC ACID
ISOBUTYL FORMATE
N-PROPYL ACETATE
ETHYL PROPIONATE
METHYL BUTYRATE
METHYL ISOBUTYRATE
PIPERIDINE
N-PENTANE
2-METHYL BUTANE
2;2-DIMETHYL PROPANE
1-PENTANOL
2-METHYL-1-BUTANOL
3-METHYL-1-BUTANOL
2-METHYL-2-BUTANOL
2;2-DIMETHYL-1-PROPANOL
ETHYL PROPYL ETHER
METHYL-T-BUTYL ETHER
BUTYLMETHYL ETHER
96.085
79.102
68.119
68.119
68.119
68.119
68.119
68.119
68.119
84.118
100.118
70.135
70.135
70.135
70.135
70.135
70.135
70.135
86.134
86.134
86.134
86.134
102.134
102.134
102.134
102.134
102.134
102.134
85.150
72.151
72.151
72.151
88.150
88.150
88.150
88.150
88.150
88.150
88.150
88.150
161.7
115.3
44.2
44.8
42.0
25.9
40.1
34.0
40.8
130.7
99.8
49.2
29.9
36.9
36.3
31.1
38.5
20.1
102.8
102.3
94.2
101.9
185.5
98.4
101.6
98.8
102.6
92.2
106.5
36.0
27.8
9.4
137.8
128.7
131.2
102.0
113.1
63.6
55.1
70.1
657.1
620.0
506.0
503.0
496.0
478.0
493.4
484.0
496.0
626.0
552.0
511.6
464.7
476.0
475.0
465.0
470.0
450.0
554.0
564.0
553.4
561.0
651.0
551.0
549.4
546.0
554.4
540.8
594.0
469.6
460.4
433.8
586.0
571.0
579.5
545.0
549.0
500.6
407.1
512.8
49.2
56.3
0.270
0.254
40.7
39.9
37.9
40.5
38.5
41.1
53.7
37.5
45.1
40.5
36.5
36.6
34.5
34.5
35.2
35.5
38.9
38.5
37.4
38.5
38.8
33.3
33.6
34.8
34.3
47.6
33.7
33.8
32.0
38.5
38.5
38.5
39.5
39.5
32.5
34.3
34.3
0.276
0.275
0.276
0.278
0.276
0.267
0.268
0.320
0.260
0.300
0.300
0.300
0.294
0.318
0.300
0.333
0.301
0.310
0.336
0.340
0.350
0.345
0.345
0.340
0.339
0.289
0.304
0.306
0.303
0.326
0.322
0.329
0.319
0.319
1156
983
772
693
676
661
690
681
686
950
921
745
640
656
649
650
662
627
810
806
803
814
939
885
887
895
898
891
862
626
620
591
815
819
810
809
783
733
741
25
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
16
20
20
20
20
20
20
20
20
20
20
54
20
20
243
244
245
246
247
248
249
250
C6F6
C6F12
C6F14
C6H3CL3
C6H4CL2
C6H4CL2
C6H4CL2
C6H5BR
PERFLUOROBENZENE
PERFLUOROCYCLOHEXANE
PERFLUORO-N-HEXANE
1;2;4-TRICHLOROBENZENE
O-DICHLOROBENZENE
M-DICHLOROBENZENE
P-DICHLOROBENZENE
BROMOBENZENE
186.056
300.047
338.044
181.449
147.004
147.004
147.004
157.010
80.2
52.5
57.1
213.0
180.4
172.8
174.1
156.0
516.7
457.2
451.7
734.9
697.3
684.0
685.0
670.0
33.0
24.3
19.0
39.8
41.0
38.5
39.5
45.2
31.0
41.7
135.1
137.3
87.5
148.3
105.7
146.0
113.7
50.7
72.2
93.9
165.3
151.4
140.3
137.6
133.8
168.5
91.2
77.2
92.2
39.0
34.2
95.2
95.2
73.9
84.8
87.8
10.5
129.8
159.3
16.6
78.2
70.2
117.2
8.8
53.8
126.8
108.2
115.5
87.2
16.8
17.1
24.8
53.1
30.9
0.339
0.329
0.442
0.401
0.360
0.359
0.372
0.324
1306
1288
1248
1495
20
20
55
20
35,169
27,005
27,591
27,047
25,163
26,084
27,256
36,593
33,285
27,315
25,213
26,126
26,084
25,514
26,322
24,116
33,662
33,494
30,647
33,746
49,823
34,206
34,206
34,248
34,101
33,386
34,248
25,791
24,702
22,768
44,380
45,217
44,129
40,612
43,124
30,522
27,646
39,691
38,644
38,812
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
CHEMICAL ENGINEERING
FORMULA
946
NO
201
202
VISB
DELHF
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
473.89
229.29
72.43
232.41
72.14
2.039
44.296E-02
2.183E-04
36.530E-09
16.0545
16.0999
2595.01
2570.24
31
27
618.50
396.83
291.58
218.66
140.26
32.95
145.70
77.87
105.51
144.44
75.78
129.79
192.76
190.33
110.66
210.55
146.83
170.36
210.39
145.95
198.75
77.29
20.93
28.09
31.78
36.34
42.58
28.97
227.97
258.83
38.64
79.17
71.89
69.96
65.65
59.70
74.82
108.35
137.16
28.198E-02
49.279E-02
46.306E-02
38.799E-02
28.110E-02
39.515E-02
35.035E-02
45.845E-02
35.977E-02
52.251E-02
36.898E-01
54.261E-02
43.292E-02
46.013E-02
41.818E-02
39.971E-02
35.090E-02
38.895E-02
43.292E-02
48.023E-02
49.907E-02
39.394E-02
50.325E-02
40.336E-02
45.008E-02
40.344E-02
6.523E-05
3.558E-04
2.579E-04
2.280E-04
6.711E-05
2.374E-04
1.913E-04
3.337E-04
1.976E-04
3.035E-04
1.382E-04
3.031E-04
2.317E-04
2.541E-04
2.178E-04
1.946E-04
1.117E-04
2.007E-04
2.107E-04
2.818E-04
2.935E-04
1.907E-04
2.931E-04
1.436E-04
1.686E-04
1.437E-04
5.476E-08
10.044E-08
54.345E-09
52.461E-09
2.352E-08
55.978E-09
40.976E-09
10.002E-08
42.622E-09
71.301E-09
5.732E-09
64.854E-09
46.808E-09
54.554E-09
44.045E-09
33.139E-09
5.807E-09
40.105E-09
31.623E-09
66.612E-09
66.654E-09
33.976E-09
66.193E-09
7.402E-09
1.439E-08
7.402E-09
18.7949
16.0910
15.9356
15.9297
15.9182
15.7392
16.0429
15.8548
15.9880
16.0897
16.0890
15.8574
15.7646
15.8251
15.9011
15.8260
15.9238
15.7179
16.1623
16.0031
14.1779
16.8138
17.6306
16.2292
16.2291
16.1620
5365.88
3095.13
2583.07
2544.34
2541.69
2344.02
2515.62
2467.40
2541.83
3193.92
2974.94
2588.48
2405.96
2459.05
2495.97
2426.42
2521.53
2333.61
3030.20
2934.87
1993.12
3410.51
4092.15
2980.47
2980.47
2935.11
5.40
61.15
39.70
44.30
41.43
41.69
45.97
39.64
42.26
66.15
58.15
41.79
39.63
42.56
40.18
40.36
40.31
36.33
58.15
62.25
103.20
40.15
86.55
64.15
64.15
64.16
77
12
29
23
23
33
43
23
23
27
1
43
53
53
53
53
47
63
46
2
2
2
77
5
7
3
77
84
201
202
18.196
39.791
41.512
8.826
30.689
6.996
18.066
34.122
14.687
40.641
16.810
53.625
0.134
13.151
1.947
10.572
11.803
21.742
14.239
1.147
2.914
30.011
13.389
19.850
15.420
19.854
53.15
28.73
53.068
3.626
9.525
16.592
3.869
9.483
9.542
12.087
12.154
62.886E-02
48.734E-02
50.660E-02
55.517E-02
50.451E-02
56.773E-02
56.815E-02
60.960E-02
53.968E-02
3.358E-04
2.580E-04
2.729E-04
3.306E-04
2.639E-04
3.481E-04
3.485E-04
4.204E-04
3.160E-04
64.267E-09
53.047E-09
57.234E-09
76.325E-09
51.205E-09
86.374E-09
86.499E-09
12.284E-08
71.217E-09
16.1004
15.8333
15.6338
15.2069
16.5270
16.2708
16.7127
15.0113
18.1336
15.3549
16.4174
15.8830
3015.46
2477.07
2348.67
2034.15
3026.89
2752.19
3026.43
1988.08
3694.96
2423.41
2913.70
2666.26
7
53
57
13
37
34
25
25
55
27
88
69
143
57
49
32
138
129
153
102
133
87
88
23
16.1940
13.9087
15.8307
16.8979
16.2799
16.8173
16.1135
15.7972
2827.53
1374.07
2488.59
4452.50
3798.23
4104.13
3626.83
3313.00
61.15
39.94
40.05
45.37
105.00
116.30
104.10
137.80
65.00
62.28
30.63
53.70
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
3
7
3
127
58
53
54
47
117
127
57
327
210
202
204
177
243
244
245
246
247
248
249
250
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
328.49
182.48
574.71
438.08
406.69
305.25
305.31
349.33
369.27
322.47
303.44
256.84
231.67
174.70
175.72
176.62
193.39
180.43
521.30
437.94
252.03
243.03
409.17
729.09
236.65
341.13
258.83
490.69
135.36
357.43
489.53
463.31
479.35
451.21
772.79
313.66
367.32
355.54
1151.10
1259.40
1148.80
1502.00
255.83
248.72
254.66
246.09
313.49
182.48
191.58
196.35
349.62
349.85
349.51
336.75
466.03
470.18
323.72
399.87
213.39
554.35
402.20
483.82
508.18
319.07
300.89
312.03
302.42
49.03
146.54
154.58
166.09
298.94
302.71
302.29
329.92
293.08
165.38
125.52
292.99
125.52
2.533
51.372E-02
2.596E-04
43.040E-09
957.27
879.98
36.283
52.670E-02
4.547E-04
14.558E-08
29.98
26.46
23.03
105.09
82.73
78.63
77.20
138.62
14.361
14.302
13.590
14.344
28.805
60.876E-02
55.056E-02
54.931E-02
55.349E-02
53.507E-02
5.623E-04
4.513E-04
4.505E-04
4.559E-04
4.080E-04
20.725E-08
14.294E-08
14.269E-08
14.478E-08
12.117E-08
8.37
14.82
15.24
146.12
165.71
57.66
136.80
59.73
53.00
59.84
43.15
64.64
67.71
277
152
105
67
67
47
62
57
62
167
136
72
52
57
57
52
62
42
139
137
133
127
222
136
137
123
947
VISA
APPENDIX C
NO
201
202
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
CHLOROBENZENE
FLUOROBENZENE
IODOBENZENE
NITROBENZENE
BENZENE
PHENOL
ANILINE
4-METHYL PYRIDINE
1;5-HEXADIENE
CYCLOHEXENE
CYCLOHEXANONE
CYCLOHEXANE
METHYLCYCLOPENTANE
1-HEXENE
CIS-2-HEXENE
TRANS-2-HEXENE
CIS-3-HEXENE
TRANS-3-HEXENE
2-METHYL-2-PENTENE
3-METHYL-CIS-2-PENTENE
3-METHYL-TRANS-2-PENTENE
4-METHYL-CIS-2-PENTENE
4-METHYL-TRANS-2-PENTENE
2;3-DIMETHYL-1-BUTENE
2;3-DIMETHYL-2-BUTENE
3;3-DIMETHYL-1-BUTENE
CYCLOHEXANOL
METHYL ISOBUTYL KETONE
N-BUTYL ACETATE
ISOBUTYL ACETATE
ETHYL BUTYRATE
ETHYL ISOBUTYRATE
N-PROPYL PROPIONATE
N-HEXANE
2-METHYL PENTANE
3-METHYL PENTANE
2;2-DIMETHYL BUTANE
2;3-DIMETHYL BUTANE
1-HEXANOL
ETHYL BUTYL ETHER
DIISOPROPYL ETHER
DIPROPYLAMINE
TRIETHYLAMINE
COMPOUND NAME
112.559
96.104
204.011
123.112
78.114
94.113
93.129
93.129
82.146
82.146
98.145
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
84.162
100.161
100.161
116.160
116.160
116.160
116.160
116.160
86.178
86.178
86.178
86.178
86.178
102.177
102.177
102.177
101.193
101.193
131.7
85.3
188.2
210.6
80.1
181.8
184.3
145.3
59.4
82.9
155.6
80.7
71.8
63.4
68.8
67.8
66.4
67.1
67.3
67.7
70.4
56.4
58.5
55.6
73.2
41.2
161.1
116.4
126.0
116.8
120.8
111.0
122.5
68.7
60.2
63.2
49.7
58.0
157.0
92.2
68.3
109.2
89.5
632.4
560.1
721.0
712.0
562.1
694.2
699.0
646.0
507.0
560.4
629.0
553.4
532.7
504.0
518.0
516.0
517.0
519.9
518.0
518.0
521.0
490.0
493.0
501.0
524.0
490.0
625.0
571.0
579.0
561.0
566.0
553.0
578.0
507.4
497.5
504.4
488.7
499.9
610.0
531.0
500.0
550.0
535.0
45.2
45.5
45.2
35.0
48.9
61.3
53.1
44.6
34.5
43.5
38.5
40.7
37.9
31.7
32.8
32.7
32.8
32.5
32.8
32.8
32.9
30.4
30.4
32.4
33.6
32.5
37.5
32.7
31.4
30.4
31.4
30.4
0.308
0.271
0.351
0.337
0.259
0.229
0.270
0.311
0.328
0.292
0.312
0.308
0.319
0.350
0.351
0.351
0.350
0.350
0.351
0.351
0.350
0.360
0.360
0.343
0.351
0.340
0.327
0.371
0.400
0.414
0.395
0.410
0.370
0.367
0.367
0.359
0.358
0.381
0.390
0.386
0.407
0.390
20
20
4
20
16
40
20
20
20
16
15
20
16
20
20
20
20
20
16
20
20
20
20
20
20
20
30
20
0
20
20
20
20
20
20
20
20
20
20
20
20
20
20
36,572
29.7
30.1
31.2
30.8
31.3
40.5
30.4
28.8
31.4
30.4
1106
1024
1855
1203
885
1059
1022
955
692
816
951
779
754
673
687
678
680
677
691
694
698
669
669
678
708
653
942
801
898
875
879
869
881
659
653
664
649
662
819
749
724
738
728
39,523
44,031
30,781
45,636
41,868
37,472
27,470
30,480
39,775
29,977
29,098
28,303
29,140
28,931
28,721
28,973
29,015
28,847
29,308
27,591
27,968
27,424
29,655
25,665
45,511
35,588
36,006
35,873
34,332
35,023
36,383
28,872
27,800
28,093
26,322
27,298
48,567
31,820
29,349
37,011
31,401
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
C7F14
C7F16
C7H5N
C7H6O
C7H6O2
C7H7NO2
C7H7NO2
PERFLUOROMETHYLCYCLOHEXANE
PERFLUORO-N-HEPTANE
BENZONITRILE
BENZALDEHYDE
BENZOIC ACID
O-NITROTOLUENE
M-NITROTOLUENE
350.055
388.051
103.124
106.124
122.124
137.139
137.139
45.6
39.2
31.4
4.8
5.5
40.8
6.2
3.7
141.2
103.5
31.2
6.5
142.5
139.9
141.2
133.2
137.9
113.5
135.1
134.9
138.5
134.2
141.2
157.3
74.3
115.2
24.8
84.2
73.5
98.9
93.2
88.2
75.9
95.4
153.7
118.2
99.9
128.6
44.0
103.2
85.5
63.2
114.8
76.3
82.5
190.8
178.8
249.8
222.1
233.1
486.8
474.8
699.4
695.0
752.0
720.0
725.0
23.3
16.2
42.2
46.6
45.6
34.0
30.5
1733
1010
1045
1075
1167
1158
20
15
20
130
20
20
42,705
50,660
45,487
46,090
294
295
296
297
298
299
300
78.2
13.2
57.2
122.4
9.2
16.0
0.664
0.341
0.371
0.371
CHEMICAL ENGINEERING
FORMULA
C6H5CL
C6H5F
C6H5I
C6H5NO2
C6H6
C6H6O
C6H7N
C6H7N
C6H10
C6H10
C6H10O
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12
C6H12O
C6H12O
C6H12O2
C6H12O2
C6H12O2
C6H12O2
C6H12O2
C6H14
C6H14
C6H14
C6H14
C6H14
C6H14O
C6H14O
C6H14O
C6H15N
C6H15N
948
NO
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
VISB
DELHF
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
477.76
452.06
565.72
276.22
252.89
331.21
99.23
69.08
187.90
33.888
38.728
29.274
56.312E-02
56.689E-02
55.643E-02
4.522E-04
4.434E-04
4.509E-04
14.264E-08
13.553E-08
14.432E-08
545.64
1405.50
1074.60
500.97
265.34
370.07
357.21
285.50
129.75
32.91
166.80
33.917
35.843
40.516
17.430
47.436E-02
59.829E-02
63.849E-02
48.818E-02
3.017E-04
4.827E-04
5.133E-04
2.798E-04
71.301E-09
15.269E-08
16.333E-08
54.512E-09
506.92
787.38
653.62
440.52
357.43
344.33
344.33
344.33
344.33
264.54
336.47
290.84
243.24
197.74
197.95
197.95
197.95
197.95
68.651
37.807
54.541
50.108
1.746
9.810
32.925
21.729
4.338
14.750
14.750
14.750
1.675
12.627
7.025
2.294
12.556
55.534
3.894
13.620
7.310
21.508
72.515E-02
55.391E-02
61.127E-02
63.807E-02
53.089E-02
53.089E-02
69.292E-02
58.113E-02
55.098E-02
56.689E-02
56.689E-02
56.689E-02
53.759E-02
51.540E-02
55.852E-02
48.274E-02
54.847E-02
72.139E-02
56.564E-02
54.889E-02
57.401E-02
49.279E-02
5.414E-04
1.953E-04
2.523E-04
3.642E-04
2.903E-04
2.717E-04
5.619E-04
3.362E-04
3.282E-04
3.341E-04
3.341E-04
3.341E-04
3.044E-04
3.007E-04
3.696E-04
2.199E-04
2.915E-04
4.086E-04
3.318E-04
2.278E-04
2.576E-04
1.938E-04
16.442E-08
1.534E-08
13.214E-09
80.135E-09
60.541E-09
48.274E-09
20.046E-08
74.567E-09
80.470E-09
79.633E-09
79.633E-09
79.633E-09
67.533E-09
73.269E-09
10.630E-08
30.417E-09
52.084E-09
82.354E-09
82.312E-09
7.913E-10
11.011E-09
35.588E-10
3295.12
3181.78
3776.53
4032.66
2788.51
3490.89
3857.52
3409.40
2728.54
2813.53
55.60
37.59
64.38
71.81
52.36
98.59
73.15
62.65
45.45
49.98
47
23
17
44
7
72
67
27
9
27
147
97
197
211
104
208
227
187
77
87
15.7527
15.8023
15.8089
16.2057
15.8727
15.8384
15.9288
15.9423
15.9124
15.9484
15.7527
15.8425
15.8012
16.0043
15.3755
2766.63
2731.00
2654.81
2897.97
2701.72
2680.52
2718.68
2725.89
2731.79
2750.50
2580.52
2631.57
2612.69
2798.63
2326.80
50.50
47.11
47.30
39.30
48.62
48.40
47.77
47.64
46.76
48.33
46.56
46.00
43.78
47.71
48.24
7
23
33
28
28
28
28
28
25
23
35
33
38
23
48
107
102
87
97
92
92
92
97
91
93
79
81
87
102
67
259.03
272.30
270.49
264.22
106.93
90.81
31.78
35.80
87.50
76.28
76.49
83.07
77.67
71.26
73.27
71.34
82.19
79.67
79.09
75.91
98.22
117.98
16.0676
16.5487
16.1454
16.1484
15.9008
16.4279
16.6748
16.2143
16.1351
15.8243
473.65
537.58
533.99
489.95
51.87
116.64
162.66
67.49
82.98
96.67
86.92
102.28
83.74
5.36
230.27
123.22
105.93
41.70
52.38
53.93
47.65
54.47
59.79
57.78
58.70
50.37
54.39
55.77
59.24
43.17
294.75
284.03
486.76
495.47
15.7165
16.1836
16.1714
15.9987
2893.66
3151.09
3092.83
3127.60
70.75
69.15
66.15
60.15
12
22
16
15
152
162
154
159
362.79
384.13
372.11
438.44
444.19
1179.40
443.32
410.58
561.11
355.52
207.09
208.27
207.55
226.67
228.86
354.94
234.68
219.67
257.39
214.48
167.30
174.42
171.74
185.68
177.90
317.78
0.25
5.02
2.14
9.63
4.10
135.65
319.03
121.96
99.65
110.36
4.413
10.567
2.386
16.634
14.608
4.811
23.626
7.503
6.460
18.430
58.197E-02
61.839E-02
56.899E-02
62.928E-02
61.504E-02
58.908E-02
53.675E-02
58.490E-02
62.928E-02
71.552E-02
3.119E-04
3.573E-04
2.870E-04
3.481E-04
3.376E-04
3.010E-04
2.528E-04
3.027E-04
3.390E-04
4.392E-04
64.937E-09
80.847E-09
50.325E-09
68.496E-09
68.203E-09
54.261E-09
41.567E-09
58.448E-09
70.715E-09
10.923E-08
16.8641
15.8366
15.7476
15.7701
15.5536
15.6802
18.0994
16.0477
16.3417
16.5939
15.8853
3558.18
2697.55
2614.38
2653.43
2489.50
2595.44
4055.45
2921.52
2895.73
3259.08
2882.38
2610.57
2719.68
57.317E-02
49.614E-02
62.928E-02
4.430E-04
2.845E-04
4.237E-04
13.490E-08
51.665E-09
10.622E-08
17
3
112
117
26.004
12.142
51.292
61.93
64.50
19
28
33
33
43
38
35
8
24
29
13
147
97
97
92
77
81
157
127
91
149
127
15.7130
15.9747
47.86
48.78
46.58
46.02
43.81
44.25
76.49
55.15
43.15
55.15
51.15
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
16.3501
17.1634
14.2028
3748.62
4190.70
2603.49
66.12
125.20
151.52
27
132
222
187
287
129
294
295
296
297
298
299
300
686.84
2617.60
314.66
407.88
2898.10
3386.70
218.97
36.80
290.40
265.86
265.86
3089.31
261.05
22.40
210.55
294
295
296
297
298
299
300
949
VISA
APPENDIX C
NO
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
C7H7NO2
C7H8
C7H8O
C7H8O
C7H8O
C7H8O
C7H8O
C7H9N
C7H9N
C7H9N
C7H9N
C7H9N
C7H9N
C7H9N
C7H9N
C7H14
C7H14
C7H14
C7H14
C7H14
C7H14
C7H14
C7H14
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16
C7H16O
P-NITROTOLUENE
TOLUENE
METHYL PHENYL ETHER
BENZYL ALCOHOL
O-CRESOL
M-CRESOL
P-CRESOL
2;3-DIMETHYLPYRIDINE
2;5-DIMETHYLPYRIDINE
3;4-DIMETHYLPYRIDINE
3;5-DIMETHYLPYRIDINE
METHYLPHENYLAMINE
O-TOLUIDINE
M-TOLUIDINE
P-TOLUIDINE
CYCLOHEPTANE
1;1-DIMETHYLCYCLOPENTANE
CIS-1;2-DIMETHYLCYCLOPENTANE
TRANS-1;2-DIMETHYLCYCLOPENTANE
ETHYLCYCLOPENTANE
METHYLCYCLOHEXANE
1-HEPTENE
2;3;3-TRIMETHYL-1-BUTENE
N-HEPTANE
2-METHYLHEXANE
3-METHYLHEXANE
2;2-DIMETHYLPENTANE
2;3-DIMETHYLPENTANE
2;4-DIMETHYLPENTANE
3;3-DIMETHYLPENTANE
3-ETHYLPENTANE
2;2;3-TRIMETHYLBUTANE
1-HEPTANOL
COMPOUND NAME
137.139
92.141
108.140
108.140
108.140
108.140
108.140
107.156
107.156
107.156
107.156
107.156
107.156
107.156
107.156
98.189
98.189
98.189
98.189
98.189
98.189
98.189
98.189
100.250
100.205
100.205
100.205
100.205
100.205
100.205
100.205
100.205
116.204
54.8
95.2
37.5
15.4
30.9
12.2
34.7
238.0
110.6
153.6
205.4
191.0
202.2
201.9
160.8
157.0
179.1
171.9
195.9
200.1
203.3
200.1
118.7
87.8
99.5
91.8
103.4
100.9
93.6
77.8
98.4
90.0
91.8
79.2
89.7
80.5
86.0
93.4
80.8
176.3
735.0
591.7
641.0
677.0
697.6
705.8
704.6
655.4
644.2
683.8
667.2
701.0
694.0
709.0
667.0
589.0
547.0
564.8
553.2
569.5
572.1
537.2
533.0
540.2
530.3
535.2
520.4
537.3
519.7
536.3
540.6
531.1
633.0
30.1
41.1
41.7
46.6
50.1
45.6
51.5
0.371
0.316
1164
867
996
1041
1028
1034
1019
942
938
954
939
989
998
989
964
810
759
777
756
771
774
679
705
684
679
687
674
965
673
693
698
690
822
20
20
20
25
40
20
40
25
0
25
25
20
20
20
50
20
16
16
16
16
16
20
20
20
20
20
20
20
20
20
20
20
20
46,875
33,201
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
C8H4O3
C8H8
C8H8O
C8H8O2
C8H10
C8H10
C8H10
C8H10
C8H10O
C8H10O
C8H10O
C8H10O
C8H10O
C8H10O
C8H10O
C8H10O
C8H10O
PHTHALIC ANHYDRIDE
STYRENE
METHYL PHENYL KETONE
METHYL BENZOATE
O-XYLENE
M-XYLENE
P-XYLENE
ETHYL BENZENE
O-ETHYLPHENOL
M-ETHYLPHENOL
P-ETHYLPHENOL
ETHYL PHENYL ETHER
2;3-XYLENOL
2;4-XYLENOL
2;5-XYLENOL
2;6-XYLENOL
3;4-XYLENOL
148.118
104.152
120.151
136.151
106.168
106.168
106.168
106.168
122.167
122.167
122.167
122.167
122.167
122.167
122.167
122.167
122.167
286.8
145.1
201.7
199.0
144.4
139.1
138.3
136.1
204.5
218.4
217.8
169.8
216.9
210.8
211.1
200.9
226.8
810.0
647.0
701.0
692.0
630.2
617.0
616.2
617.1
703.0
716.4
716.4
647.0
722.8
707.6
723.0
701.0
729.8
906
1032
1083
880
864
861
867
1037
1025
20
15
20
20
20
20
20
0
0
979
4
57.2
14.8
30.4
43.7
8.2
69.8
53.9
117.6
138.5
126.6
118.9
109.9
90.6
118.3
173.2
123.8
119.2
134.5
118.6
24.9
34.0
130.8
30.7
19.6
12.4
25.2
47.9
13.2
95.0
3.4
4.2
44.8
30.2
74.8
24.8
74.8
48.8
64.8
0.334
0.282
0.310
52.0
37.5
41.5
0.343
0.343
37.2
34.5
34.5
34.5
33.9
34.8
28.4
29.0
27.4
27.4
28.2
27.8
29.1
27.4
29.5
28.9
29.6
30.4
0.390
0.360
0.368
0.362
0.375
0.368
0.440
0.400
0.432
0.421
0.404
0.416
0.393
0.418
0.414
0.416
0.398
0.435
47.6
39.9
38.5
36.5
37.3
35.5
35.2
36.1
0.368
34.2
0.376
0.396
0.369
0.376
0.379
0.374
50,535
45,217
47,436
47,478
45,364
45,636
44,799
33,076
30,312
31,719
30,878
32,301
31,150
31,108
28,889
31,719
30,689
30,815
29,182
30,409
29,517
29,668
30,978
28,968
48,148
49,614
36,844
43,124
36,844
36,383
36,006
35,588
48,106
50,828
50,660
47,311
47,143
46,892
44,380
49,823
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
CHEMICAL ENGINEERING
FORMULA
950
NO
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
NO
VISB
467.33
388.84
1088.00
1533.40
1785.60
1826.90
255.24
325.85
367.21
365.61
370.75
372.68
915.12
1085.10
928.12
738.90
332.74
356.46
354.07
356.02
433.81
528.41
368.69
249.72
271.58
214.32
436.73
417.46
232.53
225.13
417.37
226.19
1287.00
361.83
528.64
1316.40
768.94
513.54
453.42
475.16
472.82
276.71
310.82
332.33
277.98
257.18
261.40
264.22
646.88
305.91
DELHF
50.03
94.08
128.70
132.43
125.48
68.29
66.44
70.05
72.81
85.41
119.41
138.37
129.62
136.78
127.15
154.87
62.34
86.54
187.90
195.06
192.43
206.28
199.38
202.14
201.68
189.79
204.94
332.01
371.79
147.46
86.92
254.06
19.01
17.25
17.96
29.81
145.78
146.58
144.65
157.34
162.78
161.53
161.95
156.50
DELGF
122.09
37.10
40.57
30.90
CPVAPA
CPVAPB
CPVAPC
CPVAPD
24.355
51.246E-02
2.765E-04
49.111E-09
7.398
32.276
45.008
40.633
54.805E-02
70.045E-02
72.641E-02
70.548E-02
3.357E-04
5.924E-04
6.029E-04
5.757E-04
77.707E-09
21.240E-08
20.775E-08
19.674E-08
199.33
15.989
56.815E-02
3.033E-04
46.432E-09
63.05
39.06
45.76
38.39
44.59
27.30
95.88
76.187
57.891
55.643
54.521
55.312
61.919
3.303
78.670E-02
76.702E-02
76.158E-02
75.907E-02
75.111E-02
78.419E-02
62.969E-02
4.204E-04
4.501E-04
4.484E-04
4.480E-04
4.396E-04
4.438E-04
3.512E-04
75.614E-09
10.103E-08
10.140E-08
10.170E-08
10.040E-08
93.659E-09
76.074E-09
8.00
3.22
4.61
0.08
0.67
3.10
2.64
11.01
4.27
121.00
5.146
39.389
7.046
50.099
7.046
7.046
7.046
7.046
22.944
4.907
67.617E-02
86.416E-02
68.370E-02
89.556E-02
70.476E-02
68.370E-02
68.370E-02
68.370E-02
75.195E-02
67.784E-02
76.577E-09
18.363E-08
78.335E-09
17.358E-08
78.335E-09
78.335E-09
78.335E-09
78.335E-09
10.048E-08
60.457E-09
4.455
28.248
29.580
21.210
15.851
29.165
25.091
43.099
65.398E-02
61.588E-02
64.100E-02
55.015E-02
59.620E-02
62.969E-02
60.416E-02
70.715E-02
3.651E-04
6.289E-04
3.734E-04
6.360E-04
3.734E-04
3.734E-04
3.734E-04
3.734E-04
4.421E-04
3.447E-04
213.95
1.84
122.17
118.95
121.21
130.67
4.283E-04
4.023E-04
4.071E-04
1.799E-04
3.443E-04
3.747E-04
3.374E-04
4.811E-04
10.094E-08
99.353E-09
97.217E-09
44.254E-09
75.279E-09
84.783E-09
68.203E-09
13.008E-08
ANTA
ANTB
ANTC
TMN
TMX
NO
16.0433
16.0137
16.2394
17.4582
15.9148
17.2878
16.1989
17.1492
16.3046
16.9517
16.8850
16.3066
16.7834
16.7498
16.6968
15.7818
15.6973
15.7729
15.7594
15.8581
15.7105
15.8894
15.6536
15.8737
15.8261
15.8133
15.6917
15.7815
15.7179
15.7190
15.8317
15.6398
15.3068
3914.07
3096.52
3430.82
4384.81
3305.37
4274.42
3479.39
4219.74
3545.14
4237.04
4106.95
3756.28
4072.58
4080.32
4041.04
3066.05
2807.94
2922.30
2861.53
2990.13
2926.04
2895.51
2719.47
2911.32
2845.06
2855.66
2740.15
2850.64
2744.78
2829.10
2882.44
2764.40
2626.42
233
7
97
112
97
97
97
147
77
127
127
47
102
82
77
57
13
3
13
3
3
8
20
3
9
8
19
11
17
13
7
19
60
129
137
167
330
207
207
207
167
162
187
187
207
227
227
227
162
117
127
117
129
127
127
102
127
117
117
105
115
105
112
119
106
176
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
15.9984
16.0193
16.2384
16.2272
16.1156
16.1390
16.0963
16.0195
17.9610
17.1955
19.0905
16.1673
16.2424
13.2456
16.2328
16.2809
16.3004
4467.01
3328.57
3781.07
3751.83
3395.57
3366.99
3346.65
3272.47
4928.36
4272.77
5579.62
3473.20
3724.58
3655.26
3667.32
3749.35
3733.53
90.45
53.67
69.58
73.15
108.00
74.09
111.30
33.04
63.59
41.65
44.45
80.71
72.15
73.15
72.15
56.80
51.20
52.94
51.46
52.47
51.75
53.97
49.56
56.51
53.60
53.93
49.85
51.33
51.52
47.83
53.26
47.10
146.60
136
32
77
77
32
27
27
27
77
97
97
112
147
137
137
127
157
342
187
247
243
172
167
167
177
227
227
227
187
227
227
217
207
247
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
83.15
63.72
81.15
81.15
59.46
58.04
57.84
59.95
45.75
86.08
44.15
78.66
102.40
103.80
102.40
85.55
113.90
951
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
VISA
APPENDIX C
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
COMPOUND NAME
MOLWT
TFP
TBP
TC
C8H10O
C8H11N
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H16
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18
C8H18O
C8H18O
C8H18O
C8H18O
C8H18O5
C8H19N
C8H20SI
3;5-XYLENOL
N;N-DIMETHYLANILINE
1;1-DIMETHYLCYCLOHEXANE
CIS-1;2-DIMETHYLCYCLOHEXANE
TRANS-1;2-DIMETHYLCYCLOHEXANE
CIS-1;3-DIMETHYLCYCLOHEXANE
TRANS-1;3-DIMETHYLCYCLOHEXANE
CIS-1;4-DIMETHYLCYCLOHEXANE
TRANS-1;4-DIMETHYLCYCLOHEXANE
ETHYLCYCLOHEXANE
1;1;2-TRIMETHYLCYCLOPENTANE
1;1;3-TRIMETHYLCYCLOPENTANE
CIS;CIS;TRANS-1;2;4-TRIMETHYLCYCLOPENTANE
CIS;TRANS;CIS-1;2;4-TRIMETHYLCYCLOPENTANE
1-METHYL-1-ETHYLCYCLOPENTANE
N-PROPYLCYCLOPENTANE
ISOPROPYLCYCLOPENTANE
1-OCTENE
TRANS-2-OCTENE
N-OCTANE
2-METHYLHEPTANE
3-METHYLHEPTANE
4-METHYLHEPTANE
2;2-DIMETHYLHEXANE
2;3-DIMETHYLHEXANE
2;4-DIMETHYLHEXANE
2;5-DIMETHYLHEXANE
3;3-DIMETHYLHEXANE
3;4-DIMETHYLHEXANE
3-ETHYLHEXANE
2;2;3-TRIMETHYLPENTANE
2;2;4-TRIMETHYLPENTANE
2;3;3-TRIMETHYLPENTANE
2;3;4-TRIMETHYLPENTANE
2-METHYL-3-ETHYLPENTANE
3-METHYL-3-ETHYLPENTANE
1-OCTANOL
2-OCTANOL
2-ETHYLHEXANOL
BUTYL ETHER
TETRAETHYLENE GLYCOL
DIBUTYLAMINE
TETRAETHYL SILANE
122.167
121.183
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
112.216
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
114.232
130.231
130.231
130.231
130.231
194.229
129.247
144.333
63.8
2.4
33.5
50.1
88.2
75.6
90.2
87.5
37.0
111.4
221.6
193.5
119.5
129.7
123.4
120.1
124.4
124.3
119.3
131.7
113.7
104.8
117.8
109.2
121.5
130.9
126.4
121.2
124.9
125.6
117.6
118.9
117.7
108.8
115.6
109.4
109.1
111.9
117.7
118.5
109.8
99.2
114.7
113.4
115.6
118.2
195.2
179.7
184.6
142.4
318.9
159.6
153.4
715.6
687.0
591.0
606.0
596.0
591.0
598.0
598.0
590.0
609.0
579.5
569.5
579.0
571.0
592.0
603.0
601.0
566.6
580.0
568.8
559.6
563.6
561.7
549.8
563.4
553.5
550.0
562.0
568.8
565.4
563.4
543.9
573.5
566.3
567.0
576.5
658.0
637.0
613.0
580.0
795.8
596.0
603.7
36.3
29.7
29.7
29.7
29.7
29.7
29.7
29.7
30.3
29.4
28.3
28.8
28.1
29.9
30.0
30.0
26.2
27.7
24.8
24.8
25.4
25.4
25.3
26.2
25.5
24.8
26.5
27.0
26.0
27.3
25.6
28.2
27.3
27.1
28.1
34.5
27.4
27.6
25.3
21.0
25.3
26.0
0.492
0.488
0.464
0.476
0.478
0.468
0.472
0.482
0.443
0.466
0.455
0.436
0.468
0.455
0.461
0.443
0.455
0.490
0.494
0.494
0.500
0.646
0.517
0.582
394
395
396
397
398
399
400
C9H8
C9H10
C9H10
C9H10O2
C9H12
C9H12
C9H12
INDENE
INDAN
ALPHA-METHYL STYRENE
ETHYL BENZOATE
N-PROPYLBENZENE
ISOPROPYLBENZENE
1-METHYL-2-ETHYLBENZENE
116.163
118.179
118.179
150.178
120.195
120.195
120.195
181.9
177.0
165.3
212.7
159.2
152.4
165.1
691.9
681.1
654.0
697.0
638.3
631.0
651.0
38.2
36.3
34.0
32.4
32.0
32.1
30.4
0.377
0.392
0.397
0.451
0.440
0.428
0.460
117.4
112.7
101.8
87.8
56.8
109.2
120.5
121.0
121.2
91.3
126.2
112.3
107.4
100.7
109.3
115.0
90.9
15.5
32.0
70.0
97.9
62.2
82.5
34.9
99.5
96.1
80.9
PC
VC
0.416
0.450
0.425
0.464
LDEN
TDEN
HVAP
NO
49,404
956
785
796
776
766
785
783
763
788
20
16
20
20
20
20
20
20
20
781
776
715
720
703
702
706
705
695
712
700
693
710
719
718
716
692
726
719
719
727
826
821
833
768
16
20
20
20
20
16
20
20
20
20
20
20
20
20
16
20
20
20
20
20
20
20
20
20
20
32,615
33,662
32,908
32,825
33,871
33,787
32,615
34,332
32,615
31,694
33,076
33,076
33,662
34,131
34,122
33,787
34,332
34,436
33,829
33,913
33,913
32,280
33,226
32,615
32,657
32,490
33,298
33,633
32,029
31,028
32,364
32,753
32,988
32,816
50,660
44,380
46,599
37,263
767
766
20
20
39,775
36,473
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
38,309
44,799
38,267
37,556
38,895
394
395
396
397
398
399
400
911
1046
862
862
881
20
20
20
20
20
CHEMICAL ENGINEERING
FORMULA
952
NO
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
NO
553.02
VISB
320.03
DELHF
DELGF
161.48
84.15
181.12
172.29
180.12
184.89
176.68
176.77
184.72
171.87
231.36
35.25
41.24
34.50
29.85
36.34
37.97
31.74
39.27
CPVAPA
CPVAPB
CPVAPC
CPVAPD
72.105
68.370
68.479
65.163
64.154
64.154
70.363
63.891
89.974E-02
89.723E-02
91.230E-02
88.383E-02
88.258E-02
88.258E-02
91.314E-02
88.928E-02
5.020E-04
5.137E-04
5.355E-04
4.932E-04
5.016E-04
5.016E-04
5.309E-04
5.108E-04
10.304E-08
10.986E-08
11.811E-08
10.199E-08
10.685E-08
10.685E-08
11.547E-08
11.028E-08
506.43
280.76
454.23
264.22
148.17
52.63
55.973
84.490E-02
4.924E-04
11.175E-08
418.82
427.64
473.70
643.61
237.63
240.32
251.71
259.51
446.20
244.67
437.60
474.57
467.04
238.33
257.61
246.43
82.98
94.58
208.59
215.62
212.77
212.23
224.87
214.07
219.56
222.78
220.27
213.15
211.01
220.27
224.29
216.58
217.59
211.35
215.12
360.06
104.29
92.74
16.41
12.77
13.73
16.75
10.72
17.71
11.72
10.47
13.27
17.33
16.54
17.12
13.69
18.92
18.92
21.27
19.93
120.16
365.55
334.11
88.59
4.099
12.820
6.096
89.744
9.215
9.215
9.215
9.215
9.215
9.215
9.215
9.215
9.215
9.215
7.461
9.215
9.215
9.215
9.215
6.171
25.879
14.993
6.054
7.164
9.764
72.390E-02
75.321E-02
77.121E-02
12.422E-01
78.586E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
77.791E-02
78.586E-02
78.586E-02
78.586E-02
78.586E-02
76.074E-02
76.409E-02
86.541E-02
77.288E-02
86.164E-02
80.805E-02
4.036E-04
4.442E-04
4.195E-04
1.176E-03
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
4.287E-04
4.400E-04
4.400E-04
4.400E-04
4.400E-04
3.797E-04
4.224E-04
5.280E-04
4.085E-04
2.904E-04
4.392E-04
86.750E-09
10.505E-08
88.551E-09
46.180E-08
96.966E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
91.733E-09
96.966E-09
96.966E-09
96.966E-09
96.966E-09
62.635E-09
90.644E-09
12.845E-08
80.847E-09
9.115E-08
92.486E-09
42.944
59.639
24.329
20.670
31.288
39.364
16.446
68.957E-02
78.126E-02
69.333E-02
68.873E-02
74.860E-02
78.419E-02
69.961E-02
4.340E-04
4.841E-04
4.530E-04
3.608E-04
4.601E-04
5.087E-04
4.120E-04
91.482E-09
98.474E-09
11.807E-08
50.618E-09
10.810E-08
12.912E-08
93.282E-09
1312.10
369.97
1798.00
473.50
351.17
266.56
581.42
286.54
314.93
354.34
746.50
527.45
517.17
270.80
338.47
282.65
276.22
7.83
3.94
1.21
137.33
137.08
131.17
ANTA
ANTB
ANTC
TMN
TMX
NO
16.4192
16.9647
15.6535
15.7438
15.7337
15.7470
15.7371
15.7333
15.6984
15.8125
15.7084
15.6794
15.7543
15.7756
15.8222
15.8969
15.8561
15.9630
15.8554
15.9426
15.9278
15.8865
15.8893
15.7431
15.8189
15.7797
15.7954
15.7755
15.8415
15.8671
15.7162
15.6850
15.7578
15.7818
15.8040
15.8126
15.7428
14.7108
15.3614
16.0778
20.5564
16.7307
16.6385
3775.91
4276.08
3043.34
3148.35
3117.43
3081.95
3093.95
3098.39
3063.44
3183.25
3015.51
2938.09
3073.95
3009.70
3120.66
3187.67
3176.22
3116.52
3134.97
3120.29
3097.63
3065.96
3057.05
2932.56
3029.06
2965.44
2964.06
3011.51
3062.52
3057.57
2981.56
2896.28
3057.94
3028.09
3035.08
3102.06
3017.81
2441.66
2773.46
3296.15
8215.28
3721.90
3873.18
137
72
10
17
13
11
15
14
10
20
6
0
10
9
13
21
16
16
16
19
12
13
12
3
10
5
5
6
11
13
4
4
7
7
9
10
70
72
75
32
227
49
153
3994.97
3789.86
3644.30
3845.09
3433.84
3363.60
3535.33
227
207
147
157
151
147
152
152
147
160
141
131
145
144
149
158
154
147
152
152
144
145
144
132
142
135
135
138
144
145
136
125
142
140
142
145
195
180
185
182
427
186
1
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
16.4380
16.2601
16.3308
16.2065
16.0062
15.9722
16.1253
109.00
52.80
55.30
57.31
54.02
55.08
57.76
57.00
54.57
58.15
54.59
53.25
54.20
53.23
55.06
59.99
55.18
60.39
58.00
63.63
59.46
60.74
60.59
58.08
58.99
58.36
58.74
55.71
58.29
60.55
54.73
52.41
52.77
55.62
57.84
53.47
137.10
150.70
140.00
66.15
11.50
64.15
39.33
49.40
57.00
67.15
84.15
66.01
63.37
65.85
77
77
75
88
43
38
48
277
277
220
258
188
181
194
394
395
396
397
398
399
400
953
394
395
396
397
398
399
400
VISA
APPENDIX C
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
C9H12
C9H12
C9H12
C9H12
C9H12
C9H18
C9H18
C9H18
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H20
C9H29
C9H20
1-METHYL-3-ETHYLBENZENE
1-METHYL-4-ETHYLBENZENE
1;2;3-TRIMETHYLBENZENE
1;2;4-TRIMETHYLBENZENE
1;3;5-TRIMETHYLBENZENE
N-PROPYLCYCLOHEXANE
ISOPROPYLCYCLOHEXANE
1-NONENE
N-NONANE
2;2;3-TRIMETHYLHEXANE
2;2;4-TRIMETHYLHEXANE
2;2;5-TRIMETHYLHEXANE
3;3-DIMETHYLPENTANE
2;2;3;3-TETRAMETHYLPENTANE
2;2;3;4-TETRAMETHYLPENTANE
2;2;4;4-TETRAMETHYLPENTANE
2;3;3;4-TETRAMETHYLPENTANE
COMPOUND NAME
120.195
120.195
120.195
120.195
120.195
126.243
126.243
126.243
128.259
128.259
128.259
128.259
128.259
128.259
128.259
128.259
128.259
95.6
62.4
25.5
46.2
44.8
94.5
89.8
81.4
53.5
161.3
162.0
176.0
169.3
164.7
156.7
154.5
146.8
150.8
133.6
126.5
124.1
146.1
140.2
133.0
122.2
141.5
637.0
640.0
664.5
649.1
637.3
639.0
640.0
592.0
594.6
588.0
573.7
568.0
610.0
607.6
592.7
574.7
607.6
28.4
29.4
34.6
32.3
31.3
28.1
28.4
23.4
23.1
24.9
23.7
23.3
26.7
27.4
26.0
24.8
27.2
0.490
0.470
0.430
0.430
0.433
865
861
894
880
865
793
802
745
718
20
20
20
16
20
20
20
0
20
38,560
38,435
40,068
39,272
39,063
36,090
720
717
752
16
16
20
719
20
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
C10H8
C10H12
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H14
C10H15N
C10H18
C10H18
C10H19N
C10H20
C10H20
C10H20
C10H20
C10H20
C10H20O
C10H22
C10H22
C10H22
C10H22
C10H22O
NAPHTHALENE
1;2;3;4-TETRAHYDRONAPHTHALENE
N-BUTYLBENZENE
ISOBUTYLBENZENE
SEC-BUTYLBENZENE
TERT-BUTYLBENZENE
1-METHYL-2-ISOPROPYLBENZENE
1-METHYL-3-ISOPROPYLBENZENE
1-METHYL-4-ISOPROPYLBENZENE
1;4-DIETHYLBENZENE
1;2;4;5-TETRAMETHYLBENZENE
N-BUTYLANILINE
CIS-DECALIN
TRANS-DECALIN
CAPRYLONITRILE
N-BUTYLCYCLOHEXANE
ISOBUTYLCYCLOHEXANE
SEC-BUTYLCYCLOHEXANE
TERT-BUTYLCYCLOHEXANE
1-DECENE
MENTHOL
N-DECANE
3;3;5-TRIMETHYLHEPTANE
2;2;3;3-TETRAMETHYLHEXANE
2;2;5;5-TETRAMETHYLHEXANE
1-DECANOL
128.174
132.206
134.222
134.222
134.222
134.222
134.222
134.222
134.222
134.222
134.222
149.236
138.254
138.254
153.269
140.270
140.270
140.270
140.270
140.270
156.269
142.286
142.286
142.286
142.286
158.285
217.9
207.5
183.2
172.7
173.3
169.1
178.3
175.1
177.1
183.7
196.8
240.7
195.7
187.2
242.8
180.9
171.3
179.3
171.5
170.5
216.3
174.1
155.6
160.3
137.4
230.2
748.4
719.0
660.5
650.0
664.0
660.0
670.0
666.0
653.0
657.9
675.0
721.0
702.2
690.0
622.0
667.0
659.0
669.0
659.0
615.0
694.0
617.6
609.6
623.1
581.5
700.0
40.5
35.2
28.9
31.4
29.5
29.7
29.0
29.4
28.3
28.1
29.4
28.4
31.4
31.4
32.5
31.5
31.2
26.7
26.6
22.1
0.650
971
973
860
853
862
867
876
861
857
862
838
932
897
870
820
799
795
813
813
741
90
20
20
20
20
20
20
20
20
20
81
20
20
20
20
20
20
20
20
20
21.1
23.2
25.1
21.9
22.3
0.603
730
20
0.600
830
20
444
445
446
447
448
449
C11H10
C11H10
C11H1402
C11H22
C11H22
C11H24
1-METHYLNAPHTHALENE
2-METHYLNAPHTHALENE
BUTYL BENZOATE
N-HEXYLCYCLOPENTANE
1-UNDECENE
N-UNDECANE
142.201
142.201
178.232
154.297
154.297
156.313
30.5
34.5
22.2
244.6
241.0
249.8
203.1
192.6
195.9
772.0
761.0
723.0
660.1
637.0
638.8
35.7
35.1
26.3
21.4
20.0
19.7
0.445
0.462
0.561
1020
990
1006
20
40
20
0.660
751
740
20
20
450
C12H8
ACENAPHTHALENE
152.196
95.0
270.0
796.9
32.2
0.487
120.2
105.8
67.2
80.3
31.2
88.0
51.5
75.5
57.9
73.2
42.2
78.8
14.2
43.2
30.4
17.9
74.8
41.2
66.3
42.8
29.7
6.9
49.2
25.6
0.580
0.548
0.519
0.410
0.497
0.480
0.480
0.480
0.518
36,341
36,940
34,792
34,039
33,787
36,006
35,295
34,290
32,866
34,960
43,292
39,733
39,272
37,849
37,974
37,639
39,306
36,676
36,383
35,295
50,242
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
46,055
46,055
48,986
41,198
40,905
41,533
444
445
446
447
448
449
38,142
39,398
45,552
48,944
39,356
38,519
38,519
38,686
450
CHEMICAL ENGINEERING
FORMULA
954
NO
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
NO
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
450
463.17
266.08
872.74
437.52
549.08
297.75
268.27
293.93
471.00
525.56
258.92
272.12
873.32
352.57
563.84
296.01
582.82
295.82
DELHF
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
1.93
2.05
9.59
13.94
16.08
193.43
126.53
126.78
124.64
117.02
118.03
47.35
28.998
27.310
6.942
4.668
19.590
62.517
72.934E-02
71.762E-02
63.346E-02
62.383E-02
67.240E-02
98.892E-02
4.363E-04
4.224E-04
3.326E-04
3.263E-04
3.692E-04
5.795E-04
99.981E-09
95.417E-09
66.110E-09
63.765E-09
76.995E-09
12.912E-08
103.58
229.19
241.37
243.38
254.18
231.95
237.39
237.22
242.12
236.39
112.75
24.83
24.53
22.52
13.44
35.09
34.33
32.66
34.04
34.12
3.718
3.144
45.632
60.311
54.106
67.269
54.583
54.583
67.403
54.918
81.224E-02
67.742E-02
10.555E-01
11.045E-01
10.948E-01
11.262E-01
10.890E-01
10.890E-01
11.681E-01
10.911E-01
4.509E-04
1.928E-04
7.172E-04
7.712E-04
7.746E-04
7.988E-04
7.570E-04
7.570E-04
8.612E-04
7.603E-04
97.050E-09
2.981E-08
19.866E-08
21.876E-08
22.546E-08
23.061E-08
21.420E-08
21.420E-08
25.736E-08
21.579E-08
16.1545
16.1135
16.2121
16.2190
16.2893
15.8567
15.8260
16.0118
15.9671
15.8017
15.7639
15.7445
15.8709
15.7280
15.7363
15.6488
15.8029
3521.08
3516.31
3670.22
3622.58
3614.19
3363.62
3346.12
3305.03
3291.45
3164.17
3084.08
3052.17
3341.62
3220.55
3167.42
3049.98
3269.07
45
45
56
51
48
40
57
35
39
24
18
42
77
55
45
40
52
190
190
206
198
193
186
167
175
179
163
155
147
167
167
157
140
152
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
16.1426
16.2805
16.0793
15.9524
15.9999
15.9300
15.9809
15.9811
15.9424
16.1140
16.3023
16.3994
15.8312
15.7989
3992.01
4009.49
3633.40
3512.47
3544.19
3462.28
3564.52
3543.79
3539.21
3657.22
3850.91
4079.72
3671.61
3610.66
64.64
64.23
66.07
64.59
63.57
65.21
63.71
67.61
71.33
61.66
61.94
62.24
57.57
59.31
58.21
57.13
58.19
71.29
64.98
71.77
69.03
68.10
69.87
70.00
69.22
70.10
71.18
71.72
96.15
69.74
66.49
87
92
62
53
52
50
57
55
56
62
88
112
95
90
252
227
213
203
203
199
208
205
207
214
227
287
222
197
3542.57
3437.99
3524.57
3457.85
3448.18
5539.90
3456.80
3305.20
3371.05
3172.92
3389.43
72.32
69.99
70.78
67.04
76.09
37.85
78.67
67.66
64.09
66.15
139.00
59
82
87
84
83
212
57
40
41
27
103
212
182
197
177
187
56
203
275
190
165
230
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
107
104
117
78
72
75
278
275
297
234
223
225
444
445
446
447
448
449
177
377
450
151.06
27.63
13.82
21.56
17.46
22.69
223.74
167.05
144.78
29.31
22.27
45.30
137.96
119.53
68.802
84.992E-02
6.506E-04
19.808E-08
22.990
79.340E-02
4.396E-04
85.704E-09
65.147
86.001
98.934E-02
11.020E-01
7.214E-04
8.746E-04
21.520E-08
28.265E-08
48.759
90.644E-02
6.054E-04
16.274E-08
37.417
15.265
34.068
112.457
97.670
86.709E-02
65.188E-02
91.440E-02
11.183E-01
10.446E-01
5.560E-04
2.879E-04
5.560E-04
6.607E-04
5.476E-04
14.110E-08
32.569E-09
12.874E-08
14.369E-08
89.807E-09
62.957
10.627E-01
6.305E-04
14.001E-08
1111.10
341.28
702.27
339.66
169.06
182.42
85.87
73.48
598.30
311.39
213.32
56.48
518.37
277.80
124.22
121.12
4.664
90.770E-02
5.058E-04
10.953E-08
558.61
288.37
249.83
258.74
33.24
33.58
1481.80
380.00
209.63
144.86
270.47
78.25
129.54
41.62
64.820
56.518
17.367
58.322
5.585
8.395
93.868E-02
89.974E-02
86.751E-02
11.279E-01
10.027E-01
10.538E-01
5.288E-04
8.646E-04
8.834E-04
8.956E-04
3.921E-04
11.309E-08
24.551E-08
25.849E-08
26.180E-08
34.508E-09
361.76
351.79
350.34
318.65
294.89
305.01
104.25
96.087E-02
12.322E-01
12.313E-01
12.447E-01
89.472E-02
862.89
695.42
882.36
617.57
566.26
605.50
401.93
7.913
70.372
58.833
62.341
14.570
15.9116
15.8141
15.8670
15.7884
16.0129
19.0161
16.0114
15.7848
15.7598
15.8446
15.9395
20.155E-08
18.401E-08
72.348E-09
14.729E-08
12.163E-08
12.368E-08
16.2008
16.2758
16.3363
16.0140
16.0412
16.0541
4206.70
4237.37
4158.47
3702.56
3597.72
3614.07
13.054E-08
16.3091
4470.92
116.94
116.18
217.84
216.29
64.623
88.509E-02
6.942E-04
6.469E-04
4.610E-04
6.536E-04
5.602E-04
5.799E-04
5.853E-04
78.15
74.75
94.15
81.55
83.41
85.45
81.40
955
444
445
446
447
448
449
VISB
APPENDIX C
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
VISA
MOLWT
TFP
TBP
TC
PC
VC
LDEN
TDEN
HVAP
NO
C12H10
C12H10O
C12H24
C12H24
C12H26
C12H260
C12H26O
C12H27N
DIPHENYL
DIPHENYL ETHER
N-HEPTYLCYCLOPENTANE
1-DODECENE
N-DODECANE
DIHEXYL ETHER
DODECANOL
TRIBUTYLAMINE
COMPOUND NAME
154.212
170.211
168.324
168.324
170.340
186.339
186.339
185.355
69.2
26.8
255.2
258.0
224.1
213.3
216.3
226.4
259.9
213.4
789.0
766.0
679.0
657.0
658.3
657.0
679.0
643.0
38.5
31.4
19.5
18.5
18.2
18.2
19.3
18.2
0.502
990
1066
74
30
758
748
794
835
779
20
20
20
20
20
45,636
47,143
43,375
42,998
43,668
45,636
44,380
451
452
453
454
455
456
457
458
459
460
461
462
463
C13H10
C13H12
C13H26
C13H26
C13H28
FLUORENE
DIPHENYLMETHANE
N-OCTYLCYCLOPENTANE
1-TRIDECENE
N-TRIDECANE
166.223
168.239
182.351
182.351
184.367
297.9
264.3
243.7
232.7
235.4
822.3
767.0
694.0
674.0
675.8
29.9
29.8
17.9
17.0
17.2
1006
20
766
756
20
20
45,427
45,008
45,678
459
460
461
462
463
464
465
466
467
468
C14H10
C14H10
C14H28
C14H28
C14H30
ANTHRACENE
PHENANTHRENE
N-NONYLCYCLOPENTANE
1-TETRADECENE
N-TETRADECANE
178.234
178.234
196.378
196.378
198.394
12.9
5.8
341.2
339.4
262.1
251.1
253.5
883.0
878.0
710.5
689.0
694.0
16.5
15.6
16.2
0
20
56,522
55,684
47,269
46,934
47,646
464
465
466
467
468
469
470
471
472
473
C15H12
C15H14
C15H30
C15H30
C15H32
1-PHENYLINDENE
2-ETHYLFLUORENE
N-DECYLCYCLOPENTANE
1-PENTADECENE
N-PENTADECANE
192.261
194.277
210.405
210.405
212.421
843.7
811.1
723.8
704.0
707.0
27.0
24.6
15.2
14.6
15.2
0.598
0.629
3.8
9.8
322.0
309.0
279.3
268.3
270.6
0
20
49,027
48,692
49,488
469
470
471
472
473
474
475
476
477
478
479
480
481
C16H10
C16H10
C16H12
C16H22O4
C16H32
C16H32
C16H32O2
C16H34
FLUORANTHENE
PYRENE
N-PHENYLNAPHTHALENE
DIBUTYL-O-PHTHALATE
N-DECYLCYCLOHEXANE
1-HEXADECENE
PALMIC ACID
N-HEXADECANE
202.256
202.256
204.272
278.350
224.432
224.432
256.431
226.448
936.6
892.1
840.1
26.0
26.0
26.3
0.660
0.637
0.605
4.1
63.0
17.8
393.0
362.0
316.0
334.8
297.6
284.8
348.5
286.8
750.0
717.0
791.0
717.0
13.6
13.4
19.0
14.2
482
483
484
C17H34
C17H36O
C17H36
N-DODECYLCYCLOPENTANE
HEPTADECANOL
N-HEPTADECANE
238.459
256.474
240.475
53.8
21.8
310.9
323.8
302.0
750.0
736.0
733.0
13.0
14.2
13.2
485
486
487
488
489
490
491
492
493
494
C18H12
C18H14
C18H14
C18H14
C18H34O2
C18H36
C18H36
C18H36O2
C18H38
C18H38O
CHRYSENE
O-TERPHENYL
M-TERPHENYL
P-TERPHENYL
OLEIC ACID
1-OCTADECENE
N-TRIDECYLCYCLOPENTANE
STEARIC ACID
N-OCTADECANE
1-OCTADECANOL
228.294
230.310
230.310
230.310
282.469
252.486
252.486
284.485
254.502
270.501
70.0
28.1
57.8
448.0
331.8
364.8
375.8
362.3
314.8
325.4
371.9
316.3
334.8
993.6
891.0
924.8
926.0
797.0
739.0
761.0
810.0
745.0
747.0
23.9
39.0
35.1
33.2
17.0
11.3
12.1
16.5
12.1
14.2
495
496
C19H38
C19H40
N-TETRADECYLCYCLOPENTANE
N-NONADECANE
266.513
268.529
31.8
325.8
329.9
772.0
756.0
11.2
11.1
497
498
499
C20H40
C20H42
C20H42O
N-PENTADECYLCYCLOPENTANE
N-EICOSANE
1-EICOSANOL
280.540
282.556
298.555
36.8
65.8
351.8
343.8
355.8
780.0
767.0
770.0
10.2
11.1
12.2
500
C21H42
N-HEXADECYLCYCLOPENTANE
294.567
363.8
791.0
9.7
35.2
9.6
43.2
23.9
114.0
26.8
23.1
5.4
216.5
100.5
110.0
151.0
35.2
255.0
56.8
86.8
211.8
13.3
17.6
0.713
0.720
0.718
0.534
0.780
0.830
0.880
0.946
1.000
0.736
0.769
0.784
0.779
1.035
1.054
786
763
791
769
1047
20
788
828
773
10
102
20
79,131
50,409
50,451
66,992
51,246
474
475
476
477
478
479
480
481
848
778
54
20
52,628
60,709
52,921
482
483
484
893
789
20
20
844
777
812
70
28
59
789
32
775
40
68,131
54,303
54,345
70,049
54,512
485
486
487
488
489
490
491
492
493
494
56,019
56,061
495
496
57,694
57,527
65,314
497
498
499
59,369
500
CHEMICAL ENGINEERING
FORMULA
956
NO
451
452
453
454
455
456
457
458
VISA
VISB
DELHF
DELGF
CPVAPA
CPVAPB
CPVAPC
CPVAPD
ANTA
ANTB
ANTC
TMN
TMX
NO
733.87
1146.00
654.77
615.67
631.63
723.43
1417.80
889.06
369.58
379.29
333.12
310.07
318.78
323.35
398.89
312.48
182.21
49.99
230.27
165.46
291.07
280.26
97.067
60.730
59.264
6.544
9.328
33.536
9.224
7.993
11.057E-01
92.821E-02
12.234E-01
10.978E-01
11.489E-01
10.735E-01
11.032E-01
11.978E-01
27.901E-08
13.586E-08
15.964E-08
13.410E-08
13.590E-08
16.777E-08
77.791E-09
14.486E-08
16.6832
16.3459
16.0589
16.0610
16.1134
16.3372
15.2638
16.2878
4602.23
4310.25
3850.38
3729.87
3774.56
3982.78
3242.04
3865.58
70.42
87.31
88.75
90.88
91.31
89.15
157.10
86.15
70
145
95
88
91
100
134
89
272
325
256
244
247
272
307
258
451
452
453
454
455
456
457
458
459
460
461
462
463
8.855E-04
5.870E-04
7.084E-04
6.155E-04
6.347E-04
5.535E-04
5.338E-04
6.703E-04
695.83
658.16
664.10
346.19
323.71
332.10
207
200
112
104
107
407
290
276
264
267
459
460
461
462
463
217
177
127
119
121
382
382
296
284
287
464
465
466
467
468
227
207
140
133
135
427
407
313
301
304
469
470
471
472
473
287
257
227
196
190
147
353
150
487
477
427
384
300
319
153
321
474
475
476
477
478
479
480
481
168
191
161
346
383
337
482
483
484
464
465
466
467
468
513.28
405.81
735.19
697.49
689.85
357.74
336.13
344.21
469
470
471
472
473
771.74
739.13
718.51
368.30
347.46
355.92
474
475
476
477
478
479
480
481
2588.10
925.84
767.48
336.24
378.69
357.85
366.11
385.53
757.88
375.90
1094.10
940.58
911.01
461.27
460.94
461.10
816.19
891.80
376.93
392.78
777.40
385.00
495
496
924.60
793.62
399.62
393.54
497
498
499
950.57
811.29
406.33
401.67
500
977.42
412.29
485
486
487
488
489
490
491
492
493
494
443.13
87.13
250.87
186.10
311.71
95.12
146.37
58.49
224.83
202.64
271.51
206.66
332.35
103.50
154.87
66.86
292.15
227.39
352.99
111.91
163.16
75.28
247.98
723.06
373.59
171.62
336.12
546.25
394.19
83.74
126.02
44.67
92.15
54.491
90.351E-02
5.388E-04
92.570E-09
59.951
7.118
10.463
13.167E-01
11.911E-01
12.452E-01
7.612E-04
6.674E-04
6.912E-04
17.082E-08
14.511E-08
14.897E-08
18.2166
14.4856
16.0941
16.0850
16.1355
6462.60
2902.44
3983.01
3856.23
3892.91
16.056E-08
16.056E-08
18.347E-08
15.692E-08
15.981E-08
17.6701
16.7187
16.1089
16.1643
16.1480
6492.44
5477.94
4096.30
4018.01
4008.52
17.650E-08
17.928E-08
19.590E-08
17.028E-08
17.199E-08
16.4170
16.5199
16.1261
16.1539
16.1724
4872.90
4789.44
4203.94
4103.15
4121.51
18.600E-08
17.559E-08
60.612E-09
69.710E-09
21.428E-08
18.104E-08
18.497E-08
16.4523
16.4842
16.9691
16.9539
16.1627
16.2203
18.9558
16.1841
5438.77
5203.08
5351.04
4852.47
4373.37
4245.00
7049.18
4214.91
21.855E-08
20.436E-08
19.720E-08
16.1915
15.6161
16.1510
4395.87
3672.62
4294.55
16.6038
5915.26
128.10
377
577
5884.49
4416.13
4483.13
7709.35
4361.79
3757.82
127.26
127.30
131.30
57.83
129.90
193.10
360
171
180
370
172
201
176
350
361
174
352
385
485
486
487
488
489
490
491
492
493
494
192
183
375
366
495
496
203
198
219
388
379
406
497
498
499
215
401
500
58.979
58.979
60.809
7.967
10.982
96.154
107.036
61.923
9.203
11.916
80.706
94.379
99.516
1.880
69.015
9.705
13.017
63.263
7.792
13.967
10.057E-01
10.057E-01
14.118E-01
12.858E-01
13.377E-01
11.865E-01
12.611E-01
15.077E-01
13.825E-01
14.327E-01
11.715E-01
11.916E-01
11.463E-01
12.539E-01
16.542E-01
14.750E-01
15.290E-01
16.952E-01
16.529E-01
16.241E-01
6.594E-04
6.594E-04
8.156E-04
7.210E-04
7.423E-04
7.786E-04
8.156E-04
8.717E-04
7.783E-04
7.972E-04
7.938E-04
7.930E-04
6.113E-04
6.121E-04
9.613E-04
8.298E-04
8.537E-04
9.768E-04
9.345E-04
9.081E-04
115.757
13.415E-01
8.311E-04
15.412E-08
646.02
289.22
353.99
764.51
414.83
566.85
188.45
137.08
11.329
64.209
16.643E-01
17.903E-01
9.374E-04
1.032E-03
20.486E-08
23.094E-08
100.57
36.22
14.470
8.704
17.170E-01
17.476E-01
9.592E-04
8.524E-04
20.783E-08
21.575E-08
18.2445
16.2221
16.2270
19.8034
16.1232
15.6898
24.258E-08
22.052E-08
16.2632
16.1533
4439.38
4450.44
395.28
456.07
608.13
153.99
117.40
19.43
25.498E-08
25.284E-08
25.158E-08
16.3092
16.4685
15.8233
4642.01
4680.46
3912.10
26.682E-08
16.3553
4715.69
374.63
435.43
415.87
145.58
108.98
162.41
64.929
15.491
66.093
22.383
12.581
66.683
18.845E-01
18.125E-01
19.804E-01
19.393E-01
19.498E-01
20.741E-01
1.085E-03
1.015E-03
1.140E-03
1.117E-03
1.118E-03
1.237E-03
13.40
167.90
95.85
97.94
98.93
26.13
69.39
103.00
102.70
105.40
97.30
97.90
109.70
110.60
111.80
112.40
107.20
81.70
138.10
111.80
115.20
55.08
118.70
124.20
188.10
124.00
138.10
135.60
145.10
141.10
203.10
152.10
957
738.30
853.53
482
483
484
86.67
138.00
50.07
APPENDIX C
NO
451
452
453
454
455
456
457
458
APPENDIX D
Conversion Factors for Some Common
SI Units
Length
Time
Area
Volume
Mass
Force
An asterisk (Ł ) denotes an exact relationship.
Ł 1 in.
:
25.4 mm
Ł 1 ft
:
0.3048 m
Ł 1 yd
:
0.9144 m
1 mile
:
1.6093 km
Ł 1 Å(angstrom)
:
1010 m
Ł 1 min
:
60 s
Ł1 h
:
3.6 ks
Ł 1 day
:
86.4 ks
1 year
:
31.5 Ms
Ł 1 in.2
:
645.16 mm2
1 ft2
:
0.092903 m2
1 yd2
:
0.83613 m2
1 acre
:
4046.9 m2
1 mile2
:
2.590 km2
1 in.3
:
16.387 cm3
1 ft3
:
0.02832 m3
1 yd3
:
0.76453 m3
1 UK gal
:
4546.1 cm3
1 US gal
:
3785.4 cm3
1 oz
:
28.352 g
Ł 1 lb
:
0.45359237 kg
1 cwt
:
50.8023 kg
1 ton
:
1016.06 kg
1 pdl
:
0.13826 N
1 lbf
:
4.4482 N
1 kgf
:
9.8067 N
1 tonf
:
9.9640 kN
Ł 1 dyn
:
105 N
Temperature
difference
Energy (work, heat)
Calorific value
(volumetric)
Ł1
deg F (deg R)
1 ft lbf
1 ft pdl
Ł 1 cal (internat.
table)
1 erg
1 Btu
1 hp h
Ł 1 kW h
1 therm
1 thermie
1 Btu/ft3
958
:
:
:
5
9 deg C (deg K)
1.3558 J
0.04214 J
:
:
:
:
:
:
:
4.1868 J
107 J
1.05506 kJ
2.6845 MJ
3.6 MJ
105.51 MJ
4.1855 MJ
:
37.259 kJ/m3
959
APPENDIX D
Velocity
Volumetric flow
Mass flow
Mass per unit area
Density
Pressure
Power (heat flow)
Moment of inertia
Momentum
Angular momentum
Viscosity, dynamic
Viscosity, kinematic
Surface energy
(surface tension)
Mass flux density
Heat flux density
Heat transfer
coefficient
Specific enthalpy
(latent heat, etc.)
Specific heat capacity
Thermal
conductivity
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Ł1
Ł1
Ł1
1
1
1
1
1
1
1
1
1
1
1
1
1
Ł1
1
1
Ł1
1
1
1
1
Ł1
ft/s
mile/h
ft3 /s
ft3 /h
UK gal/h
US gal/h
lb/h
ton/h
lb/in.2
lb/ft2
ton/sq mile
lb/in3
lb/ft3
lb/UK gal
lb/US gal
lbf/in.2
tonf/in.2
lbf/ft2
standard atm
atm (1 kgf/cm2 )
bar
ft water
in. water
in. Hg
mmHg (1 torr)
hp (British)
hp (metric)
erg/s
ft lbf/s
Btu/h
ton of
refrigeration
lb ft2
lb ft/s
lb ft2 /s
P (Poise)
lb/ft h
lb/ft s
S (Stokes)
ft2 /h
erg/cm2
(1 dyn/cm)
lb/h ft2
Btu/h ft2
kcal/h m2
1 Btu/h ft2 F
Ł1
Ł1
Btu/lb
Btu/lb ° F
1 Btu/h ft ° F
1 kcal/h m ° C
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
:
0.3048 m/s
0.44704 m/s
0.028316 m3 /s
7.8658 cm3 /s
1.2628 cm3 /s
1.0515 cm3 /s
0.12600 g/s
0.28224 kg/s
703.07 kg/m2
4.8824 kg/m2
392.30 kg/km2
27.680 g/cm3
16.019 kg/m3
99.776 kg/m3
119.83 kg/m3
6.8948 kN/m2
15.444 MN/m2
47.880 N/m2
101.325 kN/m2
98.0665 kN/m2
105 N/m2
2.9891 kN/m2
249.09 N/m2
3.3864 kN/m2
133.32 N/m2
745.70 W
735.50 W
107 W
1.3558 W
0.29307 W
:
:
:
:
:
:
:
:
:
:
:
:
:
:
3516.9 W
0.042140 kg m2
0.13826 kg m/s
0.042140 kg m2 /s
0.1 NŁ s/m2
0.41338 mN s/m2
1.4882 N s/m2
104 m2 /s
0.25806 cm2 /s
103 J/m2
(103 N/m)
1.3562 g/s m2
3.1546 W/m2
1.163 W/m2
:
5.6783 W/m2 K
:
:
:
:
2.326 kJ/kg
4.1868 kJ/kg K
1.7307 W/m K
1.163 W/m K
(Taken from MULLIN, J. W.: The Chemical Engineer No. 211 (Sept. 1967), 176.
SI units in chemical engineering.)
Note: Where temperature difference is involved K D° C.
APPENDIX E
Standard Flanges
Steel welding-neck flanges for nominal pressure ratings of 6, 10, 25, 40 bar.
960
961
APPENDIX E
STEEL WELDING NECK FLANGES
Nominal pressure 6 bar (1 bar D 105 N/m2 )
d1
r
d2
r
h2
h1
d3
f
b
d4
k
D
Nom.
size
Pipe
o.d.
d1
10
15
20
25
32
40
50
65
80
100
125
150
200
250
300
350
400
450
500
600
700
800
900
1000
1200
1400
1600
1800
2000
17.2
21.3
26.9
33.7
42.4
48.3
60.3
76.1
88.9
114.3
139.7
168.3
219.1
273
323.9
355.6
406.4
457.2
508
609.6
711.2
812.8
914.4
1016
1220
1420
1620
1820
2020
Flange
Raised face
Drilling
Neck
Bolting
D
b
h1
d4
f
75
80
90
100
120
130
140
160
190
210
240
265
320
375
440
490
540
595
645
755
860
975
1075
1175
1405
1630
1830
2045
2265
12
12
14
14
14
14
14
14
16
16
18
18
20
22
22
22
22
24
24
24
24
24
26
26
28
32
34
36
38
28
30
32
35
35
38
38
38
42
45
48
48
55
60
62
62
65
65
68
70
70
70
70
70
90
90
90
100
110
35
40
50
60
70
80
90
110
128
148
178
202
258
312
365
415
465
520
570
670
775
880
980
1080
1295
1510
1710
1920
2125
2
2
2
2
2
3
3
3
3
3
3
3
3
3
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
M10
M10
M10
M10
M12
M12
M12
M12
M16
M16
M16
M16
M16
M16
M20
M20
M20
M20
M20
M24
M24
M27
M27
M27
M30
M33
M33
M36
M39
No.
d2
k
d3
h2
³
r
4
4
4
4
4
4
4
4
4
4
8
8
8
12
12
12
16
16
20
20
24
24
24
28
32
36
40
44
48
11
11
11
11
14
14
14
14
18
18
18
18
18
18
22
22
22
22
22
26
26
30
30
30
33
36
36
39
42
50
55
65
75
90
100
110
130
150
170
200
225
280
335
395
445
495
550
600
705
810
920
1020
1120
1340
1560
1760
1970
2180
26
30
38
42
55
62
74
88
102
130
155
184
236
290
342
385
438
492
538
640
740
842
942
1045
1248
1452
1655
1855
2058
6
6
6
6
6
7
8
9
10
10
10
12
15
15
15
15
15
15
15
16
16
16
16
16
20
20
20
20
25
4
4
4
4
6
6
6
6
8
8
8
10
10
12
12
12
12
12
12
12
12
12
12
16
16
16
16
16
16
962
CHEMICAL ENGINEERING
STEEL WELDING NECK FLANGES
Nominal pressure 10 bar (1 bar D 105 N/m2 )
d1
r
d2
r
h2
h1
d3
f
b
d4
k
D
Nom.
size
200
250
300
350
400
450
500
600
700
800
900
1000
1200
1400
1600
1800
2000
Pipe
o.d.
d1
Flange
Raised face
D
b
h1
d4
f
219.1
273
323.9
355.6
406.4
457.2
508
609.6
711.2
812.8
914.4
1016
1220
1420
1620
1820
2020
340
395
445
505
565
615
670
780
895
1015
1115
1230
1455
1675
1915
2115
2325
24
26
26
26
26
28
28
28
30
32
34
34
38
42
46
50
54
62
68
68
68
72
72
75
80
80
90
95
95
115
120
130
140
150
268
320
370
430
482
532
585
685
800
905
1005
1110
1330
1535
1760
1960
2170
3
3
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
Drilling
Neck
Bolting
M20
M20
M20
M20
M24
M24
M24
M27
M27
M30
M30
M33
M36
M39
M45
M45
M45
No.
d2
k
d3
h2
³
r
8
12
12
16
16
20
20
20
24
24
28
28
32
36
40
44
48
22
22
22
22
25
26
26
30
30
33
33
36
39
42
48
48
48
295
350
400
460
515
565
620
725
840
950
1050
1160
1380
1590
1820
2020
2230
235
292
344
385
440
492
542
642
745
850
950
1052
1255
1460
1665
1868
2072
16
16
16
16
16
16
16
18
18
18
20
20
25
25
25
30
30
10
12
12
12
12
12
12
12
12
12
12
16
16
16
16
16
16
963
APPENDIX E
STEEL WELDING NECK FLANGES
Nominal pressure 25 bar (1 bar D 105 N/m2 )
d1
r
d2
r
h2
h1
d3
f
b
d4
k
D
Nom.
size
175
200
250
300
350
400
450
500
600
700
800
900
1000
Pipe
o.d.
d1
Flange
Raised face
D
b
h1
d4
f
193.7
219.1
273
323.9
355.6
406.4
457.2
508
609.6
711.2
812.8
914.4
1016
330
360
425
485
555
620
670
730
845
960
1085
1185
1320
28
30
32
34
38
40
42
44
46
46
50
54
58
75
80
88
92
100
110
110
125
125
125
135
145
155
248
278
335
395
450
505
555
615
720
820
930
1030
1140
3
3
3
4
4
4
4
4
5
5
5
5
5
Drilling
Neck
Bolting
M24
M24
M27
M27
M30
M33
M33
M33
M36
M39
M45
M45
M52
No.
d2
k
d3
h2
³
r
12
12
12
16
16
16
20
20
20
24
24
28
28
26
26
30
30
33
36
36
36
39
42
48
48
56
280
310
370
430
490
550
600
660
770
875
990
1090
1210
218
244
298
352
398
452
505
558
660
760
865
968
1070
15
16
18
18
20
20
20
20
20
20
22
24
24
10
10
12
12
12
12
12
12
12
12
12
12
16
964
CHEMICAL ENGINEERING
STEEL WELDING NECK FLANGES
Nominal pressure 40 bar (1 bar D 105 N/m2 )
d1
r
d2
r
h2
h1
d3
f
b
d4
k
D
Nom.
size
10
15
20
25
32
40
50
65
80
100
125
150
175
200
250
300
350
400
450
500
Pipe
o.d.
d1
Flange
Raised face
D
b
h1
d4
f
17.2
21.3
26.9
33.7
42.4
48.3
60.3
76.1
88.9
114.3
139.7
168.3
193.7
219.1
273
323.9
355.6
406.4
457.2
508
90
95
105
115
140
150
165
185
200
235
270
300
350
375
450
515
580
660
685
755
16
16
18
18
18
18
20
22
24
24
26
28
32
34
38
42
46
50
50
52
35
38
40
40
42
45
48
52
58
65
68
75
82
88
105
115
125
135
135
140
40
45
58
68
78
88
102
122
138
162
188
218
260
285
345
410
465
535
560
615
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
Drilling
Neck
Bolting
M12
M12
M12
M12
M16
M16
M16
M16
M16
M20
M24
M24
M27
M27
M30
M30
M33
M36
M36
M39
No.
d2
k
d3
h2
³
r
4
4
4
4
4
4
4
8
8
8
8
8
12
12
12
16
16
16
20
20
14
14
14
14
18
18
18
18
18
22
26
26
30
30
33
33
36
39
39
42
60
65
75
85
100
110
125
145
160
190
220
250
295
320
385
450
510
585
610
670
28
32
40
46
56
64
75
90
105
134
162
192
218
244
306
362
408
462
500
562
6
6
6
6
6
7
8
10
12
12
12
12
15
16
18
18
20
20
20
20
4
4
4
4
6
6
6
6
8
8
8
10
10
10
12
12
12
12
12
12
APPENDIX F
Design Projects
EIGHT typical design exercises are given in this appendix. They have been adapted from
Design Projects set by the Institution of Chemical Engineers as the final part of the
Institution’s qualifying examinations for professional Chemical Engineers.
F.1 ETHYLHEXANOL FROM PROPYLENE AND SYNTHESIS GAS
The project
Design a plant to produce 40,000 tonnes/year of 2-ethylhexanol from propylene and
synthesis gas, assuming an operating period of 8000 hours on stream.
The process
The first stage of the process is a hydroformylation (oxo) reaction from which the main
product is n-butyraldehyde. The feeds to this reactor are synthesis gas (CO/H2 mixture)
and propylene in the molar ratio 2 : 1, and the recycled products of isobutyraldehyde
cracking. The reactor operates at 130Ž C and 350 bar, using cobalt carbonyl as catalyst
in solution. The main reaction products are n- and isobutyraldehyde in the ratio of 4 : 1,
the former being the required product for subsequent conversion to 2-ethylhexanol. In
addition, 3 per cent of the propylene feed is converted to propane whilst some does
not react.
Within the reactor, however, 6 per cent of the n-butyraldehyde product is reduced
to n-butanol, 4 per cent of the isobutyraldehyde product is reduced to isobutanol, and
other reactions occur to a small extent yielding high molecular weight compounds (heavy
ends) to the extent of 1 per cent by weight of the butyraldehyde/butanol mixture at the
reactor exit.
The reactor is followed by a gas-liquid separator operating at 30 bar from which the
liquid phase is heated with steam to decompose the catalyst for recovery of cobalt by
filtration. A second gas-liquid separator operating at atmospheric pressure subsequently
yields a liquid phase of aldehydes, alcohols, heavy ends and water, which is free from
propane, propylene, carbon monoxide and hydrogen.
This mixture then passes to a distillation column which gives a top product of mixed
butyraldehydes, followed by a second column which separates the two butyraldehydes
into an isobutyraldehyde stream containing 1.3 per cent mole n-butyraldehyde and an
n-butyraldehyde stream containing 1.2 per cent mole isobutyraldehyde.
965
966
CHEMICAL ENGINEERING
A cracker converts isobutyraldehyde at a pass yield of 80 per cent back to propylene,
carbon monoxide and hydrogen by passage over a catalyst with steam. After separation
of the water and unreacted isobutyraldehyde the cracked gas is recycled to the hydroformylation reactor. The isobutyraldehyde is recycled to the cracker inlet. The operating
conditions of the cracker are 275Ž C and 1 bar.
The n-butyraldehyde is treated with a 2 per cent w/w aqueous sodium hydroxide and
undergoes an aldol condensation at a conversion efficiency of 90 per cent. The product of
this reaction, 2-ethylhexanal, is separated and then reduced to 2-ethylhexanol by hydrogen
in the presence of a Raney nickel catalyst with a 99 per cent conversion rate. In subsequent stages of the process (details of which are not required), 99.8 per cent of the
2-ethylhexanol is recovered at a purity of 99 per cent by weight.
Feed specifications
(i) Propylene feed: 93 per cent propylene, balance propane.
(ii) Synthesis gas: from heavy fuel oil, after removal of sulphur compounds and carbon
dioxide:
H2 48.6 per cent; CO 49.5 per cent; CH4 0.4 per cent; N2 1.5 per cent.
Utilities
(i)
(ii)
(iii)
(iv)
Dry saturated steam at 35 bar.
Cooling water at 20Ž C.
2 per cent w/w aqueous sodium hydroxide solution.
Hydrogen gas: H2 98.8 per cent; CH4 1.2 per cent.
Scope of design work required
1. Process design
(a) Prepare a material balance for the complete process.
(b) Prepare a process diagram for the plant showing the major items of equipment.
Indicate the materials of construction and the operating temperatures and pressures.
(c) Prepare energy balances for the hydroformylation reactor and for the
isobutyraldehyde cracking reactor.
2. Chemical engineering design
Prepare a chemical engineering design of the second distillation unit, i.e. for the separation
of n- and isobutyraldehyde. Make dimensioned sketches of the column, the reboiler and
the condenser.
3. Mechanical design
Prepare a mechanical design with sketches suitable for submission to a drawing office of
the n- and isobutyraldehyde distillation column.
4. Control system
For the hydroformylation reactor prepare a control scheme to ensure safe operation.
967
APPENDIX F
Data
1. Reactions
CH3 ÐCH D CH2 C H2
HŽ298 D 129.5 kJ/mol
! CH3 ÐCH2 ÐCH3
CH3 ÐCH D CH2 C H2 C CO ! CH3 ÐCH2 ÐCH2 ÐCHO
HŽ298 D 135.5 kJ/mol
or ! CH3 ÐCHÐCH3
j
CHO
HŽ298 D 141.5 kJ/mol
C3 H7 CHO C H2
! C4 H9 OH
HŽ298 D 64.8 kJ/mol
2CO C 8CO
! CO2 (CO)8
2CH3 ÐCH2 ÐCH2 ÐCHO
! CH3 ÐCH2 ÐCH2 ÐCH D CCHO C H2 O
j
C2 H5 HŽ298 D 262.0 kJ/mol
C4 H8 D C CHO C 2H2
j
C 2 H5
HŽ298 D 462.0 kJ/mol
! C4 H9 CHÐCH2 OH
j
C 2 H5
HŽ298 D 433.0 kJ/mol
2. Boiling points at 1 bar
Propylene
Propane
n-Butyraldehyde
Isobutyraldehyde
n-Butanol
Isobutanol
2-Ethylhexanol
47.7Ž C
42.1Ž C
75.5Ž C
64.5Ž C
117.0Ž C
108.0Ž C
184.7Ž C
3. Solubilities of gases at 30 bar in the liquid phase of the first gas-liquid
separator
H2
CO
Propylene
Propane
0.08
0.53
7.5
7.5
ð103
ð103
ð103
ð103
kg
kg
kg
kg
dissolved/kg
dissolved/kg
dissolved/kg
dissolved/kg
liquid
liquid
liquid
liquid
4. Vapour-liquid equilibrium of the butyraldehydes at 1 atm (Ref. 7)
T° C
x
y
73.94
72.69
71.40
70.24
69.04
68.08
67.07
65.96
64.95
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.138
0.264
0.381
0.490
0.589
0.686
0.773
0.846
0.927
968
CHEMICAL ENGINEERING
where x and y are the mol fractions of the more volatile component (isobutyraldehyde)
in the liquid and vapour phases respectively.
REFERENCES
1. Propylene and its Industrial Derivatives, HANCOCK, E. G. (ed.), John Wiley & Sons N. Y., 1973, Chapter 9,
pp. 333 367.
2. Carbon Monoxide in Organic Synthesis. Falbe-Springer Verlag, New York, 1970, pp. 1 75.
3. Chemical Engineering, 81, Sept. 30th, 1974, pp. 115 122. Physical and thermodynamic properties of CO
and CO2 .
4. Chemical Engineering, 82, Jan. 20th, 1975, pp. 99 106. Physical and thermodynamic properties of
H2 /N2 /O2 .
5. Chemical Engineering, 82, Mar. 31st, 1975, pp. 101 109. Physical and thermodynamic properties of
C2 H4 /C3 H6 /iC4 H8 .
6. Chemical Engineering, 82, May 12th, 1975, pp. 89 97. Physical and thermodynamic properties of
CH4 /C2 H6 /C3 H8 .
7. J. G. WOJTASINSKI. J. Chem. Eng. Data, 1963 (July), pp. 381 385. Measurement of total pressures for
determining liquid-vapour equilibrium relations of the binary system isobutyraldehyde-n-butyraldehyde.
8. H. WEBER and J. FALBE. Ind. Eng. Chem. 1970 (April), pp. 33 7. Oxo Synthesis Technology.
9. Hydrocarbon Processing, Nov. 1971, p. 166.
10. Hydrocarbon Processing, Nov. 1975, p. 148.
F.2 CHLOROBENZENES FROM BENZENE AND CHLORINE
The project
Design a plant to produce 20,000 tonnes/year of monochlorobenzene together with not
less than 2000 tonnes/year of dichlorobenzene, by the direct chlorination of benzene.
The process
Liquid benzene (which must contain less than 30 ppm by weight of water) is fed into a
reactor system consisting of two continuous stirred tanks operating in series at 2.4 bar.
Gaseous chlorine is fed in parallel to both tanks. Ferric chloride acts as a catalyst, and
is produced in situ by the action of hydrogen chloride on mild steel. Cooling is required
to maintain the operating temperature at 328 K. The hydrogen chloride gas leaving the
reactors is first cooled to condense most of the organic impurities. It then passes to an
activated carbon adsorber where the final traces of impurity are removed before it leaves
the plant for use elsewhere.
The crude liquid chlorobenzenes stream leaving the second reactor is washed with water
and caustic soda solution to remove all dissolved hydrogen chloride. The product recovery
system consists of two distillation columns in series. In the first column (the “benzene
column”) unreacted benzene is recovered as top product and recycled. In the second
column (the “chlorobenzene column”) the mono- and dichlorobenzenes are separated.
The recovered benzene from the first column is mixed with the raw benzene feed and
this combined stream is fed to a distillation column (the “drying column”) where water is
removed as overhead. The benzene stream from the bottom of the drying column is fed
to the reaction system.
APPENDIX F
969
Feed specifications
(i) Chlorine: 293 K, atmospheric pressure, 100 per cent purity.
(ii) Benzene: 293 K, atmospheric pressure, 99.95 wt per cent benzene, 0.05 wt per cent
water.
Product specifications
(i) Monochlorobenzene: 99.7 wt per cent.
(ii) Dichlorobenzene: 99.6 wt per cent.
(iii) Hydrogen chloride gas: less than 250 ppm by weight benzene.
Utilities
(i)
(ii)
(iii)
(iv)
(v)
Stream: dry saturated at 8 bar and at 28 bar.
Cooling water: 293 K.
Process water: 293 K.
Caustic soda solution: 5 wt per cent NaOH, 293 K.
Electricity: 440 V, 50 Hz, 3 phase.
Scope of design work required
1. Process design
(a) Prepare a materials balance for the process including an analysis of each reactor
stage (the kinetics of the chlorination reactions are given below). Onstream time
may be taken as 330 days per year.
(b) Prepare energy balances for the first reactor and for the chlorobenzene column (take
the reflux ratio for this column as twice the minimum reflux ratio).
(c) Prepare a process flow diagram for the plant. This should show the major items of
equipment with an indication of the materials of construction and of the internal
layout. Temperatures and pressures should also be indicated.
2. Chemical engineering design
Prepare a sieve-plate column design for the chlorobenzene distillation and make dimensioned sketches showing details of the plate layout including the weir and the downcomer.
3. Mechanical design
Prepare a mechanical design of the chlorobenzene column, estimating the shell thickness,
the positions and sizes of all nozzles, and the method of support for the plates and the
column shell. Make a dimensioned sketch suitable for submission to a drawing office.
4. Safety
Indicate the safety measures required for this plant bearing in mind the toxic and
inflammable materials handled.
970
CHEMICAL ENGINEERING
Data
1. The reactions
(1) C6 H6 + Cl2
! C6 H5 Cl + HCl
(2) C6 H5 Cl + Cl2 ! C6 H4 Cl2 + HCl
The dichlorobenzene may be assumed to consist entirely of the para-isomer and the
formation of trichlorobenzenes may be neglected.
The rate equations can be written in first-order form when the concentration of dissolved
chlorine remains essentially constant. Thus:
rB D k1 xB
rM D k1 xB k2 xM
rD D k2 xM
where r is the reaction rate,
k1 is the rate constant for reaction (1) at 328 K D 1.00 ð 104 s1 ,
k2 is the rate constant for reaction (2) at 328 K D 0.15 ð 104 s1
and x denotes mol fraction.
The subscripts B, M and D denote benzene, monochlorobenzene and dichlorobenzene
respectively.
Yields for the reactor system should be calculated on the basis of equal liquid residence
times in the two reactors, with a negligible amount of unreacted chlorine in the vapour
product streams. It may be assumed that the liquid product stream contains 1.5 wt per
cent of hydrogen chloride:
Reference: BODMAN, SAMUEL W. The Industrial Practice of Chemical Process Engineering, 1968, The
MIT Press.
2. Solubilities
Solubility of the water/benzene system (taken from Seidell, A. S., Solubilities of Organic
Compounds, 3rd edn, Vol. II, 1941, Van Nostrand).
Temperature (K)
293
303
313
323
g H2 O/100 g C6 H6
g C6 H6 /100 g H2 O
0.050
0.175
0.072
0.190
0.102
0.206
0.147
0.225
3. Thermodynamic and physical properties
C6 H6
liquid
Heat of formation at 298 K
(kJ/kmol)
Heat capacity (kJ/kmol K)
298 K
350 K
400 K
450 K
500 K
49.0
136
148
163
179
200
C6 H6
gas
C6 H5 Cl
liquid
C6 H5 Cl
gas
82.9
7.5
46.1
82
99
113
126
137
152
161
170
181
192
92
108
121
134
145
C6 H4 Cl2
liquid
42.0
193
238
296
366
C6 H4 Cl2
gas
5.0
103
118
131
143
155
971
APPENDIX F
C6 H6
liquid
C6 H6
gas
C6 H5 Cl
liquid
C6 H5 Cl
gas
C6 H4 Cl2
liquid
C6 H4 Cl2
gas
Density (kg/m3 )
298
350
400
450
500
K
K
K
K
K
872
815
761
693
612
1100
1040
989
932
875
298
350
400
450
500
K
K
K
K
K
0.598 ð 103
0.326 ð 103
0.207 ð 103
0.134 ð 103
0.095 ð 103
0.750 ð 103
0.435 ð 103
0.305 ð 103
0.228 ð 103
0.158 ð 103
298
350
400
450
500
K
K
K
K
K
0.0280
0.0220
0.0162
0.0104
0.0047
0.0314
0.0276
0.0232
0.0177
0.0115
1230
1170
1100
1020
Viscosity (Ns/m2 )
Surface tension (N/m)
0.697
0.476
0.335
0.236
ð
ð
ð
ð
103
103
103
103
0.0304
0.0259
0.0205
0.0142
REFERENCES
1. PERRY, R. H. and CHILTON, C. H. Chemical Engineers’ Handbook, 5th edn, 1973, McGraw-Hill.
2. KIRK-OTHMER, Encyclopaedia of Chemical Technology, 2nd edn, 1964, John Wiley & Sons.
F.3 METHYL ETHYL KETONE FROM BUTYL ALCOHOL
The project
Design a plant to produce 1 ð 107 kg/year of methyl ethyl ketone (MEK).
Feedstock: Secondary butyl alcohol.
Services available:
Dry saturated steam at 140Ž C.
Cooling water at 24Ž C.
Electricity at 440 V three-phase 50 Hz.
Flue gases at 540Ž C.
The process
The butyl alcohol is pumped from storage to a steam-heated preheater and then to a
vaporiser heated by the reaction products. The vapour leaving the vaporiser is heated to
its reaction temperature by flue gases which have previously been used as reactor heating
medium. The superheated butyl alcohol is fed to the reaction system at 400Ž C to 500Ž C
where 90 per cent is converted on a zinc oxide brass catalyst to methyl ethyl ketone,
hydrogen and other reaction products. The reaction products may be treated in one of the
following ways:
(a) Cool and condense the MEK in the reaction products and use the exhaust gases as
a furnace fuel.
(b) Cool the reaction products to a suitable temperature and separate the MEK by
absorption in aqueous ethanol. The hydrogen off gas is dried and used as a furnace
972
CHEMICAL ENGINEERING
fuel. The liquors leaving the absorbers are passed to a solvent extraction column,
where the MEK is recovered using trichlorethane. The raffinate from this column
is returned to the absorber and the extract is passed to a distillation unit where the
MEK is recovered. The trichlorethane is recycled to the extraction plant.
Scope of design work required
1.
2.
3.
4.
Prepare material balances for the two processes.
On the basis of the cost data supplied below decide which is the preferable process.
Prepare a material flow diagram of the preferred process.
Prepare a heat balance diagram of the preheater vaporiser superheater reactor
system.
5. Prepare a chemical engineering design of the preheater vaporiser superheater
reactor system and indicate the type of instrumentation required.
6. Prepare a mechanical design of the butyl alcohol vaporiser and make a dimensioned
sketch suitable for submission to a drawing office.
Data
Process data
Outlet condenser temperature D 32Ž C.
Vapour and liquid are in equilibrium at the condenser outlet.
Calorific value of MEK D 41,800 kJ/kg.
Cost data
Selling price of MEK
Steam raising cost
Cost of tower shell
Cost of plates
Cost of reboiler
Cost of heat exchanger (per distillation column)
Cost of solvent extraction auxiliaries
Cost of absorbtion and distillation column packing,
supports and distributors
Cost of tanks (surge, etc.)
Cost of control of whole plant
Cost of instrumentation for control of recovery section
Cost of electricity for pumps
Pump costs (total)
Cost of cooling water for whole plant
D
D
D
D
D
D
D
£9.60 per 100kg
£0.53 per 106 kJ
£2000
£2000
£2500
£8000
£1000
D
D
D
D
D
D
D
£2000
£1000
£9000
£4500
£5000
£3000
£5000
Reactor data
The “short-cut” method proposed in Ref. 1 may be used only to obtain a preliminary
estimate of the height of catalyst required in the reactor. The reactor should be designed
APPENDIX F
973
from first principles using the rate equation, below, taken from Ref. 1.
rA D
C⊲PA,i PK,i PH,i /K⊳
PKi ⊲1 C KA PA,i C KAK PA,i /PK,i ⊳
where PA,i , PH,i , and PK,i are the interfacial partial pressures of the alcohol, hydrogen
and ketone in bars, and the remaining quantities are as specified by the semi-empirical
equations below:
log10 C D
5964
C 8.464
Ti
log10 KA D
3425
C 5.231
Ti
log10 KAK D C
486
0.1968
Ti
In these equations, the interfacial temperature Ti is in Kelvin, the constant C is in
kmol/m2 h, KA is in bar1 , and KAK is dimensionless.
The equilibrium constant, K is given in Ref. 1 (although the original source is Ref. 2)
by the equation:
2790
C 1.510 log10 Ti C 1.871
log10 K D
Ti
where K is in bar.
Useful general information will be found in Ref. 3.
REFERENCES
1. PERONA, J. J. and THODOS, G. AIChE Jl, 1957, 3, 230.
2. KOLB, H. J. and BURWELL, R. L. (Jr.) J. Am. Chem. Soc., 1945, 67, 1084.
3. RUDD, D. F. and WATSON, C. C. Strategy of Process Engineering, 1968 (New York: John Wiley & Sons
Inc.).
F.4 ACRYLONITRILE FROM PROPYLENE AND AMMONIA
The project
Design a plant to produce 1 ð 108 kg/year of acrylonitrile (CH2 :CH.CN) from propylene
and ammonia by the ammoxidation process.
Feedstock:
Ammonia: 100 per cent NH3 .
Propylene: Commercial grade containing 90 per cent C3 H6 , 10 per cent paraffins,
etc., which do not take any part in the reaction.
Services available:
Dry saturated steam at 140Ž C.
Cooling water at 24Ž C.
Other normal services.
974
CHEMICAL ENGINEERING
The process
Propylene, ammonia, steam and air are fed to a vapour-phase catalytic reactor (item A).
The feedstream composition (molar per cent) is propylene 7; ammonia 8; steam 20; air 65.
A fixed-bed reactor is employed using a molybdenum-based catalyst at a temperature of
450Ž C, a pressure of 3 bar absolute, and a residence time of 4 seconds. Based upon a
pure propylene feed, the carbon distribution by weight in the product from the reactor is:
Acrylonitrile
Acetonitrile
Carbon dioxide
Hydrogen cyanide
Acrolein
Unreacted propylene
Other by products
58
2
16
6
2
15
1
per
per
per
per
per
per
per
cent
cent
cent
cent
cent
cent
cent
The reactor exit gas is air-cooled to 200Ž C and then passes to a quench scrubber (B)
through which an aqueous solution containing ammonium sulphate 30 wt per cent and
sulphuric acid 1 wt per cent is circulated. The exit gas temperature is thereby reduced
to 90Ž C.
From the quench scrubber (B) the gas passes to an absorption column (C) in which the
acrylonitrile is absorbed in water to produce a 3 wt per cent solution. The carbon dioxide,
unreacted propylene, oxygen, nitrogen and unreacted hydrocarbons are not absorbed and
are vented to atmosphere from the top of column (C).
The solution from the absorber (C) passes to a stripping column (D) where acrylonitrile
and lower boiling impurities are separated from water. Most of the aqueous bottom product
from the stripping column (D), which is essentially free of organics, is returned to the
absorber (C), the excess being bled off. The overhead product is condensed and the
aqueous lower layer returned to the stripping column (D) as reflux.
The upper layer which contains, in addition to acrylonitrile, hydrogen cyanide, acrolein,
acetonitrile, and small quantities of other impurities, passes to a second reactor (E)
where, at a suitable pH, all the acrolein is converted to its cyanohydrin. (Cyanohydrins are sometimes known as cyanhydrins.) The product from the reactor (E) is fed to
a cyanohydrin separation column (F), operating at reduced temperature and pressure, in
which acrolein cyanohydrin is separated as the bottom product and returned to the ammoxidation reactor (A) where it is quantitatively converted to acrylonitrile and hydrogen
cyanide.
The top product from column (F) is fed to a stripping column (G) from which hydrogen
cyanide is removed overhead.
The bottom product from column (G) passes to the hydroextractive distillation
column (H). The water feed rate to column (H) is five times that of the bottom product
flow from column (G). It may be assumed that the acetonitrile and other by-products are
discharged as bottom product from column (H) and discarded. The overhead product from
column (H), consisting of the acrylonitrile water azeotrope, is condensed and passed to a
separator. The lower aqueous layer is returned to column (H).
The upper layer from the separator is rectified in a column (I) to give 99.95 wt per
cent pure acrylonitrile.
APPENDIX F
975
Scope of design work required
1.
2.
3.
4.
Prepare a material balance for the process.
Prepare a material flow diagram of the process.
Prepare a heat balance for the reactor (A) and quench column (B).
Prepare a chemical engineering design of reactor (A) and either column (B) OR
column (D).
5. Prepare a mechanical design of the condenser for stripping column (D) and make a
dimensioned sketch suitable for submission to a drawing office.
6. Indicate the instrumentation and safety procedure required for this plant bearing in
mind the toxic and inflammable materials being handled.
REFERENCES
1. HANCOCK, E. H. (ed.) Propylene and its Industrial Derivatives, 1973 (London: Ernest Benn Ltd.).
2. SOKOLOV, N. M., SEVRYUGOVA, N. N. and ZHAVORONKOV, N. M. Proceedings of the International
Symposium on Distillation, 1969, pages 3 : 110 3 : 117 (London: I Chem E).
F.5 UREA FROM AMMONIA AND CARBON DIOXIDE
The project
A plant is to be designed for the production of 300,000 kg per day of urea by the reaction
of ammonia and carbon dioxide at elevated temperature and pressure, using a total-recycle
process in which the mixture leaving the reactor is stripped by the carbon dioxide feed
(DSM process, references 1 to 4).
Materials available
(1) Liquid ammonia at 20Ž C and 9 bar, which may be taken to be 100 per cent pure.
(2) Gaseous carbon dioxide at 20Ž C and atmospheric pressure, also 100 per cent pure.
All normal services are available on site. In particular, electricity, 440-V three-phase
50 Hz; cooling water at a maximum summer temperature of 22Ž C; steam at 40 bar with
20Ž C of superheat.
The on-stream time is to be 330 days/year, and the product specification is fertilisergrade urea prills containing not more than 1.0 per cent biuret.
The process
The reaction which produces urea from ammonia and carbon dioxide takes place in two
stages; in the first, ammonium carbamate is formed:
2NH3 C CO2 ⇀
↽ NH2 COONH4
In the second, the carbamate is dehydrated to give urea:
NH2 COONH4 ⇀
↽ CO⊲NH2 ⊳2 C H2 O
976
CHEMICAL ENGINEERING
Both reactions are reversible, the first being exothermal and going almost to completion,
whilst the second is endothermal and goes to 40 to 70 per cent of completion.
Ammonia and carbon dioxide are fed to the reactor, a stainless steel vessel with a series
of trays to assist mixing. The reactor pressure is 125 bar and the temperature is 185Ž C.
The reactor residence time is about 45 minutes, a 95 per cent approach to equilibrium
being achieved in this time. The ammonia is fed directly to the reactor, but the carbon
dioxide is fed to the reactor upwardly through a stripper, down which flows the product
stream from the reactor. The carbon dioxide decomposes some of the carbamate in the
product stream, and takes ammonia and water to a high-pressure condenser. The stripper
is steam heated and operates at 180Ž C, whilst the high-pressure condenser is at 170Ž C
and the heat released in it by recombination of ammonia and carbon dioxide to carbamate
is used to raise steam. Additional recycled carbamate solution is added to the stream in
the high-pressure condenser, and the combined flow goes to the reactor.
The product stream leaving the stripper goes through an expansion valve to the lowpressure section, the operating pressure there being 5 bar. In a steam-heated rectifier,
further ammonia and carbon dioxide are removed and, with some water vapour, are
condensed to give a weak carbamate solution. This is pumped back to the high-pressure
condenser.
A two-stage evaporative concentration under vacuum, with a limited residence-time in
the evaporator to limit biuret formation, produces a urea stream containing about 0.5 per
cent water which can be sprayed into a prilling tower.
Physico-chemical data
Heats of reactions: 2NH3 C CO2 ! NH2 COONH4 C 130 kJ
NH2 COONH4 ! CO(NH2 )2 C H2 O 21 kJ
Properties of urea:
Density at 20Ž C D 1.335 g/cm3
Heat of solution in water D 250 J/g
Melting point D 133Ž C
Specific heat D 1.34 J/g at 20Ž C
Reactor and stripper design
The relationships between temperature, pressure, and composition for the Urea CO2
NH3 H2 O system are given in References 5 and 6. These are equilibrium relationships.
The reaction velocity may be obtained from the graph in Figure 5 of Reference 5, which
is reproduced below for ease of reference (Figure F1). Some stripper design data appear
in Reference 7.
Scope of design work required
1. Prepare a mass balance diagram for the process, on a weight per hour basis, through
to the production of urea prills.
2. Prepare an energy balance diagram for the reactor stripper high-pressure condenser
complex.
APPENDIX F
Figure F1.
977
Rate of dehydration of carbamate
3. Prepare a process flow diagram, showing the major items of equipment in the correct
elevation, with an indication of their internal construction. Show all major pipe lines
and give a schematic outline of the probable instrumentation of the reactor and its
subsidiaries.
4. Prepare an equipment schedule, listing the main plant items with their size,
throughput, operating conditions, materials of construction, and services required.
5. Prepare an outline design of the reactor and carry out the chemical engineering
design of the stripper, specifying the interfacial contact area which will need to be
provided between the carbon dioxide stream and the product stream to enable the
necessary mass transfer to take place.
6. Prepare a mechanical design of the stripper, which is a vertical steam-heated tubebundle rather like a heat exchanger. Show how liquid is to be distributed to the
tubes, and how the shell is to be constructed to resist the high pressure and the
corrosive process material.
7. Prepare a detailed mechanical design of the reactor in the form of a general
arrangement drawing with supplementary detail drawings to show essential
constructional features. Include recommendations for the feed of gaseous ammonia,
carbon dioxide and carbamate solution, the latter being very corrosive. The design
should ensure good gas-liquid contact; suitable instrumentation should be suggested,
and provision included for its installation. Access must be possible for maintenance.
8. Specify suitable control systems for the maintenance of constant conditions in the
reactor against a 15 per cent change in input rate of ammonia or carbon dioxide,
and examine the effect of such a change, if uncorrected, on the steam generation
capability of the high-pressure condenser.
REFERENCES
1.
2.
3.
4.
KAASENBROOD, P. J. C. and LOGEMANN, J. D. Hydrocarbon Processing, April 1969, pp. 117 121.
PAYNE, A. J. and CANNER, J. A. Chemical and Process Engineering, May 1969, pp. 81 88.
COOK, L. H. Hydrocarbon Processing, Feb. 1966, pp. 129 136.
Process Survey: Urea. Booklet published with European Chemical News, Jan. 17th, 1969, p. 17.
978
CHEMICAL ENGINEERING
5. FREJACQUES, M. Chimie et Industrie, July 1948, pp. 22 35.
6. KUCHERYAVYY, V. I. and GORLOVSKIY, D. M. Soviet Chemical Industry, Nov. 1969, pp. 44 46.
7. VAN KREVELEN, D. W. and HOFTYZER, P. J. Chemical Engineering Science, Aug. 1953, 2(4) pp. 145 156.
F.6 HYDROGEN FROM FUEL OIL
The project
A plant is to be designed to produce 20 million standard cubic feet per day (0.555 ð 106
standard m3 /day) of hydrogen of at least 95 per cent purity. The process to be employed
is the partial oxidation of oil feedstock.1 3
Materials available
(1) Heavy fuel oil feedstock of viscosity 900 seconds Redwood One (2.57 ð 104 m2 /s)
at 100Ž F with the following analysis:
Carbon
Hydrogen
Sulphur
Calorific value
Specific gravity
85 per cent wt
11 per cent wt
4 per cent wt
18,410 Btu/lb (42.9 MJ/kg)
0.9435
The oil available is pumped from tankage at a pressure of 30 psig (206.9 kN/m2 gauge)
and at 50Ž C.
(2) Oxygen at 95 per cent purity (the other component assumed to be wholly nitrogen)
and at 20Ž C and 600 psig (4140 kN/m2 gauge).
Services available
(1) Steam at 600 psig (4140 kN/m2 gauge) saturated.
(2) Cooling water at a maximum summer temperature of 25Ž C.
(3) Demineralised boiler feedwater at 20 psig (138 kN/m2 gauge) and 15Ž C suitable
for direct feed to the boilers.
(4) Electricity at 440 V, three-phase 50 Hz, with adequate incoming cable capacity for
all proposed uses.
(5) Waste low-pressure steam from an adjacent process.
On-stream time
8050 hours/year.
Product specification
Gaseous hydrogen with the following limits of impurities:
CO
CO2
N2
CH4
H2 S
1.0 per cent vol maximum
1.0 per cent vol maximum
2.0 per cent vol maximum
1.0 per cent vol maximum
Less than 1 ppm
(dry
(dry
(dry
(dry
basis)
basis)
basis)
basis)
979
APPENDIX F
Ž
The gas is to be delivered at 35 C maximum temperature, and at a pressure not less
than 300 psig (2060 kN/m2 gauge). The gas can be delivered saturated, i.e. no drying
plant is required.
The process
Heavy fuel oil feedstock is delivered into the suction of metering-type ram pumps which
feed it via a steam preheater into the combustor of a refractory-lined flame reactor. The
feedstock must be heated to 200Ž C in the preheater to ensure efficient atomisation in the
combustor. A mixture of oxygen and steam is also fed to the combustor, the oxygen being
preheated in a separate steam preheater to 210Ž C before being mixed with the reactant
steam.
The crude gas, which will contain some carbon particles, leaves the reactor at approximately 1300Ž C and passes immediately into a special waste-heat boiler where steam at
600 psig (4140 kN/m2 gauge) is generated. The crude gas leaves the waste heat boiler at
250Ž C and is further cooled to 50Ž C by direct quenching with water, which also serves to
remove the carbon as a suspension. The analysis of the quenched crude gas is as follows:
H2
CO
CO2
CH4
H2 S
N2
47.6 per
42.1 per
8.3 per
0.1 per
0.5 per
1.40 per
cent
cent
cent
cent
cent
cent
vol
vol
vol
vol
vol
vol
(dry
(dry
(dry
(dry
(dry
(dry
basis)
basis)
basis)
basis)
basis)
basis)
100.0 per cent vol (dry basis)
For the primary flame reaction steam and oxygen are fed to the reactor at the
following rates:
Steam
Oxygen
0.75 kg/kg of heavy fuel oil feedstock
1.16 kg/kg of heavy fuel oil feedstock
The carbon produced in the flame reaction, and which is subsequently removed as
carbon suspension in water, amounts to 1.5 per cent by weight of the fuel oil feedstock
charge. Some H2 S present in the crude gas is removed by contact with the quench water.
The quenched gas passes to an H2 S removal stage where it may be assumed that H2 S is
selectively scrubbed down to 15 parts per million with substantially nil removal of CO2 .
Solution regeneration in this process is undertaken using the waste low-pressure steam
from another process. The scrubbed gas, at 35Ž C and saturated, has then to undergo
CO conversion, final H2 S removal, and CO2 removal to allow it to meet the product
specification.
CO conversion is carried out over chromium-promoted iron oxide catalyst employing
two stages of catalytic conversion; the plant also incorporates a saturator and desaturator
operating with a hot water circuit.
Incoming gas is introduced into the saturator (a packed column) where it is contacted
with hot water pumped from the base of the desaturator; this process serves to preheat
the gas and to introduce into it some of the water vapour required as reactant. The gas
then passes to two heat exchangers in series. In the first, the unconverted gas is heated
980
CHEMICAL ENGINEERING
against the converted gas from the second stage of catalytic conversion; in the second
heat exchanger the unconverted gas is further heated against the converted gas from
the first stage of catalytic conversion. The remaining water required as reactant is then
introduced into the unconverted gas as steam at 600 psig (4140 kN/m2 gauge) saturated
and the gas/steam mixture passes to the catalyst vessel at a temperature of 370Ž C. The
catalyst vessel is a single shell with a dividing plate separating the two catalyst beds
which constitute the two stages of conversion. The converted gas from each stage passes
to the heat exchangers previously described and thence to the desaturator, which is a
further packed column. In this column the converted gas is contacted countercurrent with
hot water pumped from the saturator base; the temperature of the gas is reduced and the
deposited water is absorbed in the hot-water circuit. An air-cooled heat exchanger then
reduces the temperature of the converted gas to 40Ž C for final H2 S removal.
Final H2 S removal takes place in four vertical vessels each approximately 60 feet
(18.3 m) in height and 8 feet (2.4 m) in diameter and equipped with five trays of ironoxide absorbent. Each vessel is provided with a locking lid of the autoclave type. The
total pressure drop across these vessels is 5 psi (35 kN/m2 ). Gas leaving this section of
the plant contains less than 1 ppm of H2 S and passes to the CO2 removal stage at a
temperature of 35Ž C.
CO2 removal is accomplished employing high-pressure potassium carbonate wash with
solution regeneration.4
Data
I. Basic data for CO conversion section of the plant
(a) Space velocity
The space velocity through each catalyst stage should be assumed to be 3500 volumes
of gas plus steam measured at NTP per volume of catalyst per hour. It should further be
assumed that use of this space velocity will allow a 10Ž C approach to equilibrium to be
attained throughout the possible range of catalyst operating temperatures listed below.
(b) Equilibrium data for the CO conversion reaction
For
pCO ð pH2 O
Kp D
pCO2 ð pH2
Temp. (K)
Kp
600
3.69 ð 102
700
1.11 ð 101
800
2.48 ð 101
(c) Heat of reaction
CO C H2 O ⇀
↽ CO2 C H2
H D 9.84 kcal.
II. Basic data for CO2 removal using hot potassium carbonate
solutions
The data presented in Ref. 4 should be employed in the design of the CO2 removal section
of the plant. A solution concentration of 40 per cent wt equivalent K2 CO3 should be
employed.
APPENDIX F
981
Scope of design work required
1. Process design
(a) Calculate, and prepare a diagram to show, the gas flows, compositions, pressures
and temperatures, at each main stage throughout the processes of gasification and
purification.
(b) Prepare a mass balance diagram for the CO conversion section of the plant including
the live steam addition to the unconverted gas. Basic data which should be employed
for the CO conversion process are presented in the Appendix.
(c) Prepare an energy-balance diagram for the flame reactor and for the associated
waste-heat boiler.
(d) Prepare a process flow-diagram showing all major items of equipment. This need
not be to scale but an indication of the internal construction of each item (with
the exception of the flame reactor, waste-heat boiler and quench tower) should be
given. The primary H2 S removal stage need not be detailed.
(e) Prepare an equipment schedule for the CO conversion section of the plant, specifying major items of equipment.
2. Chemical engineering design
(a) Prepare a detailed chemical engineering design of the absorber on the CO2 removal
stage.
(b) Prepare a chemical engineering design for the saturator on the CO conversion
section.
3. Mechanical design
Make recommendations for the mechanical design of the CO2 removal absorber,
estimating the shell and end-plate thickness and showing, by means of sketches suitable
for submission to a design office, how:
(a) the beds of tower packing are supported,
(b) the liquid is distributed.
Develop a detailed mechanical design of the CO conversion reactor, paying particular
attention to the choice of alloy steels versus refractory linings, provisions for thermal
expansion, inlet gas distribution, catalyst bed-support design, facilities for charging and
discharging catalyst and provisions for instrumentation.
4. Control
Prepare a full instrumentation of flow-sheet of the CO conversion section of the plant,
paying particular attention to the methods of controlling liquid levels in the circulating
water system and temperatures in the catalyst beds. Derive the unsteady-state equations
which would have to be employed in the application of computer control to the CO
conversion section of the plant.
REFERENCES
1. J. H. GARVIE, Chem. Proc. Engng, Nov. 1967, pp. 55 65. Synthesis gas manufacture.
2. Hydrocarbon Processing Refining Processes Handbook. Issue A, Sept. 1970, p. 269.
982
CHEMICAL ENGINEERING
3. S. C. SINGER and L. W. TER HAAR, Chem. Eng Prog., 1961, 57, pp. 68 74. Reducing gases by partial
oxidation of hydrocarbons.
4. H. E. BENSON, J. H. FIELD and W. P. HAYNES, Chem. Eng Prog., 1956, 52, pp. 433 438. Improved process
for CO2 absorption uses hot carbonate solutions.
F.7 CHLORINE RECOVERY FROM HYDROGEN CHLORIDE
The project
A plant is to be designed for the production of 10,000 tonnes per annum of chlorine by
the catalytic oxidation of HCl gas.
Materials available
(1) HCl gas as by-product from an organic synthesis process. This may be taken to be
100 per cent pure and at 20Ž C and absolute pressure of 14.7 psi (100 kN/m2 ).
(2) Air. This may be taken to be dry and at 20Ž C and absolute pressure of 14.7 psi
(100 kN/m2 ).
Services available
(1) Steam at 200 psig (1400 kN/m2 ).
(2) Cooling water at a maximum summer temperature of 24Ž C.
(3) A limited supply of cooling water at a constant temperature of 13Ž C is also
available.
(4) Electricity at 440 V, three-phase, 50 Hz.
On-stream time
8000 hours/year.
Product specification
Gaseous chlorine mixed with permanent gases and HCl. The HCl content not to exceed
5 ð 105 part by weight of HCl per unit weight of chlorine.
The process
HCl is mixed with air and fed into a fluidness bed reactor containing cupric
chloride/pumice catalyst and maintained at a suitable temperature in the range 300 400Ž C.
The HCl in the feed is oxidised, and the chlorine and water produced in the
reaction, together with unchanged HCl and permanent gases, are passed to a packed
tower cooler/scrubber, operating somewhat above atmospheric pressure, where they are
contacted with aqueous HCl containing 33 36 per cent by weight of HCl. This acid enters
the cooler/scrubber at about 20Ž C. Most of the water and some of the HCl contained in
the gases entering the cooler/scrubber are dissolved in the acid. The liquid effluent from
the base of the cooler/scrubber flows to a divider box from which one stream passes to the
top of the cooler/scrubber, via a cooler which lowers its temperature to 20Ž C, and another
983
APPENDIX F
stream passes to a stripping column (“expeller”). Gas containing 98 per cent by weight
of HCl (the other constituents being water and chlorine) leaves the top of the expeller
and is recycled to the reactor. A mixture of water and HCl containing 20 22 per cent by
weight of HCl leaves the base of the expeller. This liquid passes, via a cooler, to the top
of an HCl absorber, which is required to remove almost the whole of the HCl contained
in the gases leaving the cooler/scrubber. The liquid leaving the base of the HCl absorber,
containing 33 36 per cent by weight of HCl, is divided into two streams, one of which
flows to the expeller while the other is collected as product. The gaseous chlorine leaving
the top of the HCl absorber passes to a drier.
Data
Reactor
Catalyst particle size distribution (U.S. Patent 2746 844/1956)
Size range
(m)
50
100
150
200
250
300
100
150
200
250
300
350
Cumulative weight percentage
undersize (at upper limit)
0.39
15.0
58.0
85.0
96.6
99.86
Density of catalyst: 40 lb/ft3 (640 kg/m3 ).
Voidage at onset of fluidisation: 0.55.
Particle shape factor: 0.7.
Heat of reaction: 192 kcal/kg of HCl (H D 29, 340 kJ/kmol).
(Arnold, C. W. and Kobe, K. A., Chem. Eng, Prog., 1952, 48, 293.)
Gas residence time in reactor: 25 seconds,
Quant, J. et al., Chem. Engr, Lond., 1963, p. CE224.
Cooler/scrubber and expeller
The overall heat-transfer coefficient between the gas and liquid phases can be taken to be
5.0 Btu/h ft2 degF (28 W/m2 Ž C).
Scope of design work required
1. Prepare a mass balance diagram for the process, up to but not including the drier, on
the basis of weight/hour. Base the calculation on 10,000 long tons/year of chlorine
entering the drier together with permanent gases, water and not more than 5 ð 105
parts by weight of HCl per unit weight of chlorine.
2. Prepare an energy balance diagram for the reactor and cooler/scrubber system.
3. Prepare a process flow diagram, up to but not including the drier, showing all the
major items of equipment, with indications of the type of internal construction, as
984
4.
5.
6.
7.
8.
9.
10.
11.
CHEMICAL ENGINEERING
far as possible in the corrected evaluation. The diagram should show all major pipe
lines and the instrumentation of the reactor and the cooler/scrubber system.
Prepare an equipment schedule listing all major items of equipment and
giving sizes, capacities, operating pressures and temperatures, materials of
construction, etc.
Present a specimen pipeline sizing calculation.
Work out the full chemical engineering design of the reactor and cooler/scrubber
systems.
Calculate the height and diameter of the expeller.
Prepare a mechanical design of the cooler/scrubber showing by dimensioned
sketches suitable for submission to a draughtsman how:
(a) The tower packing is to be supported.
(b) The liquid is to be distributed in the tower.
(c) The shell is to be constructed so as to withstand the severely corrosive conditions inside it.
Discuss the safety precautions involved in the operation of the plant, and the
procedure to be followed in starting the plant up and shutting it down.
Develop the mechanical design of the reactor and prepare a key arrangement
drawing, supplemented by details to make clear the essential constructional features.
The study should include recommendations for the design of the bed and means of
separation and disposal of dust from the exit gas stream, and should take account
of needs connected with thermal expansion, inspection, maintenance, starting and
stopping, inlet gas distribution, insertion and removal of catalyst, and the positioning
and provision for reception of instruments required for control and operational
safety. Written work should be confined, as far as possible, to notes on engineering
drawings, except for the design calculations, the general specification and the justification of materials of construction.
Assuming that the plant throughout may vary by 10 per cent on either side of its
normal design value due to changes in demand, specify control systems for:
(i) regulation of the necessary recycle flow from the cooler/scrubber base, at the
design temperature; and
(ii) transfer of the cooler/scrubber make liquor to the expeller.
REFERENCES
ARNOLD, C. W. and KOBE, K. A. (1952) Chem. Engng Prog. 48, 293.
FLEURKE, K. H. (1968) Chem. Engr., Lond., p. CE41.
QUANT, J., VAN DAM, J., ENGEL, W. F., and WATTIMENA, F. (1963) Chem. Engr., Lond., p. CE224.
SCONCE, J. S. (1962) Chlorine: Its Manufacture, Properties, and Uses (New York: Rheinhold Publishing Corporation).
F.8 ANILINE FROM NITROBENZENE
The project
Design a plant to make 20,000 tonnes per annum of refined aniline by the hydrogenation
of nitro-benzene. The total of on-stream operation time plus regeneration periods will be
7500 hours per year.
APPENDIX F
985
Materials available:
Nitrobenzene containing < 10 ppm thiophene.
Hydrogen of 99.5 per cent purity at a pressure of 50 psig (350 kN/m2 ).
Copper on silica gel catalyst.
Services available:
Steam at 200 psig (1400 kN/m2 ) 197Ž C, and 40 psig (280 kN/m2 ) 165Ž C.
Cooling water at a maximum summer temperature of 24Ž C.
Town’s water at 15Ž C.
Electricity at 440 V, three-phase 50 Hz.
Product specification:
Aniline
Nitrobenzene
Cyclohexylamine
Water
99.9 per cent w/w min.
2 ppm max.
100 ppm max.
0.05 per cent w/w max.
The process
Nitrobenzene is fed to a vaporiser, where it is vaporised in a stream of hydrogen (three
times stoichiometric). The mixture is passed into a fluidness bed reactor containing copper
on silica gel catalyst, operated at a pressure, above the bed, of 20 psig (140 kN/m2 ). The
contact time, based on superficial velocity at reaction temperature and pressure and based
on an unexpanded bed, is 10 seconds. Excess heat of reaction is removed to maintain the
temperature at 270Ž C by a heat-transfer fluid passing through tubes in the catalyst bed.
The exit gases pass through porous stainless-steel candle filters before leaving the reactor.
The reactor gases pass through a condenser/cooler, and the aniline and water are
condensed. The excess hydrogen is recycled, except for a purge to maintain the impurity
level in the hydrogen to not more than 5 per cent at the reactor inlet. The crude aniline
and water are let down to atmospheric pressure and separated in a liquid/liquid separator,
and the crude aniline containing 0.4 per cent unreacted nitrobenzene and 0.1 per cent
cyclo-hexylamine as well as water, is distilled to give refined aniline. Two stills are used,
the first removing water and lower boiling material, and the second removing the higher
boiling material (nitrobenzene) as a mixture with aniline. The vapour from the first column
is condensed, and the liquid phases separated to give an aqueous phase and an organic
phase. A purge is taken from the organic stream to remove the cyclo-hexylamine from the
system, and the remainder of the organic stream recycled. The cyclo-hexylamine content
of the purge is held to not greater than 3 per cent to avoid difficulty in phase separation.
In the second column, 8 per cent of the feed is withdrawn as bottoms product.
The purge and the higher boiling mixture are processed away from the plant, and the
recovered aniline returned to the crude aniline storage tank. The aniline recovery efficiency
in the purge unit is 87.5 per cent, and a continuous stream of high-purity aniline may be
assumed.
986
CHEMICAL ENGINEERING
The aqueous streams from the separators (amine-water) are combined and steam stripped
to recover the aniline, the stripped water, containing not more than 30 ppm aniline or
20 ppm cyclo-hexylamine, being discharged to drain.
Regeneration of the catalyst is accomplished in place using air at 250 350Ž C to burn
off organic deposits. Regeneration takes 24 hours, including purging periods.
The overall yield of aniline is 98 per cent theory from nitrobenzene, i.e. from 100 mols
of nitrobenzene delivered to the plant, 98 mols of aniline passes to final product storage.
Scope of design work required
1. Prepare a material balance on an hourly basis for the complete process in weight
units.
2. Prepare a heat balance for the reactor system, comprising vaporiser, reactor and
condenser/cooler.
3. Draw a process flow diagram for the plant. This should show all items of equipment
approximately to scale and at the correct elevation. The catalyst regeneration.
equipment should be shown.
4. Chemical engineering design.
(a) Vaporiser
Give the detailed chemical engineering design, and give reasons for using the
type chosen. Specify the method of control.
(b) Reactor
Give the detailed chemical engineering design for the fluidness bed and heat
transfer surfaces. Select a suitable heat transfer fluid and give reasons for your
selection. Do not attempt to specify the filters or to design the condenser/cooler in
detail.
(c) Crude aniline separator
Specify the diameter, height and weir dimensions and sketch the method of
interface level control which is proposed.
(d) Amine water stripper
Give the detailed chemical engineering design of the column.
5. Prepare a full mechanical design for the reactor. Make a dimensioned sketch suitable
for submission to a drawing office, which should include details of the distributor,
and show how the heat transfer surfaces will be arranged. An indication of the
method of supporting the candle filters should be shown, but do not design this in
detail.
6. Prepare an equipment schedule detailing all major items of equipment, including
tanks and pumps. A specimen pipeline sizing calculation for the reactor inlet pipe
should be given. All materials of construction should be specified.
7. Describe briefly how the plant would be started up and shut down, and discuss
safety aspects of operation.
8. Write a short discussion, dealing particularly with the less firmly based aspects of
the design, and indicating the semi-technical work which is desirable.
987
APPENDIX F
Data
1. Catalyst properties:
(a) Grading:
0 20
20 40
40 60
60 80
80 100
100 120
120 140
140 150
> 150
m:
m:
m:
m:
m:
m:
m:
m:
m:
3
7
12
19
25
24
10
Negligible
per cent w/w
per cent w/w
per cent w/w
per cent w/w
per cent w/w
per cent w/w
per cent w/w
Negligible.
(b)
(c)
(d)
(e)
Voidage at minimum fluidisation, 0.45.
Shape factor, 0.95.
Bulk density at minimum fluidisation, 50 lb/ft3 (800 kg/m3 ).
Life between regenerations 1500 tonne of aniline per ton of catalyst, using the
feedstock given.
2. Exothermic heat of hydrogenation. H298 D 132, 000 CHU/lb mol (552,000 kJ/k
mol).
3. Mean properties of reactor gases at reactor conditions:
Viscosity
0.02 centipoise (0.02 mNs/m2 )
Heat capacity at constant pressure 0.66 CHU/lbŽ C (2.76 kJ/kgŽ C)
Thermal conductivity
0.086 CHU/hr ft2 (Ž C/ft) (0.15 W/mŽ C)
4. Pressure drop through candle filters D 5 psi⊲35 kN/m2 ⊳.
5. Density of nitrobenzene:
Temp. ° C
Density g/cm3
0
15
30
50
1.2230
1.2083
1.1934
1.1740
6. Latent heat of vaporisation of nitrobenzene:
Temp. ° C
Latent heat CHU/lb
(kJ/kg)
100
125
150
175
200
210
104
101
97
92.5
85
79
(434)
(422)
(405)
(387)
(355)
(330)
988
CHEMICAL ENGINEERING
7. Latent heat of vaporisation of aniline:
Temp. ° C
Latent heat CHU/lb
(kJ/kg)
100
125
150
175
183
133.5
127
120
110
103.7
(558)
(531)
(502)
(460)
(433)
8. Specific heat of aniline vapour D 0.43 CHU/lbŽ C (1.80 kJ/kgŽ C).
9. Solubility of aniline in water:
Temp. ° C
per cent w/w aniline
20
40
60
100
3.1
3.3
3.8
7.2
10. Solubility of water in aniline:
Temp. ° C
per cent w/w water
20
40
60
100
5.0
5.3
5.8
8.4
11. Density of aniline/water system:
Density g/cm3
Temp. ° C
Water layer
Aniline layer
0
10
20
30
40
50
60
70
1.003
1.001
0.999
0.997
0.995
0.991
0.987
0.982
1.035
1.031
1.023
1.014
1.006
0.998
0.989
0.982
12. Partition of cyclo-hexylamine between aniline and water at 30Ž C:
w/w per cent cyclohexylamine in
aniline
w/w per cent water
in aniline
w/w per cent cyclohexylamine in
water
w/w per cent aniline
in water
1.0
3.0
5.0
5.7
6.6
7.7
0.12
0.36
0.57
3.2
3.2
3.2
13. Partition coefficient of nitrobenzene between aniline layer and water layer:
Ca.l. /Cw.l. D 300.
989
APPENDIX F
14. Design relative velocity in crude aniline-water separator: 10 ft/h (3 m/h).
15. Equilibrium data for water-aniline system at 760 mm Hg abs:
Mole fraction water
Temp ° C
Liquid
Vapour
184
170
160
150
140
130
120
110
105
100
99
0
0.01
0.02
0.03
0.045
0.07
0.10
0.155
0.20
0.30
0.35 0.95
0.985
0.9896
0.9941
0.9975
0.9988
0
0.31
0.485
0.63
0.74
0.82
0.88
0.92
0.94
0.96
0.964
0.9641
0.9642
0.9735
0.9878
0.9932
16. Equilibrium data for cyclo-hexylamine-water system at 760 mm Hg abs:
Mole fraction cyclo-hexylamine
Liquid
Vapour
0.005
0.010
0.020
0.030
0.040
0.050
0.100
0.150
0.200
0.250
0.065
0.113
0.121
0.123
0.124
0.125
0.128
0.131
0.134
0.137
17. Temperature coefficient for aniline density
0 100Ž C).
0.054 lb/ft3 Ž C(0.86 kg/m3 Ž C) (range
REFERENCES
1. U.S. Patent 2,891,094 (American Cyanamid Co.).
2. PERRY, R. H., CHILTON, C. H. and KIRKPATRICK, S. D. (eds) Chemical Engineers’ Handbook, 1963, 4th edn,
Section 3 (New York: McGraw-Hill Book Company, Inc.).
3. LEVA, M. Fluidization, 1959 (New York: McGraw-Hill Book Company, Inc.).
4. ROTTENBURG, P. A. Trans. Instn. Chem Engrs, 1957, 35, 21.
As an alternative to Reference 1 above, any of the following may be read as background information to the
process:
5. Hyd. Proc. and Pet. Ref., 1961, 40, No. 11, p. 225.
6. STEPHENSON, R. M. Introduction to the Chemical Process Industries, 1966 (New York: Reinhold Publishing
Corporation).
7. FAITH, W. L., KEYES, D. B. and CLARK, R. L. Industrial Chemicals, 3rd edn, 1965 (New York: John Wiley
& Sons Inc.).
8. SITTIG, M. Organic Chemical Processes, 1962 (New York: Noyes Press).
APPENDIX G
Equipment Specification (Data) Sheets
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
Vessel data sheet
Column tray data sheet
Heat exchanger data sheet
Plate heat exchanger data sheet
Centrifugal pump data sheet
Reciprocating pump data sheet
Rotary positive pump data sheet
Mixer data sheet
Conveyor data sheet
Relief and safety valve data sheet
Design Data Sheets
(1) Data sheet for pressure vessel design
990
991
APPENDIX G
Equipment No. (Tag)
Vessel data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
No. REQUIRED
2
CAPACITY
SPECIFIC GRAVITY OF CONTENTS
3
COMPUTED (yes or no)
SHELL
4
JACKET FULL/HALF COIL
INTERNAL COIL
5
CONTENTS
6
DIAMETER
7
LENGTH
8
DESIGN CODE
9
MAX. WORKING PRESSURE
10
DESIGN PRESSURE
11
MAX. WORKING TEMP
12
DESIGN TEMP
13
TEST PRESSURE (HYDROSTATIC)
14
TEST PRESSURE (AIR)
15
MATERIALS
16
JOINT FACTOR
17
CORROSION ALLOWANCE
18
THICKNESS
19
END TYPE
THICKNESS
JOINT FACTOR
20
END TYPE
THICKNESS
JOINT FACTOR
21
TYPE OF SUPPORT
THICKNESS
MATERIAL
22
WIND LOAD DESIGN
RADIOGRAPHY %
STRESS RELIEF
23
INTERNAL BOLTS MATERIAL
TYPE
NUTS
24
EXTERNAL BOLTS MATERIAL
TYPE
NUTS
INSULATION (SEP. ORDER)
INSULATION FITTING ATTACHMENT BY
26
GASKET MATERIAL
INSPECTION BY
27
25
PAINTING
28
WEIGHT
EMPTY
29
FULL OF LIQUID
OPERATING
30
INTERNALS and EXTERNALS
DATE OF ENQUIRY
ORDER No.
DRG. No.
DATE OF ORDER
31
32
MANUFACTURER
33
REMARKS AND NOTES:- UNLESS OTHERWISE STATED ALL FLANGE BOLT HOLES TO BE
34
OFF-CENTRE OF VESSEL CENTRE LINES N/S and E/W (NOT RADIALLY)
35
37
38
39
40
A
41
B
42
C
43
D
44
E
45
F
46
G
47
H
48
H
49
K
50
K
51
M
52
N
53
P
REF
54
No.
DUTY
BRANCH
NOM BORE
PIPE WALL
mm/Ins
THICKNESS
TYPE
CLASS
MATERIAL
RANGE SPEC
BRANCH
55
REMARKS 56
COMPEN’N
57
Prepared
3
6
Checked
2
5
59
Approved
1
4
60
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
58
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
992
CHEMICAL ENGINEERING
Equipment No. (Tag)
Column Tray data sheet
(PROCEED)
Operating Data
TOP
Descript. (Func.)
Sheet No.
OR TOP
AND BOTTOM
BOTTOM
1
2
TOWER INSIDE DIAMETER (Inches) (mm)
3
TRAY SPACE (Inches) (mm)
4
TOTAL TRAYS IN SECTION
5
6
Internal Conditions at Tray Number
7
VAPOUR TO TRAY
8
RATE (lb/hr) (kg/hr)
9
DENSITY (lb/ft3) (kg/m3 )
10
PRESSURE (psi) (kg/cm2) (Bar g) (Bar a)
11
TEMPERATURE (° F) (° C)
12
LIQUID FROM TRAY
13
RATE (lb/hr) (kg/m3)
14
DENSITY (lb/ft3) (kg/m3)
15
TEMPERATURE (° F) (° C)
16
VISCOSITY cP
17
NUMBER OF LIQUID FLOW PATHS
18
19
Technical/Mechanical Data
20
TOWER MANHOLE INSIDE DIAMETER (Inches) (mm)
21
TRAY MATERIAL
22
TRAY THICKNESS
23
CAP MATERIAL
24
HOLDDOWN MATERIAL
25
NUTS and BOLTS MATERIAL
26
SUPPORT RING MATERIAL
27
SUPPORT RING SIZE (Inches) (mm)
28
DOWNCOMER BOLT BAR THICKNESS (Inches) (mm)
29
CORROSION ALLOWANCE
31
30
TRAYS (Inches) (mm)
32
TOWER ATTACHMENTS (Inches) (mm)
33
TRAYS NUMBERED FROM TOP TO BOTTOM
34
TRAY MANWAY REMOVAL FROM
35
36
37
DATE OF ENQUIRY
DATE OF ORDER
38
ORDER No.
DRG. No.
39
MANUFACTURER
40
NOTES
42
(1) INTERNAL VAPOUR AND LIQUID LOADINGS AT THE LIMITING SECTIONS ARE REQUIRED TO ENSURE PROPER TRAY DESIGN.
43
41
DENSITIES ARE REQUIRED AT ACTUAL INSIDE TOWER CONDITIONS OF TEMPERATURE and PRESSURE. VISCOSITY IS NOT
44
REQUIRED UNLESS GREATER THAN 0.7 cp
45
46
(2) CROSS OUT DIMENSION UNITS WHICH DO NOT APPLY. TRAY SUPPLIER TO ADVISE.
47
REMARKS
48
49
50
51
52
53
54
55
56
57
Prepared
3
6
58
Checked
2
5
59
Approved
1
4
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
60
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
993
APPENDIX G
Equipment No. (Tag)
Heat Exchanger data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
SIZE
2
TYPE
No. OF UNITS
3
SHELLS PER UNIT
HORIZONTAL CONNECTED IN (parallel or series)
4
SURFACE PER UNIT
SURFACE PER SHELL
5
6
Performance of one Unit
7
SHELL SIDE
TUBE SIDE
8
FLUID CIRCULATING
9
TOTAL FLUID ENTERING
10
IN
OUT
IN
OUT
11
VAPOUR
12
LIQUID
13
STEAM
14
WATER
15
NON-CONDENSABLES
16
FLUID VAPOURISED OR CONDENSED
17
SPECIFIC GRAVITY LIQUID
18
Mol Wt VAPOUR
19
Mol Wt NON-CONDENSABLES
20
VISCOSITY LIQUID
21
LATENT HEAT
22
SPECIFIC HEAT
23
THERMAL CONDUCTIVITY
24
TEMPERATURE
25
OPERATING PRESSURE
26
VELOCITY
27
No. OF PASSES
28
PRESSURE DROP
ALLOW
CALC.
ALLOW
CALC.
29
FOULING RESISTANCE
30
HEAT EXCHANGED
MTD (CORRECTED
TRANSFER RATE SERVICE
31
CLEAN
32
33
Construction of one Shell
34
DESIGN PRESSURE
35
TEST PRESSURE
36
DESIGN TEMPERATURE
37
METAL TEMPERATURE
38
TUBES
No. OD
THICKNESS
LENGTH
SHELL
I.D.
SHELL COVER
40
CHANNEL
CHANNEL COVER
FLTNG HEAD COVER
41
FLOATING
42
TUBE SHEET STATIONARY
PITCH
39
BAFFLES CROSS
TYPE
SPACING % CUT
43
TUBE SUPPORTS
TYPE
SPACING
44
LONG BAFFLE
TYPE
SEAL
45
IMPINGEMENT BAFFLE
TYPE
SEAL STRIPS
46
TYPE OF JOINT
TUBE
TUBE ATTACHMT
47
GASKETS SHELL IN
CHANNEL
FLOATING HEAD
48
CONNECTIONS SHELL IN
INTERCONN
SHELL OUT
49
CONNECTIONS CHANNEL IN
INTERCONN
CHANNEL OUT
50
TUBE SIDE
51
CORROSION ALLOWABLE SHELL SIDE
EXPANSION BELLOWS
BOLTS
NUTS
52
DESIGN CODE
X-RAY
S.R.
53
INSPECTION
PAINTING
INSULATION
54
WEIGHT OF ONE UNIT EMPTY
OPERATING
DATE OF ENQUIRY
55
DRG. No.
56
DATE OF ORDER
ORDER No.
INSPECTION FITTING ATTACHMENT BY
MANUFACTURER
57
Prepared
3
6
Checked
2
5
59
Approved
1
4
60
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
58
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
994
CHEMICAL ENGINEERING
Equipment No. (Tag)
Plate Heat Exchanger data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
TYPE
SERVICE OF UNITS
TOTAL HEAT LOAD FOR ALL UNITS
2
PROCESS
3
No. OF UNITS
4
kcal/hr:Btu/hr
5
6
Process Data for one Plate Heat Exchanger
HOT FLUID
7
COLD FLUID
8
FLUID CIRCULATED
9
TOTAL FLUID
kg/hr :lb/hr
10
LIQUID
kg/hr :lb/hr
11
STEAM
kg/hr :lb/hr
12
VAPOUR
kg/hr :lb/hr
13
NON-CONDENSABLES
kg/hr :lb/hr
14
FLUID CONDENSED
kg/hr :lb/hr
15
Mol Wt VAPOUR
16
TEMPERATURE IN
° C :°
17
TEMPERATURE OUT
C :F
18
SPECIFIC GRAVITY
19
SPECIFIC HEAT
20
THERMAL CONDUCTIVITY
kcal/hr/° C/m :Btu/hr/° F/ft
21
VISCOSITY
cP
22
LATENT HEAT
kcal/kg :Btu/lb
23
PASSES
24
PASSAGES PER PASS
25
ALLOWABLE/CALCULATED PRESSURE LOSS
kg/cm2 :psi
26
TOTAL No. OF PLATES
27
HEAT TRANSFER AREA
m2 :ft2
28
HEAT LOAD
kcal/hr :Btu/hr
29
OVERALL COEFFICIENT (CLEAN)
kcal/hr/m2/° C :Btu/hr/ft2/° F
30
OVERALL COEFFICIENT (DESIGN)
kcal/hr/m2/° C :Btu/hr/ft2/° F
31
FOULING
32
33
Mechanical Data for one Plate Heat Exchanger
LMTD. (CORR)
34
FRAME SIZE
EMPTY WEIGHT
DESIGN PRESSURE
kg/cm2
kg:lb
FLOODED WEIGHT
psig
TEST PRESSURE
35
kg/cm2
kg :lb
36
psig
37
° C :° F
DESIGN TEMPERATURE
38
CONNECTIONS
39
40
41
Materials of Construction
42
FRAME
FINISH
43
PLATES
FINISH
44
GASKETS
45
BUSHES
46
SHIELD RECOMMENDED FOR TEMPERATURE ABOVE 100° C 212° F
INCLUDED/NOT INCLUDED
DATE OF ENQUIRY
ORDER No.
47
DATE OF ORDER
48
DRG. No.
49
MANUFACTURER
50
REMARKS
51
52
53
54
55
56
57
Prepared
3
6
58
Checked
2
5
59
Approved
1
4
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
60
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
995
APPENDIX G
Equipment No. (Tag)
Centrifugal Pump data sheet
(PROCEED)
Function
Sheet No.
1
Operating Data
NUMBER OF MACHINES
2
Installed
working
standby
TYPE
3
4
LIQUID
5
Bar a
max.
suction
Volts
press.
press.
press.
AVAILABLE N.P.S.H.
CAPACITY
PRESSURES
ELECTRICAL SUPPLY
COOLING WATER SUPPLY
SEALING WATER SUPPLY
STEAM SUPPLY
6
VISCOSITY
Sp GRAVITY
min.
discharge
phase
temp.
temp.
temp.
press.
press.
normal
differentic
cycles
flow
flow
flow
temp.
temp.
temp.
VAPOUR PRESSURE
7
8
9
10
11
12
13
14
15
WORKING TEMPERATURE
16
pH
17
ANALYSIS
18
19
Technical Data
20
PUMP DRAWING No.
DRIVER ITEM No
SPEED rcm
TYPE OF DRIVE
SAFE MINIMUM FLOW
ABSORBED POWER REQD.
21
SHUT OFF HEAD
MAX. RECOMMEND’D kW OF DRIVER
24
N.P.S.H.
INSTALLED kW OF DRIVER
25
PUMP EFFICIENCY
SPEED OF DRIVER
26
PERFORMANCE CURVE No.
SPEED RATIO
27
DRTN OF ROTN (FACING COUPLING)
POWER FACTOR
28
TYPE OF GLAND OR SEAL
MOTOR EFFICIENCY
29
BALANCE ARRANGEMENT
DRIVER ITEM No.
30
COOLING WATER REQUIRED
DETAILS OF LUBRICATOR
31
SEALING WATER REQUIRED
TYPE OF BASEPLATE
32
DETAILS OF CONNECTIONS
SUPPLIER OF DRIVER
33
SUCTION
COUPLING
34
DISCHARGE
TYPE OF COUPLING
35
TYPE OF COUPLING GUARD
22
max
normal
23
DRIVER HALF COUPLING FITTED BY
36
TYPE OF THRUST BEARING
FOUNDATION BOLT SUPPLIER
37
TYPE OF JOURNAL BEARING
MOTOR DESIGN CODE
38
TYPE OF GEAR AND MAKER
MOTOR TEMP CLASS
39
FULL LOAD TORQUE
MOTOR PROTECTION TYPE
40
STARTING TORQUE
IMPELLER SIZE (MAX.)
41
IMPELLER SIZE (MIN.)
IMPELLER SIZE (INSTALLED)
42
43
Materials of Construction
44
SHAFT
GLAND SLEEVE
LINING
IMPELLER
NECK BUSH
46
45
BALANCE DISC OR PISTON
GLAND PACKING OR SEAL
47
IMPELLER WEAR RINGS
LANTERN RING
48
CASING WEARING RINGS
THRUST BEARING
CASING
BASEPLATE
49
50
51
Design Standards and Inspection
52
HYDROSTATIC TEST PRESS
DESIGN CODE
MAX ERECTION WEIGHT
SHIPPING WEIGHT
TOTAL WEIGHT
54
DRG. and DATA REQUIREMENTS
SHIPPING VOLUME
INSPECTION
55
DATE OF ORDER
ORDER No.
DRG. No.
DATE OF ENQUIRY
MANUFACTURER
Prepared
3
6
Checked
2
5
59
Approved
1
4
60
Date
Service
Engineering
Process
REV
Company
By
53
56
57
Appr.
Date
REV
Address
58
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
996
CHEMICAL ENGINEERING
Equipment No. (Tag)
Reciprocating Pump data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
2
Installed
NUMBER OF MACHINES
working
standby
TYPE
3
4
LIQUID
5
AVAILABLE N.P.S.H.
Bar a
CAPACITY
max.
min.
normal
7
PRESSURES
suction
Volts
press.
press.
press.
discharge
phase
temp.
temp.
temp.
press.
press.
differentic
cycles
flow
flow
flow
temp.
temp.
temp.
8
ELECTRICAL SUPPLY
COOLING WATER SUPPLY
SEALING WATER SUPPLY
STEAM SUPPLY
6
VISCOSITY
Sp GRAVITY
VAPOUR PRESSURE
WORKING TEMPERATURE
pH
9
10
11
12
13
14
15
16
ANALYSIS
17
18
Technical Data
PUMP DRAWING No.
19
MAX. ABSORBED POWER REQD.
20
SPEED rpm
EFFICIENCY
21
PLUNGER DIA and SPEED
MAX. RECOMMENDED kW OF DRIVER
22
STROKE
INSTALLED kW OF DRIVER
23
N.P.S.H. REQUIRED
SPEED OF DRIVER
24
CAPACITY CONTROL
SPEED RATIO
25
TYPE OF DRIVE
DIR’N OF ROTN (FACING COUPLING)
26
TYPE OF GLAND
DETAILS OF LUBRICATOR
27
TYPE VALVES
TYPE OF BASEPLATES
28
COOLING WATER REQUIRED
RELIEF VALVE SET PRESSURE
29
SEALING WATER REQUIRED
TYPE OF BEARINGS
30
DETAILS OF CONNECTIONS
SUPPLIER OF DRIVER
31
SUCTION
COUPLING
32
DISCHARGE
DRIVER HALF COUPLING FITTED BY
33
STARTING TORGUE
TYPE OF COUPLING and MAKER
TYPE OF GEAR and MAKER
34
TYPE OF TORQUE CONVERTER and MAKER
TYPE OF DRIVE
DIRECT
35
GEAR
36
37
Materials of Construction
38
CYLINDERS
CRANK CASE
39
VALVE HEAD
CRANKSHAFT
40
VALVE SEAT
CONNECTING ROD
41
VALVE SPRING
CROSS HEAD
42
CYLINDER BORE SURFACE HEAD
CROSS HEAD GUIDES
43
PLUNGER
CROSSHEAD PIN
44
PISTON RINGS
BEARINGS
45
GLAND CASING
BASEPLATE
46
GLAND PACKING
RELIEF VALVE
47
LANTERN RING
GASKETS/‘O’ RINGS
48
49
Design Standards and Inspection
50
DESIGN CODE
MAX. ERECTION WEIGHT
51
HYDROSTATIC TEST PRESS.
SHIPPING WEIGHT
52
INSPECTION REQUIREMENTS
SHIPPING VOLUME
53
DRG. and DATA REQUIREMENTS
TOTAL WEIGHT
54
DATE OF ENQUIRY
DATE OF ORDER
55
DRG. No.
ORDER No.
56
MANUFACTURER
57
Prepared
3
6
58
Checked
2
5
59
Approved
1
4
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
60
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
997
APPENDIX G
Equipment No. (Tag)
Rotary Positive Pump data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
2
Installed
NUMBER OF MACHINES
working
standby
TYPE
3
4
LIQUID
5
Bar a
max.
suction
Volts
press.
press.
press.
AVAILABLE N.P.S.H.
CAPACITY
PRESSURES
ELECTRICAL SUPPLY
COOLING WATER SUPPLY
SEALING WATER SUPPLY
STEAM SUPPLY
6
min.
discharge
phase
temp.
temp.
temp.
normal
differentic
cycles
flow
flow
flow
7
8
9
10
11
12
VISCOSITY
press.
temp.
13
Sp GRAVITY
press.
temp.
temp.
14
VAPOUR PRESSURE
WORKING TEMPERATURE
15
16
pH
17
ANALYSIS
18
19
Technical Data
20
PUMP DRAWING No.
DRIVER ITEM No.
SPEED rpm
TYPE OF DRIVE
SAFE MINIMUM FLOW
ABSORBED POWER
21
SHUT OFF HEAD
MAX. RECOMMENDED kW OF DRIVER
24
N.P.S.H.
INSTALLED kW OF DRIVER
25
PUMP EFFICIENCY
SPEED OF DRIVER
26
PERFORMANCE CURVE No.
SPEED RATIO
27
DR’N OF ROTN (FACING COUPL’G)
POWER FACTOR
28
TYPE OF GLAND OR SEAL
MOTOR EFFICIENCY
29
BALANCE ARRANGEMENT
DRIVER ITEM No.
30
COOLING WATER REQUIRED
DETAILS OF LUBRICATOR
31
SEALING WATER REQUIRED
TYPE OF BASEPLATE
32
DETAILS OF CONNECTIONS
SUPPLIER OF DRIVER
33
SUCTION
COUPLING
34
DISCHARGE
TYPE OF COUPLING
35
TYPE OF COUPLING GUARD
DRIVER HALF COUPLING FITTED BY
36
TYPE OF THRUST BEARING
FOUNDATION BOLT SUPPLIER
37
TYPE OF GEAR AND MAKER
MOTOR DESIGN CODE
38
FULL LOAD TORQUE
MOTOR TEMP CLASS
39
STARTING TORQUE
MOTOR PROTECTION TYPE
40
22
max
normal
MOTOR PROTECTION TYPE
23
41
42
Materials of Construction
43
SHAFT
GLAND SLEEVE
LINING
ROTOR
GLAND PACKING AND SEAL
44
45
STATOR
LANTERN RING
46
CASING
THRUST BEARING
47
LANTERN RING
48
49
Design Standards and Inspection
50
DESIGN CODE-PUMP
SHIPPING VOLUME
51
HYDROSTATIC TEST PRESS.
MAX. ERECTION WEIGHT
52
INSPECTION
SHIPPING WEIGHT
53
DRG. and DATA REQUIREMENTS
TOTAL WEIGHT
54
DATE OF ORDER
ORDER No.
55
DRG. No.
56
DATE OF ENQUIRY
MANUFACTURER
57
Prepared
3
6
Checked
2
5
59
Approved
1
4
60
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
58
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
998
CHEMICAL ENGINEERING
Equipment No. (Tag)
Mixer data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
No. OF MACHINES
2
WORKING
STANDBY
3
SIZE OF CHARGE
4
RATE OF CHARGING
5
TIME ACTUALLY MIXING
CONTIN. DUTY
INTERMIT. DUTY
6
TYPE OF MIXING (turbulent/moderate/light)
7
SOLIDS CONTENT
SOLIDS S.G.
LIQUID VISCOSITY
LIQUIDS S.G.
8
9
SLURRY VISCOSITY (APPARENT)
10
PARTICLE SIZE ANALYSIS
11
SOLIDS SETTLING VELOCITY
12
13
Vessel Data
14
DEPTH OF VESSEL
15
DEPTH OF LIQUID
MAX
NORMAL
MIN
16
ANGLE OF AGITATOR
17
SIZE OF APERTURE FOR IMPELLER
18
WORKING PRESSURE
19
WORKING TEMPERATURE
20
DEPTH OF VESSEL
21
22
Technical Data
23
TYPE OF MIXER
24
No. OF BLADES
DRAWING No.
25
No. OF SETS OF BLADES
ELECTRICITY SUPPLY
SPEED
ABSORBED POWER (hp/kW)
Volts
phase
Hz
26
27
SHAFT DIAMETER
TYPE OF MOTOR
28
CRITICAL SPEED
RECOMMENDED MOTOR POWER (hp/kW)
29
TYPE OF SEAL OR GLAND
RECOMMENDED MOTOR SPEED (rpm)
30
METHOD OF SUPPORT
INERTIA
31
TOTAL LOAD
STARTING TORQUE
32
WITHDRAWAL HEIGHT REQUIRED
OPERATING TORQUE
33
TYPE OF BEARINGS
TYPE OF GEAR BOX
33
ANGLE OF BLADES
VEE BELT/DIRECT DRIVE
34
36
Design Standards and Inspection
37
DESIGN CODE
MAX. ERECTION WEIGHT
38
HYDROSTATIC TEST PRESSURE
SHIPPING WEIGHT
39
DRGS and DATA REQ.
SHIPPING VOLUME
40
INSPECTION
TOTAL WEIGHT
41
42
Materials of construction
SHAFT
43
IMPELLER
44
SEAL OR GLANDS
46
SUPPORTS
45
VESSEL
BEARINGS
47
48
DATE OF ENQUIRY
DATE OF ORDER
49
DRG. No.
ORDER No.
50
MANUFACTURER
51
REMARKS
53
54
55
56
57
Prepared
3
Checked
Approved
Date
Service
Engineering
Process
6
58
2
5
59
1
4
REV
Company
By
Appr.
Date
REV
Address
60
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
999
APPENDIX G
Equipment No. (Tag)
Conveyor data sheeet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
2
No. REQUIRED
OVERALL LENGTH
3
HOPPER WIDTH
WEIGHT UNLADEN
4
WEIGHT LADEN
5
CONVEYOR TYPE
WIDTH
6
CONVEYOR LENGTH HORZ. SECTN
ELEVATED SECTION
7
BUCKET TYPE
SPACING
8
BELT SPEED
VARIABLE/RXED
9
BELT TENSION
DRIVE
10
POWER CONSUMPTION
POWER SUPPLY
11
12
Safety Characteristics
13
MATERIAL TO BE CONVEYED
14
MASS FLOW RATE
15
BULK DENSITY
16
MATERIAL OF CONSTRUCTION
17
BELT
BEARING TYPE
18
HOPPER
19
BUCKET
BEARING SPACING
20
DATE OF ENQUIRY
DATE OF ORDER
22
DRG. No.
ORDER No.
23
21
MANUFACTURER
24
25
SPECIAL CHARACTERISTICS
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
Prepared
3
6
Checked
2
5
59
Approved
1
4
60
Date
Service
Engineering
Process
REV
Company
By
Appr.
Date
REV
Address
58
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
1000
CHEMICAL ENGINEERING
Equipment No. (Tag)
Relief and Safety Value data sheet
(PROCEED)
Descript. (Func.)
Sheet No.
1
Operating Data
2
LOCATION
3
PURPOSE
4
SET PRESSURE
Bar a
CAPACITY
kg/hr
5
MEDIUM
°C
at
6
MOLECULAR WEIGHT
7
DENSITY
kg/m3
VISCOSITY
cP
8
9
10
ACCUMULATION
DESIGN CODE
11
BLOWDOWN
12
MAXIMUM BACK PRESSURE
13
TEMPERATURE OF FLUID BLOWING (EXIT FROM NOZZLE)
14
TYPE OF VALVE
15
CALCULATED AREA
16
INSTALLED AREA
MAXIMUM CAPACITY
kg/hr
COEFFICIENT OF DISCHARGE
17
18
PIPE VESSEL DESIGN PRESSURE
DESIGN TEMPERATURE
19
PIPE/VESSEL HYDROSTATIC PRESS
20
PIPE/VESSEL DRG. No.
21
22
Technical Data
23
MANUFACTURER’S TYPE AND SERIAL No.
24
VALVE INLET CONNECTION
25
VALVE OUTLET CONNECTION
26
ADJUSTING SCREW CAP
LIFTING GEAR Yes/No
ADJUSTING BLOWD’N RING Yes/No
TEST GAG Yes/No
27
28
29
Materials of Construction
30
SPRING
31
BODY
32
TRIM
33
BODY DESIGN PRESSURE
ERECTION WEIGHT
34
BODY HYDROSTATIC TEST PRESS
SHIPPING WEIGHT
35
SHIPPING VOLUME
36
INSPECTION BY
37
CERTIFICATION and DOCUMENTATION REQUIREMENT
38
39
DATE OF ENQUIRY
DATE OF ORDER
40
ORDER No.
DRG. No.
41
MANUFACTURER
42
REMARKS
44
43
45
46
47
48
49
50
51
52
53
54
55
56
57
Prepared
3
Checked
Approved
Date
Service
Engineering
Process
6
58
2
5
59
1
4
REV
Company
By
Appr.
Date
REV
Address
60
By
Appr.
Date
61
62
Equipment No.
63
Project No.
64
1001
APPENDIX G
Data Sheet for Pressure Vessel Design
Customer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Order No . . . . . . . . . . . . . . . . . . .
Vessel name . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Equipment No . . . . . . . . . . . . . .
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Drawing/sketch No . . . . . . . . . . . . . . . . . . . . . . . . .
Design Code . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Design temperature . . . . . . . . Ž C.
Design pressure . . . . . . . . . . . . . . . . . . . . . kN/m2
Design liquid level . . . . . . . . . . . . . . . . . . . m
Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Density . . . . . . . . . . . . . . kg/m3
Service connections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydraulic test pressure . . . . . . . . . . . . . . . . kN/m2
Vessel classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Joint efficiencies:
Shell . . . . . . . . . . . . . . . . . . .
Heads . . . . . . . . . . . . . . . . . .
Materials of construction: Shell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Heads . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nozzles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Flanges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corrosion alowances:
shell . . . . . . . . . . . . . . . . . . . mm
Heads . . . . . . . . . . mm
Nozzles . . . . . . . . . . . . . . . . mm
Notes/comments
Prepared by . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Checked by . . . . . . . . . . . . . .
Date . . . . . . . . . . . . . . . . . . . . .
Date . . . . . . . . . . . . . . . .
APPENDIX H
Typical Shell and Tube Heat Exchanger
Tube-sheet Layouts
(a)
(b)
(c)
(d)
Fixed tube-sheet exchanger
U-tube exchanger
Floating-head exchanger with split backing ring
Pull through floating-head exchanger
Reproduced with permission from Heat Exchanger Design, E. A. D. Saunders (Longman Group).
1002
APPENDIX H
1003
(a) Typical tube layout for a fixed tubesheet exchanger 740 i/Dia. shell, single pass, 780-tubes, 19.05 o/Dia.
on 23.8125 pitch, 30° angle.
1004
CHEMICAL ENGINEERING
(b) Typical tube layout for a U-tube exchanger 740 i/Dia. shell, 2-pass, 246 U-tubes, 19.05 o/Dia. on 25.4
pitch, 45° angle.
1005
APPENDIX H
(c) Typical tube layout for a split backing ring floating-head exchanger. 740 i/Dia. shell, 6-pass, 580 tubes,
19.05 o/Dia. on 25.4 pitch, 30° angle.
ž
Denotes 13 Dia. sealing bars.
1006
CHEMICAL ENGINEERING
(d) Typical tube layout for a pull-through floating-head exchanger. 740 i/Dia. shell, 4-pass, 370 tubes 19.05
o/Dia. on 25.4 pitch, 90° angle.
ž
Denotes 13 Dia. sealing bars.
Author Index
Note: Figures are indicated by italic page numbers, Tables by emboldened numbers
Abrams 346
Abulnaga, B. 423
Aerstin, F. 744
Agarwal, V. K. 482
Ailor 292
Alani, G. H. 336
Allen, D. H. 29, 270
Alleva, R. Q. 507
Alliot, E. A. 883
Ally, F. C. 903
Ambler, C. M. 415, 418, 419
Amundson, N. R. 545
Ang, M. L. 395
Antoine, C. 331
Aoki, T. 640
Aris, R. 29
Arlt, W. 619
Arnold, C. W. 984
Ashafi, C. R. 360
Askquith, W. 368
Auger, C. P. 310
Aungier, R. H. 479
Austin, D. G. 134, 195
Austin, G. T. 310
Azbel, D. S. 863
Baasel, W. D. 10, 28
Baines, D. 303
Baker, J. R. 469
Baker-Counsell, J. 903
Balemans, A. W. M. 392
Barlow, J. A. 108
Barnea, E. 443
Barnicki, S. D. 566
Barnwell, J. 110
Barrow, M. H. 10
Barton, J. 366
Basta, N. 310
Battino, R. 351
Beams, J. W. 419, 420
Bechtel, L. B. 244
Bednar, H. H. 810, 839, 857
Begg, G. A. J. 478
Beightler, C. S. 25
Bell, K. J. 671, 693, 695, 716, 721
Bellman, R. 29
Bendall, K. 298
Benedek, P. 169
Benedict, M. 341
Bennett, J. G. 425
Benson, H. E. 982
Benson, S. W. 339
Berge, C. 20
Bergman, D. J. 850
Bergman, H. L. 770, 773, 774
Bernstein, I. M. 298
Bertrand, L. 233
Beveridge, G. S. G. 25, 28
Bhattacharya, B. C. 847 8
Bias, D. 370
Bier, T. H. 423
Billet, R. 434, 588, 592
Billingsley, D. S. 520, 544
Birchall, H. 878
Biskup, B. 70, 314
Bloch, H. P. 108, 479
Boas, A. H. 27, 28
Bohn, M. S. 634
Boland, D. 102
Bolles, W. L. 548, 557, 566, 575, 599
Bolliger 777
Bond, M. P. 758
Bosniakovic, 74
Bott, T. R. 636, 640, 744, 758
Boublik, T. 331, 339
Bowersox, J. P. 403
Boyd, G. M. 286, 287
Boyko, L. D. 712
Bradley, D. 421, 422, 423
Brandt, D. 896
Bravo, J. L. 593
Brennan, D. 270
Bretsznajder, S. 314, 320, 321, 322
Brian, P. L. T. 347
Briggs, D. E. 768
Brinkley, W. K. 516, 522
Britton, L. G. 367
Brodkey, R. S. 470
Bromley, L. A. 320, 734
Bronkala, W. J. 407
Brown, D. 391
Brown, G. G. 557
Brown, R. 769
Brown, R. L. 479
Brownell, L. E. 819, 828, 836, 839, 847, 850, 857
Buckley, P. S. 233
Bullington, L. A. 576
1007
1008
AUTHOR INDEX
Burchard, J. K. 549
Burklin, C. R. 12
Burley, J. R. 765
Burwell, R. L. Jr 973
Buse, F. 109
Butcher, C. 593, 903
Butt, L. T. 301, 303
Butterworth, D. 659, 663, 667, 699, 710, 713, 739
Cajander, B. C. 342
Callahan, J. L. 548
Cameron, J. A. 108, 479
Canner, J. A. 977
Capps, R. W. 219
Carson, B. E. 796
Carson, P. A. 360, 363, 392
Case, J. 795
Casey, R. J. 4
Caudle, P. G. 900
Chabbra, R. P. 202
Chada, N. 109
Chaddock, D. H. 3
Chaflin, S. 199
Champion, F. A. 292
Chan, H. 549, 553
Chand, J. 760
Chang, H-Y. 527
Chang, P. 333, 556
Chantry, W. A. 729
Chao, K. C. 342
Chapman, F. S. 201
Chase, J. D. 566, 571, 578
Chauvel, A. 270
Cheaper, T. A. 361
Chen, J. C. 736
Chen-Chia, H. 767
Cheremisnoff, N. P. 370, 410, 863
Cheryan, M. 434
Chilton, C. H. 106, 150, 971, 989
Chilver, A. H. 795
Chittendenden, D. H. 4
Cho, Y. L. 634
Christensen, J. H. 20
Chu, J. C. 339
Chudgar, M. M. 313
Chueh, C. F. 323, 324
Chueh, P. L. 348
Church, D. M. 729, 745
Chuse, R. 796
Cicalese, J. J. 578
Clapeyron, B. P. E. 874
Clark, B. 300
Clark, E. E. 295
Clark, R. L. 989
Clever, H. L. 351
Colburn, A. P. 186, 525, 556, 599, 712, 721, 723
Cole, J. 434
Collier, J. G. 723, 731
Collins, G. K. 742
Comyns, A. E. 310
Conant, A. R. 900
Conder, J. R. 347
Constantinescu, S. 450
Cook, L. H. 977
Cookfair, A. S. 310
Cooper, A. 758
Cooper, C. D. 903
Cooper, P. J. 459
Cooper, W. F. 367
Cornell, C. F. 409
Cornell, D. 598
Costich, E. W. 473
Coughanowr, D. R. 228
Cox, S. 392
Crittenden, B. 446
Cross, J. 366
Crowe, C. M. 169
Cruickshank, F. R. 339
Czermann, J. J. 602
Dabyburjor, D. B. 348
Dahlstrom, D. A. 409
Dano, S. 29
Danowsky, F. M. 108, 479
Dantzig, G. B. 29
Darby, R. 202
Davidson, J. 201
Davies, G. A. 460
Davies, J. F. 566
Davies, W. T. 903
Davis, J. A. 578
Day, M. F. 287
Day, R. W. 423
Deal, C. H. 347
Debham, J. B. 879
DeGhetto, K. 839
Deily, J. E. 300
De Minjer, C. H. 313
Denyer, M. 305
Derr, E. L. 347
De Santis, G. J. 201
Deshpande, P. B. 544
Devore, A. 671, 705
Devotta, S. 111
Dewitt, D. P. 634, 636
Dhodapkar, S. 448
Diaz, H. E. 253
Dickenson, T. C. 410
Dillon, C. P. 284
Dimoplon, W. 477
Doherty, M. F. 517
Dol, J. D. 548
Domalski, E. S. 339
Donaldson, R. A. B. 102
Donohue, D. A. 670
Doolin, J. H. 200, 201, 212
Doraiswamy, L. K. 325, 326
Dorsey, J. W. 745
Douglas, J. M. 111
Dreisbach, R. R. 331
Drew, T. B. 721
Driebeek, N. J. 29
AUTHOR INDEX
Dryden, I. 103
Duffin, J. H. 502, 503, 545
Dunford, H. 124
Dunn, K. S. 107
Dunn, R. F. 124
Duxbury, H. A. 369
Eagle, A. 666
Eckenfelder, W. W. 904
Eckert, J. S. 234, 592, 593, 598
Eckhoff, R. K. 366
Edgar, T. E. 25, 28, 29
Edison, A. G. 723
Edmister, W. C. 70, 516
Eduljee, H. E. 550, 571
Edwards, M. F. 470, 473, 779
El-Halwagi, M. M. 124
Ellerbe, R. W. 546
Emerson, W. H. 659, 758
Engel, W. F. 984
Erbar, J. H. 523, 524
Escoe, A. K. 795, 839, 840, 847
Estrup, C. 247
Eucken, A. 321
Evans, F. L. 616, 667, 771
Evans, L. S. 295, 301, 303
Everett, H. J. 473
Fair, J. R. 548, 549, 553, 566, 570, 571, 574, 593,
598, 599, 619, 742, 767
Faith, W. L. 989
Falbe, J. 968
Falcke, F. K. 304
Fang, C. S. 527
Farr, J. R. 810, 839, 869, 873, 877, 878
Farrer, D. 366
Faupel, J. H. 828
Fawcett, H. H. 360
Featherstone, W. 518
Fedons, R. F. 338
Fenoglio, F. 716
Fenske, M. R. 523
Fensom, D. H. 300
Ferguson, R. M. 666
Field, J. H. 982
Field, P. 366
Fischer, R. 435
Fisher, F. E 828
Fisher, H. G. 369
Fisher, J. 659
Fletcher, P. 779
Fleurke, K. H. 984
Flood, J. E. 410
Flower, J. R. 115
Fontana, M. G. 284, 291, 301
Forster, K. 732
Fossett, H. 476
Fournier, G. 270
Frank, O. 638, 662, 667, 711, 721, 722, 723, 742
Frank, W. I. 390
1009
Frazer, M. J. 4
Fredenslund, A. 347, 545
Freese, C. E. 839
Frejacques, M. 978
Fryer, D. M. 873
Fuller, E. N. 331, 332
Furzer, I. A. 745
Gambill, W. R. 334
Garay, P. N. 479
Garrett, D. E. 243, 247, 248, 251, 253
Garrett-Price, B. A. 640
Garside, J. 438
Garvie, J. H. 981
Geddes, R. L. 526, 544
Genereaux, R. P. 219, 220
George, W. 896
Gere, J. M. 795
Gerunda, A. 460
Gester, J. A. 548
Ghaly, M. A. 721
Gibson, S. B. 390
Giddings, J. C. 331, 332
Gilissen, F. A. H. 561
Gill, D. R. 593
Gilliland, E. R. 502, 507, 523
Gilmore, G. H. 722
Glitsch, H. C. 562, 565, 566
Gloyer, W. 723, 724
Gmehling, J. 347, 545
Golden, D. M. 339
Gordon, J. E. 286
Gordon, T. T. 310
Gorlovskiy, D. M. 978
Graham, R. W. 731
Grant 901
Grant, I. D. R. 671, 723
Gray, J. B. 470, 474 5, 779
Grayson, H. G. 342
Grayson, L. 906
Green, A. E. 360
Green, D. W. 105, 204, 217, 218, 227, 228, 292,
295, 314, 348, 401, 410, 426, 428, 437, 447,
448, 455, 468, 470, 476, 546, 619, 623, 636,
649, 713, 773, 796, 861, 865
Greenbaum, S. 315
Gretton, A. T. 476
Grichar, G. N. 423
Grills, D. M. 141
Grossel, S. S. 548, 598
Gugan, K. 366
Guha, P. 298
Gundersen, T. 111
Gupte, N. S. 736
Guthrie, K. M. 243, 251 2, 253
Gyokhegyi, S. L. 602
Haas, J. R. 542
Hachmuth, K. H. 186
Haggenmacher, J. E. 328
1010
AUTHOR INDEX
Hala, E. 331, 339
Hall, R. S. 253
Hall-Taylor, N. S. 713
Hamielee, A. E. 169
Hamner, N. E. 292
Hancock, E. G. 968
Hancock, E. H. 975
Hansen, C. 370
Hanson, C. 618
Hanson, D. N. 502, 503, 545, 577
Happle, J. 243, 251, 266
Harnby, N. 470
Harries, D. P. 296
Harrington, P. J. 578
Harris, W. J. 286
Hart, D. R. 546
Hartnell, J. P. 634
Harvey, J. F. 810, 873
Hathaway, C. 896
Haugen, G. R. 339
Hay, J. J. 602
Haynes, W. P. 982
Hengstebeck, R. J. 493, 500, 507, 516, 518, 526,
544, 546
Henke, G. E. 545
Henley, E. J. 23, 54, 172
Henry, B. D. 839
Hesler, W. E. 897
Hetenyi, M. 810
Heumann, W. L. 903
Hewitt, G. F. 634, 636, 713, 744, 758
Heywood, N. 482
Hicks, R. W. 473
Hilland, A. 305
Hills, R. F. 296
Himmelblau, D. M. 25, 28, 29, 75
Hinchley, P. 103
Hiorns, F. J. 468
Hiplin, H. G. 342
Hirata, M. 331, 339, 343, 344
Hirshland, H. E. 476
Hirst, R. 360
Hodson, J. R. 566, 569
Hoffman, T. N. 169
Hoftyzer, P. J. 978
Holdrich, R. G. 408
Holdridge, D. A. 304
Holland, C. D. 542, 544
Holland, F. A. 111, 201, 266
Holman, J. P. 634
Holmann, E. C. 121
Holmes, R. C. 313
Hooper, W. B. 442, 443
Horsley, L. H. 346
Horzella, T. I. 459
Hougen, O. A. 721
Houghland, G. S. 578
House, F. F. 896
Howard, W. B. 364
Hoyle, R. 214
Hsu, Y. 731
Huang, C-J. 566, 569
Hughes, R. 434
Hughmark, G. A. 742
Hullcoop, R. 305
Humphrey, J. L. 618, 619, 623, 624
Hunt, C. d’A. 577
Husain, A. 168
Hutchinson, A. J. L. 578
Hutchinson, H. P. 169
Hyatt, N. 381
Incropera, F. P. 634, 636
Irving, J. B. 321
Jackson, J. 602
Jacob, K. 448
Jacobs, J. K. 201
James, R. 108, 479
Jamieson, D. T. 321
Jandiel, D. G. 201
Jasper, J. J. 335
Jasper, McL. T. 878
Jawad, M. H. 810, 839, 869, 873, 877, 878, 879
Jeffreys, G. V. 721
Jenett, E. 109
Jenike, A. W. 482
Jenny, F. T. 519
Johnson, A. I. 169
Johnson, J. R. 482
Jones, A. G. 437
Jones, C. J. 4
Jones, D. A. 367
Jones, J. B. 233
Jones, M. G. 482
Jones, R. L. 476
Jordan, D. G. 243, 251, 266
Josefowitz, S. 335
Jowitt, R. 295
Kaasenbrood, P. J. C. 977
Kaess, D. 896
Kalani, G. 238
Karassik, I. J. 210, 479
Karman, von T. 829
Katz 754
Keith, F. W. 419, 420
Keller, G. E. 618, 623, 624
Kelley, R. E. 576
Kenny, W. F. 101
Kentish, D. N. W. 218
Kern, D. Q. 320, 649, 657, 664, 667, 670, 672,
680, 683, 710, 721, 723, 741, 744, 745, 751,
767, 768, 769, 771
Kern, R. 201, 896
Kesler, M. G. 341
Keyes, D. B. 989
Khokar, Z. H. 470
Kiely, G. 905
Kiene, A. 547
Kift, M. H. 141
AUTHOR INDEX
Kimla, A. 483
King, C. J. 493, 500
King, R. 360
Kirk, R. E. 310, 971
Kirkbride, C. G. 526
Kirkpatrick, S. D. 989
Kister, H. Z. 493, 542, 548, 566, 592, 593, 616
Kletz, T. A. 361, 381, 390, 391
Klip, A. 742
Knapp, H. 341
Knapp, W. G. 598, 599
Kobe, K. A. 69, 336, 351, 984
Koch, R. 562, 566
Koch, W. H. 450
Kojima, K. 313, 347, 508
Kolb, H. J. 973
Kraus, A. D. 768, 769
Kraus, M. N. 458
Kreith, F. 634
Kremser, A. 186
Kroger, D. G. 769
Kruzhilin, G. N. 712
Kucheryavyy, V. I. 978
Kudchadker, A. P. 336
Kumar, A. 517
Kumar, H. 758, 761
Kutateladze, S. S. 712
Kuzniar, J. 566
Kwauk, M. 18, 19, 502
Kwong, J. N. S. 341
Lake, G. F. 878
Lamé, G. 874
Lamit, L. G. 218
Landels, H. H. 304
Lang, H. J. 251
Langer, B. F. 867
Lapidus, L. 102
Larson, M. A. 439
Lavanchy, A. C. 419, 420
Lavery, K. 368
Lawley, H. G. 381
Lee, B. I. 341
Lee, C. Y. 556
Lee, D. C. 745
Lee, J. 470
Lee, W. 20, 24
Lee, W. C. 710
Lees, F. P. 360, 366, 390, 395
Leesley, M. E. 168
Lenoir, J. M. 342
Lerner 769
Leung, W. W-F. 415
Leva, M. 604, 989
Lever, D. A. 302
Lewis, D. J. 378
Lewis, J. R. 362, 364
Lewis, W. K. 318, 504, 543, 548
Licht, W. 450
Liebson, I. 576
Linek, J. 339
1011
Linley, J. 415
Linnhoff, B. 102, 111, 115, 122, 124
Lipak, B.G. 227
Liu, Y. A. 102
Llewellyn, D. T. 295
Lockett, M. J. 566
Logemann, J. D. 977
Long, W. 839
Lo Pinto, L. 723
Lord, C. R. 309
Lord, R. C. 667
Lorentz, G. 304
Lowe, R. E. 765
Lowenstein, J. G. 557
Lowrance, W. W. 362
Lowrison, G. C. 465, 468
Ludwig, E. E. 201, 562, 566, 636, 640, 649, 657,
672, 769
Luyben, W. L. 233
Lyda, T. B. 244
Lydersen, A. L. 336, 337
Lyle, O. 305, 900
Lynn, R. E. 336
Lyster, W. N. 520, 544
MacFarland, A. 552
MacMichael, D. B. A. 110
MacMillan, A. 367
Madden, J. 899
Maddox, R. N. 523, 524
Magnussen, T. 347
Mah, S. H. 169
Mahajan, K. K. 857
Mainwarring 903
Mais, L. G. 410
Maizell, R. E. 309
Makovitz, R. E. 777
Malleson, J. H. 303
Malone, M. F. 517
Maloney, J. O. 204, 217, 227, 228, 292, 295, 314,
348, 401, 410, 426, 428, 437, 447, 448, 455,
468, 470, 476, 546, 619, 623, 636, 649, 713,
773, 796, 861, 865
Manning, W. R. D. 876, 877, 879
Markham, A. E. 351
Marshall, P. 481
Marshall, V. C. 361, 366, 465, 466, 468
Marshall, V. O. 850
Masek, J. A. 217
Mason, D. R. 122
Mason, J. C. 179
Masso, A. H. 102
Masters, K. 432
Matheson, G. L. 543
Mathews, J. F. 336
Mathews, T. 368
Matley, J. 253
Matthews, C. W. 403
Maxwell, J. B. 535
Mayfield, F. D. 745
McCabe, W. L. 505
1012
McClain, R. W. 565
McClintock, N. 896
McGrath, R. V. 879
McGregor, W. C. 434
McKetta, J. J. 310
McNaught, J. M. 721
McNaughton, J. 253
Meade, A. 479
Mecklenburgh, J. C. 892, 896
Megyesy, E. F. 836, 839, 840, 847
Mehra, Y. R. 616
Mehta, M. 403
Meili, A. 110
Meissner, R. E. 896
Mendoza, V. A. 364
Merims, R. 892
Merrick, R. C. 198
Mersham, A. 438
Mersmann, A. 437, 438
Micha, K. 483
Michelsen, M. L. 347
Milberger, E. C. 548
Miles, F. D. 104, 150, 156, 165
Miller, R. 101
Miller, S. A. 310
Mills, D. 482
Minton, P. E. 667, 765
Mises, von R. 876
Mizrahi, J. 443
Moir, D. N. 423
Moore, A. 368
Moore, D. C. 293
Moore, G. Z. 745
Moore, R. E. 291
Morley, P. G. 368
Morris, B. G. 419
Morris, C. P. 110
Morris, G. A. 602
Moser, F. 111
Moss, D. R. 795, 839, 840, 847, 857
Mostinski, I. L. 733
Motard, R. L. 169
Mott, R. L. 795
Mottram, S. 302
Mueller, A. C. 657, 671, 693, 696
Mukherjee, R. 769
Mullin, J. W. 437, 959
Mumford, C. J. 360, 363, 392
Munday, G. 366
Murphree, E. V. 547
Murphy, G. 368
Murphy, J. J. 850
Murrill, P. W. 228
Murti, P. S. 742
Mutzenburg, A. B. 435
Myer 879
Myers 470, 754
Myers, A. L. 54
Naess, L. 111
Nagahama, K. 331, 339
AUTHOR INDEX
Nagata, S. 473
Nagiev, M. F. 172
Naphtali, L. M. 545
Napier, D. H. 367
Nayyar, M. L. 194, 218
Neerkin, R. F. 201
Nelson, J. G. 836
Nemhauser, G. L. 29
Nesmeyanov, A. N. 331
Newman, S. A. 348
Nienow, A. W. 470
Nishida, N. 102
Nolte, C. B. 219, 221, 222, 223
Norman, W. S. 616
Norton, F. H. 305
Null, H. R. 342, 347, 348, 548
Nusselt, W. 710
O’Connell, H. E. 550, 551
O’Connell, J. P. 314
O’Donnell, W. J. 867
O’Neal, H. E. 339
Ohe, S. 331, 339
Okumoto, Y. 601
Oldershaw, C. F. 548
Oldshue, J. Y. 476
Olsen, P. I. 548, 598
Onda, K. 601
Orr, C. 410
Oscarson, J. L. 312
Othmer, D. F. 310, 313, 335, 971
Owen, R. G. 710
Ozisik, M. N. 634, 636
Page, J. S. 243, 253
Palen, J. W. 640, 671, 732, 745, 750, 751, 752
Pantelides, C. C. 169
Parker, D. V. 757
Parker, K. 459
Parker, N. H. 428, 435, 437
Parker, R. O. 659
Parkins, R. 233
Parkinson, J. S. 368
Parmley, R. O. 479
Parry, C. F. 368
Patel, P. M. 527
Patoczka, J. 904
Patton, B. A. 565
Paul, R. 339
Payne, A. J. 977
Pearson, G. H. 199
Peckner, D. 298
Peng, D. Y. 342
Penney, N. R. 472
Penny, W. R. 779
Perona, J. J. 973
Perry, R. H. 105, 106, 154, 165, 204, 217, 218,
227, 228, 292, 295, 314, 348, 401, 410, 426,
428, 437, 447, 448, 455, 468, 470, 476, 546,
AUTHOR INDEX
619, 623, 636, 649, 713, 773, 796, 861, 865,
971, 989
Peters, M. S. 27, 219, 221, 222,
223, 253
Pieratti, G. J. 347
Pikulik, A. 253
Pitblado, R. M. 396
Pitts, F. H. 527
Plocker, U. 341
Polak, J. 331, 339
Poling, B. E. 314, 320, 328, 339, 341, 342, 346,
347
Polya, G. 4
Pontinen, A. J. 545
Poole, G. 369
Porter, H. F. 411
Porter, K. E. 721
Porter, M. C. 434
Porton, J. W. 102
Power, R. B. 479
Prabhudesai, R. K. 447
Prasher, C. L. 465
Pratt, T. H. 367
Prausnitz, J. M. 314, 320, 328, 339, 341, 342, 345,
346, 347, 348, 937
Preece, P. E. 141
Prickett, R. D. 742
Pritchard, B. L. 565
Prosser, L. E. 476
Prugh, R. N. 390
Pryce Bayley, D. 460
Pulford, C. 899
Purchas, D. B. 410
Purohit, G. P. 253
Quant, J.
984
Rabald, E. 292
Raimbault, C. 270
Raju, K. S. N. 760
Rase, H. F. 10, 218, 483, 485, 486
Rasmussen, E. J. 236
Rasmussen, P. 347, 545
Reay, D. A. 110
Reddy, P. J. 742
Redlich, O. 341
Redmon, O. C. 445
Reed, C. E. 502
Reid, R. C. 314, 320, 328, 339, 341, 342, 346, 347,
937
Reid, R. W. 476
Reinders, W. 313
Reisner, W. 482
Rennie, F. W. 410
Renon, H. 345
Revie, R. W. 284
Richardson, J. F. 202
Ridley, J. 360
Rihani, D. H. 325, 326
Ritter, R. B. 640
1013
Robbins, L. A. 618, 623
Roberts, E. J. 403
Robinson, C. S. 507
Robinson, D. B. 342
Rocha, J. A. 619
Rogers, A. S. 339
Rogowski, Z. W. 364
Rohsenow, W. M. 634
Roper, D. L. 479
Rose, A. 545
Rose, L. M. 168
Rosen, E. M. 23, 54, 172
Rosenzweig, M. D. 469
Ross, C. 795
Ross, T. K. 284
Rottenburg, P. A. 989
Rousar, I. 483
Rowe, D. 300
Rowley, R. L. 312
Rubin, F. L. 698, 769
Rubin, L. C. 341
Rudd, D. F. 5, 20, 24, 25, 29, 102, 973
Ruff, C. 305
Ruhemann, S. 361
Rushton, A. 408
Rushton, J. H. 473
Russel, J. 879
Russell, D. A. 367
Russo, T. J. 896
Rutledge, G. P. 315
Ryan, D. L. 479
Ryon, A. D. 443
Sandholm, D. P. 545
Santoleri, J. J. 107
Sargent, G. D. 448
Sarma, N. V. L. S. 742
Saunders, E. A. D. 634, 647, 649, 654, 765, 1002
Saxman, T. E. 303
Schechter, R. S. 25, 28
Scheiman, A. D. 850
Schettler, P. D. 331, 332
Schlunder, E. U. 634
Schmutzler, A. F. 335
Schneider, G. G. 459
Schnitzer, H. 111
Schrodt, V. N. 545
Schroeder, T. 415
Schultz, J. M. 84
Schweitzer, P. A. 284, 401, 410, 438, 448
Sconce, J. S. 984
Scott, K. 483
Scott, K. S. 434
Scott, R. 244
Scudder, C. M. 878
Seader, J. D. 342
Sedriks, A. J. 298
Seed, G. M. 795
Seider, W. D. 54, 169
Seifert, W. F. 900
Seki, H. 313, 508
1014
Sevens, G. 396
Sevryugova, N. N. 975
Shadbolt, N. 899
Shaddock, A. K. 303
Shah, A. N. 578
Shah, M. M. 736
Shannon, P. T. 169
Sharna 470
Shaw, R. 339
Shaw, S. J. 396
Shelley, S. 897
Shelton, D. C. 896
Sherwood, D. R. 218
Sherwood, T. K. 937
Shih, C. C. 745
Shinskey, F. G. 228, 232, 233
Shunta, J. P. 233
Sieder, E. N. 663
Sigmund, P. M. 552
Signales, B. 442
Siirola, J. J. 102
Silver, L. 721, 722
Silverman, D. 900
Simpson, D. 363
Simpson, L. L. 201, 219
Simpson, W. G. 363
Singer, S. C. 982
Singh, J. 105
Singh, K. P. 654, 795, 863, 869
Sittig, M. 989
Skellene, K. R. 745
Slusser, R. P. 667
Small, W. M. 750, 751, 752
Smith, B. D. 19, 516, 522, 523, 542, 544,
553, 562
Smith, E. 198
Smith, N. 479
Smith, P. 198
Smith, R. 124, 517
Smith, W. T. 315
Smoker, E. H. 512
Smolensky, J. F. 364
Snyder, N. H. 745
Soave, G. 341
Sohnel, O. 438
Sokolov, N. M. 975
Soler, A. I. 654, 795, 863, 869
Somerville, G. F. 502, 503, 545
Sorel, E. 503
Sorensen, J. M. 619
Souders, M. 316, 557
Southwell, R. V. 826
Speirs, H. M. 146
Spiegel, P. J. 459
Spires, G. L. 636, 744, 758
Squires, L. 318
Stairmand, C. J. 450, 453
Stavenger, P. 403
Steinmeyer, D. E. 723
Stephens, M. B. 141
Stephenson, R. M. 150, 153, 339, 989
Sterbacek, Z. 70, 314
AUTHOR INDEX
Sternling, C. V. 745
Stoecker, W. F. 25, 27, 28, 29
Stout, E. 304
Straitz, J. F. 364
Strauss 903
Strauss, N. 448, 450, 459
Stread, C. W. 342
Street, G. 744
Strelzoff, S. 150, 161
Strigle, R. F. 588, 592
Sugden, S. 335
Sullivan, S. L. 520, 544
Sundmacher, K. 547
Sutherland, K. 410
Sutherland, K. S. 416
Suziki, M. 446
Svarovsky, L. 408, 423
Swanson, A. C. 323, 324
Swanson, R. W. 548
Swearingen, J. S. 108, 479
Sweeney, R. F. 545
Taborek, J. 640, 671, 710, 716, 732, 745,
751
Tait, R. 392
Takeuchi, H. 601
Tang, S. S. 839
Tang, Y. S. 731
Tarleton, S. 408
Tate, G. E. 663
Tatterson, G. B. 470
Tausk, P. 70, 314
Taylor, B. T. 381
Taylor, J. H. 249
Ter Haar, L. W. 982
Thew, M. T. 423
Thiele, E. W. 505, 544
Thodos, G. 973
Thomas, W. J. 446, 578
Thome, J. R. 723, 731
Thrift, C. 565
Timmerhaus, K. D. 27, 219, 221, 222, 223,
253
Timoshenko, S. 795, 829, 834
Timperley, D. A. 295
Tinker, T. 669, 670
Tochigi, K. 313, 347, 508
Tomkins, A. G. 107
Tong, L. S. 731
Toor, H. L. 549
Tortorella, A. J. 896
Touloukian, Y. S. 311
Townsend, D. W. 111, 124
Treybal, R. E. 347, 597, 618, 619, 621
Tribus, M. 733
Trilling, D. C. 825
Trom, L. 757
Trouton, F. T. 328
Trowbridge, M. E. O’K. 418
Tsederberg, N. V. 320
Tsien, H-S. 829
AUTHOR INDEX
Tudhope, J. S. 321
Turner, M. 298
Uhl, W. W. 470, 474 5, 779
Ulrich, G. D. 253
Underwood, A. J. V. 525
Urbaniec, K. 27, 29
Usher, J. D. 758
Valle-Riestra, J. F. 266, 270
Van Dam, J. 984
van Edmonds, S. 744
Van Krevelen, D. W. 978
Van Winkle, M. 552
Veatch, F. 548
Vela, M. A. 186
Verburg, H. 561
Vital, T. J. 548, 598
Vivian, B. E. 198
Von Bertele, O. 201
Wakeman, R. 408
Walas, S. M. 201, 210, 341, 342, 346, 401, 428,
447, 546
Walk, K. 903
Walsh, R. 339
Walsh, T. J. 578
Walton, A. K. 403
Wang, J. C. 545
Wang, S. L. 339
Ward, A. S. 408
Ward, D. J. 721
Warde, E. 298
Wardle, I. 122
Watase, K. 313, 508
Waterman, L. L. 445
Watkin, A. T. 904
Watson, C. C. 5, 24, 25, 29, 973
Watson, F. A. 266
Watson, K. M. 329
Wattimena, F. 984
Webb, G. B. 341
Webb, R. L. 736
Webber, W. O. 768
Weber, H. 968
Weber, H. F. 321
Webster, G. R. 216
Weightman, M. E. 108, 479
Weil, N. A. 850
Weisert, E. D. 299
Wells, A. A. 287
Wells, G. L. 5, 27, 29, 168, 360, 392, 395
1015
Werner, R. R. 322
Wessel, H. E. 265
West, R. E. 253
Westerburg, A. W. 169
Westlake, J. R. 179
Westwater, J. W. 722
Whitaker, R. 897
White, S. L. 351
Whittle, D. K. 390
Wichterle, I. 331, 339
Wigley, D. A. 287
Wilcon, R. F. 351
Wilde, D. J. 25
Wilding, W. V. 312
Wilke, C. R. 333, 556, 577
Wilkinson, J. K. 266
Wilkinson, W. L. 473, 779
Williams, N. 29
Williams-Gardner, A. 428
Wills, C. M. R. 879
Wilson, G. M. 342
Wilson, G. T. 249
Wimpress, N. 771, 773
Windenburg, D. F. 825
Winn, F. W. 525
Winter, P. 169
Wojtasinski, J. G. 968
Wolosewick, F. E. 857
Wood, W. S. 360
Woods, D. R. 169
Wright, D. C. 301, 303
Yang, W. 312
Yang, W.-C. 455
Yarden, A. 745, 751
Yaws, C. L. 316, 320, 331, 527
Yilmaz, S. B. 742, 745
Yokell, S. 796
York, R. 313
Young, C. L. 347
Young, E. H. 768, 819, 828, 836, 847, 850, 857
Zanker, A. 423, 424
Zappe, R. W. 198
Zenz, F. A. 455
Zhavoronkov, N. M. 975
Zick, L. P. 847, 879
Zuber, N. 732, 733
Zughi, H. D. 470
Zuiderweg, F. J. 561, 566
Zundel, N. A. 312
Zwolinsk, B. J. 336
Subject Index
Note: Figures are indicated by italic page numbers, Tables by emboldened numbers
Absorption columns
costs 268
design of 604 9
flow-sheet calculations 186
packed 588, 594 7
plate efficiency 550 1
Acceptable corrosion rates 288 9
Acceptable risk, and safety priorities 390 2
Accident hazards, control of 394
Accuracy required, of engineering data 312 13
Acetone manufacture 63 6, 176 85, 508 12
Acid-resistant bricks and tiles 304
Acrylonitrile manufacture (design exercise)
973 5
Activity coefficients, liquid phase
correlations for 342 6
NRTL equation 345
UNIQUAC equation 346
Wilson equation 342 5
prediction of 346 8
at infinite dilution 347
by ASOG method 347
by group contribution methods 347 8
by UNIFAC method 347
from azeotropic data 346
from mutual solubility data 347
Acyclic form, design problem 23
Adiabatic expansion and compression 62
Adiabatic flash (distillation), calculations 501
Adsorption 446
Agitated thin-film evaporators 435, 436
Agitated vessels
baffles in 779
heat transfer in 778 81
power requirements 473 5
Agitation nozzles in jackets 775, 776
Agitators
costs 259
power consumption 473 5
selection of 472 3
side-entering 476
types 470 1
Air, compressed (supply) 264, 901
Air-cooled exchangers 637, 769, 770
Air filters 458 9
Alarms, safety 235
Algebraic method, for material balances 42 4
Allocation of fluid streams in heat exchangers
660
Aluminium and alloys 299 300
costs 293, 294
properties 285, 286
American cost figures, conversion of 249, 253
American Institute of Chemical Engineers (AIChE)
Center for Chemical Process Safety 390
Design Institute for Emergency Relief Systems
369
Design Institute for Physical Properties
312, 314
on HAZOP technique 381
on site selection and plant layout 892
plate efficiency prediction method 553 6
American National Standards Institute (ANSI) 12
flow-sheet symbols 134
standards on flanges 865
American Petroleum Institute (API) 12
API 620 standard 879
API 650 standard 879
API 661 standard 769
American Society of Mechanical Engineers (ASME)
12
on noise control 370
see also ASME code
American Society for Testing Materials (ASTM) 12
Ammonia, aqueous, enthalpy concentration diagram
74
Anchor bolt chair design, skirt supports
852, 856
Ancillary buildings 894 5
Aniline manufacture (design exercise) 984 9
Antoine equation 147, 328, 331, 513, 514
API see American Petroleum Institute
Aqueous wastes, treatment of 904 5
AS-EASY-AS spreadsheet program 125, 180
ASME code (pressure vessels) 795, 796, 873
ASOG method 347
Aspen DPS simulation software 169
ASPEN simulation software 169
Attainment, plant 7, 30, 143
Authorisation estimates 243 4
Autofrettage 878 9
Autoignition temperature 364
Automatic control schemes 228 9
Automatic control valves 199
Axial-flow compressors 83, 477, 478
Azeotropic data, estimation of activity coefficients
from 346
1017
1018
SUBJECT INDEX
Baffle cuts 650
Baffles
for condensers 650, 651
in agitated vessels 472, 779
in heat exchangers 641, 650 2
Bag filters 458
Balancing chemical equations 36 7
Ball valves 198
Bar (unit of pressure) 14
Bara (unit of pressure) 14
Barg (unit of pressure) 14
Barrels (unit of quantity) 14, 15
Base rings, skirt supports 850 1
Basis for calculations, choice of 40
Batch distillation 546
control of 235
Batch dryers 428
Batch processes 7
flow-sheet presentation 140
optimisation of 29 30
vs continuous processes 7
Batch reactors 483
Battery limits, meaning of term 253
Bed limiters, in packed columns 615
Bellman’s Principle of Optimality 29
Bell’s method for heat exchanger design 671,
693 702
bypass correction factor 696 7, 707
cross-flow zone pressure drop 698 9, 708
end zone pressure drop 702, 709
ideal cross-flow heat transfer coefficient 693 5
ideal tube pressure drop 699
leakage correction factor 697 8, 707 8
shell-side heat transfer coefficient 693
tube row correction factor 695 6, 706
window zone correction factor 696, 707
window zone pressure drop 699, 708 9
Belt conveyors 259, 481 2
Belt filters 413, 414
Benedict Webb Rubin (B W R) equation 341
Berl saddles 590, 591, 592
HTU calculations 600
Best Practicable Means (BPM) concept 905
Billion, meaning of term 36
Biological oxygen demand (BOD) 904, 905
Biological treatment of waste (activated sludge)
904
Biparte graphs 20 1
in examples 21 4
BLEVE (explosion) 366
Blind (blank) flanges 859
Block diagrams 134
BOD (biological oxygen demand) 904, 905
Boilers
costs 259
see also Fired heaters; Reboilers; Waste-heat
boilers
Boiling heat-transfer coefficient, estimation of 732
Boiling heat-transfer fundamentals 731 2
Boiling liquid expanding vapour cloud explosion
(BLEVE) 366
Bolted closures (pressure vessels) 816
Bolted flanged joints 858 67
Bowl classifiers 405
Boyko Kruzhilin correlation 713
BPM (Best Practicable Means) concept 905
Bracket supports 856 8
Branches and openings, compensation for 822 5
Break-even point, in cash flow 271
Brick linings 304
British Material Handling Board (BMHB), on design
of silos and bunkers 482
British Standards
BS 131 287
BS 490 482
BS 1553, Part 1 (piping diagram symbols) 134,
908
BS 1560 865
BS 1600 217
BS 1646 195
BS 2000 364
BS 2654 (storage tanks) 879
BS 2915 368
BS 3274 (heat exchangers) 642 4, 644, 647
BS 3606 645
BS 4504 (flanges) 865
BS 4994 (reinforced plastics vessels) 796
BS 5345, Part 1 367
BS 5501 367
BS 5908 365
BS 5938 (electrical equipment) 367
BS EN ISO 14401 903
BS/PD 5500 (pressure vessels) 216, 392, 795,
796, 811, 813, 815, 826, 860 1, 864, 867
on flow-sheet and piping diagram symbols 134,
195, 908
British Standards Institution (BSI) 12
Catalogue 295
British Valve and Actuators Manufacturers
Association (BVAMA), technical data manual
199
Brittle fracture, in metals 286
Bromley equation (film boiling) 734
Brown K10 (B K10) equation 342
Bubble-cap plates 558, 559, 561
Bubble-point calculations 498, 533
Bucket elevators 482
Budgeting estimates 243 4
Bunkers 482
Burn-out, boiling 732
Bursting discs 368
Butterfly valves 199
Bypass correction factor, heat exchangers 696 7,
707
Bypass streams, in material balances 53 4
CAD (computer-aided design)
drawings 11
flow-sheet drafting 140 1
flow-sheeting 168 71
heat exchangers 692 3
P & I diagrams 195
plant layout 898 9
SUBJECT INDEX
Calculation sheets 10 11
Calculations, basis of 40, 140
Callandria evaporators 435
Calorific value calculations, waste gases 106
Canned pumps 216
Capital charges 265 6
Capital costs
direct 251 2
estimation of 243 4
indirect 252 3
Carbon, as construction material 305
Carbon steel 295
costs 293, 294
properties 285, 286
Carbon steel pipe
costs 221
economic/optimum diameter calculations 221,
222 3
Cartridge plates (in columns) 562 3
Cascade control 231, 235
Cash flow 270 2
Cash-flow diagram 271 2
Centrifugal compressors 83, 259, 477, 478
Centrifugal filters 414, 420 2
Centrifugal pressure 879 81
Centrifugal pumps
characteristic (performance) curves 208, 209,
480
control of 210, 231
data sheet for 995
efficiency 207, 209, 480
operating ranges 480, 481
selection of 199 201
Centrifugal separators
gas solids 450 60
liquid liquid 446
Centrifuges 415 22
classification by particle size 416
classifying 406
costs 259
critical speed 882 3
disc bowl 417, 418
filtration 414, 415, 420 2
fixed-spindle 881
mechanical design of 879 83
precession in 883
scroll discharge 417 18
sedimentation 415 20
self-balancing 881, 883
solid bowl 418
tubular bowl 417
Ceramic packings 590, 591, 592
Ceramics 303 5
Chao Seader (C S) equation 342
Check lists, safety 392 4
Check valves 199
CHEMCAD simulation package 169
Chemical Abstracts 312
Chemical Engineering cost index 245, 248
Chemical engineering projects, organisation of
7 10
Chemical manufacturing processes, overview 5 7
1019
Chemical Marketing Reporter (CMR) 261
Chen’s method for forced convective boiling
736 40
Chlorine manufacture (design exercise) 982 4
Chlorobenzene manufacture (design exercise)
968 71
Chromatography 447
CIA (Chemical Industries Association), publications
378
Circulating liquor crystallisers 439, 440
Circulating magma crystallisers 438, 439, 440
Clad plate 294
Clamp-ring floating-head heat exchanger 643
Clarifiers 408 9, 410
Classification
centrifuges 416
crushing/grinding equipment 465
flanges 864
hazardous zones (electrical) 367
mixtures 350, 351
pressure vessels 795
Classifiers 405
Classifying centrifuges 406
Climate, site selection influenced by 894
Closed recycle systems, flow-sheet calculations
175
Coalescers 445, 446
Codes and standards 12 13
for heat exchangers 644 5
for pressure vessels 795 6
Coefficient of performance, heat pumps 111
Co-generation (combined heat and power)
900 1
Coils
heat transfer coefficients 637 8, 778
pressure drop in 778
Column auxiliaries 616
Column packings 304, 589 93
costs 259
Column pressure, selection of in distillation 496
Column sizing, approximate 557
Column tray data sheet 992
COMAH Regulations 394
Combined heat and power (cogeneration) 900 1
Combined loading on pressure vessels 831 44
Combustion
excess air in 45
heats of 80 1
Combustion gases, heat capacity data 69
Comminution equipment 465 8
selection of 465 7
Community considerations, in site selection 894
Compensation for branches and openings 822 5
Compound (high-pressure) vessels 877 8
Compressed air 901
costs 264
Compressibility factor 82, 315 16, 353
typical values 87
Compressibility functions 84
typical values 88 9
Compression of gases, work done during 81 2
Compressive stresses, pressure vessels 834 5
1020
SUBJECT INDEX
Compressors
axial-flow 83, 477, 478
centrifugal 83, 477, 478
costs 259
efficiencies 83, 84
electrical drives for 93
multistage 90 3
power calculations 93, 160 1
reciprocating 84, 477, 478
selection of 477, 478
types 478
Computer-aided design see CAD
Computer methods
cost estimation 278
distillation columns 542 57
plant layout modelling 898 9
process control 236, 238
project evaluation 278
risk analysis 395 6
Concrete, corrosion resistance 931, 933, 935
Condensation
heat transfer fundamentals 710
inside and outside vertical tubes 711 16,
714 15
inside horizontal tubes 716 17
mean temperature difference 717
of mixtures 719 23
on horizontal tubes 710 11, 725
Condensers 709 28
configurations 709
control of 230
costs 268
desuperheating in 718
pressure drop in 723
sub-cooling of condensate 718 19
Confined vapour cloud explosion (CVCE) 366
Conical sections and end closures (pressure vessels)
819 21
‘Coning’, in plate columns 566
Conservation of energy 60 1
Conservation of mass 34 5
Constraints, on flows and compositions 41
Construction categories, pressure vessels 813
Construction materials see Materials of construction
Contamination, by corrosion products 294
Contingency allowances 243, 252
Continuous circulation band dryers 430
Continuous processes 7
reactors 483 4
vs batch processes 7
Control
of condensers 230
of distillation columns 231 3
of heat exchangers 230 1
of major industrial accident hazards 394
of reactors 233 5
of reboilers 230 1
of toxic materials 363
of vaporisers 230 1
Control and instrumentation 227 9
Control of Major Accident Hazards (COMAH)
Regulations 394
Control of Substances Hazardous to Health
(COSHH) Regulations 363
Control systems 229 35
automatic 228 9
cascade control 231, 235
design guide rules 228 9
flow control 229
level control 229
pressure control 229
ratio control 231, 233
temperature control 230
Control valves
pressure drop across 201
selection and design of 199
symbols 195
failure mode 195 6
Convective boiling 735 40
Conversion, in chemical reactors 47 8, 184
Conversion factors for units 15
Conveyor dryers 430
Conveyors 481 2
costs 259
data sheet for 999
Cooler-condensers see Partial condensers
Cooling water 901
costs 264
COP (coefficient of performance) 111
Copper and alloys 299
costs 293, 294
properties 285, 286
Cornell’s method for prediction of HTUs in packed
columns 599 600, 607 8
Correction factor, for log mean temperature
difference, in heat exchangers 656 9
Corresponding states, physical properties 314
Corrosion 287 92
effect of stress on 290 1
erosion corrosion 291
galvanic 289 90
high-temperature oxidation 291
intergranular 290
pitting 290
uniform 288 9
Corrosion allowance 813
Corrosion charts 292, 917 35
Corrosion fatigue 291
Corrosion products, contamination by 294
Corrosion rate
acceptable rates 288 9
definition 288
effect of concentration on 289
effect of stress on 290
effect of temperature on 289
Corrosion resistance
designing for 305
listed (chart) 917 35
selecting for 292 3
stainless steels 297 8
COSHH Regulations 363
Cost escalation 245 7
Cost estimation
computer programs for 278
SUBJECT INDEX
cost of preparing estimates 244
factorial method 219, 250 3, 260
for piping 219 20
historical-costs approach 247 9
in Dow F & E Index calculations 375 7
operating costs 261 70
rapid methods 247 50
step counting methods 249 50
Cost indices 245
Costing 243 70
Costs
capital 244, 265 6
construction materials 293 4, 302
equipment 253 60
fixed 260 1, 267, 270
insurance 266
laboratory 265
maintenance 262
miscellaneous materials 262
operating labour 262, 265
plant overheads 265
plastics 302
raw materials 262, 263 4
royalties and licence fees 266
shipping and packaging 262
supervision 265
taxes 266
utilities (services) 262, 264
variable 261, 267, 269
CPE plant cost index 245, 246
Creep 287
Critical buckling pressure 825 6
Critical buckling stress 834
Critical constants 336 8
Critical heat flux
forced-convection reboilers 741
in boiling 733
kettle reboilers 751
thermosyphon reboilers 745
Critical speed, centrifuges 882 3
Cross-flow plates 557 8
Crushers
costs 259
selection of 465 8
Crystallisation 437 40
selection of equipment 440
Crystallisers
circulating liquor 439, 440
circulating magma 438, 439, 440
scraped-surface 438 9, 440
tank 438, 440
CVCE (explosion) 366
Cyclone separators (gas liquid) 460
Cyclones 404 5, 449, 450 60
design of 450 7
for liquid liquid separation 446
for liquid solid separation 422 6
for solid solid separation 404 5
performance curves 452 3
pressure drop in 453 5, 456 7
reverse-flow 450, 451
1021
Cylindrical shells, buckling under external pressure
825 8
Cylindrical vessels 479, 801 2, 815
optimum proportions 26 7
weight calculations 836
Data collection 3
Data sheets, equipment 990 1001
Dead weight loads on vessels 835 6, 841 2
Decanters 440 5
piping arrangement for 444 5
Dechema Corrosion Handbook 292
DECHEMA data collection 339, 343
DECHEMA liquid liquid equilibrium data collection
339, 346, 619
DECHEMA vapour liquid equilibrium data
collection 343, 346
Decibel (unit of noise measurement) 370
Deflagrations 365 6
Deflection of tall columns 839
Degrees of freedom, in design 16
Delaware research program, heat exchanger design
671
Demineralised water 901
costs 264
Demister pads 460, 723
Dense-medium separators 406
Density 314 16
of gases and vapours 315 16
of insulation 836
of liquids 314
prediction using equations of state 353
Depreciation 266, 272
DePriester charts 348, 349 50, 500
Description rule procedure (distillation) 502
Design
nature of 1 5
selection of solutions 4 5
Design constraints 1, 2
external constraints 2, 141
in flow-sheet calculations 141
internal constraints 2, 141
Design Council guide 284
Design factors (factors of safety) 13
DESIGN II simulation package 169
Design Institute for Emergency Relief Systems
(DIERS) 369
Design loads, for pressure vessels 814
Design objectives 3
instrumentation and control schemes 227 8
Design pressure, pressure vessels 810
Design process 2
Design projects (exercises) 965 89
2-ethylhexanol 965 8
acrylonitrile 973 5
aniline 984 9
chlorine (from hydrogen chloride) 982 4
chlorobenzenes 968 71
hydrogen (from fuel oil) 978 82
methyl ethyl ketone 971 3
urea 975 8
1022
SUBJECT INDEX
Design relationships 16
Design strength (stress), pressure vessels
811 12
Design stress factor 811
typical values listed 811
Design temperature, pressure vessels 810
Design variables
and information flow 15 19
in distillation 20, 501 3
selection of 19 20
Desuperheating in condensers 718
Detonations 365
Dew-point calculations 498, 533
Diaphragm pumps 480, 481
Diaphragm valves 198
Dichloroethane (EDC), manufacture of 147 50
DIERS (Design Institute for Emergency Relief
Systems) 369
Differential condensation 720
Differential energy balance 100
Diffusion coefficients (diffusivities) 331 4
gases 331 2
liquids 333 4
Dilation of vessels 809
Dimpled jackets 776, 777
DIN 28004 (symbols) 134, 195
DIPPRTM databases 312
Direct capital costs 251
Direct-contact heat exchangers 766 7
Direct-heated evaporators 434
Dirt factors (fouling factors) 638, 640
Disc bowl centrifuges 417, 418
Disc filters 413
Discontinuity stresses 810
Discounted cash flow (DCF) analysis 272 3
Discounted cash flow rate of return (DCFRR)
273 4, 275
Dissolved liquids, separation of 446 7
Dissolved solids, separation of 434 40
Distillation 446, 494 6
basic principles 497 501
batch 546
binary systems, design methods 503 15
design variables in 501 3
equimolar overflow 504 5
low product concentrations 507 12
multicomponent, short-cut methods 517 42
number of columns 517
operating lines 505, 506, 511
q-line procedure 505 6, 509 10
reactive 547
rigorous solution procedures 542 6
sequencing of columns 517
short-cut methods 517 42
stage efficiency 506, 507
stage vapour and liquid flows not constant 507
steam 546 7
see also Multicomponent distillation
Distillation columns
control of 231 3
design of 493 557
column pressure 496
feed point location 496
reflux considerations 495 6
energy balance in 63 6
flow-sheet calculations 186 7
packed 593 4
with heat pumps 110 11
see also Plate construction; Plate efficiency
Distribution coefficient (K value) 342
Dollars (US$), conversion to Pounds Sterling (£)
249, 253
Domed heads (pressure vessels) 816, 818 19
Double pipe heat exchangers 255, 768 9
Double seals 216
Double tube-sheets, in heat exchangers 653
Dow fire and explosion index (Dow F & E I)
371 81
calculations 379 81
form for 374, 380
procedure for 371, 372
general process hazards 372 3
material factors 371 2, 373
potential loss 375 7
preventive and protective measures 377
special process hazards 373, 375
Downcomer residence time 578 9
Downcomers 558, 563 4
back-up of liquid in 577 9
Dowtherm heat-transfer fluid 105, 900
Drawings 10, 11
computer-generated 11
Dropwise condensation 710
Drum dryers 433 4
Drum filters 259, 413
Dryers
conveyor 430
costs 259
drum 433 4
fluidised-bed 431
pneumatic 432
rotary 259, 430 1
spray 432, 433
tray 428 9, 430
Drying 426 34
equipment selection for 427
Duplex steels 298
Dust explosions 366
Dynamic programming (optimisation) 29
Dynamic pumps
selection of 199 201
see also Centrifugal pumps
Dynamic wind pressure 838 9
DYNSIM simulation package 169
Earthquake loads 839 40
Eccentric loads, on tall vessels 840
Economic evaluation of projects 270 8
Economic pipe diameter 219 21
for carbon steel 221
for stainless steel 221
general equation 220
SUBJECT INDEX
Economic Trends (Central Statistical Office)
249
Effectiveness NTU method (heat exchanger
analysis) 636
Effluent disposal 893 4, 902
Elastic stability 798, 834 5, 843 4
Elasticity modulus, typical values 286
Electric motors, efficiencies listed 93
Electrical drives, for compressors/pumps 93
Electrical energy 62
Electrical equipment, as ignition source(s) 367
Electricity 15, 900
costs 264
Electrostatic precipitators 459, 460
Electrostatic separators 407, 408
Ellipsoidal heads (pressure vessels) 817, 819
Encyclopedia of Chemical Technology (Kirk &
Othmer) 310
Endothermic reactions 60
ENERGY 1 (simple energy balance program) 93 5
code listing 94
examples of use 95 7, 162, 163
Energy
conservation of 60 1
electrical 62
equivalence with mass 34
heat 62
internal 61
kinetic 61
potential 61
Energy balances
calculations 93 9
fundamentals 60 132
in distillation 497, 504
over reactors 76
steady state 62 6
unsteady state 99 100
see also MESH equations
Energy recovery 101 11
by heat exchange 101 2
by heat pumps 110 11
by waste-heat boilers 102 3
from high-pressure streams 107 9
from high-temperature reactors 103 5
from vent gases 105 7
from wastes 107
maximum, heat exchanger network design for
118
savings from 101
Engineered safety 361
Engineering data, accuracy required 312 13
Engineering Index/Engineering Information 312
Engineering Sciences Data Unit (ESDU) 312
ESDU 73031 design guide 695
ESDU 78031 design guide 778
ESDU 83038 design guide 671, 706
ESDU 84023 design guide 711, 723
ESDU 87019 design guide 654
ESDU 92003 design guide 663
ESDU 93018 design guide 663
ESDU 98003 98007 design guides 636
Wind Engineering Series 839
1023
Enthalpy
calculations 66
definition 63
of formation see Heats of formation
of mixtures 71 3
of reaction see Heats of reaction
of vaporisation see Latent heat
specific, calculation of 67 8
prediction using equations of state 353
Enthalpy concentration diagrams 73 5
nitric acid manufacture 165
Enthalpy pressure temperature entropy diagrams
see Mollier diagrams
Entrainment
from sieve plates 570 1
plate design affected by 556 7
Environmental auditing 906
Environmental considerations
in plant design 902 6
in site selection 893 4
Environmental control legislation 905
Environmental impact assessment 906
Equal area method of compensation 823 5
Equation-based simulation programs 169 71
Equations of state 341 2
density prediction using 353
enthalpy prediction using 353
Equilibria data sources 339, 343
Equilibrium flash calculations (distillation)
499 501
Equilibrium separators, flow-sheet calculations
187
Equilibrium stages (in distillation) 498
Equipment costs, estimation of 253 60
Equipment data/specification sheets 10, 11,
990 1001
Equipment selection, specification and design
400 92
Equivalence, of mass and energy 34
Equivalent (hydraulic mean) diameter, heat
exchanger tubes 663 4
Equivalent pipe diameter(s) 204, 205 6
Erbar Maddox correlation, multicomponent
distillation 516, 523, 524, 529 30
Erosion corrosion 291
ESDU see Engineering Sciences Data Unit
Essential materials see Raw materials
Estimates
types 243 4
see also Cost estimation
Ethyl alcohol, specific enthalpy calculation 67 8
Ethylene, heat capacity calculation 71
2-Ethylhexanol manufacture (design exercise)
965 8
Eucken’s equation 321
European Chemical News (ECN) 261
European Standards
EN 1092 865
EN 13445 795
EN ISO 14401 903
European Union (EU), regulations and guidelines
362, 796, 905
1024
SUBJECT INDEX
Evaporators 434 7
auxiliary equipment 437
costs 259
direct-heated 434
forced-circulation 435, 436
long-tube 435
selection of 436 7
short-tube 435
wiped-film 435, 436
Excess air in combustion 45
Excess reagent 46
Exothermic reactions 60, 75
Expansion of gases, work done during 81 2
Expert systems, in plant layout modelling 899
Explosions 365 6
confined vapour cloud 366
deflagrations 365 6
detonations 365
dust 366
sources of ignition 366 8
unconfined vapour cloud 366
see also BLEVE; CVCE
Expression (pressing) 426
External floating-head heat exchangers 643, 644
External pressure, vessels subject to 825 9
Extraction see Solvent extraction
Extraction columns 623
flow-sheet calculations 186
Extraction equipment, selection of 617 18
Extractor design 618 23
Extrinsic safety 361
Fabrication properties of metals and alloys 285
Factorial method of costing 250 3
example of use 219
procedure 260
Factors of safety 13
Failure mode, control valves 195 6
Failure, theories of 797 8
Fatal Accident Frequency Rate (FAFR) 391
Fatigue 286
in pressure vessels 872
Fault trees, in hazard analysis 389 90
Feed preparation 6
Feed-point location (distillation) 496, 506, 526
Feed stocks see Raw materials
Fenske equation 516, 523 5
Film boiling 734
Film mass transfer coefficients 601
Filmwise condensation 710
Filter media 410 11, 458
Filters
bag 458
belt 413, 414
centrifugal 414, 420 2
costs 259
disc 413
drum 259, 413
factors when selecting 411
gas solids 458 9
leaf 412 13
liquid solid 412 14
nutsche 412
pan 414
plate-and-frame 259, 412
Filtration
of gases 458 9
of liquids 409 14
Filtration centrifuges 415, 420 2
types 422
Fin effectiveness 767
Finned tubes, in heat exchangers 767 8
Fire bricks 304 5
Fire and explosion index see Dow fire and explosion
index
Fire precautions 365, 377
Fire protection of structures 370
Fire-tube boiler, as waste-heat boiler 104
Fired heaters 635, 769 75
construction of 770 1
design 771 4
heat transfer in 772 3
pressure drop in 774
stack design 774 5
thermal efficiency 775
types 770, 771
Fixed capital 244
estimation factors 252
Fixed operating costs 260 1, 267, 270
Fixed-spindle centrifuges 881
Fixed-tube plate exchanger 642, 1003
Flame arrestors/traps 364
Flame-proofing of equipment 367
Flammability 363 5
limits 364, 365
Flanged joints 217, 858 67
design of flanges 862 5
flange faces 861 2
gaskets in 859 61
types of flanges 858 9
Flanges
blind (blank) 859
classification of 864
on pressure vessel ends and closure 816, 817,
819
standard 865 6, 960 4
Flash distillation 17 18, 499
calculations 499 501
information flow in calculations 20
Flash dryers 432
Flash-point 364
Flat plate end-closures 817 18
Flat plates, stresses in 805 8
Flixborough disaster 294, 366
Floating cap plates 559 60
Floating-head heat exchangers 642 3, 1005 6
Flooding
in extraction columns 623
in packed columns 601
in plate columns 566
in vertical condenser tubes 713
FLOSHEET software 141
example of use 137
SUBJECT INDEX
Flotation separators 407
Flow control 229
Flow-induced vibrations, in exchanger tubes 653 4
Flow-sheet calculations
basis for calculations 142 3
scaling factor 143
time basis 142 3
combined heat and material balances 144 68
design constraints 141
dichloroethane manufacture 147 50
equilibrium stage 143 4
fixed stream compositions 144
liquid liquid equilibria 149 50
liquid vapour equilibria 146 9
manual 141 68
nitric acid manufacture 150 68
reactors 143
water gas reaction 144 6
Flow-sheet presentation 133 41
basis shown for calculations 140
block diagram 134
computer-aided drafting 140 1
equipment identification 140
examples 136 8
information to be shown 135
layout 139
nitric acid plant 136 7
of batch processes 140
pictorial representation 134
precision of data 139 40
stream flow-rates 134
symbols 134
utilities (services) 140
Flow-sheeting 133 93
computer-aided 168 71
simulation programs 168 71
Flows and compositions, constraints on 41
Fluid streams, allocation of, in heat exchangers
660
Fluidised-bed dryers 431
Fluidised-bed reactors 485
Fog formation in condensers 723
Forced-circulation evaporators 435, 436
Forced-circulation reboilers 729
design of 740 1
Forced-convective boiling coefficient, estimation of
736 40
Forster Zuber correlation 732
Fouling, shell-side pressure drop affected by 705
Fouling factors (coefficients) 638, 640, 757
Francis weir formula 572
Friction factors
cross-flow tube banks 700
heat exchanger tubes 668, 748
pipes 202
shell-side 674
Froth flotation processes 407
Froth height, in downcomer 578
Fuel, costs 264
Fugacity coefficient 339, 340, 353
Full-faced flanges 861
Fuller equation 331, 585
1025
Furnaces
costs 259
see also Fired heaters
Gallons, imperial (UK) compared with US 14 15
Galvanic corrosion 289 90
Gas-cleaning equipment 448 60
selection of 449
Gas holders 479
Gas liquid separators 460 5
horizontal 463 5
settling velocity in 461
vertical 461 2
Gas oil, physical properties 680
Gas solids separation 448
Gas solids separators
cyclones 449, 450 60
filters 458 9
gravity settlers 448, 449
impingement separators 448, 449, 450
Gas solubilities 351
Gaseous wastes
energy recovery from 105 7
treatment of 903
Gases
costs 264
densities 315 16
diffusion coefficients 331 2
mixing of 468
pressure drop calculations 202
storage of 479
thermal conductivities 321 2
transport of 477 9
viscosities 320
Gasketed plate heat exchangers 255, 638,
756 64
Gaskets 757, 859 61
Gate valves 197, 198
pressure loss across 204
Geddes Hengstebeck equation 523, 526 8
Glass
as construction material 304
corrosion resistance 931, 933, 935
Glass fibre reinforced plastics (GRP) 302 3
see also Thermosetting materials
Glass linings 304
Globe valves 198
pressure loss across 204
Gold, as construction material 301
Graphite, corrosion resistance 931, 933, 935
Gravity settlers (gas solids separators)
448, 449
Grayson Stread (G S) equation 342
Grid representation, heat exchanger networks 117
Grinding 465
selection of equipment 465 7
Grizzly screens 402
Group contribution techniques, physical properties
predicted using 314, 321, 339, 347 8
Guest’s theory 798
1026
SUBJECT INDEX
Half-pipe jackets 775 6
Hardness of materials 286
and comminution equipment 465
typical values 286
Hastelloys 299
Hazard analysis 389 90
see also Dow Index; Mond Index
Hazard and operability (HAZOP) studies 381 9
basic principles 381 2
guide words explained 383, 384
procedure 384 5
worked example 385 9
Hazardous wastes, disposal/treatment of 903
Hazardous zone classification (electrical) 367
Hazards 361 70
explosions 365 6
flammability 363 5
high-temperature 369 70
ionising radiation 368
noise 370
pressure 368 9
toxicity 361 3
Heads and closures for pressure vessels 815 22
choice of 816 17
conical ends 819 21
domed ends 816, 817, 818 19
flat ends 816, 817 18
Health & Safety at Work etc. Act (HSAWA) 363
Health & Safety Executive (HSE) 363, 394, 395
Heat capacity 67, 322 8
effect of pressure on 70 1
gases 325 8
ideal gas state 70
mean 68 9
solids and liquids 322 5
Heat cascade, in process integration 116 17
Heat exchange, energy recovery by 101
Heat exchanger networks 101 2, 117 23
design above pinch temperature 118 19
design below pinch temperature 119 20
design for maximum energy recovery 118
grid representation 117
minimum number of exchangers 121 2
minimum temperature difference in 114, 122 3
in threshold problems 123 4
Heat exchangers
air-cooled 769, 770
allocation of fluid streams 660
analysis by effectiveness NTU method 636
CAD design 692 3
control of 230 1
costs 254 5
data sheets for 993 4
design procedures 635 6, 670 709, 684
direct-contact 766 7
double-pipe 255, 768 9
finned tubes in 767 8
fluid physical properties 661
gasketed plate 255, 756 64
low-fin tubes in 768
mean temperature difference in 655 9
minimum temperature difference in 122 3
plate-fin 764 5
pressure drop in 661
pressure-drop limitations of design methods
705 6
shell-and-tube 254, 640 62
shells in 647
spiral 765
standards and codes for 644 5
tube-plates/sheets in 647 9, 867 9
tubes in 645 7
types 634
welded plate 764
see also Shell and tube exchangers
Heat, meaning of term 62
Heat pumps 110 11
performance coefficient 111
Heat transfer
basic theory 635 6 j-factor 664 6
to vessels 775 81
Heat transfer coefficients
agitated vessels 778 81
boiling 732
mixtures 752
coils 778
condensation of mixtures 721 2
condensing steam 717
convective boiling 736, 740
film boiling 734
overall 635, 636 8
typical values 637 8, 639
plate heat exchangers 759 60, 763
shell-side 677 8, 681 2, 687 8, 693, 708
tube-side 662 6, 676 7, 681
water in tubes 666
Heat transfer coils 637 8, 778
Heat transfer fluids 105, 900
Heats of combustion 80
nitrogen compounds 80
Heats of formation 79, 339
Heats of mixing (solution) 71 3
Heats of reaction 75 9
calculation of 79, 80
correction for temperature 75
effect of pressure on 77 9
prediction of 339
standard 75
Height of equivalent theoretical plate (HETP) 498
packed columns 593 4
Height of equivalent theoretical stage (HETS),
extraction columns 623
Height of transfer unit (HTU)
prediction for packed columns 597 602
Cornell’s method 599 601, 607 8
nomographs 602
Onda’s method 601 2, 608 9
typical values 598
Hemispherical heads (pressure vessels) 817,
818 19
Hengstebeck’s method, multicomponent distillation
518 21
Henry’s law 351
Heterogeneous reactions 484
SUBJECT INDEX
High-alloy stainless steels 298
High-pressure streams, energy recovery from
107 9
High-pressure vapour liquid equilibria 348
High-pressure vessels 795, 873 9
compound vessels 877 8
fundamental equations 873 6
High-temperature hazards 369 70
High-temperature materials 287
High-temperature oxidation, of steels 291
High-temperature reactors, energy recovery from
103 5
Historical-costs approach (cost estimation) 247 9
Hold-down plates, in packed columns 615
Homogeneous reactions 484
Hoppers 482
HSAWA see Health & Safety at Work etc. Act
HTFS (Heat Transfer and Fluid Services) 634, 692,
742, 744
HTRI (Heat Transfer Research Inc.) 634, 640, 742,
751
HTU see Height of transfer unit; Transfer units
Hydraulic conveying 482
Hydraulic gradient, on plates 574
Hydraulic jigs 405, 406
Hydraulic mean diameter, in heat exchangers
663 4
Hydraulic presses 426
Hydrocarbons, K-values 348
Hydrocylones 404 5, 422 6, 446
Hydrogen embrittlement 292
Hydrogen manufacture (design exercise) 978 82
Hydroseparators 405
Hygiene, industrial 362
Hypac packing 590, 591
Hypalon 303
Hyprotech program suite 169, 517
HYSYS simulation package 169
ICARUS program 278
Ideal tube bank
heat transfer coefficients 693 5
pressure drop 699
Ignition sources 366 8
Immiscible solvents 623
Imperial gallons (UK) 14 15
Impingement separators (gas solid) 448, 449, 450
Incineration of wastes 107, 903, 904
Inconel 287, 299
Independent components, number of 40 1
Indirect capital costs 252 3
Industrial hygiene 362
Inert gas 902
costs 264
Inflammable see Flammability
Inflation (cost) 245 7, 274
Information flow
and design variables 15 19
and structure of design problems 20 4
diagrams 171, 172, 177
Information sources
1027
on manufacturing processes 309 11
on physical properties 311 12
Inherently safe equipment 361
see also Intrinsically safe equipment
In-line mixers 469 70
Institute of Metallurgists 286
Institution of Chemical Engineers (IChemE)
on cost estimation 221, 249, 250, 251, 253
on dust and fume control 448
on process integration 111, 120, 122, 124
on safety 361
on waste minimisation 902
Instrumentation and control objectives 227 8
Instrumentation symbols 196 7
Instruments 227
Insulation, density 836
Insurance costs 266
Intalox saddles 590, 591
Integral condensation 720 1
Integral heats of solution 72 3
Intergranular corrosion 290, 298
Interlocks (safety) 236
Internal coils 777 8
Internal energy 61
Internal floating-head heat exchangers 642 3
Internal reboiler 730
International Critical Tables (ITC) 311
Internet sources 311
Interval temperature, in problem table method 115,
116
Intrinsic safety 361
Intrinsically safe equipment (electrical) 361, 367
Investment criteria 275
Ion exchange 447
Ionising radiation 368
Iron and alloys 295 6
costs 293, 294
properties 285, 286
Isentropic efficiency 82, 83, 84
Isentropic expansion and compression 62
Isentropic work, calculation of 82
ISO (International Organization for Standardization)
12
Isometric drawings, piping 223
Isothermal expansion and compression 62
j-factor, in heat transfer 664 6
Jacketed vessels 775 7
heat transfer in 638, 777
mechanical design of 825 31
Jackets
heat transfer in 777
pressure drop in 777
Joint efficiency, welded joints 812 13
Journal of Chemical Engineering Data 312
K-values 342
for hydrocarbons 348
Kern’s design method for heat exchangers 671 93
overall heat transfer coefficient 678, 682
1028
SUBJECT INDEX
Kern’s design (Continued)
pressure drop calculations 679, 682 3
procedure 672 5
shell nozzle pressure drop 675
shell-side coefficient calculations 677 8, 681 2
tube-side coefficient calculations 676 7, 681
Kettle reboilers 644, 729, 730, 731
design of 750 5
Key components in multicomponent distillation,
selection of 516
Kinetic energy 61
Kirkbride equation, in multicomponent distillation
526, 530 1
Knovel information sources 311
Laboratory costs 265
Labour availability, site selection influenced by
893
Labour costs 262, 265
Ladders, weights 836
Lamé’s equations 874
Land considerations, in site selection 894
Landfill 904
Lang factors 251
Lantern rings, in pump shaft seals 214
Lap-joint flanges 859
Latent heat of vaporisation 328 30
effect of temperature on 329
of mixtures 329 30
LD50 (lethal dose fifty) 362
Leaching 446, 447
Lead, as construction material 285, 286, 300
Leaf filters 412 13
Leakage correction factor, heat exchangers 697 8,
707 8
Lee Kesler Plocker (L K P) equation 341
Legislation, environmental control 905
Level control 229
Lewis Matheson method, in multicomponent
distillation 519, 543 4
Lewis Sorel method (distillation) 504 5
Licence fees 266
Limiting reagent 46
Linear algebra methods, multicomponent distillation
545 6
Linear programming (optimisation) 29
Liquid-cyclones 404 5, 422 6
Liquid density 314 15
Liquid distributors, in packed columns 610 11,
612 13
Liquid gas separators 460 5
Liquid hold-up, in packed columns 615 16
Liquid liquid equilibria 348
in flow-sheet calculations 149 50
Liquid liquid extraction 617 24
of dissolved liquids 447
see also Solvent extraction
Liquid liquid separators 440 6
Liquid phase activity coefficient
ASOG method 347
sour water 348
UNIFAC method 347
UNIQUAC equation 346
Liquid redistribution, in packed columns 612 14
Liquid solid separators 408 34
Liquid vapour equilibria see Vapour liquid
equilibria
Liquid vapour separators 460 5
Liquid viscosities 316 20
effect of pressure 319
of mixtures 319 20
variation with temperature 317 19
Liquid wastes
energy recovery from 107
treatment of 903 4
Liquids
density 314
diffusion coefficients 333 4
heat capacities 322 5
mixing of 468 76
storage of 481, 879
thermal conductivities 321
transport of 479 81
Loads, on pressure vessels 814, 835
Local community considerations, in plant location
894
Local taxes 266
Location considerations 892 4
Lockhart Martinelli two-phase flow parameter 736
Logarithmic mean temperature difference (LMTD)
655 6
correction factors for heat exchangers 656 9
Long-tube evaporators 435
Loss prevention 360 99
check list 392
Low-fin tubes, in heat exchangers 768
Low-grade fuels, energy recovery from 105
M-TASC software 692
McCabe Thiele method, in distillation 505 6,
521, 579, 585
Magnetic separators 407
Mains frequencies, in UK and USA 15
Maintenance 896
costs 262
Major Accident Prevention Policy (MAPP) 394
Major hazard installations 394, 840
Manufacturing processes, sources of information on
309 11
Marketing area, site selection affected by 892 3
Marshall and Swift (M & S) equipment cost index
245
Mass
conservation of 34 5
equivalence with energy 34
Mass transfer coefficients, film (column) 601
Material balances
by-pass streams affecting 53 4
choice of basis for calculations 40
choice of system boundary 37 40
constraints on flows and compositions 41 2
in distillation 497, 504
SUBJECT INDEX
fundamentals 34 59
general algebraic method 42 4
general procedure 56 7
number of independent components 40 1
purge affecting 52 3
recycle streams in 50 2
simple programs 168
tie components in 44 6
units for compositions 35 6
unsteady-state calculations 54 6
see also MESH equations
Material factors, in Dow F & E Index 372 3,
374
Material properties 284 95
corrosion resistance 287 92
creep 287
effect of temperature on 287
fatigue 286
hardness 286
stiffness 285
tensile strength 285
toughness 286
Materials of construction 295 305
aluminium and alloys 299 300
bricks and tiles 304
carbon 305
copper and alloys 299
corrosion chart 917 35
costs 293 4
fabrication chart 285
glass 303 4
Hastelloys 299
Inconel 287, 299
iron and steel 295 6
lead 300
mechanical properties 284 7
Monel 298 9
plastics 301 3
platinum 301
for pressure vessels 811, 812
refractories 304 5
stainless steels 296 8
stoneware 304
tantalum 300
titanium 300
zirconium and alloys 300
Matrix exchangers 764
Maximum heat flux see Critical heat flux
Maximum principal stress theory of failure 797
Maximum shear stress 797, 876
Maximum shear stress theory of failure 797 8,
834, 876
Maximum strain energy theory of failure 798
Mean heat capacities 68 9
Mean temperature difference
in condensers 717
in heat exchangers 655 9
in reboilers/vaporisers 752
Mechanical design 794 891
centrifuges 879 83
jacketed vessels 825 31
piping systems 216 18
1029
pressure vessels 794 814
thin-walled vessels 815 25
Mechanical properties 284 7
effect of temperature on 287
Mechanical seals 214 16
Membrane filtration 434
Membrane stresses in shells 798 805, 879
MESH (Material balance, Equilibrium, Summation,
Heat energy) equations 498, 502, 515
Metals and alloys 295 301
corrosion resistance (chart) 918 23
costs 293
fabrication properties 285
mechanical properties 286
physical properties 297, 662
Methyl ethyl ketone manufacture (design exercise)
971 3
Microprocessors, in process control 236, 238
Minimum number of heat exchangers in network
121 2
Minimum reflux ratio 495
Underwood equation 525 6
Minimum shell thickness (heat exchangers) 647
Minimum temperature difference, in heat exchangers
114, 122 3
Minimum wall thickness, pressure vessels 814
Miscellaneous materials, costs 262
Miscellaneous pressure losses 202, 204
Mixers see Mixing equipment
Mixing
of gases 468
of liquids 468 76
of pastes and solids 476
Mixing equipment 468 76
data sheet for 998
flow-sheet calculations 185
for gases 468
for liquids 468 76
for solids and pastes 476
Mixtures
boiling heat transfer coefficients 744, 752
classification of 350, 351
condensation of 719 23
enthalpy 71 3
heat capacities 323
latent heat of vaporisation 329 30
surface tension 335
thermal conductivity 322
viscosity 319 20
Modular construction 897
Mollier diagrams 82 4
Mond Index 378 9
Monel 298 9
costs 293, 294
properties 285, 286
Mostinski equation 733, 740
Multicomponent distillation
distribution of non-key components 526 8
general considerations 515 17
key components 516
non-key components 516, 526 8
number and sequencing of columns 517
1030
SUBJECT INDEX
Multicomponent (Continued)
plate efficiency prediction 556
pseudo-binary systems 518 21
rigorous solution procedures 542 6
short-cut methods 517 42
Erbar Maddox method 523, 524, 529 30
Fenske equation 523 5
Geddes Hengstebeck equation 523, 526 8
Hengstebeck’s method 518 21
Kirkbride equation 526, 530 1
Smith Brinkley method 522 3
Underwood equation 525 6
Multilayer pressure vessels 877 8
Multiple pinches 124
Multiple utilities (pinch technology) 124
Multistage compressors 90 3
Murphree plate efficiency 547
NACE (National Association of Corrosion
Engineers), corrosion data survey 291, 292
Narrow-faced flanges 862
Net cash flow 271, 272
Net future worth (NFW) 272, 275
Net positive suction head (NPSH) 212 13
Net present worth (NPW) 272, 275
NFPA (National Fire Protection Association),
publications 369
NFV see Net future worth
Nickel and alloys 298
costs 293, 294
properties 285, 286
Nitration acid 41
Nitric acid manufacture 150 68
absorber 156 8, 166 8
air compressor 387
air filter 387
ammonia vaporiser 161, 388
cooler-condenser 153 6, 164 6
energy recovery from 108 9, 168
hazard evaluation calculations 380 1
HAZOP study 385 9
mixing tee 162
reactor (oxidiser) 151 3, 162, 389
waste-heat boiler 153, 163 4
Nitrogen compounds, heats of combustion 80
Noise 370, 905
Nomographs, prediction of HTUs in packed columns
602
Non-key components, distribution of, in
multicomponent distillation 526 8
Non-Newtonian fluids, pressure drop calculations
202
Non-return valves 199
Nozzles, in jacketed vessels 775, 776
NPSH (net positive suction head) 212 13
NPV see Net present worth
NRTL (non-random two-liquid) equation 345,
347
NTU (Number of Transfer Units), in heat exchangers
636
Nucleate boiling 732
Number of columns 517
Number of heat exchangers in network 121 2
Number of independent components 40 1
Number of velocity heads
heat exchangers 667
pipe fittings and valves 204
Nusselt model of condensation laminar flow 710
Nusselt number, heat exchangers 662 3, 664
Nutsche filters 412
Occupational Exposure Limit (OEL) 362
O’Connell’s correlation (plate efficiency) 550 1
Oldershaw column 548
Onda’s method for prediction of HTUs in packed
columns 601 2, 608 9
Openings, compensation for 822 5
Operating costs 260 70
estimation of 261 70
Operating labour costs 262, 265
Operating lines (distillation) 505, 506, 511
Operating manuals 11
Optimisation 24 30
analytical methods 27
dynamic programming 29
general procedure 25
gradient method 29
linear programming 29
method of steepest ascent/descent 29
multiple variable problems 27 9
of batch/semi-continuous processes 29 30
of cylinder 26 7
of shell-and-tube exchanger 690, 692
search methods 28 9
simple models 25 7
Optimum pipe diameter 219 22
Optimum proportions, cylindrical vessels
26 7
Optimum reflux ratio 496
Optimum sequencing of columns 517
Organisation, of chemical engineering projects
7 10
Orifice scrubbers 459
Oscillating screens 403
Oslo crystalliser 439
Ovality (out-of-roundness) of vessels 826 7
Overall heat transfer coefficients 635, 636 8
definition 635
typical values 637 8
Overheads (costs)
direct 265
plant 265
Oxidation, high-temperature, of steel 291
P & I diagrams see Piping and Instrumentation
diagrams
Packaging costs 262
Packed bed reactors 485
Packed column design 587 616
bed height 593 7
column diameter (capacity) 602 4, 606 7
SUBJECT INDEX
design procedure 589
plates vs packing 588 9
selection of packing 589 93
size of packing 591
Packed columns
control of 234
flooding in 601
hold-down plates 615
installing packings into 615
internal fittings in 609 16
liquid distributors 610 11, 612 13
liquid hold-up in 615 16
liquid redistribution in 612 14
packing support 609 10
Packed glands 213 14
Packing characteristics 591
Packing, effective area of 601
Packing efficiencies, typical values 598
Packing size considerations 592
Packings for columns 589 97
costs 259
wetting rates 616
Paints (protective coatings) 305
Pall rings 259, 590, 591
Pan filters 414
Partial condensers (cooler-condensers) 719
design of 722 3
in nitric acid manufacture 153 6, 164 6
Parts per billion (ppb) 36
Parts per million (ppm) 36
Pastes, mixing of 476
Patents 310
Pay-back time 271, 274, 275
Peclet number 555
Peng Robinson (P R) equation 342
Percentage by volume (v/v) 35
Percentage by weight (w/w) 35
Perforated plate see Sieve plate
Performance coefficient, heat pumps 111
Petrochemicals Notebook 310
PFD see Process Flow Diagram
Phase equilibria 339 40
choice of method
for design calculations 350 1
flow chart for 351, 352
Phase equilibrium data 339 53
Physical properties
information sources 170 1, 311 12, 680
prediction of 313 14, 556
Physical property data bank(s) 170 1, 937 57
PID see Piping and Instrumentation diagrams
Pinch point (in distillation) 495
Pinch technology 111 15
four-stream problem 113 14
multiple utilities 124
simple two-stream problem 112 13
Pinch (temperature) 114
design of heat exchanger network above 118 19
design of heat exchanger network below 119 20
significance of 115
Pipe diameter see Economic...; Equivalent...;
Optimum pipe diameter
1031
Pipe fittings 217
pressure loss in 204
Pipe friction factor 202, 203
Pipe-line calculations (pressure drop) 201 6,
224 6
Pipe roughness 202
Pipe schedule number 216 17
Pipe size selection 218 25
Pipe stressing 217 18
Pipe supports 217
Pipe velocities, typical values 218 19
Pipe wall thickness 216 17
Piping and instrumentation 194 242
Piping and Instrumentation (P & I) diagrams 133,
194 7
symbols 195 7, 908 16
typical example 237
Piping, mechanical design of 216 18
Piping systems, layout and design of 218
Pitting corrosion 290
Plait point, solvent extraction 619
Plant attainment 7, 30, 143
Plant layout 896 9
factors 896 7
techniques 897 9
visual impact 905
Plant layout models
computer-generated 898 9
expert systems 899
physical model 897 8
Plant location, factors affecting 892 4
Plant overheads (costs) 265
Plant services (utilities) 6 7
costs 262, 264
flow-sheet presentation 140
Plant supplies, costs 262
Plastics, as construction materials 301 3
Plate construction 561 5
downcomers 563 4
sectional plates 562
side-stream and feed points 564, 565
stacked plates 562 3
structural design 564 5
tolerances 564
Plate contactors 557 65
Plate design 565 87
see also Sieve plate design
Plate efficiency 498, 547 56
AIChE method 553 6, 585 6
correction for entrainment 556 7
definitions 547 8
effect of plate parameters on 556
O’Connell’s correlation 550 2
prediction of 548 50
typical values 549
Van Winkle’s correlation 552, 597
Plate-and-frame filters 259, 412
Plate-fin exchangers 764 5
Plate heat exchangers 756 65
advantages 756 7
costs 255
data sheet for 994
1032
Plate heat (Continued)
design of 757 8
disadvantages 757
flow arrangements 758, 759
heat transfer coefficients 759 60
pressure drop 761
selection of 756 7
temperature correction factor 758 9
Plate separators 445
Plate spacing 557
Plates (contacting)
costs 258, 560
liquid flow on 560, 569
operating range 560 1, 566
selection of 560 1
weight 836
Platinum, as construction material 301
Plug valves 197, 198
pressure loss across 204
Pneumatic conveying 482
Pneumatic dryers 432
Point efficiency 547
Political considerations, in site selection
894
Polyethylene 302
manufacture of 91 3
Polypropylene 302
Polytetrafluoroethylene (PTFE) 302
Polytropic compression and expansion 84 9
Polytropic efficiency 83
Poly(vinyl chloride) (PVC) 301 2
Poly(vinylidene fluoride) (PVDF) 302
Ponchon Savarit graphical method 75, 507
Pool boiling 731, 732 3
Positive displacement compressors 478
Positive displacement pumps 199, 201, 480
selection of 481
see also Reciprocating pumps; Rotary pumps
Potential energy 61
Potential loss, in Dow F & E Index calculations
375 7
Power (electricity) 900
costs 264
Power requirements
agitated vessels 473 5
pumps 206 8
Poynting correction 240
PPDS (Physical Property Data Service) 312
Prandtl number
condensate film 712
gases 320
heat exchangers 663
Precession in centrifuges 883
Precipitation 438
Prediction of physical properties
critical constants 336 8
density 314 16
diffusion coefficients 331 4
latent heat of vaporisation 328 30
specific heat 322 8
surface tension 335 6
thermal conductivity 320 2
SUBJECT INDEX
vapour pressure 330 1
viscosity 316 20
Preliminary estimates 243
Present value or worth see Net present worth
Pressing (expression) 426
Pressure
centrifugal 879 81
heat capacity affected by 70 1
heat of reaction affected by 77 9
Pressure control 229
Pressure drop
coils 778
condensers 723
control valves 201
cyclones 453 5, 456 7
fired heaters 774
heat exchanger shells 698 702, 705 6
heat exchanger tubes 661, 666 7
pipelines 201 6, 224 5
pipes 201 6
plate heat exchangers 761, 763 4
sieve plates 575 7
Pressure hazards 368 9
Pressure losses, miscellaneous 202, 204
Pressure relief devices 368
Pressure testing, pressure vessels 872 3
Pressure vessel design 794 879
for external pressure 825 31
fundamental principles 796 810
general considerations 810 14
Pressure vessels
classification of 795
codes and standards for 795 6
combined loading of 831 44
construction categories 813
costs 256 7
data sheet for 1001
data/specification requirements 794
design of 794 879
fatigue in 872
heads and closures for 815 22
high-pressure 873 9
materials of construction 811, 812
minimum wall thickness 814
pressure testing of 872 3
Preventative measures 377, 378
Principal stresses 795, 796 7, 833 4
PRO/II simulation package 169
Problem table method, in process integration
115 17
PROCEDE software package 141
Process control, use of computers 236, 238
Process Engineering index 245, 246, 248, 401
Process flames, as ignition sources 367
Process flow diagram (PFD) 133
examples 136 8, 172, 176
Process hazards, in Dow F & E Index 372 3, 375
Process integration 111 27
composite curves 113
heat cascade in 116 17
heat exchanger networks 117 23
importance of pinch temperature 115
SUBJECT INDEX
maximum energy recovery 118
minimum number of exchangers 121 3
other process operations 124 7
pinch technology 111 15
problem table method 115 17
stream splitting in 120
Process manuals 11
Process stream, in design calculations 17
Process water 901
Product storage 6
Project documentation 10 11
Project evaluation 270 8
computer methods 278
Project manager 9
Project organisation 7 10
Projects, types 4
Proof stress 285
typical values 286
Protective coatings (paints) 305
Pseudo-binary systems, multicomponent distillation
518 21
Pseudo-fresh feeds 175
PTFE (polytetrafluoroethylene) 302
Pump efficiency, centrifugal pumps 207, 209, 480
Pump shaft seals 213 16
Pumping power 206, 220, 480
Pumps 199 216
characteristic (performance) curves 208, 209
control of 210, 231
data/specification sheets 227, 995 7
net positive suction head 212 13
power requirements 206 8
selection of 199 201, 481
system curve (operating line) 210 12
see also Centrifugal pumps; Diaphragm pumps;
Reciprocating pumps; Rotary pumps
Purchased equipment cost see Equipment costs
Purge streams, in material balances 52 3
Purification stage 6
PVC (poly(vinyl chloride)) 301 2
PVDF (poly(vinylidene fluoride)) 302
q-line (distillation) 505 6, 509 10
Quantitative risk analysis 390
computer software for 395 6
Quench towers 766
QUESTIMATE (software) 278
Rake classifiers 405
Random packings 591 2
Raoult’s law 340
Rapid methods for cost estimation 247 50
Raschig rings 590, 591
Rate of return (ROR) 273, 275
Rating methods, for distillation columns 543
Ratio control 231, 233
Raw materials
costs 261, 263
site selection influenced by 893
storage of 5 6
1033
Reaction yield 48 50, 159, 184
Reactive distillation 547
Reactor design
batch or continuous processing 483 4
homogeneous or heterogeneous reactions 484
procedure 486
requirements to be satisfied 483
Reactor types 484 5
fluidised bed 485
packed bed 485
stirred tank 484 5
tubular 485
Reactors 6, 482 6
control of 233 5
costs 259
flow-sheet calculations 151 3, 185
Reboiler design 728 55
forced-circulation reboilers 740 1
kettle reboilers 750 5
thermosyphon reboilers 741 50
Reboilers
control of 230 1
costs 268
selection of 729 31
types 729
Reciprocating compressors 84, 259, 477, 478
Reciprocating pumps 201, 231, 996
Reciprocating screens 403
Recovery columns, costs 268
Rectifying section (distillation column) 494
Recycle of information 24
Recycle processes 50 2
manual flow-sheet calculations 171 87
Recycling of waste 902 3
Redlich Kwong (R K) equation 341, 353
Redlich Kwong Soave (R K S) equation
341
Reflux, in distillation 495 6
Reflux ratio 495
minimum 495, 525 6
optimum 496
total 495
Refractory materials 304 5
Refrigeration 901
costs 264
Relative volatility 340
Relaxation methods, multicomponent distillation
545
Relief valves 368, 1000
Revolving screens 403
Riffled tables 405 6
Rings (column packing) 590, 591, 592
costs 259
Risk analysis
computer software for 395 6
see also Dow fire and explosion index
ROSPA (Royal Society for the Prevention of
Accidents), publications 369
Rotary compressors 478
Rotary dryers 259, 430 1
Rotary pumps 480, 481, 997
Royal Society of Chemistry, publications 363
1034
Royalties 266
Rubber 303
corrosion resistance
SUBJECT INDEX
930, 932, 934
Saddle supports 844 8
design of 847 8
stress in vessel wall due to 846 7
Saddles (column packing) 590, 591, 592
costs 259
SAFETI software 396
Safety and loss prevention 360 99
Safety cases 396
Safety check lists 392 4
Safety factors (design factors) 13
Safety hazards 361 70
Safety literature 360
Safety trips 236
Safety valves 368, 1000
Scaling factor
in cyclone design calculations 450, 453
in flow-sheet calculations 143, 159
Scraped-surface crystallisers 438 9, 440
Screening (sieving) 401 4
Screens
grizzly 402
oscillating 403
reciprocating 403
revolving 403
selection of 403, 404
sifting 403
vibrating 403
Screw conveyors 482
Screw presses 426
Screwed flanges 859
Screwed joints 858
Scroll discharge centrifuges 417 18
Scrubbers, for gas cleaning 459
Sea dumping of waste 904
Sea water, corrosion in 289, 920 1
Sealing strips, in pull-through bundle exchangers
670
Seal-less pumps 216
Seals, pump shaft 213 16
Secondary stresses 809 10
Sectional plates (in column) 562
Sedimentation centrifuges 415 22
liquid liquid separation 446
sigma theory for 418 20
Sedimentation equipment, selection of 419,
420
Segmental baffles, in heat exchangers 650, 651
Seismic analysis 840
Self-balancing centrifuges 881, 883
Sensitivity analysis, of costs 274
sep, Evaporators 434 7
Separation
of dissolved liquids 446 7
of dissolved solids 434 40
Separation columns 493 633
see also Absorption columns; Distillation columns;
Extraction columns
Separation processes 6, 401 65
crystallisation 437 40
drying 426 34
evaporation 434 7
filtration of gases 458 9
filtration of liquids 409 14
gas liquid 460 5
gas solid 448 60
in centrifuges 415 22
in cyclones 404 5, 422 6
liquid liquid 440 6
liquid solid 408 34
selection of 402, 403, 409
solid solid 401 8
Sequencing of columns 517
Sequential-modular simulation programs 169, 171
Services see Utilities
Settling chambers 448
Settling tanks (decanters) 440 5
Shaft seals 213 16
Shafts, whirling of 882
Shah’s method (for forced convective boiling) 736,
739
Shell and header nozzles 653
Shell and tube exchangers
advantages 640 1
allocation of fluid streams 660
as condensers 709 28
baffles in 641, 650 2
Bell’s design method 671, 693 702
construction details 640 54
costs 254
cross-flow zone 703
pressure drop 698 9
design methods 670 709
designation 649 50
effect of fouling on pressure drop 705
flow-induced vibrations in 653 4
fluid physical properties in design 661 2
fluid velocities 660
general design considerations 660 2
Kern’s design method 671 93
minimum shell thickness 647
nomenclature of parts 641
overall heat transfer coefficients 637, 678, 688
passes in 647, 649
pressure-drop limitations of design methods
705 6
shell and bundle geometry 702 6
shell-to-bundle clearance 646, 686
shell passes (types) 649, 650
shell-side flow patterns 669 70
shell-side geometry 702 5
shells 647
standards and codes for 644 5
support plates in 652
temperature driving force 655 9
tie rods in 652
tube arrangements 645 6, 648, 685 6, 1002 6
tube count 647 9
tube sheets (plates) 652 3
tube-side heat transfer coefficients 662 6
SUBJECT INDEX
tube-side passes 647
tube-side pressure drop 666 8
tube sizes 645, 686
types 641, 642 4
window zone 703
pressure drop 699
Shell passes (types), in heat exchangers 649, 650
Shell-side flow patterns 669 70
Shell-side heat transfer coefficient
Bell’s method 693, 708
Kern’s method 677 8, 681 2, 687 8, 725 6
Shell-side nozzle pressure drop 675
Shell-side pressure drop 705 6, 727 8
Shells of revolution, membrane stresses in
798 805
Shipping costs 262
Short-cut methods, distillation 517 42
Short-tube evaporators 435
Shrink-fitted compound vessels 877
SI units 14
conversion factors 15, 958 9
Side-entering agitators 476
Side streams, take-off from plates 564, 565
Sieve plate 558, 559, 561
performance diagram 566
Sieve plate design 565 87
areas 567
diameter 567 9, 580 1
downcomer liquid back-up 577 9, 583
entrainment correlation 570 1
hole pitch 574, 584
hole size 573
hydraulic gradient 574
liquid-flow arrangement 569, 581
liquid throw 575
perforated area 572 3, 584
pressure drop 561, 575 7, 582 3
procedure 567
weep point 571 2
weir dimensions 572
Sieving 401 4
Sifting screens 403
Sigma theory for centrifuges 418 20
Silicate materials 303 5
Silver, as construction material 301
Simple material balance programs 168
SIMPLEX algorithm 29
Simulation packages 168 71
Sink-and-float separators 406
Site layout 894 6
Site selection, factors affecting 892 4
Six-tenths rule 247
Skirt supports 845, 848 56
base ring and anchor bolt design 850 3
skirt thickness 848 50
Skirts, on pressure vessel ends and closure 816,
817, 819
Slip-on flanges 858, 859, 866
Smith Brinkley method, in multicomponent
distillation 522 3
Smoker equations 512 15
Solid bowl centrifuges 418
1035
Solid liquid extraction (of dissolved liquids) 447
Solid liquid separators 408 34
Solid solid separators 401 8
Solid wastes
energy recovery from 107
treatment of 904
Solids
drying of 426 34
heat capacities 322 5
mixing of 476
storage of 482
thermal conductivity 320
Solution, integral heats of 72 3
Solvent extraction 446, 447, 617 24
extractor design 618 23
immiscible solvents 623
selection of equipment 617 18
supercritical fluids 624
Solvent selection 617
Souders Brown equation 557
Souders’ equation 316
Sour-water systems 348
Specific enthalpy
calculation of 67 8
prediction using equations of state 353
Specific heats 322 8
of mixtures 323
of solids and liquids 322 5
Specific speed of pumps 200
Specification sheets (equipment data sheets) 10, 11,
227, 990 1001
Spherical pressure vessels 479, 802, 815
Spiral heat exchangers 765
Split-fraction coefficient(s) 173
estimation of 177 9
guide rules for various unit operations 185 7
Split-fraction concept 172 5
example of use 176 85
Spray dryers 432, 433
Spreadsheets
economic analysis 273
energy balance calculations 91 3, 97 9
liquid-phase activity coefficients 344, 345
mass balance calculations 179 83
for net present worth 273
for optimum pipe diameter 220 1
problem table (in process integration) 125
Stack design, fired heaters 774 5
Stacked plates (in column) 562 3
Stainless steel(s) 296 8
corrosion resistance 297 8
costs 293, 294
duplex steels 298
high-alloy steels 298
properties 285, 286, 297
surface finish 295
types 296, 297
Stainless steel pipe
costs 221
economic/optimum diameter calculations 221
Standard flanges 865 6, 960 4
Standard heats of formation 79
1036
SUBJECT INDEX
Standard heats of reaction 75
calculation of 79, 80
Standard integral heat of solution 72
Standards 12 13
for heat exchangers 644 5
see also API...; British Standards; Codes
Static electricity 367
Steam 900
condensing heat transfer coefficient 717
costs 264
Steam distillation 546 7
Steam jet ejectors 479
Steel
costs 293, 294
properties 285, 286
see also Carbon steel; Stainless steel
Stefan Boltzmann equation 772
Step counting methods, in cost estimation 249 50
Stiffened vessels, resistance to failure 835
Stiffening rings for pressure/vacuum vessels 828 9
Stiffness, of materials 285
Stirred tank reactors 484 5
control of 235
Stirred tanks, mixing in 470 5
Stoichiometric factor 49
Stoichiometry 36 7
Stokes’ law 442
Stoneware 304
corrosion resistance 931, 933, 935
Storage
of gases 479
of liquids 481, 879
of raw materials 5 6
of solids 482
Storage tanks, design of 879
Stream dividers, flow-sheet calculations 185
Stress corrosion cracking 290 1, 298
Stress factors 811
Stresses, in flat plates 805 8
Stripping columns 587
flow-sheet calculations 186
Stripping section (distillation column) 494
Structured packings 592 3
Sub-cooling in condensers 718 19
Sugden’s parachor 335
Sulphur dioxide manufacture 604 9
Supercritical fluids, extraction using 624
Supervision costs 265
Surface finish 295
Surface tension 335 6
column packing 601
of mixtures 335
Symbols, flow sheet/piping diagram 195 7,
908 16
System boundary, choice of 37 40
Tables, separation process 405 6
Tall columns 517
deflection of 839
eccentric loads on 840
wind loads on 837 9
Tank crystallisers 438, 440
Tanks
costs 259
design of 879
Tantalum 300
Taxes 266, 272
TEMA standards 640, 644, 647, 652, 657, 867
Temperature control 230
Temperature correction factor, heat exchangers
656 9
Temperature cross, heat exchangers 655
Temperature driving force
in condensers 720 1
in heat exchangers 655 9
Temperature effects, on material properties 287
Tensile strength 285
typical values 286
Theories of failure 797 8
Thermal conductivity 320 2
gases 321 2
liquids 321
metals 297, 662
mixtures 322
solids 320
Thermal efficiency, fired heaters 775
Thermal expansion, in piping systems 218
Thermal stress 810
Thermodynamics, first law 60
Thermoplastic materials 301, 924 9
Thermosetting materials 301, 925, 927, 929
Thermosyphon reboilers 729, 730, 731
design of 741 50
Thick-walled vessels see High-pressure vessels
Thickeners 405, 408 9
Thiele Geddes method, multicomponent distillation
544 5
Thin-walled vessels 795, 815 22, 834
Threshold Limit Value (TLV) 362
Threshold problems, heat exchanger networks for
123 4
Tie components, in material balances 44 6
Tile linings 304
Titanium 285, 286, 293, 300
Torispherical heads (pressure vessels) 804 5, 817,
819
Torque loads, on vessels 841
Total reflux ratio 495
Toughness 286
Toxic materials, control of 363
Toxicity 361 3
Trace quantities, effects 139 40, 294
Transfer units
prediction of height 597 602
see also Height of transfer unit
Transport
in site selection 893
of gases 477 9
of liquids 479 80
of solids 481 2
Tray data sheet 992
Tray dryers 428 9, 430
Trays see Plates
SUBJECT INDEX
1037
U-tube heat exchanger 642, 1004
as vaporiser 752 5
Ullman’s Encyclopedia of Industrial Technology
310
Ultimate oxygen demand (UOD) 904
Ultimate tensile strength (UTS) 285
Unconfined vapour cloud explosions 366
Under-pressure (vacuum) 369
Underwood equation 525 6
UNIFAC method 347, 349
limitations 348
UNIQUAC (universal quasi-chemical) equation
346, 349
Units
conversion factors 15, 958 9
for compositions in material balances 35 6
systems 14 15
Unsteady-state energy balance calculations 99 100
Unsteady-state material balance calculations 54 6
UOD (ultimate oxygen demand) 904
Urea manufacture (design exercise) 975 8
US dollars, exchange rates 249, 253
US units 14 15, 248
Utilities (services) 6 7, 900 2
costs 262, 264
flow-sheet presentation 140
site selection influenced by 893
UTS (ultimate tensile strength) 285
diaphragm 198
gate 197, 198
globe 198
plug 197, 198
Van Winkle’s correlation (plate efficiency) 552
Van-stone flanges 859
Vaporisers
control of 230 1
design of 728 55
see also Reboilers
Vaporisation, latent heat of 328 30
Vapour liquid equilibria
in flow-sheet calculations 146 9
at high pressures 348
prediction of 346 8
Vapour liquid equilibrium data 339
Vapour liquid separators 460 5
Vapour pressure 330 1
Vapours, density 315 16
Variable operating costs 261, 267, 269
Velocity heads, number of
heat exchangers 667
pipe fittings and valves 204
Vent gases, energy recovery from 105 7
Vent piping 369
Venturi scrubbers 459
Vessel data sheet 991
Vessel heads 815 22
under external pressure 829 30
Vessel jackets 775 7
Vessel shapes 799
Vessel supports 844 58
brackets 845, 856 8
saddles 844 8
skirts 845, 848 56
Vibrating screens 403
Vinyl chloride, manufacture of 77 9
Viscosity 316 20
gases 320
liquids 316 20
effect of pressure 319
variation with temperature 318 20
mixtures of liquids 319 20
Viscosity correction factor, in heat transfer 666,
691
Visual impact of plant 905
Viton 303
Vitreous enamel, corrosion resistance 931,
933, 935
Volume basis of composition 35
Vacuum pumps 479
Vacuum relief 369
Vacuum vessels see Pressure vessel design, for
external pressure
Valve plates 559 60, 561
Valve selection 197 9
Valve types
ball 198
butterfly 199
check/non-return 199
Washing of gases 459
Waste
aqueous, treatment of 904 5
biological treatment of 904
discharge to sewers 905
dumping at sea 904
energy recovery from 105 7
gaseous 105 7, 903
incineration of 107, 904
landfill 904
TREB4 program 744
Tresca’s theory 798
Trips, safety 236
Trouton’s rule 328
Tube plates see Tube sheets
Tube rolling 652 3
Tube sheets (plates) 652 3
design procedures 867 9
layouts 647 9, 1002 6
Tube vibrations, flow-induced 653 4
Tube-side heat transfer coefficients, heat exchangers
662 6, 676 7, 681, 726
Tube-side pressure drop, heat exchangers 666 8,
728
Tubular bowl centrifuges 417
Tubular Heat Exchangers Manufacturers Association
see TEMA
Tubular reactors 485
Turbo-expanders 108
Turn-down ratio 561
1038
Waste (Continued)
liquid 107, 903 4
reduction of 902
solid 107, 904
Waste management 902 3
Waste recycling 902 3
Waste-heat boilers 102 3
in nitric acid manufacture 153, 163 4
Water
costs 264
demineralised 264, 901
for general use 901
heat transfer coefficient in tubes 666
physical properties 680
Water-cooling towers 766
Water-gas reaction 144 6
Water-tube boiler, as waste-heat boiler 103
Weber equation 321
Weep point, in sieve plate design 571 2
Weeping, in plate columns 566
Weight
contacting plates 836
insulation 836
ladders 836
platforms 836
vessels 836
Weight basis of composition 35
Weight loads, on pressure vessels 835 6
Weir dimensions, sieve plates 572
Weld decay 290
Welded joint design 869 72
SUBJECT INDEX
Welded joint efficiency 812 13
Welded plate closures (pressure vessels) 816
Welded plate heat exchangers 764
Welding-neck flanges 858, 859, 960 4
Wet scrubbers 459
Wetting rates, column packings 616
Whirling of shafts 882
Wilke Chang equation 333, 334, 585
Wilson equation 342 5
advantage(s) 343
examples of use 344 5
program for 343
Wind loads on vessels 837 9, 842
Wind pressure on columns 838 9
Wind-induced vibrations in columns 839
Wiped-film evaporators 435, 436
Wire-wound vessels 878
Wood, corrosion resistance 931, 933, 935
Work done 61 2
during compression/expansion 81 2
Working capital 244
Worm conveyors 482
Wound vessels 878
WWW (World Wide Web) 310
Yield, in chemical reactors 48 50, 159, 184
Zirconium and alloys 300
Zuber correlation 733, 751