GCP Vol 1 PDF (2022 Edition)

GAS CONDITIONING AND PROCESSING
Volume 1: The Basic Principles

Exclusively for use by G-4 Repsol course participants from the 11-July-2022 session.
9th Edition
This book is based upon, and is the successor to, the classic work of the same title
authored by Dr. John M. Campbell, Sr. from 1966-2013.
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In Memory of Dr. John M. Campbell
Dr. John Campbell passed away on 12 September, 2013. He founded John M. Campbell & Company
in 1968 and authored the first edition of Gas Conditioning and Processing which was published in the same
year. Dr. Campbell enjoyed a distinguished career in the oil and gas industry beginning in the late 1940s
and was recognized with numerous awards including the John Franklin Carll Distinguished Professional
Award from the Society of Petroleum Engineers in 1978 and the Hanlon Award from the Gas Processor’s
Association in 1987.
Dr. Campbell was not only widely acknowledged as a technical leader in the industry, but also as
an outstanding educator. He attended the University of Oklahoma from 1946-1951 receiving Masters and
Doctoral degrees in Chemical Engineering. During this time he was first introduced to teaching when he
was given lecture responsibilities in several undergraduate classes.
After 3 years in industry, Dr. Campbell returned to the University of Oklahoma as a professor in
the Department of Petroleum Engineering where he remained until 1968, including 12 years as head of the
department.
During this time Dr. Campbell developed and taught several short courses for companies in the
oil and gas business worldwide. These experiences paved the way for the success he enjoyed over the
following 25 years and as an instructor and consultant.
"I met Dr. Campbell when I joined the company in 1980. He was a remarkable person and a natural
leader. He had the unique ability to distill complex topics into understandable pieces. He was technically
brilliant, but understood the human side of our business. I am proud to have known him and enjoyed his
friendship. I will miss him."
—Bob Hubbard
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TABLE OF CONTENTS
Chapter 1
.....................................................................................................................................................................................Page #
INTRODUCTION................................................................................................................................................................................1
BASIC TERMINOLOGY....................................................................................................................................................................3
Elements and Atoms.............................................................................................................................................................3
Chemical Compounds and Molecules..................................................................................................................................3
Physical Compounds............................................................................................................................................................3
Relative Atomic Mass (Weight)...........................................................................................................................................3

Relative Molecular Mass (Weight).......................................................................................................................................4
The Mol.................................................................................................................................................................................4
Valence..................................................................................................................................................................................4
Mixture.................................................................................................................................................................................4
BASIC HYDROCARBON NOMENCLATURE................................................................................................................................5
Paraffin Series (Alkanes) Formula: Cn H2n+2.......................................................................................................................5
Olefin or Ethylene Series (Alkenes) Formula: Cn H2n..........................................................................................................6
Acetylenic or Alkyne Series Formula: Cn H2n-2...................................................................................................................7
Diolefins Formula: Cn H2n-2.................................................................................................................................................7
Aromatic (Benzene) Series Formula: Cn H2n-6....................................................................................................................7
Naphthene Series Formula: Cn H2n......................................................................................................................................8
TYPICAL COMPOUNDS IN PRODUCTION/PROCESSING SYSTEMS......................................................................................8
Common Contaminants Found in Natural Gas...................................................................................................................9
Alcohols..............................................................................................................................................................................10
Amines................................................................................................................................................................................10
Glycols................................................................................................................................................................................11
Acids, Bases and Salts........................................................................................................................................................11
Radicals..............................................................................................................................................................................11
ANALYSIS OF MIXTURES.............................................................................................................................................................12
BASIC UNITS OF MEASUREMENT.............................................................................................................................................14
Presenting Numbers...........................................................................................................................................................15
Mass, Force and Weight.....................................................................................................................................................15
Length, Area and Volume..................................................................................................................................................16
Density................................................................................................................................................................................17
Pressure...............................................................................................................................................................................18
Temperature........................................................................................................................................................................18
Work and Power..................................................................................................................................................................18
Heat Energy........................................................................................................................................................................19
Viscosity.............................................................................................................................................................................19
Volumetric-Mass Conversions...........................................................................................................................................19
APPENDIX 1A — SUMMARY OF CONVERSION FACTORS....................................................................................................22
TABLE OF CONTENTS i
Chapter 2
.....................................................................................................................................................................................Page #
GAS CONDITIONING AND PROCESSING OVERVIEW............................................................................................................25
Typical Well Stream Compositions....................................................................................................................................26
SALEABLE PRODUCTS AND QUALITY SPECIFICATIONS.....................................................................................................29
Sales Gas/Residue Gas Specifications ..............................................................................................................................29
Liquid Hydrocarbon Products............................................................................................................................................33
GAS PROCESSING SCHEMES.......................................................................................................................................................34
Gas Conditioning................................................................................................................................................................34
Gas Processing / NGL Extraction......................................................................................................................................37

Stabilization / Fractionation.............................................................................................................................................. 40
Liquid Product Treating.....................................................................................................................................................41
Nitrogen Rejection and Helium Recovery ........................................................................................................................41
PRODUCTION FACILITIES.............................................................................................................................................................42
Crude Oil............................................................................................................................................................................42
Produced Water .................................................................................................................................................................42
PROCESS SELECTION & DESIGN BASIS....................................................................................................................................43
SUMMARY....................................................................................................................................................................................... 44
REFERENCES.................................................................................................................................................................................. 44
APPENDIX 2A — EXAMPLE NGL SPECIFICATIONS...............................................................................................................45
Chapter 3
.....................................................................................................................................................................................Page #
PHYSICAL PROPERTIES OF HYDROCARBON SYSTEMS.......................................................................................................47
GAS PROPERTIES – EQUATIONS OF STATE..............................................................................................................................48
Ideal Gas Law.....................................................................................................................................................................48
Compressibility Factor and Nonideal P-V-T Equations.....................................................................................................49
Other Correlations for z......................................................................................................................................................59
Gas Viscosity......................................................................................................................................................................60
LIQUID PHYSICAL PROPERTIES..................................................................................................................................................61
Distillation Characteristics................................................................................................................................................61
Characterization Parameters..............................................................................................................................................62
Liquid Density....................................................................................................................................................................66
API Gravity........................................................................................................................................................................66
General Correlations..........................................................................................................................................................67
General Nomographs..........................................................................................................................................................67
Corresponding States Methods..........................................................................................................................................70
Summary of Liquid Density Correlations.........................................................................................................................72
Liquid Viscosity.................................................................................................................................................................73
USEFUL CONVERSION FACTORS FOR CHAPTER 3................................................................................................................74
REFERENCES...................................................................................................................................................................................75
APPENDIX 3A — PHYSICAL CONSTANTS OF HYDROCARBONS .....................................................................................76
APPENDIX 3B — THE KATZ CORRELATION AND KAY’S RULE.........................................................................................81
APPENDIX 3C — WICHERT AZIZ METHOD FOR SOUR NATURAL GASES .................................................................... 84
APPENDIX 3D — (COSTALD) ......................................................................................................................................................86
ii VOLUME 1: THE BASIC PRINCIPLES

Chapter 4
.....................................................................................................................................................................................Page #
QUALITATIVE PHASE BEHAVIOR..............................................................................................................................................87
SINGLE COMPONENT SYSTEMS.................................................................................................................................................87
P-T Plot for Single Component Systems............................................................................................................................88
Vapor Pressure of Hydrocarbons.......................................................................................................................................89
MULTI-COMPONENT SYSTEMS..................................................................................................................................................91
Effect of Composition........................................................................................................................................................92
APPLICATION OF PHASE ENVELOPES......................................................................................................................................97
Reservoir Behavior.............................................................................................................................................................97
Facility Phase Behavior......................................................................................................................................................99
Practical Suggestions.......................................................................................................................................................101
REFERENCES ................................................................................................................................................................................101
Chapter 5
.....................................................................................................................................................................................Page #
VAPOR-LIQUID EQUILIBRIUM BEHAVIOR.............................................................................................................................103
EQUILIBRIUM VAPORIZATION RATIO...................................................................................................................................103
Partial Pressure Concept..................................................................................................................................................104
Fugacity Derived K Values..............................................................................................................................................105
K Value Charts.................................................................................................................................................................106
K Values for C6+ Fractions..............................................................................................................................................107
VAPOR-LIQUID EQUILIBRIUM (VLE) CALCULATIONS...................................................................................................... 113
Bubblepoint....................................................................................................................................................................... 113
Dewpoint.......................................................................................................................................................................... 114
Flash Calculation.............................................................................................................................................................. 115
Accuracy of Equilibrium Calculations............................................................................................................................ 116
STAGE SEPARATION.................................................................................................................................................................... 117
CONVERSION CALCULATIONS.................................................................................................................................................122
Conversion Between Liquid, Mol or Mass......................................................................................................................122
Well Stream Test Separator Recombination....................................................................................................................122
Basic Conversion Factors.................................................................................................................................................124
LIQUID PRODUCT VAPOR PRESSURE SPECIFICATIONS.....................................................................................................125
REFERENCES.................................................................................................................................................................................129
APPENDIX 5A — K VALUE CHARTS........................................................................................................................................130
Chapter 6
.....................................................................................................................................................................................Page #
WATER-HYDROCARBON PHASE BEHAVIOR.........................................................................................................................147
WATER CONTENT OF GASES.....................................................................................................................................................147
Partial Pressure and Fugacity...........................................................................................................................................147
Empirical Water Content Charts......................................................................................................................................148
TABLE OF CONTENTS iii

Water Content of Sour Gases...........................................................................................................................................151
Effect of Nitrogen and Heavy Hydrocarbons on Water Content.....................................................................................153
Water Content Applications.............................................................................................................................................153
Saturated Water Content in Equilibrium with Hydrates.................................................................................................154
WATER DEWPOINT ANALYZERS..............................................................................................................................................155
GAS HYDRATES............................................................................................................................................................................156
Hydrate Equilibrium........................................................................................................................................................159
HYDRATE PREDICTION CORRELATIONS...............................................................................................................................160
HYDRATE PREVENTION.............................................................................................................................................................170
Inhibition in the Presence of Salts in Produced Water.................................................................................................... 174

Inhibitor Losses to the Hydrocarbon Phase..................................................................................................................... 174
Calculation Summary....................................................................................................................................................... 176
Crystallization (Freezing) of Glycols............................................................................................................................... 181
Inhibitor Selection............................................................................................................................................................ 181
Inhibition in Refrigeration Systems.................................................................................................................................183
Inhibitor Regeneration.....................................................................................................................................................183
MEG Regeneration in Production Systems.....................................................................................................................185
Low Dosage Hydrate Inhibitors (LDHIs)........................................................................................................................187
REFERENCES.................................................................................................................................................................................190
APPENDIX 6A — TREKELL-CAMPBELL METHOD .........................................................................................................192
Chapter 7
.....................................................................................................................................................................................Page #
BASIC THERMODYNAMICS AND APPLICATION OF ENERGY BALANCES....................................................................201
BASIC THERMODYNAMIC CONCEPTS....................................................................................................................................201
System and Surroundings................................................................................................................................................202
Basic Thermodynamic Accounting.................................................................................................................................202
Mass Balance....................................................................................................................................................................202
Energy Balance.................................................................................................................................................................203
Specific Applications........................................................................................................................................................205
The Second Law of Thermodynamics – Entropy........................................................................................................... 206
Relationship Between Thermodynamic Properties.........................................................................................................208
APPLICATIONS OF THERMODYNAMICS............................................................................................................................... 209
CHOICE OF SYSTEM.....................................................................................................................................................................210
Units of Measurement......................................................................................................................................................210
Effect of Phase Condition................................................................................................................................................. 211
Enthalpy Calculation Alternatives................................................................................................................................... 211
Enthalpy Correlations for Pure Substances..................................................................................................................... 216
Enthalpy Correlations for Mixtures ................................................................................................................................ 218
Enthalpy Calculations for Mixtures.................................................................................................................................221
REFERENCES.................................................................................................................................................................................223
APPENDIX 7A – ENTHALPIES FOR HYDROCARBON FLUIDS............................................................................................224
iv VOLUME 1: THE BASIC PRINCIPLES

Chapter 8
.....................................................................................................................................................................................Page #
FLUID FLOW..................................................................................................................................................................................239
Evaluation of Friction Factor........................................................................................................................................... 240
Non-Newtonian Liquids...................................................................................................................................................243
NEWTONIAN LIQUID FLOW..................................................................................................................................................... 244
Valves and Fittings...........................................................................................................................................................249
Economic Pipe Diameter..................................................................................................................................................252
Excessive Velocity............................................................................................................................................................253
Pressure Surges ...............................................................................................................................................................254

Liquid Line Looping.........................................................................................................................................................255
GAS FLOW......................................................................................................................................................................................258
Standard Equations..........................................................................................................................................................259
Characteristics of Gas Transmission Systems.................................................................................................................263
Maximum Velocity...........................................................................................................................................................263
Corrections Due to Elevation Changes in Gas Pipelines............................................................................................... 264
Gas Line Looping.............................................................................................................................................................265
Transient Flow in Gas Pipelines.......................................................................................................................................268
TEMPERATURE CHANGES IN PIPING.....................................................................................................................................268
Overall Heat Transfer Coefficient (Uo) ...........................................................................................................................270
Ground Temperature Tg ...................................................................................................................................................272
Above Ground Lines .......................................................................................................................................................273
MULTIPHASE FLOW.....................................................................................................................................................................274
Flow Regimes...................................................................................................................................................................274
Liquid Hold Up.................................................................................................................................................................276
Dimensionless Groups.....................................................................................................................................................277
MULTIPHASE FLOW CORRELATIONS.....................................................................................................................................278
Horizontal Two-Phase Flow.............................................................................................................................................280
Vertical Two-Phase Flow.................................................................................................................................................289
SLUGGING......................................................................................................................................................................................290
Severe Slugging................................................................................................................................................................292
Production Ramp-Up Slugging........................................................................................................................................294
Erosional Velocity............................................................................................................................................................297
Slug Mitigation.................................................................................................................................................................297
Dense Phase Pipelines......................................................................................................................................................298
APPLICATION OF THE TECHNOLOGY.................................................................................................................................... 300
Physical Properties Correlations......................................................................................................................................301
MULTIPHASE FLOW SPLITTING...............................................................................................................................................301
MECHANICAL DESIGN OF PIPING............................................................................................................................................302
Flanges............................................................................................................................................................................. 304
REFERENCES.................................................................................................................................................................................305
APPENDIX 8A – ALLOWABLE WORKING PRESSURES FOR CARBON STEEL PIPING....................................................307
TABLE OF CONTENTS v
Chapter 9
.....................................................................................................................................................................................Page #
PROCESS CONTROL AND INSTRUMENTATION.................................................................................................................... 315
CONTROL OBJECTIVES AND CONCEPTS............................................................................................................................... 316
Feedback Control Systems............................................................................................................................................... 316
CONTROL MODES.........................................................................................................................................................................320
Controllers........................................................................................................................................................................320
On/Off...............................................................................................................................................................................320
Proportional Control.........................................................................................................................................................321
Integral (Reset).................................................................................................................................................................324
Derivative (Rate)..............................................................................................................................................................325
Controller Action Applications........................................................................................................................................326
CONTROL LOOP CONFIGURATIONS........................................................................................................................................326
Direct Acting/Reverse Acting..........................................................................................................................................326
Split-Range Control..........................................................................................................................................................327
Cascade and Feed Forward Control.................................................................................................................................328
Ratio Control....................................................................................................................................................................330
CONTROL VALVES.......................................................................................................................................................................330
Valve Selection ................................................................................................................................................................333
INSTRUMENTATION....................................................................................................................................................................337
Level Measurement..........................................................................................................................................................337
Pressure Measurement.....................................................................................................................................................339
Temperature Measurement.............................................................................................................................................. 340
Flow Measurement...........................................................................................................................................................341
REFERENCES.................................................................................................................................................................................347
APPENDIX 9A – DEFINITION OF TERMS......................................................................................................................... 348-349
APPENDIX 9B – STANDARD CONTROL SYMBOLS...............................................................................................................353
Chapter 10
.....................................................................................................................................................................................Page #
RELIEF AND FLARE SYSTEMS..................................................................................................................................................355
Overpressure Protection...................................................................................................................................................356
Causes of Overpressure....................................................................................................................................................356
Relief and Flare Systems..................................................................................................................................................358
PRESSURE RELIEF DEVICE........................................................................................................................................................359
Conventional Pressure Relief Valve ................................................................................................................................359
Balanced Bellows Relief Valve........................................................................................................................................360
Pilot Operated Relief Valve..............................................................................................................................................361
Buckling Pin Valves.........................................................................................................................................................361
Rupture Discs...................................................................................................................................................................362
Vapor Relief Valve Sizing................................................................................................................................................362
Relief Valve Installation...................................................................................................................................................364
vi VOLUME 1: THE BASIC PRINCIPLES

FLARE HEADER SYSTEMS.........................................................................................................................................................368
Flare Header Purge Gas Requirements............................................................................................................................369
Flare Knockout Drum (KO).............................................................................................................................................370
Flare Tips and Stack.........................................................................................................................................................370
Flare Radiation.................................................................................................................................................................371
SAFETY INSTRUMENTED SYSTEM..........................................................................................................................................374
DEPRESSURIZATION/ BLOWDOWN.........................................................................................................................................376
Fires..................................................................................................................................................................................376
Calculating Depressurization Rates.................................................................................................................................376
Atmospheric Venting........................................................................................................................................................377
Environmental..................................................................................................................................................................378
REFERENCES.................................................................................................................................................................................378
Appendix
.....................................................................................................................................................................................Page #
APPENDIX A — TYPICAL PFD SYMBOLS ..............................................................................................................................379
APPENDIX B — GENERAL CONVERSION FACTORS............................................................................................................381
APPENDIX C — THERMODYNAMIC DATA.............................................................................................................................389
REFERENCES.................................................................................................................................................................................405
INDEX............................................................................................................................................................................................. 407
LIST OF FIGURES
Chapter 1
Figure # .....................................................................................................................................................................................Page #
1.1 Methane, Ethane, and Propane.............................................................................................................................................5
1.2 Normal Butane and Isobutane..............................................................................................................................................6
1.3 Ethylene and Propylene........................................................................................................................................................6
1.4 1-Butene and 2-Butene.........................................................................................................................................................7
1.5 Acetylene..............................................................................................................................................................................7
1.6 Butadiene..............................................................................................................................................................................7
1.7 BETX Compounds (Benzene, Toluene, Ethylbenzene, Xylene).........................................................................................8
1.8 Cyclohexane..........................................................................................................................................................................8
1.9 Acid Gas Compounds and Water.........................................................................................................................................9
1.10 General Mercaptan, Methyl Mercaptan and Ethyl Mercaptan............................................................................................9
1.11 Carbonyl Sulfide, Carbon Disulfide, Thiophene.................................................................................................................9
1.12 Methanol and Ethanol........................................................................................................................................................10
1.13 Diethanol Amine and Methyldiethanol Amine.................................................................................................................10
1.14 Commonly Used Glycols – Monoethylene Glycol, Diethylene Glycol, Triethylene Glycol.............................................10
1.15 Chromatogram of Condensed Liquid.................................................................................................................................13
Chapter 2
Figure # .....................................................................................................................................................................................Page #
2.1 Gas Gathering and Processing in the Total Production System .......................................................................................25
2.2 Example Product / Impurities Disposition from a Gas Processing Plant..........................................................................26
2.3 Common Terminology and Composition of Products...................................................................................................29
TABLE OF CONTENTS vii

2.4 Example Gas Processing Facility Block Flow Diagram....................................................................................................34
2.5 Range of NGL Extraction in Gas Conditioning and Processing Facilities.......................................................................38
2.6a Shrinkage Value of NGL Components as a Function of Gas Price – SI Units.................................................................38
2.6b Shrinkage Value of NGL Components as a Function of Gas Price – FPS Units..............................................................39
2.7 Example Integrated Production Facility............................................................................................................................43
Chapter 3
Figure # .....................................................................................................................................................................................Page #
3.1a Compressibility Factors for Low Molecular Weight Natural Gas, MW = 17.40 (SI).......................................................50
3.1b Compressibility Factors for Low Molecular Weight Natural Gas, MW = 17.40 (FPS)....................................................50
3.2b Compressibility Factors for Low Molecular Weight Natural Gas, MW = 18.85 (FPS)....................................................51
3.3a Compressibility Factors for Low Molecular Weight Natural Gas, MW = 20.30 (SI)................................................... 52
3.3b Compressibility Factors for Low Molecular Weight Natural Gas, MW = 20.30 (FPS)............................................... 52
3.4b Compressibility Factors for Low Molecular Weight Natural Gas, MW = 23.20 (FPS)...................................................53
3.5 Vapor Pressure (a) and Reduced Vapor Pressure (b) of Methane and Propane................................................................56
3.6 Approximate Pseudo-Critical Properties of Sweet Natural Gas.......................................................................................59
3.7 Lee et al., Equation for Hydrocarbon Gas Viscosity (µg).................................................................................................60
3.8 Some Representative TBP Distillation Curves..................................................................................................................62
3.9 Relative Density vs. MW for Generalized Hydrocarbon Fractions..................................................................................63
3.10 Relative Density vs. Boiling Point for Generalized Hydrocarbon Fractions....................................................................63
3.11 Correlations Relating Various Characterization Variables and Liquid Properties...........................................................65
3.12 Relative Density of Liquid Hydrocarbon Mixtures...........................................................................................................68
3.13 Relative Density of Paraffin Hydrocarbon Mixtures at their Bubblepoint Pressure........................................................69
3.14 Effect of Temperature and Pressure on the Density of Hydrocarbon Liquids..................................................................70
3.15 Viscosity of Pure Paraffin Hydrocarbons..........................................................................................................................73
3.16 Kinematic Viscosity vs. Temperature, and Other Properties, for a Wide Range of Traditional Crude Oils...................74
3B.1 Katz Compressibility Factor Chart....................................................................................................................................82
3C.1 Correction Factor Chart for Sour Gases............................................................................................................................85
Chapter 4
Figure # .....................................................................................................................................................................................Page #
4.1 P-V-T Diagram for a Single Component System...............................................................................................................88
4.2 P-T Diagram for a Single Component System...................................................................................................................88
4.3 Vapor Pressure Chart for Paraffin Hydrocarbons............................................................................................................. 90
4.4 Vapor Pressure Chart for Normal Paraffin Hydrocarbons Based on Normal Boiling Point........................................... 90
4.5 Typical Phase Diagram for a Multi-Component Natural Gas Mixture.............................................................................92
4.6 T-P-x Diagram for C2-nC7 System.....................................................................................................................................93
4.7 Effect of Composition on Phase Envelope, Ethane and n-Heptane Binary......................................................................93
4.8 Effect of C6+ Characterization on Phase Envelope for Non-Associated Gas...................................................................94
4.9a Effect of CO2 on Volatile Oil Phase Behavior...................................................................................................................95
4.9b Effect of H2S on Volatile Oil Phase Behavior...................................................................................................................96
4.9c Effect of N2 on Volatile Oil Phase Behavior......................................................................................................................96
viii VOLUME 1: THE BASIC PRINCIPLES

4.10 Characteristic Phase Envelopes for Five Reservoir Types................................................................................................97
4.11 Black Oil Reservoir............................................................................................................................................................97
4.12 Volatile Oil Reservoir.........................................................................................................................................................97
4.13 Gas Condensate Reservoir.................................................................................................................................................98
4.14 Dry Gas Reservoir..............................................................................................................................................................98
4.15 The Effect of Composition on Initial Producing GOR............................................................................................................98
4.16 Pump Suction Pressure Conditions....................................................................................................................................99
4.17 Effect of Pressure on Dewpoint Control Processing Temperatures..................................................................................99
4.18 Cooling of a Gas in Facility Piping..................................................................................................................................100
4.19 Process Flow Diagram for an Amine System Inlet...........................................................................................................100

4.20 High Pressure Pipeline Phase Envelope..........................................................................................................................100
Chapter 5
Figure # .....................................................................................................................................................................................Page #
5.1 Separator Equilibrium Vaporization................................................................................................................................104
5.2 Partial Pressure Schematic...............................................................................................................................................104
5.3 Plot of ln K vs. Tc2............................................................................................................................................................108
5.4 ln K vs. Tc2 for Data from Example 5.1 ........................................................................................................................... 110
5.5 ln K vs. Tc2 to Determine C10 -C12 K-values .................................................................................................................... 111
5.6 KP Plot Used to Estimate C10 -C12 K-Values (SI Units)....................................................................................................112
5.7 Another Correlation for Estimating Hydrocarbon Boiling Point.................................................................................... 113
5.8 Two-Stage (or Three-Stage) Separation........................................................................................................................... 117
5.9 Stage Separation System.................................................................................................................................................. 118
5.10 Example Phase Envelopes for 4-Stage Separation System.............................................................................................121
5.11 Liquid Production and Compression Power vs. Number of Separation Stages..............................................................121
5.12 Schematic of an RVP Sample Cylinder...........................................................................................................................126
5.13 Schematic of an LPG Sample Cylinder...........................................................................................................................126
5.14 Vapor Pressures vs. Temperature for Typical C5+ NGL..................................................................................................127
5.15 Reid Vapor Pressure vs. True Vapor Pressure for Crude Oil..........................................................................................128
Chapter 6
Figure # .....................................................................................................................................................................................Page #
6.1a Water Content of Sweet, Lean Natural Gas (SI Units)....................................................................................................149
6.1b Water Content of Sweet, Lean Natural Gas (FPS Units).................................................................................................150
6.2a Water Content Ratios — Sour Gas (SI Units)..................................................................................................................152
6.2b Water Content Ratios — Sour Gas (FPS Units)..............................................................................................................152
6.3 Water Content of 5.31% C3 — 94.69% C1 Gas in Equilibrium with Hydrate and Metastable Liquid...........................154
6.4 Schematic of Natural Gas Hydrate Lattices....................................................................................................................157
6.5 Hydrate Forming Conditions for Natural Gas Components............................................................................................159
6.6 Phase Behavior of Propane-Water System.......................................................................................................................159
6.7 General Hydrate Formation Characteristics of a Gas Mixture.......................................................................................160
6.8 Conditions for Formation of Natural Gas Hydrates........................................................................................................160
6.9 Vapor-Solid K Values for Methane and Ethane...............................................................................................................162
6.10 Vapor-Solid K Values for Propane...................................................................................................................................163
TABLE OF CONTENTS ix
6.11 Vapor-Solid K Values for iso-Butane...............................................................................................................................163
6.12 Vapor-Solid K Values for CO2 and H2S...........................................................................................................................164
6.13 Vapor-Solid Equilibrium Constants for n-Butane...........................................................................................................165
6.14a Hydrate Chart for Gases Containing H2S SI Units..........................................................................................................167
6.14b Hydrate Chart for Gases Containing H2S FPS Units......................................................................................................168
6.15 Hydrate Suppression vs. Inhibitor Concentration in Mol %, Comparison of Correlation and Data..............................172
6.16 Molar Percent to Weight Percent Conversions for MEG and MeOH..............................................................................173
6.17 Hydrate Inhibition with Methanol and NaCl................................................................................................................... 174
6.18a Methanol K-Values in Natural Gas, SI Units................................................................................................................... 175
6.18b Methanol K-Values in Natural Gas, FPS Units................................................................................................................ 175

6.19 Liquid-Liquid Distribution Ratios for Methanol and Hydrocarbons..............................................................................176
6.20 Freezing Points of MEG-Water Solutions........................................................................................................................ 181
6.21 Comparison of Physical Properties of Pure MeOH and MEG........................................................................................182
6.22 Typical Mechanical Refrigeration Plant with MEG Injection System (for Rich Wet Inlet Gas)....................................184
6.23a Example MEG Reclamation Unit....................................................................................................................................186
6.23b MEG Reclamation Unit Salt Extraction Options............................................................................................................186
6.24 Hydrate Formation............................................................................................................................................................187
6.25 Hydrate Prevention with Thermodynamic Inhibitor.......................................................................................................188
6.26 Hydrate Prevention with LDHIs......................................................................................................................................189
6A.1(a) Hydrate Prediction Correlations at 6.9 MPa [1000 psia].................................................................................................193
6A.1(b) Hydrate Prediction Correlations at 13.8 MPa [2000 psia]...............................................................................................194
6A.2(a) Hydrate Prediction Correlations at 20.7 MPa [3000 psia]...............................................................................................195
6A.3(a) Hydrate Prediction Correlations at 34.5 MPa [5000 psia]...............................................................................................197
6A.4 Hydrate Prediction Correlations for Non-Hydrate Formers............................................................................................199
Chapter 7
Figure # .....................................................................................................................................................................................Page #
7.1 Simple Schematic of a System, Surroundings and Boundary.........................................................................................202
7.2 Mass Accounting..............................................................................................................................................................202
7.3 Overall Energy Balance Example................................................................................................................................... 204
7.4 Crude Oil System Pump...................................................................................................................................................210
7.5 Compressor and After-Cooler System.............................................................................................................................210
7.6 Heat Capacity of 0.6 Relative Density Natural Gas........................................................................................................212
7.7 Heat Capacity of 0.70 Relative Density Natural Gas.......................................................................................................212
7.8 Heat Capacity of 0.80 Relative Density Natural Gas......................................................................................................213
7.9 Correlation for Estimating Latent Heat of Hydrocarbon Fluids.....................................................................................215
7.10 Crude Oil Vaporization Characteristics........................................................................................................................... 216
7.11a Pressure-Enthalpy Diagram for Propane (SI Units)........................................................................................................219
7.11b Pressure-Enthalpy Diagram for Propane (FPS Units) ....................................................................................................220
7.12 Energy Balance Schematic...............................................................................................................................................221
7A.1(a) Enthalpy, kJ/kg Hydrocarbon Liquid...............................................................................................................................225
x VOLUME 1: THE BASIC PRINCIPLES

7A.1(b) Enthalpy, Btu/lbm Hydrocarbon Liquid..........................................................................................................................225
7A.2(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 100 kPa...............................................................................................................226
7A.2(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 15 psia............................................................................................................226
7A.3(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 1.0 MPa..............................................................................................................227
7A.3(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 150 psia..........................................................................................................227
7A.4(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 1.4 MPa.............................................................................................................228

7A.7(a) Enthalpy, kJ/kg Hydrcarbon Gas P = 3.5 MPa................................................................................................................231
7A.10(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 800 psia.........................................................................................................234
7A.12(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 7.0 MPa...............................................................................................................236
7A.12(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 1000 psia........................................................................................................236
Chapter 8
Figure # .....................................................................................................................................................................................Page #
8.1 Friction Factors Using Moody Correlations....................................................................................................................241
8.2 Shear Curves of Newtonian and Non-Newtonian Fluids................................................................................................243
8.3a Pressure Drop for Hydrocarbon Liquids in Smooth Pipe – SI Units............................................................................. 246
8.3b Pressure Drop for Hydrocarbon Liquids in Smooth Pipe – FPS Units...........................................................................247
8.4 Resistance of Valves and Fittings to Flow of Fluids .......................................................................................................251
8.5 Economic Pipe Diameter..................................................................................................................................................252
8.6 Velocity of Liquids in Standard Piping as a Function of Flow Rate...............................................................................253
8.7 Schematic of a Looped Piping System.............................................................................................................................255
8.8 Pipeline Friction Factor Correlation Comparisons..........................................................................................................261
8.9 Comparison of the Colebrook-White Equation to the AGA Equation Friction Factor...................................................262
8.10 Pipeline Elevation Schematic.......................................................................................................................................... 264
8.11 Head Change.................................................................................................................................................................... 264
8.12 Gas Pipeline Temperature Profile....................................................................................................................................269
TABLE OF CONTENTS xi
8.13 Buried Pipeline Diagram..................................................................................................................................................271
8.14 Various Two-Phase Horizontal Flow Regimes................................................................................................................274
8.15 Vertical Two-Phase Regimes...........................................................................................................................................275
8.16 Example Relationship for Liquid Holdup Fraction and Total Liquid Holdup.................................................................277
8.17 Flow-Pattern Map of Mandhane for Horizontal Two-Phase Flow in Pipes....................................................................280
8.18 Flow Regime Map for Horizontal Two-Phase Flow—Taitel-Duckler Correlation.........................................................280
8.19 Near-Horizontal Line.......................................................................................................................................................282
8.20 Liquid Collecting in a Low Spot......................................................................................................................................282
8.21 Pipeline Pressure Loss and Liquid Holdup vs. Gas Flow Rate.......................................................................................282
8.22 Flanigan’s Liquid Head Factor.........................................................................................................................................284

8.23 Flanigan’s Efficiency Correlation....................................................................................................................................285
8.24 Eaton Liquid Holdup Correlation.....................................................................................................................................286
8.25 Pipeline Liquid Holdup....................................................................................................................................................289
8.26 Duns and Ros Vertical Flow Regimes.............................................................................................................................289
8.27 Idealized Slug Unit...........................................................................................................................................................291
8.28 Slug Formation Steps.......................................................................................................................................................292
8.29 Example Liquid Production Exiting a Pipeline Following an Increase in Flow Rate....................................................294
8.30 Pipeline Pigs / Scrapers....................................................................................................................................................298
8.31 Multiphase Flow Splitting-Branch of the Tee..................................................................................................................301
8.32 Behavior of Two-Phase Grid System...............................................................................................................................302
8.33 Pipe Flange...................................................................................................................................................................... 304
8.34 Maximum Pressure Rating vs. Temperature for Carbon Steel Flanges (Materials Group 1.1)—B16.5....................... 304
Chapter 9
Figure # .....................................................................................................................................................................................Page #
9.1 Simple Level Control System........................................................................................................................................... 316
9.2 Process Control Block Diagram for Level Control System............................................................................................. 317
9.3 Control Loop Stability......................................................................................................................................................320
9.4 Output of a Level Controller............................................................................................................................................322
9.5 Level in Separator at Normal Flow – No Offset..............................................................................................................323
9.6 Level in Separator when Liquid Flow Increases 50% – Offset Present..........................................................................323
9.7 Open Loop Response Characteristics of a P+I Controller..............................................................................................324
9.8 Closed Loop Response Characteristics of a P+I Controller............................................................................................325
9.9 Open Loop Response Characteristics of a P+D Controller.............................................................................................325
9.10 Examples of Controller – Control Valve Combinations..................................................................................................327
9.11 J-T Bypass Control on an Expander.................................................................................................................................327
9.12 Simple Temperature Control............................................................................................................................................328
9.13 Cascade Control System...................................................................................................................................................328
9.14 Feed-Forward Control System.........................................................................................................................................329
9.15 Air Control for a Claus Plant............................................................................................................................................330
9.16 Schematics of Different Types of Control Valves...........................................................................................................331
9.17 Globe Valve......................................................................................................................................................................332
9.18 Butterfly Valve..................................................................................................................................................................332
xii VOLUME 1: THE BASIC PRINCIPLES

9.19 Control Valve Forces........................................................................................................................................................332
9.20 Cage-guided Control Valve..............................................................................................................................................333
9.21 Performance of Valve Trim..............................................................................................................................................334
9.22 Pneumatic Spring and Diaphragm Actuator....................................................................................................................336
9.23 Coriolis Meter...................................................................................................................................................................342
9.24 Sonic Flow Meter.............................................................................................................................................................342
9.25 Turbine Meter...................................................................................................................................................................343
9.26 Schematic of an Orifice Plate...........................................................................................................................................343
9.27 Schematic of a Venturi Meter......................................................................................................................................... 344
9.28 Sliding Vane Meter.......................................................................................................................................................... 344

9.29 Multiphase Flow Meter Operational Ranges...................................................................................................................346
9B.1 Some Standard Control Symbols (See also ANSI/ISA-S5.1 to S5.5)..............................................................................353
Chapter 10
Figure # .....................................................................................................................................................................................Page #
10.1 Independent Protection Layers for a Facility...................................................................................................................355
10.2 Example Relief and Flare System....................................................................................................................................358
10.3 Conventional Safety Relief Valve....................................................................................................................................359
10.4 Balanced Bellows Safety Relief Valve.............................................................................................................................360
10.5 Balanced Bellows Back Pressure Correction Factor.......................................................................................................360
10.6 Pilot Operated Relief Valve..............................................................................................................................................361
10.7 Pressure Relationship for Pressure Relief Valves............................................................................................................365
10.8 Flare Header System........................................................................................................................................................368
10.9 Purge Gas Reduction Equipment.....................................................................................................................................369
10.10 Flame Front Generator.....................................................................................................................................................370
10.11 Dimensional References for a Flare Stack.......................................................................................................................372
10.12 High Integrity Protection System....................................................................................................................................375
10.13 Vessel Depressuring.........................................................................................................................................................377
10.14 Flare Gas Recovery System.............................................................................................................................................378
LIST OF TABLES
Chapter 1
Table # .....................................................................................................................................................................................Page #
1.1 Relative Atomic Mass (Weight) of Common Oil and Gas Elements..................................................................................3
1.2 Common Paraffin Names, Formulas, and Molecular Weights............................................................................................5
1.3 Paraffin Isomers....................................................................................................................................................................6
1.4 Table of Common Acid Radicals.......................................................................................................................................11
1.5 Example Analysis of a Hydrocarbon Mixture...................................................................................................................13
1.6 Summary of SI Metric Prefixes..........................................................................................................................................14
1.7 Presenting Numbers...........................................................................................................................................................15
1.8 Force and Mass Units.........................................................................................................................................................16
TABLE OF CONTENTS xiii

Chapter 2
Table # .....................................................................................................................................................................................Page #
2.1 Example Inlet Gas Compositions.......................................................................................................................................27
2.2 Example Shale Gas Compositions.....................................................................................................................................27
2.3 Example Coalbed Methane Compositions.........................................................................................................................27
2.4 Generalized NGL Content of Natural Gas.........................................................................................................................28
2.5 Example Well Stream Impurities and their Associated Problems....................................................................................28
2.6 Example Sales-Gas / Transportation Specifications..........................................................................................................29
2.7 Heating Values for Typical Natural Gas Components.......................................................................................................30
2.8 NGL Product and Markets.................................................................................................................................................33

2.9 Example Mercury Concentration Levels in Produced Natural Gas..................................................................................37
2A.1 Example Propane / Butane and Propane Butane Mix Specifications................................................................................45
2A.2 Example Butane and Natural Gasoline Specifications......................................................................................................45
2A.3 Example Y-Grade, Ethane and Ethane Propane Mix Specifications................................................................................46
2A.4 Natural Gasoline Basic Specifications...............................................................................................................................46
Chapter 3
Table # .....................................................................................................................................................................................Page #
3.1 Physical Constants..............................................................................................................................................................57
3.2 Generalized Properties of Petroleum C6+ Groups........................................................................................................... 64
3.3 General API Gravity Ranges for Liquid Hydrocarbons....................................................................................................66
3A.1(a) Physical Properties of Select Fluids – SI......................................................................................................................77-78
3A.1(b) Physical Properties of Select Fluids – FPS.................................................................................................................. 79-80
Chapter 5
Table # .....................................................................................................................................................................................Page #
5.1 Test Separator Data..........................................................................................................................................................109
5.2 KP Plot..............................................................................................................................................................................112
5.3 K-Values............................................................................................................................................................................112
5.4 Comparison of Experimental and Predicted Liquefaction.............................................................................................. 117
5.5 Summary Material Balance for 4-Stage Separation System Shown in Figure 5.9.........................................................120
5.6 Stage Separation Guidelines(excluding Stock Tank).......................................................................................................121
Chapter 6
Table # .....................................................................................................................................................................................Page #
6.1 McLeod-Campbell Component Factors...........................................................................................................................166
6.2 Inhibitor Properties..........................................................................................................................................................173
6.3 Glycol Losses.................................................................................................................................................................... 174
6.4 Comparison of MeOH and MEG Advantages and Disadvantages.................................................................................182
6.5 Comparison of KHIs and AAs Advantages and Disadvantages.....................................................................................189
Chapter 8
Table # .....................................................................................................................................................................................Page #
8.1 Equation Substitutions for Small and Large Pipes..........................................................................................................245
8.2 Pipe Diameter Guideline Example...................................................................................................................................252
xiv VOLUME 1: THE BASIC PRINCIPLES

8.3 Equations for Lines in Parallel.........................................................................................................................................257
8.4 Summary of Gas Flow Equations....................................................................................................................................260
8.5 Characteristics of Gas Transmission Systems.................................................................................................................263
8.6 Equations for Looped Gas Flow Systems........................................................................................................................266
8.7 Typical Overall Heat Transfer Coefficient Values for Gas Pipelines..............................................................................271
8.8 Values of R and ha............................................................................................................................................................273
8.9 Summary of Two-Phase Flow Correlations.....................................................................................................................279
8.10 Pros and Cons of Produced Natural Gas Transportation Options..................................................................................299
8A.1 Allowable Working Pressures for Carbon Steel Piping – SI (CA = 1 mm)..............................................................307-308
8A.2 Allowable Working Pressures for Carbon Steel Piping – SI (CA = 3 mm)..............................................................309-310
8A.3 Allowable Working Pressures for Carbon Steel Piping – FPS (CA = 1/16 inch)..................................................... 311-312
8A.4 Allowable Working Pressures for Carbon Steel Piping – FPS (CA = 1/8 inch)....................................................... 313-314
Chapter 9
Table # .....................................................................................................................................................................................Page #
9.1 Proportional Control.........................................................................................................................................................321
9.2 Control Modes vs. Application........................................................................................................................................326
9.3 Effect of Increase in Process Input to Controller and Control Valve Movement...........................................................327
9.4 Equal-Percentage Valve Characteristics .........................................................................................................................335
9.5 Control Valve Selection Criteria......................................................................................................................................335
9.6 Actuator Advantages/Disadvantages...............................................................................................................................336
9.7 Conditions That Favor the use of Valve Positioner..........................................................................................................337
9.8 Level Measurement Technologies....................................................................................................................................338
9.9 Pressure Measurement Technologies...............................................................................................................................339
9.10 Temperature Measurement Technologies....................................................................................................................... 340
9.11 Instrument Technologies Used in Multiphase Meters—No Fluid Separation................................................................346
9.12 Instrument Technologies Used in Multiphase Separation...............................................................................................346
9A.1 Example Instrumentation Legend....................................................................................................................................348
Chapter 10
Table # .....................................................................................................................................................................................Page #
10.1 Relief Scenarios................................................................................................................................................................357
10.2 C PRV Coefficient............................................................................................................................................................363
10.3 API Orifice Area/Inlet Pipe Area....................................................................................................................................364
10.4 Effect of Thermal Radiation............................................................................................................................................372
10.5 Safety Integrity Levels.....................................................................................................................................................374
TABLE OF CONTENTS xv
1
INTRODUCTION
The First Edition of “Gas Conditioning and Processing” was published in 1968. This Ninth Edition
retains much of the clear, concise and practical explanations of engineering fundamentals presented in the
original edition 45 years ago. Today, virtually all engineering calculations in the area of gas processing are
performed using computer simulation. This evolution of computational capability is a welcome and necessary
development for today’s practitioners and allows significantly more accurate analyses of design options and
variations in operating conditions. Unfortunately, it has lessened the user’s appreciation of the necessity in
understanding the fundamentals which govern applications of the technology as well as the recognition of
limitations and shortcomings in the correlations used and the data which underlie them.
The emphasis in these two volumes continues to be centered on providing relatively simple calcula-
tions and correlations that provide reliable answers to and promote understanding of the applications involved
in moving natural gas and associated liquids from the wellhead to the market. We continue to modify, delete,
or add to the technical content, but the goal remains the same: providing reliable, credible information to
enhance the ability of the individual professional.
Over his 60 years of service to our industry, John Campbell assembled a list of observations to help
guide the conduct of practicing engineers. A short list of these has been compiled under the Campbell Rules of
Engineering, below.
SOME CAMPBELL LAWS OF ENGINEERING

• “Knowledge of the basic fundamentals is the required foundation for successful professional practice.”
• “The utility of a computer calculation is frequently limited by the user’s real knowledge of the physical sys-
tem involved and not by the software complexity.”
• “One cannot calculate reliably what one cannot measure reliably.”
• “Many calculations have as their primary purpose the justification of pre-conceived opinions or positions
(biases) rather than to obtain knowledge.”
• “The true precision and/or accuracy of a calculation result can be no better than that of the least certain
input parameter, i.e., significant figures matter.”
• “Conventional wisdom can never be more than a partial truth because it is based on the past and assumes
no change in the interim.”
• “There is no such thing as a single equation or correlation that is equally valid for all mixtures across the
full range of conditions under which they may exist.”
• “The validity and usefulness of a computation is not necessarily proportional to its complexity.”
CHAPTER 1 1
INTRODUCTION
As implied in the final “Campbell Rule”, many of the simple appearing approaches presented in
these books may actually give more realistic results than some of the more complex simulation programs
now available. Accordingly, one of the primary uses of these two volumes is to check the credibility of
simulation calculations.
Another use is to provide a “quickie” calculation for use in the early feasibility and planning of a
project; or, to troubleshoot and/or improve operating efficiency.
Simplicity has its virtues, but it also imposes limitations. One should not extrapolate the corre-
lations beyond their stated limits without awareness of the increased uncertainty involved. Some of the
factors affecting this are discussed throughout the book.
There are many figures and tables throughout this book that illustrate simple relationships between
the variables. They serve two functions: 1) to better understand how a process or piece of equipment works
and 2) to serve as a basis for judgment — always a necessary ingredient in the engineering process.
Before addressing the details, remember that the professional decision process depends on factors
that are not quantitative or calculable. These include economic, political, cultural, legal, and moral issues
that may turn out to have a greater effect on the final decision than the technical aspects. Engineering cannot
be practiced in a vacuum.
All of the systems discussed in these two volumes are governed by a small group of fundamental
laws and concepts. Understanding these, and their nomenclature, is critical. The most important are:
• The physical properties of the fluids and solids
• The vapor-liquid-solid behavior of a substance as a function of pressure, temperature, and

composition
• The concept of equilibrium
• The use of P-V-T correlations, including equations of state, to predict the phase behavior as
well as the thermodynamic and physical properties of systems
• The use of combination rules for the prediction of mixture behavior from that of individual
pure components present in the mixture
• Thermodynamic concepts that govern the conservation of mass and energy, and the calculation
of the energy changes in process equipment
• Rate equations which describe the rate of something happening in terms of the driving and
resisting forces, the area through which the transfer takes place and the configuration of the
system
In addition, it is required that the practitioner have reasonable literacy in the mathematical, chemical,
and physical sciences.
The remainder of this chapter summarizes some of the terms and nomenclature that will be used
throughout the book. One complication in this area is the inconsistency of numerical systems used through-
out the world. So, dual units are used in the hope that most users will be reasonably happy (even though
not totally satisfied).
With these thoughts in mind, let us begin our journey through the book.
2 VOLUME 1: THE BASIC PRINCIPLES

INTRODUCTION
BASIC TERMINOLOGY
Throughout this book basic chemistry and physics terminology will be used. A brief review follows.
Elements and Atoms

All matter is composed of elements which cannot be broken down or subdivided into smaller
entities by ordinary means. Over 100 materials have been found (or created) which are classified as
elements. These include carbon, hydrogen, sulfur, oxygen, nitrogen and helium: all materials occurring in
petroleum systems.
The atom is the basic unit of each element that can combine with itself or the atoms of other
elements to form a compound.
Chemical Compounds and Molecules

A compound is a substance composed of more than one atom that satisfies both of the following
conditions.
1. The atoms have combined chemically.
2. The compound formed possesses properties different from the atoms of which it is composed.
Chemical compounds are formed by the union of atoms. The molecule is the unit of a compound. A
molecule of water is H2O, two atoms of hydrogen combined with one atom of oxygen.
A diatomic molecule is formed by the combination of two atoms of the same element. Nitrogen
(N2) and oxygen (O2) are the most common examples.
Physical Compounds
A type of physical compound, called a clathrate, may be formed. A gas hydrate is one example of a
clathrate. These compounds are relatively unstable.
Relative Atomic Mass (Weight) Table 1.1

Relative Atomic Mass (Weight) of Common
In forming a compound, elements Oil and Gas Elements
always combine according to fixed mass Atom Symbol Relative Atomic Weight
ratios. It is convenient to use relative atomic
Hydrogen H 1
weight, the relative mass of the atoms of
Carbon C 12
different elements, to express these ratios.
Currently, Carbon-12 is used as the reference Nitrogen N 14
or standard, being assigned the relative Oxygen O 16
atomic weight of 12. On this basis, the Sulfur S 32
relative atomic weights of elements found in
common oil and gas compounds are shown in Table 1.1 (to the nearest whole number).
A relative atomic weight of one element contains about the same number of atoms as a relative
atomic weight of any other element. One gram of hydrogen and 12 grams of carbon each contain about
6 ´ 1023 (Avogadro’s number) atoms. Since relative weights represent a fixed number of atoms, they may
be substituted for atoms in calculations.
CHAPTER 1 3
INTRODUCTION
Relative Molecular Mass (Weight)

The relative molecular weight of a molecule is the sum of the relative atomic weights of the atoms
combining to produce the molecule. For example, water has a relative molecular weight of 18 (H2O = 2 + 16 = 18).
A diatomic molecule like oxygen (O2) has a molecular weight of 32.
The Mol
The term “mol” is the historical abbreviation of the words “gram molecule.” The current definition
of the mol is: “The mol is the amount of substance of a system which contains as many elementary entities
as there are atoms in 0.012 kilogram of Carbon-12.” These elementary entities must be specified but include
atoms, molecules, ions, electrons, etc.

The quantity 0.012 kg is 12 g, the relative atomic weight of carbon. Thus, the mol can be defined
for engineering usage as that mass in grams equal numerically to the sum of the relative atomic weights of
the atoms in the molecule of that substance.
By virtue of the definition, whenever the mol is used as a mass quantity without a prefix, a mass
in grams is implied. If a relative molecular or atomic weight is expressed in pounds mass or kilogram, we
will use the terms lb-mol and kmol, respectively, to denote this is not a standard mol. A kilomol (kmol) is
simply 1000 mol.
1 kmol = 1000 mol = 2.205 lb-mol
1 lb-mol = 454 mol
Throughout this book the mol will be used in many cases as a mass term in those processes where
no chemical changes occur. It is particularly useful for gas calculations. At a given pressure and tempera-
ture equal volumes of different ideal gases contain the same number of molecules. At 0°C [32°F] and
101.325 kPa [14.696 psia] a mol of any gas contains about 6 ´ 1023 molecules and occupies a volume of
22.4 liters. One kmol of gas contains about 6 ´ 1026 molecules in SI units.
Valence
Valence is a measure of the ability of atoms to form molecules by filling the electron shells of
the atoms involved. The valence number is plus or minus, denoting the number of excess or shortage of
electrons needed to fill its outer shell.
The question of atomic bonding is a complex subject involving many factors, as discussed in
standard chemistry references. The concept is mentioned only to point out that the number of bonds or
linkages used in the structural formulas that follow in the next section reflect the valence of the atoms in
these compounds.
Mixture
A mixture is a combination of elements and compounds which may be separated by physical means.
The properties of the mixture are a reflection of the properties of the constituents.
Natural gas and crude oil are mixtures of different compounds. They are analyzed by separating the
mixture into its component parts and identifying each by its properties.

INTRODUCTION
BASIC HYDROCARBON NOMENCLATURE

By definition, a hydrocarbon is any compound composed solely of carbon and hydrogen atoms.
These atoms can combine in a number of ways to satisfy valence requirements. For convenience, these are
separated into “families” or homologous series, each of which is given a name.
The carbon atoms can link together to form “chains” or “rings.” Crude oil and natural gas mixtures
consist primarily of “straight or branched chain” hydrocarbon molecules, the bulk of which are paraffins.
Paraffin Series (Alkanes) Formula: CnH2n+2

Hydrocarbons in this series are saturated compounds. All four carbon bonds are connected either to
another carbon atom or a hydrogen atom, with one such atom for each bond.
Notice that all names end in –ane; the ending used for the paraffin series. In each case, the number
of hydrogen atoms is two times the number of carbon atoms plus two more for the ends of the chain.
The paraffin hydrocarbons are the most stable of the four “families” because all valence bonds are
fully satisfied as indicated by the single line linkage. Most paraffin reactions involve the replacement of
hydrogen atoms with other atoms; the carbon linkage remains stable.
Each successive compound in the paraffin series is created by adding a carbon and two hydrogen
molecules to the previous molecule. The incremental change in relative molecular weight is thus fourteen.
Long chains containing scores of carbon atoms in series may be formed. However, the only ones
normally identified by name contain ten or less carbon atoms.
H H H H H H
H C H H C C H H C C C H
H H H H H H
Methane, CH4 Ethane, C2H6 Propane, C3H8
Figure 1.1 Methane, Ethane, and Propane
Table 1.2
Common Paraffin Names, Formulas, and Molecular Weights
Name Formula Mol. Wt. Name Formula Mol. Wt.

Methane CH4 16 Hexane C6H14 86
Ethane C2H6 30 Heptane C7H16 100
Propane C3H8 44 Octane C8H18 114
Butane C4H10 58 Nonane C9H20 128
Pentane C5H12 72 Decane C10H22 142
CHAPTER 1 5
INTRODUCTION
In referring to a given paraffin hydrocarbon, the abbreviation C3 for propane, C4 for butane, etc.
may be used. Statements like “propanes plus fraction (C3+)” refer to a mixture composed of propane and
larger molecules.
Paraffin Isomers. When the paraffin series molecule contains four or more carbon atoms there are
different ways these can be connected without affecting the formula. Compounds which have the same
chemical formula but a different molecular structure are called isomers. They have the same molecular
weight yet possess different physical and chemical properties.
There are only two isomers of butane. In the structural diagram shown for iso-butane we could
draw the carbon atom above instead of below the carbon chain. But, this would be just a “mirror image” of
the molecule as drawn. It is the same molecule with the same properties. The adjective “normal” is used to
designate a molecule with the carbon atoms in a straight line.

An “isomer” has the same formula but a different arrange- Table 1.3
Paraffin Isomers
ment of the carbon atoms. In a compositional analysis, these
are often abbreviated as “n” and “i” respectively. Paraffin No. Isomers
C1 Methane 0
Table 1.3 provides the number of paraffin isomers
possible for C1-C10, and C15. The number of possible isomers C2 Ethane 0
increases dramatically with the number of carbons present in C3 Propane 0
the molecule. C4 Butane 2
C5 Pentane 3
H H H H H H H C6 Hexane 5
H C C C C H H C C C H C7 Heptane 9
C8 Octane 18
H H H H H C H
C9 Nonane 35
H H H
C10 Decane 75
Normal Butane, nC4 Isobutane, iC4
C15 Pentadecane 4,347
Figure 1.2 Normal Butane and Isobutane
Olefin or Ethylene Series (Alkenes) Formula: CnH2n

The olefin group of compounds is a simple straight chain series in which all the names end in -ene.
Ethylene (ethene) is the simplest molecule in the series, and is shown in Figure 1.3 along with propylene.
Hydrocarbons in this series combine easily
H H H H H with other atoms like chlorine and bromine, without
the replacement of a hydrogen atom. Olefins are called
C C H C C C H
= =
unsaturated hydrocarbons, because they have double
H H H bonds.
Ethylene Propylene
(Ethene, H2C = CH2) (Propene, H2C = CHCH3) The maximum bonding capacity of the carbon
atom is not fully satisfied by hydrogen or carbon
Figure 1.3 Ethylene and Propylene atoms. Two adjacent carbon atoms form a “temporary”
or double bond (in the absence of other available
atoms) to meet bonding requirements fixed by valence. It is a necessary but unstable alliance. The structural
formula for the olefins uses a double line to indicate the double carbon-carbon linkage, which is the most
reactive point in the molecule.
With four or more carbon atoms, isomers also may result from the position of the double bond as
well as the arrangement of the carbon atoms.

INTRODUCTION
These molecules possess many different properties. They

may furthermore react at the double bond or be split into two H H H H
molecules at the double bond to form compounds with different H C
=
C C C H
characteristics.
H H
The concentration of olefins in natural gas is typically insig- 1-Butene, CH3CH2CH = CH2
nificant. Certain crude oils contain them in measurable amounts.
H H H H
Acetylenic or Alkyne Series Formula: CnH2n-2
H C C C C H
=
This series is of basic importance only in certain refining

H H
and petrochemical applications. Acetylene is the most important

member of this series. The structure and formula for acetylene is 2-Butene, CH3CH = CHCH3
shown in Figure 1.5.
Figure 1.4 1-Butene and 2-Butene
There is a triple bond between the carbon atoms. This satisfies
the valence requirements but the carbon linkage is very weak.
Acetylene is even more reactive than the olefins. Carbon dislikes the H C C H
sharing of three valence linkages even more than sharing two. Acetylene not Acetylene, C2H2
only is unsaturated, it is almost unstable chemically. In the liquid state it is
explosive if subjected to a sudden shock. Figure 1.5 Acetylene
Diolefins Formula: CnH2n-2 H H
C= C= H
The diolefins have the same formula as acetylene. The members of this H C C
series contain two double linkages. They normally are named by replacing the
-ane for the corresponding paraffins by -diene. H H
Diolefins are primarily of concern in petrochemical plants. Butadiene Butadiene, C4H6

is a primary ingredient in synthetic rubber compounds. The structure and
formula for butadiene is shown in Figure 1.6. Figure 1.6 Butadiene
All of these unsaturated compounds are reactive. They may be hydrogenated. Liquid cooking oils
(unsaturated) may be hydrogenated to form solid fats.
These compounds also polymerize: the process wherein a very large molecule is built up from the
reaction of small identical molecules (monomers). Ethylene and propylene polymerize to form polyethyl-
ene and polypropylene, the basic ingredients in plastic materials. Acetylene polymerizes to form benzene,
a cyclic hydrocarbon.
Aromatic (Benzene) Series Formula: CnH2n-6

Aromatic is the word used to describe an unsaturated hydrocarbon molecule where the carbon
atoms form a ring, a cyclic compound. Benzene is the parent compound of this series. Other common
aromatic compounds include ethylbenzene, toluene, and xylene. The chemical formulas and structures for
these compounds are shown in Figure 1.7. These compounds are commonly referred to as BETX.
Since these aromatics are unsaturated, they react readily. They may be oxidized to form organic
acids. They also promote foaming and other operational problems in the production and handling of crude
oil and natural gas. In addition, relative to paraffins, aromatics are significantly more soluble in water and
water-based solvents such as glycol, amine, and methanol.
CHAPTER 1 7
INTRODUCTION
BETX is an environmental concern in our industry. Benzene and ethylbenzene are known carcino-
gens. Toluene and xylene are respiratory and digestive irritants. As a result, they all have environmental
emission limits. Due to their solubility in water based solvents, significant amounts of BETX components
may be absorbed in gas dehydration and gas treating contactors, i.e., glycols, amines, and physical solvents.
These absorbed BETX compounds are subsequently stripped from the solvent streams in the solvent regen-
erator. For glycol units, this stream was historically vented to atmosphere. This practice is no longer allowed
in many countries and treatment of the vent stream to reduce BETX emissions is required. For amine units,
this stream may be vented to atmosphere or fed to a sulfur plant, where hydrocarbons can deactivate the
catalyst in the reactor beds.
H
H
H C H
H
H H H H H C H
C
C =
C H C C C H C C H
= = =
H C C H C C H H C C H
=
H H C C H
=
=
H C= C H C= C H C= C H C
C H C H C
H C H
H H H
H
Benzene, C6H6 Ethylbenzene, C6H5CH2CH3 Toluene, C6H5CH3 Para-Xylene, C6H4(CH3)2
Figure 1.7 BETX Compounds (Benzene, Ethylbenzene, Toluene, Xylene)
Most crude oils and condensates contain only a small amount of aromatics. Some contain signifi-
cant amounts. Any analysis of crude oil and natural gas should include aromatics. They have significantly
different physical properties from paraffins. Even small amounts can influence physical behavior and affect
design and operation.
H H Naphthene Series Formula: CnH2n

H H
C The naphthene series has a ring structure but is saturated. Naphthenes
H C C H are found in most crude oils and condensates. Being saturated molecules, they
are not very reactive. Cyclohexane is a common member of this series. Its
H C C H structure and formula is provided in Figure 1.8.
H C
H
Cyclohexane’s molecule is structurally similar to benzene except that
H H
it is saturated. Like benzene, on chromatographic analysis it appears between
Cyclohexane, C6 H12
n-hexane and n-heptane. Other common naphthenic compounds include
Figure 1.8 Cyclohexane cyclopentane (C5H10), methylcyclopentane (C6H12), and methylcyclohexane
(C7H14).
TYPICAL COMPOUNDS IN PRODUCTION/PROCESSING SYSTEMS

In the gathering, production, conditioning, and processing of natural gas and its associated liquids,
the primary concern is the behavior of hydrocarbons with 10 or less carbon atoms (C1-C10). The concentra-
tion of naphthenic and aromatic hydrocarbons is generally much lower than the paraffins. The presence of
common contaminants found in natural gas must also be taken into consideration.
In addition, natural gas and natural gas liquids are “treated” or “conditioned” by use of alcohols,
glycols, amines, and other solvents.

INTRODUCTION
Common Contaminants Found in Natural Gas

Acid Gases
Carbon dioxide (CO2) and hydrogen sulfide (H2S) are relatively common contaminants in natural
gas. These gases are often referred to as acid gases because when dissolved in water they form weak acids.
In water-wet systems, these compounds can cause significant corrosion issues depending upon the concen-
trations and operating pressure of the system. Water is the most common contaminant in natural gas streams.
“Sour” gas or crude is a common term used in the industry. The term sour generally applies to the presence
of hydrogen sulfide and/or other organic sulfur compounds in the gas or crude stream in amounts that are
greater than the product concentration limits.
Hydrogen sulfide is toxic to humans. It will S O

O =
C O=
H H H H
burn to form SO2 which is a respiratory irritant
and is a contributor to acid rain. H2S can form Carbon Dioxide, CO2 Hydrogen Sulfide, H2 S Water, H2O
an iron sulfide scale (which is pyrophoric) as a

Figure 1.9 Acid Gas Compounds and Water
corrosion by-product with steel.
Mercaptans
Compounds with the general formula RSH are known as mercaptans (thiols). They may be regarded
as sulfur alcohols since the formula is the same if you replace the oxygen atom in the (OH) radical with a
sulfur atom.
H H H
R S H H C S H H C C S H
H H H
Mercaptans, where R Methyl Mercaptan Ethyl Mercaptan
is an alkyl radical (Methanethiol, CH3SH) (Ethanethiol, CH3CH2SH)
Figure 1.10 General Mercaptan, Methyl Mercaptan and Ethyl Mercaptan
Other Carbon-Sulfur Compounds

There are several other carbon-sulfur compounds present in sour petroleum fluids. These are discussed
in greater detail in Volume 4 of this series, “Gas Treating and Sulfur Recovery” by R.N. Maddox and D.J.
Morgan. Some examples are shown in Figure 1.11.
Sulfur is a very reactive element that
O C S H H
= =
combines chemically with many other elements and
Carbonyl Sulfide, COS C C
compounds. Its compounds react with carbon steel to
=
=
form sulfides and oxides of iron. Many compounds C

S
C
S C S H H
= =
polymerize and form the “sludge” so common in sour Thiophene,
Carbon Disulfide, CS2
petroleum systems. This sludge is often corrosive and HC=CH–S–HC=CH
should be removed by filtration.
Figure 1.11 Carbonyl Sulfide, Carbon Disulfide, Thiophene
Other Contaminants
On occasion, natural gas streams will also contain inerts, which are chemical compounds that are
non-reactive. The common inerts found are: Nitrogen (N2), Argon (Ar), and Helium (He). Mercury can be
found in trace levels (parts per billion) in natural gas streams which can contaminate the piping, and can
cause catastrophic failure of aluminum components (such as brazed aluminum heat exchangers) in process-
CHAPTER 1 9
INTRODUCTION
ing facilities. Mercury is toxic to humans. Oxygen (O2) is not naturally occurring in the reservoir. However,
it can enter the production system through leaks in low pressure points in the system. The presence of oxygen
increases corrosion and degrades gas treating solvents.
Less common, but problematic is NORM (naturally occurring radioactive materials), generally
uranium and thorium and their daughter products, radon, lead isotopes plus radium 226 and radium 228.
These compounds may be present in the produced water from the reservoir and can contaminate the facility
equipment and piping resulting in hazardous maintenance conditions for personnel. Solid materials such as
sand produced from the reservoir, corrosion by-products, solid sulfur, salts, waxes and asphaltenes (found in
crude production only) may also be present.
Alcohols
Simple alcohols are formed from the

H H H
addition of a single hydroxyl radical to an alkyl
radical. The name of the alcohol ends in “ol,” or the H C OH H C C OH
name of the alkyl radical is followed by the word
H H H
“alcohol.”
Methanol Ethanol
The molecular structures and formulas for (Methyl Alcohol, CH3OH) (Ethyl Alcohol, C2H5OH)
methanol and ethanol are shown in Figure 1.12.
Figure 1.12 Methanol and Ethanol
Amines
There are a number of common organic
compounds formed by the reaction of organic H H H H
materials with ammonia (NH3). In this reaction one HO C C HO C C
or more hydrogen atoms are replaced by an organic H
H H H H
radical. The word “amine” is used commonly to
N H N C H
denote this type of compound. There are a large H H H H
number of amines used in the chemical industry. H
HO C C HO C C
The alkanol amines, particularly diethanol
amine (DEA) and methyldiethanol amine (MDEA) H H H H
shown in Figure 1.13, are commonly used for treating Diethanolamine, DEA Methyldiethanolamine, MDEA
sour gases and liquids. As the names indicate, the
alkanol amines may be considered a combination of Figure 1.13 Diethanol Amine and Methyldiethanol Amine
an alcohol and ammonia.
A more detailed discussion of amines can be found in Chapter 19, and Volume 4 of this series, “Gas
Treating and Sulfur Recovery”.
H H
CH2CH2 OH CH2 O CH2CH2 OH
HO C C OH O
CH2CH2 OH CH2 O CH2CH2 OH
H H
Monoethylene Glycol, MEG Diethylene Glycol, DEG Triethylene Glycol, TEG
Figure 1.14 Commonly Used Glycols – Monoethylene Glycol, Diethylene Glycol, Triethylene Glycol

INTRODUCTION
Glycols
The glycols are a family of chemicals, sometimes called diols. They may be regarded as complex
alcohols since they contain alkyl and hydroxyl radicals. Glycols used for dehydration and are based on the
ethyl radical.
As with most compounds containing hydroxyl groups, the glycols react readily with other
compounds and elements.
Acids, Bases and Salts Table 1.4

Table of Common Acid Radicals
Acids and bases are important in
Acid Radical
the handling of petroleum-water mixtures, (anion) Symbol Acid Formula
processing, and other such functions of the
petroleum industry. Chloride Cl–1 Hydrochloric HCl
Carbonate CO3–2 Carbonic H2CO3
Except for water and hydroxides
(compounds containing the OH radical), all Sulfate SO4 –2 Sulfuric H2SO4
inorganic compounds of hydrogen are acids. Nitrate NO3–1 Nitric HNO3
They consist of hydrogen combined with an
Phosphate PO4 –3 Phosphoric H3PO4
acid radical (anion).
Notice that hydrogen (valence of +1) combines with the acid radical in a proportion such that the
net valence of the compound formed is zero. This is the rule to be followed in all compound formation.
Since the valence of the sulfate radical is –2, it takes two hydrogens.
The combination of a metal cation such as sodium with the hydroxyl anion (OH) produces a base.
Sodium hydroxide (NaOH) is commonly called caustic.
pH. The acidity or alkalinity of a material is measured on a scale similar to that of a thermometer.
This pH scale is the logarithm of the reciprocal of the hydrogen ion concentration. It runs between 0 and
14. A pH of 7 is neutral. Acids have a pH less than 7; bases (alkaline solutions) have a pH greater than 7.
Since pH is a logarithmic function, a solution possessing a pH of 5.0 is 100 times more acidic than
one with a pH of 7.0.
Radicals
A radical represents a group of atoms that act as a single unit in the formation of many common
compounds.
Alkyl Radical. The simpler paraffins often react by replacing one hydrogen with some other radical
or element. These example alkyl radicals have the formulas:
CnH2n + 1 = (CH3) , (C2H5) , (C3H7)

methyl ethyl propyl
The parenthesis indicates the radical group. The alkyl radical normally has a valence of +1.
In many cases the alkyl radical is indicated by the symbol “R.” The formula for methanol is CH3OH;
for ethanol it is C2H5OH. Both may be written as R1OH and R2OH respectively. When “R” is used unsub-
scripted the specific alkyl radical is not identified; it is used only to show general reaction characteristics.
CHAPTER 1 11
INTRODUCTION
Hydroxyl Radical (OH). This combination occurs in many common compounds. It combines with
hydrogen to form water — H(OH) or H2O; with metallic salts like sodium, calcium and magnesium to form
hydroxides (bases, caustics); and with alkyl radicals to form alcohols, such as methanol, ethanol, etc.
SO 4= , SO 3= If radicals like these combine with hydrogen, an acid is formed. When combined with
elements like sodium, calcium, magnesium, and barium, a salt is formed (which occurs commonly in water
systems). The scale formed in water systems is caused by precipitation of salts like these. The common
names for some common radicals of this type are:
SO4= — sulfate — carbonate

— sulfite
SO3= — bicarbonate
Each of the radicals has a valence found from the valence of its elements. The hydroxyl radical (OH)
has a valence of minus one and is nearly always written as (OH)–1. It therefore combines in proportions fixed
by this valence: H(OH), NaOH, Mg(OH)2, so that the sum of plus and minus valences equals zero.
ANALYSIS OF MIXTURES
A routine analysis of a hydrocarbon mixture is shown in Table 1.5. Notice that only paraffin hydro-
carbons are shown. This is not entirely correct, although the paraffins may be the predominant series present.
Notice also that all molecules heptane and larger are lumped together as a heptanes plus (C7+) fraction.
The hydrocarbon portion of an analysis like this usually is obtained from a chromatograph. When
the output from this technique is printed graphically a series of “peaks” are shown rising from a base line.
The area under the peak for any component is proportional to the amount of that component in the mixture.
The instrument is calibrated using standard samples of known analysis so that peak area can be converted
to the amount present.
Figure 1.15 is an example of a chromatogram (chart) from a chromatographic analysis. When the
ordinary peak height is so low it is difficult to measure, it is attenuated (multiplied). The attenuation factor
is used to convert the peak height shown for analysis.
The chromatograph used to obtain Figure 1.15 was capable of showing hydrocarbons other than
paraffins. Notice that all of these occur in the C6 thru C9 range of molecules. Many chromatographs, particu-
larly those used for routine gas analyses, are unable to detect all of these components. In these instances,
hydrocarbons heavier than nC5 are often reported as C6+ or (as shown in Table 1.5) C6 and C7+. Analyses
which report the concentration of species heavier than C6 or C7 are referred to as extended analyses. For
liquid hydrocarbons and reservoir fluids, extended analyses may show hydrocarbons beyond C30.
Frequently, extended analyses will report the heavier hydrocarbons as C6, C7, C8, etc. and not
identify the individual molecular species in the carbon number “cut”. When analyses are reported in this
way C6 includes all the components which exit the chromatograph between the nC5 and (including) nC6
peaks, C7 includes all species between nC6 up through nC7 and so on. As can be seen from Figure 1.15, this
means that some molecules with 6 carbon atoms, e.g., benzene, cyclohexane and methylcyclopentane are
actually reported as C7.
Note that when an extended analysis is reported as C6, C7, C8, etc. the carbon number “cut” does
not represent a pure component but rather several components. For example, in the C7 “cut” there are 9
paraffin isomers, 2 naphthenes and 1 aromatic, or 12 different molecules. Proper characterization of these
“cuts” is important to accurately model the fluid behavior. A common default characterization is to assume
that the cut is a normal paraffin, i.e., C6 = nC6, C7 = nC7, etc. The properties of the n-paraffin, e.g., boiling

INTRODUCTION
point, density, molecular weight are often significantly different than the average properties for the cut.
Characterization methods will be discussed in more detail in Chapter 3.
C6+
Ethane C7+
C6 C7 C8 C9 Table 1.5
Example Analysis of a
Hydrocarbon Mixture
Propane
Component Mol%
Methylcyclohexane
Nitrogen 0.34
Carbon Dioxide 0.91
Detector Response
Methylcyclopentane
Sulfur (as H2S) 0.50

Cyclohexane
Methane (C1)
n - Heptane
21.36
i - Pentane
n - Pentane
Ethane (C2) 36.78

Propane (C3) 10.21
n - Hexane
n - Butane
i-Butane (iC4) 6.38

n-Butane (nC4) 9.84
i-Pentane (iC5) 2.63
n - Octane
i - Butane
n-Pentane (nC5) 4.01

Toluene
Benzene
Hexanes (C6) 3.90

n - Nonane
Methane
Heptanes Plus (C7+) 3.14

Total 100.00
Attenuation
× 80 × 16 × 8 ×2 Mol wt. C7+ = 118
Factors
Time Rel. Density C7+ = 0.71
Figure 1.15 Chromatogram of Condensed Liquid
Commonly accepted standards for analysis of hydrocarbon fluids by gas chromatography are
shown below:
• GPA 2261: Analysis for Natural Gas and Similar Gaseous Mixtures by Gas Chromatography
• GPA 2286: Test method of Extended Analysis for Natural Gas and Similar Gaseous Mixtures
by Temperature Programmed Gas Chromatography
• ISO 6974: Natural gas – Determination of hydrogen, inert gases and hydrocarbons up to C8 –
Gas Chromatographic method
• ISO 6975: Natural Gas – Extended analysis – Gas Chromatographic method
Many operating problems are the direct result of inadequate analysis. This may result from failure to:
1. Analyze for CO2 and sulfur compounds
2. Identify the presence of aromatics and other nonparaffin hydrocarbons
3. Adequately characterize the heavier fractions
CHAPTER 1 13
INTRODUCTION
These will be discussed in more detail in subsequent chapters. There are, however, some general
guidelines.
1. Always analyze for CO2 and H2S. Sulfur contents as low as 3-10 parts per million may prove
troublesome. If the sulfur content (reported as H2S) is higher than this, a special analysis for
carbonyl sulfide (COS), carbon disulfide (CS2) and mercaptans is worthwhile.
2. Some crude oils and condensates may contain up to 20-30% aromatics. Ignoring aromatic com-
ponents can compromise the mechanical design and reduce validity of equilibrium calculations.
3. If the gas is from a separator, characterizing the heaviest fraction through C7+ may be adequate
for production facility design. If it is wellbore gas it may not be adequate. Crude oil may need
to be characterized through C20+ to achieve reliable equilibrium predictions.
The prompt and proper analysis of representative samples is a critical factor. Any calculation is an
exercise in futility unless the analyses used are reliable. Inadequate sampling and analysis is a major cause
of system problems. A sampling program should be planned carefully.
BASIC UNITS OF MEASUREMENT

Dual SI/FPS units are used throughout these books. This is a necessary compromise because some
of the world’s petroleum industry uses FPS (oilfield) units. Since it is not economically feasible to publish
separate editions, dual units are used. There is some element of frustration involved, but we have found that
dual units help make the user more “bilingual,” a useful trait.
Metric units of the System Internationale (SI) are the primary units in these texts. The SI system
possesses many advantages. It is not ambiguous; only one unit is defined for each quantity. Each unit
also possesses a unique, carefully defined symbol. A decimal (powers of ten) relationship exists between
multiples of units. The system of units also has been chosen in such a way that equations between numerical
values and quantities both possess the same form. In a coherent system like this no conversion factors are
needed in the equations so long as one expresses all quantities in basic or derived units.
However, it is not feasible to express all quantities in basic or derived units, particularly when dealing
with pressure and energy. Very large or small numbers result, which are inconvenient to handle arithmetically
or are difficult to compare. Thus, a series of prefixes has been approved, as shown in Table 1.6.
Table 1.6
Summary of SI Metric Prefixes
SI Prefix
SI Symbol, Use Meaning in
Multiplication Factor Prefix Roman Type Pronunciation (U.S.) Meaning (U.S.) Other Countries
1 000 000 000 000 000 000 = 1018 exa E ex’ a (a as in a bout) one quintillion times trillion
1 000 000 000 000 000 = 1015 peta P as in p etal one quadrillion times thousand billion
1 000 000 000 000 = 1012 tera T as in terra ce one trillion times billion
1 000 000 000 = 109 giga G jig’a (a as in a bout) one billion times milliard
1 000 000 = 106 mega M as in mega phone one million times
1 000 = 103 kilo k as in kilo watt one thousand times
100 = 102 hecto h heck’ toe one hundred times
10 = 10 deka da deck’a (a as in a bout) ten times
0.1 = 10 -1 deci d as in deci mal one tenth of
0.01 = 10 -2 centi c as in senti ment one hundredth of
0.001 = 10 -3 milli m as in mili tary one thousandth of
0.000 001 = 10 -6 micro m as in micro phone one millionth of
0.000 000 001 = 10 -9 nano n nan’oh (an as in an t) one billionth of + milliardth
0.000 000 000 001 = 10 -12 pico p peek’ oh one trillionth of + billionth
0.000 000 000 000 001 = 10 -15 femto f fem’ toe ( fem as in fem inine) one quadrillionth of thousand billionth
0.000 000 000 000 000 001 = 10 -18 atto a as in an ato my one quintillionth of trillionth

INTRODUCTION
Experience has shown that the use of over 2 to 3 significant figures is unrealistic. Prefixes are thus
chosen to stay within this guideline. In a few selected cases, alternate units are allowed to minimize the
need for prefixes.
Consistent with this, conversion factors herein are rounded off. This policy is compatible with the
accuracy of data being addressed by the calculation.
Of course, there are cases with large or small numbers where the zeros are significant. To limit their
use, one of the following conventions will be used.
Presenting Numbers
The traditional use of commas and periods has been changed. A comma or period is used only to
denote a decimal point. For a number with more than four digits a space is now left where a comma or
period was used to denote groups of three numbers. Either of these power forms is acceptable.
Table 1.7
Presenting Numbers
New Old
1 200 000.00 1,200,000.00 or 1.200.000,00
1200.00 or 1 200.00 1,200.00 or 1200.00 or 1.200,00
0.104 0.104 or 0,104
0.001 04 0.00104 or 0,00104
Numbers containing many zeros as significant figures are written conveniently as follows:
1,200,000 = 1.2 ´ 106 = 1.2(E + 06)
0.00104 = 1.04 ´ 10 –3 = 1.04(E – 03)
All measurements are approximations of exact values and contain some defined amount of exper-
imental uncertainty. The experimental uncertainty is represented in the use of significant figures. For
example, if a mass is reported to be 35.3 kg, the number of significant figures in the measurement is 3. This
implies that the mass has been measured to the nearest 0.1 kg and would have an absolute uncertainty of
plus or minus 0.1 kg. Understanding and appropriately applying the use of significant figures is important
for engineering calculations.
Engineering calculations manipulate measured variables with a defined number of significant
figures. The solutions of these calculations must be rounded off as the final result of the calculation cannot
be more accurate than the data that has been used.
For addition and subtraction operations, the result is rounded off so that it has the same number
of digits as the measured variable having the fewest decimal places. For multiplication and division, the
solution should be rounded off so as to have the same number of significant figures as the variable with the
least number of significant figures.
Mass, Force and Weight

Mass as a quantity is a measure of the amount of matter in a body by virtue of which it possesses
inertia. The basic units of mass used most commonly (pound-mass and kilogram) are specified as the name
for the mass of specific bodies of platinum iridium preserved as standards.
CHAPTER 1 15
INTRODUCTION
Force is the result when a mass is accelerated. This acceleration may be due to gravitational effects
or imposed artificially. The basic relationship between mass and force is:
(1.1)
Where: m = mass
a = acceleration
gc = proportionality constant for force
One of the major differences between SI metric and the earlier metric systems is the manner in
which the force-mass relationship is handled. Table 1.8 shows five systems that have been used. Column
(5) shows the SI metric system units. Column (1) shows the FPS system units.
Table 1.8
Force and Mass Units
(1) (2) (3) (4) (5)

Mass lbm lbm kg g kg
Length ft ft m cm m
Time sec sec s s s
Force lbf poundal* kgf dyne N
a 32.17 ft/sec2 1.0 ft/sec2 9.81 m/s2 981 cm/s2 1.0 m/s2
lbm-ft lbm-ft kg m g cm kg m
gc 32.17 1.0 pdl-sec2 9.81 1.0 1.0 N s2
lbf-sec2 kgf s2 dyne s2
*Poundal is the name given to the unit ft-lb/sec2.
Note that the newton (N) is the force required to accelerate one kilogram at the rate of one meter
per second squared. This is a coherent equation since the proportionality constant is unity.
In using Equation (1.1), note that the name for the force unit is governed by the mass unit, the
acceleration rate specified and the numerical value of the proportionality constant.
Weight is a term to be avoided even though it is often used to denote mass. Weight is a measurement
of the attraction of gravity on a given mass. It thus varies with the magnitude of gravity. Weight is really a
force.
The differentiation between weight and force has been muddled by the definition of a pound force
(lbf) as a pound of mass (lbm) subject to the earth’s gravitational acceleration of 32.17 ft/sec2 at 45° latitude
and sea level. By setting the proportionality constant equal to this acceleration, a pound force (weight) was
equal numerically to a pound mass. In the SI metric system no such ambiguity exists. The basic unit of force
is the newton (N) and the basic unit of mass is the kilogram (kg).
This standard acceleration = 32.17 ft/sec2 = 9.81 m/s2. It is the one used normally to convert force
to pressure.
Length, Area and Volume

The standard unit of length is the meter (m). Common length units employed are the millimeter
(mm), centimeter (cm), decimeter (dm) and kilometer (km).
1 m = 1000 mm = 100 cm = 10 dm = 0.001 km
1 m = 3.28 ft, 1 ft = 0.305 m
1 statute mile = 1.61 km, 1 km = 0.621 statute mile

INTRODUCTION
Area is expressed in the same length units squared.
1.0 m2 = 1.0 ´ 106 mm2 = 100 dm2 = 10.76 ft2

1.0 hectare (ha) = 1.0 ´ 104 m2 = 2.47 acres
1.0 sq mile = 2.59 km2 = 259 hectares
The basic volume term is cubic meters. The liter (L) is an allowable name for the cubic decimeter.
The API barrel (bbl), which is 42 U.S. gallons, is not a part of the SI metric system, but is still widely used
to denote liquid production volumes in the oil industry worldwide.
1 m3 = 1000 dm3 = 1000 L = 35.31 ft3

1 L = 0.001 m3 = 1000 cm3 = 0.0351 ft3 = 61 in3

1 ft3 = 0.0283 m3 = 28.3L = 7.48 U.S. gal. = 6.23 U.K. gal. (Imperial gallon)
1 bbl = 0.159 m3 = 159 L = 5.61 ft3 = 42 U.S. gal. = 35 U.K. gal.
Density
The usual units are kg/m3 or lbm/ft3. Density varies with pressure and temperature. Standard or
reference density usually is reported at standard atmospheric pressure and some temperature like 0°C,
15°C, 25°C, 60°F or 77°F. For most engineering calculations involving large amounts of liquid, the standard
density is adequate. For custody transfer and gases, an actual density is necessary at the P and T of the calcu-
lation.
1 kg/m3 = 0.001 g/cm3 = 0.0624 lb/ft3

1 lb/ft3 = 16.02 kg/m3 = 0.016 g/cm3
1 g/cm3 = 1000 kg/m3 = 1.0 kg/L = 62.4 lb/ft3
Relative density is the density of the system divided by that of a reference substance at specified
conditions. Relative density is the preferred SI metric term replacing specific gravity. The reference for
liquid is water and for gas is air.
(t liquid) (t gas) (MW gas)
cL (t water) cg (t air) (1.2)
(MW air)
In solving Equation (1.2), the density of water usually can be taken as 1000 kg/m3, 1.0 g/cm3, 1.0
kg/L or 62.4 lbm/ft3. MW of air is taken as 28.96 (or 29).
Where: MW = relative molecular weight
The relative density of an oil may be expressed in API gravity, °API. The equation is:
141.5 % 141.5
cL = API = c – 131.5
131.5 + % API L
(1.3)
For a constant molecular weight, the relative density for different hydrocarbon families follows:
cLparaffins < cLnapthenes < cLaromatics
Understanding the trend in relative density at a constant molecular weight for the hydrocarbon
families is a key principle when accounting for the density of liquids in the production process. A highly
aromatic liquid stream will have a higher density than that of a highly paraffinic liquid stream.
CHAPTER 1 17
INTRODUCTION
Pressure
Pressure is the force exerted per unit area. The standard pressure term is the pascal (Pa) = 1 N/m2.
This is a small pressure unit, 1 lbf/in2 (psi) = 6895 Pa. A pressure of 500 psi would be 3 447 500 Pa, an
awkward number to handle and deal with. So, the kilopascal (kPa) and megapascal (MPa) are used most
commonly. The use of the term kgf/cm2 as a measure of pressure virtually has disappeared. In some areas
the term bar is used as a special name for 100 kPa.
Absolute pressure is used in most engineering calculations. In FPS units an “a” is added to indicate
absolute pressure (psia, psfa); “g” is added for gauge pressure (psig, psfg). In SI metric no suffix will be
used for absolute pressure. A statement P = 138 kPa implies an absolute pressure. If a gauge pressure is used
it will be written P = 37 kPa(g).

100 kPa = 1 bar = 0.987 atm = 1.02 kgf/cm2 = 14.50 psi
14.696 psia = 1 atm (std) = 101.325 kPa = 1.01 bar = 1.03 kgf/cm2
Fluid Head. A vertical column of gas or liquid will exert a pressure on the bottom. This head,
expressed in feet or meters, may be converted to a pressure term by the equation:
P = A(t)(H)(g/gc) (1.4)
SI FPS
Where: t= fluid density kg/m3 lb/ft3
H= fluid column m ft
g= grav. acceleration (std) 9.81 m/s2 32.17 ft/sec2
gc = prop. constant 1.0 kg•m/N•s2 32.17 lbm-ft/lbf-sec2
P= pressure kPa psi
A= unit conversion factor 0.001 0.0069
Actual gravitational acceleration will vary by site, but the use of standard values normally is satisfactory.
Temperature
The SI units are degrees Celsius (°C) and Kelvin (K). The term “centigrade” is discouraged.
°C = 0.556 (°F – 32) °F = (1.8)(°C) + 32
K = °C + 273 °R = °F + 460
Degrees Fahrenheit (°F) and Rankine (°R) are the corresponding values in the FPS system of
units. Absolute temperature is used in many engineering calculations.
Work and Power

The units of work are force times a distance. Power is the time rate of doing work. The standard
work units are the joule (J) = 1.0 Nm and the ft-lbf. Once again the joule is a very small unit so the kilojoule
(kJ) or megajoule (MJ) normally is used.
1 kJ = 0.001 MJ = 737 ft-lbf
In rotating equipment and heat transfer applications we are concerned with power. The watt (W)
and horsepower (hp) are the most common terms.
1.0 W = 1.0 J/s 1.0 kW = 3600 kJ/h = 1.34 hp
1.0 hp = 550 ft-lbf/sec 1.0 hp = 0.746 kW = 2686 kJ/h

INTRODUCTION
Heat Energy
As noted in later chapters, heat energy must have the equivalent units as work and power in order to
make calculations involving the conversion between them. In SI metric the joule is used also for heat energy;
the British Thermal Unit (Btu) is the FPS counterpart. There are several definitions of the Btu, but the Inter-
national Table value will be used for all conversions. For our purposes the differences are trivial.
1.0 Btu = 1.055 kJ = 778 ft-lbf
1.0 kW = 3600 kJ/h = 3413 Btu/h
1.0 hp = 2545 Btu/h = 2686 kJ/h
Energy per unit mass will be expressed in kJ/kg and Btu/lbm, in most instances.
1.0 Btu/lbm = 2.326 kJ/kg = 6.46 × 104 kW•h/kg
Viscosity
Viscosity is a parameter which physically represents the drag forces caused by the attractive forces
in adjacent fluid layers. It might be considered the internal friction between molecules, separate from that
between the fluid and the solid wall.
The poise was the original unit: 1 poise = 1 (dyne-sec)/cm2. For petroleum systems the centipoise
(cp) is the most convenient unit. It may be expressed in force units or equivalent mass units. In SI metric
the Pa•s is the preferred unit.
1.0 cp = 0.001 Pa•s = 0.001 kg/(m•s) = 6.72 ´ 10–4 lbm/(ft-sec)
Most calculations in this book use dynamic viscosity. However, dynamic viscosity divided by
density is known as kinematic viscosity with the primary unit being the centistoke (cSt).
1.0 cSt = 1.0 mm2/s = 1.08 ´ 10-5 ft2/sec
Volumetric-Mass Conversions
The standard cubic foot and the standard cubic meter are a result of historical contracts for the
metering and custody transfer of natural gas. In engineering calculations, it is necessary to convert these
volume terms to an appropriate mass term. This is routine but a nuisance.
This standard volume is designated at some prescribed base pressure and temperature. In the U.S.
the historical base temperature has been 60°F; the historical base pressure in the range of 14.4-15.025 psia,
depending on the organization. In recent years 14.696 psia, the standard atmospheric pressure, has been the
most common pressure used. This is the base pressure adopted for FPS units in this book.
In the SI system two sets of base conditions have emerged. A normal cubic meter (Nm3) uses the
base conditions of 0°C (273.15 K) and 1 atmosphere (101.325 kPa). A standard cubic meter (std m3) uses
the same pressure base but the temperature base is 15°C (288.15 K). Both are used in the industry. We have
adopted the standard cubic meter for purposes of this book.
SI: Ps = 101.325 kPa (1 atm), Ts = 15°C = 288.15 K
FPS: Ps = 14.696 psia, Ts = 60°F = 519.67°R
The following basic conversion factors apply at these conditions:
SI: 23.64 m3/kmol, 42 300 kmol/106 std m3 Density air = 1.22 kg/m3
FPS: 379.5 ft3/lb-mol, 2635 lb-mol/MMscf Density air = 0.0764 lb/ft3
CHAPTER 1 19
INTRODUCTION
Example 1.1: Derive the standard molar volume from the ideal gas law in SI and FPS units.
SI Solution:
From the ideal gas law, which is discussed in detail in Chapter 3, we know:
PV = nRT
V
Rearranging for n ,
V RT
n P
kPa•m3
At standard conditions: Ps = 101.325 kPa, Ts = 15◦C = 288.15 K, R = 8.314 kmol•K
kPa•m3
V 8.314 kmol•K (288.15 K)
Therefore:
n 101.325 kPa
V m3
n = 23.64 kmol at standard conditions
FPS Solution:
From the ideal gas law, which is discussed in detail in Chapter 3, we know:
PV = nRT
V V RT
Rearranging for n ,
n P
psia-ft3
At standard conditions: Ps = 14.696 psia, Ts = 60◦F= 519.67 ◦R, R = 10.732 lb-mol◦R
psia-ft3
10.732 lb-mol-ºR (519.67ºR)
V
Therefore: n 14.696 psia
V ft
n 379.5 at standard conditions
lb-mol
In FPS units, M is the Roman numeral for one thousand; thus MM is one million. MMscf, MMSCF,
and MMCF are alternate ways of writing “one million standard cubic feet.” In the metric system, “M”
stands for “mega,” the prefix for 106 or (E+06). To avoid confusion, millions of standard cubic meters will
be written out or abbreviated as 106 std m3.
The subscript “s” always means standard conditions. The abbreviation “std” is not required if the
“s” subscript is used as shown.
In the most common conversion, a volumetric flow rate per day is converted to a mass rate per hour.
The use of lb-mol or kmol often is a convenient mass unit if no chemical reaction is occurring.

INTRODUCTION
Example 1.2: The inlet flow to a gas processing facility is 7.0 ´ 106 std m3/d [248 MMscfd]. The
relative density of the gas is 0.7. Determine the mass flow rate into the facility in
kg/h [lb/h].
SI Solution:
Step 1: Determine the MW
MW = (0.7)(28.96 kg/kmol) = 20.3 kg/kmol
Step 2: Determine the mass flow rate in kg/hr:
7.0  106 std m3 1 d 1kmol 20.3 kg kg

mass flow d 24 h h
kmol
FPS Solution:
Step 1: Determine the MW
MW = (0.7)(28.96 lb/lb-mol) = 20.3 lbm/lb-mol
Step 2: Determine the mass flow rate in lb/hr:
248 MMscf 1 d 1 lb-mol 20.3 lb lbm

mass flow day 24 hr 379.5 scf 553 000
lb-mol hr
Several useful conversion factors are summarized in Appendix 1A at the end of this chapter. In
making these conversions there are some small “round-off” deviations that have no significance in the
calculations wherein they are used.
In using conversion factor summaries, which are presented differently, remember the following
relationships.
Unit A ´ Conversion Factor B = Unit C
(ft) ´ (12) = inches, (kg) ´ (1000) = g, OR
One Unit of A = Conversion Factor B ´ Unit C
1.0 ft = 12 inches, 1.0 kg = 1000 g
It is easy to get the conversion backward, particularly when using unfamiliar units.
CHAPTER 1 21
INTRODUCTION
APPENDIX 1A – SUMMARY OF CONVERSION FACTORS
LENGTH 1 m = 3.281 ft = 39.37 in = 100 cm = 1000 mm

1 ft = 0.305 m = 12 in = 30.5 cm = 305 mm
1 statute mile = 1.61 km, 1 km = 0.621 statute mile
AREA 1 m2 = 10 000 cm2 = 10.76 ft2 = 1549 in2

1 hectare = 10 000 m2 = 2.47 acres, 1 acre = 0.405 hectares
1 sq mile (section) = 2.59 km2 = 259 hectares
VOLUME 1 m3 = 35.31 ft3 = 6.29 bbl = 1000 L

1 L = 0.001 m3 = 1000 cm3 = 0.035 ft3 = 61 in3
1 ft3 = 0.0283 m3 = 28.3 L
bbl (API) = 0.159 m3
1 bbl (API) = 159 L = 5.61 ft3
MASS 1 kg = 2.205 lbm = 1000 g

1 lbm = 0.454 kg = 454 g
1 ton (metric) = 1000 kg = 2205 lbm = 1 Mg
DENSITY 1 kg/m3 = 0.001 g/cm3 = 0.0624 lbm/ft3

1 lbm/ft3 = 16.02 kg/m3 = 0.016 02 g/cm3
1 g/cm3 = 1000 kg/m3 = 62.4 lbm/ft3 = 1.0 kg/L
FORCE 1 N = 0.225 lbf = 0.102 kgf

1 kgf = 9.81 N = 2.205 lbf
1 lbf = 4.45 N = 0.454 kgf
PRESSURE 1 bar = 14.50 psi = 0.987 atm = 1.02 kg/cm2

1 bar = 100 000 N/m2 = 100 kPa
1 psi = 6.895 kPa
TEMPERATURE °C = 0.556 (°F – 32), K = °C + 273

°F = (1.8)(°C) + 32, °R = °F + 460
STANDARD CONDITIONS
SI FPS
Molar Volume, Molar Volume,
Pressure, kPa Temperature °C m3/kmol Pressure, psia Temperature, °F ft 3/lb-mol
100 15 23.96 14.696 60 379.5
100 0 22.71 14.65 60 380.5
101.325 15 23.64 14.73 60 378.4
101.325 0 22.41 15.025 60 371.1
Note: highlighted cells are the basis for these texts.

INTRODUCTION
SI UNITS Bar = 100 000 N/m2 = 100 000 Pa = 1.02 kg/cm2 = 100 kPa
Standard Conditions: 15°C and 101.325 kPa
1 000 000 std m3 = 106 std m3 = 42 300 kmol
There are 23.64 std m3/kmol at 15°C and 101.325 kPa
Density of air at 15°C and 101.325 kPa = 1.22 kg/m3
Density of gas at 15°C and 101.325 kPa = (gg)(1.22 kg/m3)
1 m3 = 1000 liters; 1 liter = 1000 cm3
1 g/cm3 = 1000 kg/m3
FPS UNITS Standard Conditions: 60°F and 14.7 psia (This Text)
1 000 000 std cu ft = 1 MMscf = 2635 lb-mol
Density of air at 60°F and 14.7 psia = 0.0764 lb/ft3
There are 379.5 scf/lb-mol
1 ft3 = 7.48 U.S. gal = 6.23 U.K. gal
1 bbl = 42 U.S. gal = 35 U.K. gal = 5.61 ft3
CONVERSIONS 1 std ft3 (@ 60°F and 14.7 psia) = 0.0283 std m3 (@ 15°C and 101.325 kPa)
BETWEEN 1 std m3 (@ 15°C and 101.325 kPa) = 35.40 std ft3 (@ 60°F and 14.7 psia)
UNITS
1 bbl = 159 L = 0.159 m3
1 m3 = 35.31 ft3 liquid = 264 U.S. gal = 220 U.K. gal = 6.29 bbl
1 L = 0.264 U.S. gal = 0.22 U.K. gal = 0.0353 ft3
CONVERSIONS Standard Volumetric Flow to “In-Situ” or Actual Volumetric Flow

USING SI Units:
STANDARD
VOLUMETRIC std m3 Ps T 1d m3
FLOW d P Ts z actual
86 400s s
FPS Units:
scf Ps T 1 day ft3
day P Ts z 86 400sec actual sec
Standard Volumetric Flow to Mass Flow

SI Units:
std m3 1 kmol 1d kg
d  g 28.96 s
23.64 std m3 86 400s
FPS Units:
scf 1 lb-mol 1 day lbm
day 379.5 scf cg 28.96 86 400 sec sec
Mass Flow to Actual Volumetric Flow

SI Units:
qa = `
m j c kg mc m3 m m3
= = actual
t s kg s
FPS Units:
qa = ` t j = ` j
m lbm c ft3 m ft3
= actual
min lbm min
CHAPTER 1 23
24
VOLUME 1: THE BASIC PRINCIPLES
2
GAS CONDITIONING
AND PROCESSING OVERVIEW

Production of natural gas is the first step in the value chain that takes gas from the reservoir to the
customer (typically at the burner tip). An integral and essential part of the value chain is the midstream
sector. “Midstream” refers to the gathering, compression, and processing functions required between the
wellhead and the transmission system.
Midstream assets and activities are found at any location where natural gas is produced, transported,
or sold. For example, in North America the first gas-gathering and processing facilities were installed circa
1910, primarily to extract casing-head gasoline from solution gas produced with the crude oil. In Europe,
CO2 for EOR Sales Gas to Pipeline

Gas Lift and Gas to LNG
Injection
Gas to GTL
Crude Oil Ethane

Propane
Gas i-Butane LPG NGLs
Processing n-Butane
Module
Natural Gasoline
Plant Condensate
Sulfur
Field condensate
Compression Field Treating

(optional) (optional)
Solution Gas Produced

Gas
Oil Gas Gas

Production Well Well Production Well
Separators Separators
Gas Cap or
Associated Gas
Non-associated Gas
Oil Water Water

Water
Figure 2.1 Gas Gathering and Processing in the Total Production System(2.1)
CHAPTER 2 25
GAS CONDITIONING AND PROCESSING OVERVIEW
the midstream sector developed in the 1960’s with large non-associated-gas fields in the southern North Sea
and in the Groningen field in the Netherlands. Industry development in the Middle East was spurred by the
huge associated-gas-gathering and processing projects initiated by Saudi Aramco in the late 1970’s and early
1980’s. Figure 2.1 shows a schematic of the gas-gathering and processing facilities in the total production
system.
One of the principal objectives of the gas-processing industry is to condition the gas for sale. Natural
gas must meet several specifications before it can enter the transmission system. In locations where Natural
Gas Liquid (NGL) markets, transportation, and infrastructure exist, it may be desirable to extract NGLs
from the gas for economic reasons. This is often referred to as gas processing and / or NGL extraction. Gas
processing typically results in sales-gas and NGL products.
Both of these areas will be discussed in more detail later in this chapter. Figure 2.2 shows a schematic
representation of the disposition of the products and impurities from a gas processing plant.
Inlet Stream From Reservoir Impurities

• Water • Mercury
• Helium • Nitrogen
• Nitrogen • Carbon Dioxide
• Carbon Dioxide • Hydrogen Sulfide
• Hydrogen Sulfide (often converted to sulfur)
• Methane • Mercaptans and other
• Ethane Sulfur Compounds
• Propane (often converted to sulfur)
• i-Butane
• n-Butane Other Products
• Pentanes + • Helium
• Mercaptans • Nitrogen
• Other Sulfur Compounds • Carbon Dioxide
• Mercury • Sulfur
• Other
Gas Conditioning
To Pipeline Gas
and Processing
To LNG
To GTL
NGL Products
• Ethane
• Propane
• i-Butane
• n-Butane
• Pentanes Plus
Water
Figure 2.2 Example Product / Impurities Disposition from a Gas Processing Plant
Typical Well Stream Compositions

The quantity, composition, temperature and pressure of the inlet stream to the facility is a key
parameter in the design and operation of a gas conditioning or gas processing facility. Gas compositions
vary widely. Table 2.1 provides a few example compositions. From a design and operational standpoint the
focus is generally on the impurities and the concentration of NGL components (lean vs. rich).

Table 2.1
Example Inlet Gas Compositions
Component Lean Rich High Nitrogen High CO2

(mol %) Sweet Gas Sweet Gas Sour Gas Content Gas Content Gas
He 0.00 0.00 0.00 0.43 0.00
N2 1.75 0.38 0.30 15.68 0.65
CO2 0.23 0.57 4.10 0.05 10.07
H 2S 0.00 0.00 8.90 0.00 0.00
C1 92.61 79.00 73.00 71.90 86.32
C2 3.53 8.56 7.50 6.16 1.84

C3 0.58 4.96 2.60 3.58 0.49
iC4 0.33 1.95 0.50 0.41 0.11
nC4 0.09 2.51 1.00 0.92 0.11
iC5 0.08 0.70 0.40 0.19 0.04
nC5 0.03 0.55 0.30 0.22 0.0.03
C6 + 0.77 0.82 1.40 0.46 0.34
MW 18.01 22.10 22.60 20.70 19.76
Relative Density 0.62 0.76 0.78 0.71 0.68
There is much emphasis today on “unconventional gas” notably shale gas and coalbed methane.
Shale gas compositions are similar to gas from conventional reservoirs since the gas in place has not
migrated from the source rock (shale) to conventional reservoir rock (e.g., sandstone or carbonate). Table
2.2 provides example shale gas compositions from four U.S. shale gas plays. Table 2.3 provides example
coalbed methane (CBM) compositions from three U.S. plays. In addition to composition, temperature
and pressure are critical factors in the design and operation of the midstream facilities is the production
profile and its relationship to the surface pressure. In many cases, communication between the sub-surface
engineers and the facilities/process engineers who design and/or operate the gas processing plant is limited.
This can lead to “gaps in knowledge” on both sides of the system resulting in inadequate designs, higher
capital and operating costs, and reduced production rates.
Table 2.2 Table 2.3

Example Shale Gas Compositions Example Coalbed Methane Compositions
Component Component San Powder Black

(mol %) Barnett Marcellus Haynesville Fayetteville (mol %) Juan River Warrior
C1 80-94 79-95 95 97 C1 92 98.6 95
C2 3-12 3-16 0.1 1 C2 — 0.1 —
C3 0-5 1-4 0 0 C3 — — —
CO2 0.3-2.7 0.1-1 4.8 1 CO2 8 1.1 —
N2 1-8 0.2-0.4 0.1 0.7 N2 — — 5
CHAPTER 2 27
The general designation of a natural gas in terms of “super-lean”, lean, medium, and rich is in
relation to the amount of NGL components present in the inlet gas stream. This quantity not only affects the
type of processing required, but also the economic viability of NGL extraction options. Table 2.4 provides
typical ranges of NGL content of natural gases based upon these general categories. The units are tonnes of
NGL per 106 std m3 of gas in SI units, and U.S. gallons of NGL/Mscf of gas in FPS units.
Table 2.4
Generalized NGL Content of Natural Gas
Gas NGL Content, NGL Content, Gas

Characterization tonnes/106 std m3 C2+ U.S. gal/ Mscf C2+ Relative Density % C1
“Super”-lean < 100 < 1.5 < 0.62 > 94

Lean < 160 < 2.5 < 0.65 > 90
Medium 160 - 330 2.5 - 5 0.65 - 0.75 80 - 90
Rich > 330 >5 > 0.75 < 80
Note: assumes “normal” gas compositions, ie., minimal amounts of N2, CO2, H2S
As noted in Figure 2.2 there are several contaminants or impurities frequently present in natural
gas. These impurities must often be removed by conditioning to produce saleable gas and liquid products.
These contaminants can cause operating problems if the facility is not equipped to deal with them, such as a
proper corrosion inhibitor program or appropriate materials of construction. Typical well-stream impurities
with a list of their associated problems are provided in Table 2.5.
Table 2.5
Example Well Stream Impurities and their Associated Problems
Contaminant / Impurity Associated problem(s)

Can result in corrosion, hydrate formation, and freezing. There are concentra-
H 2O
tion limits in saleable products (gas and liquids).
It is toxic, flammable, and has a strong unpleasant odor. It burns to SO2, which
is corrosive and highly toxic. In wet systems, H2S can result in corrosion (both
H 2S
pitting and sulfide stress cracking). There are concentration limits for sales
gas and liquid products.
CO2 is corrosive in water wet systems and it reduces the gas heating value and
CO2 Wobbe number. There are limits on CO2 concentration in sales gas and liquid
products.
Can cause corrosion and fouling in reboilers of solvent systems. Adds to total
RSH, COS, CS2 sulfur content and has a strong unpleasant odor. There are limits on concen-
trations in gas and liquid products.
It is toxic & corrosive in water wet systems (amalgam corrosion) and causes
liquid metal embrittlement of aluminum equipment and piping. There are lim-
Hg
its on Hg concentration in the feed gas to low temperature processing facilities
and also in liquid products.
Decreases the heating value of the gas. There are concentration limits for sales
N2
gas.

SALEABLE PRODUCTS AND QUALITY SPECIFICATIONS

The typical products from a natural gas
processing facility are: Methane (C1)
1. “Sales” gas, also referred to as Residue
Ethane (C2)
Gas, or Pipeline Gas
2. Natural Gas Liquids (NGLs) Propane (C3)
LPG
3. Liquefied Petroleum Gas (LPG) Butanes (C4)
4. Liquefied Natural Gas (LNG) NGL
Natural Gas Heavier Fractions
5. Stabilized Condensate Exiting Well also referred to as:
6. Other: C5+

a. Helium Pentanes plus
Natural Gasoline
b. Nitrogen Condensate
c. Carbon Dioxide (for enhanced
oil recovery (EOR)) Non-Hydrocarbons:
d. Sulfur e.g. H2O, CO2, H2S, N2, Hg, etc.
Figure 2.3 provides common terminology Boiling Point at 1 atm Temperature LPG = Liquefied Petroleum Gas
for different products in the oil and gas industry and Butane (normal) -0.5°C [31.1°F] NGL = Natural Gas Liquids
Butane (iso) -12°C [10.4°F] LNG = Liquefied Natural Gas
provides an indication of the typical components Propane -42°C [-43.6°F] CNG = Compressed Natural Gas
present in these products. Ethane -89°C [-128.2°F]
Methane -162°C [-259.6°F]
Sales Gas/Residue Gas Specifications

Figure 2.3 Common Terminology and Composition of
Natural gas must meet several specifications Products
before it can enter the transmission system. The
main component in a typical sales gas is methane, with decreasing amounts of ethane, propane, butane and
C5+ sometimes present. As discussed previously, there are also usually impurities present whose quantities
Table 2.6
Example Sales-Gas / Transportation Specifications
Specification North America Europe Middle East

Water Content (North America)
Water Dewpoint 4-7 lbm H2O/MMscf –10 to –12°C at
0°C at 6900 kPa
(Europe, Middle East) 7000 kPa
Hydrocarbon 14-40°F at 0 to –5°C at 5°C at any pressure less

Dewpoint specified pressure P < 7000 kPa than delivery pressure
CO2 concentration 1-3 mol % 2-3 mol % 3 mol %
N2 concentration 2-3 mol % * 2-3 mol % * N/A

Total Inerts 3-5 mol % * N/A N/A
H2S concentration 0.25-1.0 grain/100 scf 5-7 mg/Nm3 4 mg/std m3
Total Sulfur 0.5-20 grain/100 scf 10-150 mg/Nm3 120 mg/std m3
Mercaptan concentration 0.25-1.0 grain/100 scf 6-15 mg/Nm3 15 mg/std m3
Oxygen 0.1-0.2 % (mol) 10 ppmv (mol) 0.1 mol %
Heating Value [HHV] 950-1200 Btu/scf 40-46 MJ/Nm3 1040-1080 Btu/scf
Wobbe Index N/A 51-56 MJ/Nm3 N/A
N/A = not available * = often not specified Note: 1 lbm = 7000 grains
CHAPTER 2 29
are limited by the sales gas quality specifications. Historically, these specifications have been referred to as
“sales gas specifications”, but in many areas they are actually transportation specifications. This is because
gas from many producers will be transported in “open-access” gas pipelines to the gas buyers along the
pipe route. The sales agreement may be between the producer and the buyer, but it is unlikely the buyer will
actually receive the producer’s molecules. In North America and the UK, producers negotiate transporta-
tion agreements with pipelines and must meet the shipper’s transportation specifications before the pipeline
operator will accept the gas. Table 2.6 shows some example sales/transportation specifications in North
America, Europe, and the Middle East.
Any or all of the following quality provisions are normally included in a sales contract:
Heating Value
This is typically expressed as a gross (higher) or net (lower) heating value per unit or volume of
gas. Where the gas contains non-combustibles like N2 and CO2, the Wobbe number may be applied in
addition to heating value.
The “gross” or “higher” heating value is the heat produced on combustion of the gas with the
theoretical amount of air required if the water formed by combustion is cooled to the reference tempera-
ture and then condensed. The “net” or “lower heating” value is the comparable quantity of heat produced
when the water formed remains in the vapor state (this is normally what happens in actual combustion
equipment). The heating value specifications vary depending on the market served and almost always refer
to the higher heating value. Customers on the gas transmission system require heating values to fall in a
range compatible with their combustion equipment. In general, the heating value specification in North
America is lower than in most European and Asian markets. This is because almost all of the gas sold in
North America has undergone deep NGL extraction in a gas processing plant.
The heating value may be expressed in several energy units. The megajoule (MJ) or British Thermal
Unit (Btu) are used most commonly. The following conversions are convenient:
1 MMBtu = 1 000 000 Btu = 1055 MJ = 10 therms
1000 Btu/scf = 37.3 MJ/std m3 *
*Standard conditions: 60°F and 14.7 psia, 15°C and 101.325 kPa
Table 2.7 provides heating values for typical natural gas components. The heating value of a gas
mixture may be calculated from Equation (2.1).
Table 2.7
Heating Values for Typical Natural Gas Components
HHV per Unit Volume of Dry Gas @

Component 15°C and 101.325 kPa 60°F and 14.696 psia
Methane 37.7 MJ/std m3 1010.0 Btu/ft3
Ethane 66.0 1769.6
Propane 94.0 2516.1
iso-Butane 121.4 3251.9
n-Butane 121.8 3262.3
iso-Pentane 149.3 4000.9
n-Pentane 149.7 4008.9
Hexane 177.6 4755.9

HHVmix = / ^HHVih^y ih (2.1)

Where: HHVi = higher heating value of a gas component
yi = mol fraction of component in gas
The Wobbe number is defined as follows:

HHV
Wobbe No. = (2.2)
c
SI FPS
Where: HHV = higher heating value of the gas MJ/std m3 Btu/scf
c = relative density of the gas
The Wobbe number is a measure of fuel interchangeability. Two gases with the same Wobbe number
will theoretically give the same heat release at the burner tip for the same pressure drop across the burner
orifice, assuming that the temperature and pressure remain the same. It is widely used in Europe, where the
composition of the gas entering the transmission system can vary from location to location. It is not often
specified in North America, where the gas composition does not vary significantly from supplier to supplier
due to the level of gas processing.
Example 2.1: Calculate the higher heating value (HHV) and Wobbe number for the gas below using
the values from Table 2.7
Gas Composition: MW Calculation:
Comp. mol% MW Comp. yi MW (yi)(MW)
N2 2.0 28 N2 0.020 28.0 0.56
CO2 1.0 44 CO2 0.010 44.0 0.44
C1 89.5 16 C1 0.895 16.0 14.32
C2 5.5 30 C2 0.055 30.0 1.65
C3 2.0 44 C3 0.020 44.0 0.88
17.85
Total 100.0 Total 1.000 MWmix use 17.9
17.9
Heating Value Calculations: rel t = 29.0 = 0.617
SI Solution: FPS Solution:
Comp. yi HHV MJ/m3 (yi)(HHVi) HHV Btu/scf (yi)(HHVi)

N2 0.020 0.0 0.00 0 0
CO2 0.010 0.0 0.00 0 0
C1 0.895 37.7 33.75 1010.0 904
C2 0.055 66.0 3.63 1769.6 97
C3 0.020 94.4 1.88 2516.1 50
Total 1.000 HHVmix = 39.26 HHVmix = 1052
39.26 1052

Wobbe No = Wobbe No =
0.617 0.617
= 49.98 MJ/m3 = 1339 Btu/scf
CHAPTER 2 31
Water Content (Dewpoint)

This specification will be stated as the mass of water per unit volume of gas or the
maximum allowable water dewpoint temperature at a specified pressure. In the U.S., this specifica-
tion is typically 3-7 lbm H2O/MMscf [50-110 mg/std m3] which is equivalent to a water dewpoint
of 32°F at 1000 psia. In Europe and Canada, a typical water specification is 50-60 mg/std m3
[3-4 lbm/MMscf], which is equivalent to a water dewpoint of about –10°C [14°F] at 7000 kPa [1000 psig].
If a water dewpoint is specified it must be stated at a reference pressure, which typically is the pipeline
operating pressure.
Hydrocarbon Dewpoint (HCDP)

Hydrocarbon dewpoint specifications vary with climate and buyer. In North America and Europe,
typical values range from –10 to 5°C [14 to 41°F]. HCDP must also be referenced to a pressure. In many
contracts, it is required that the HCDP be met at any pressure in the transmission system. Because the highest
dewpoint temperature will be at the cricondentherm pressure (discussed in Chapter 4), this specification
often is considered a cricondentherm specification. Some contracts state the allowable liquid hydrocarbon
content, e.g., 15 mg/std m3 [9.3 ´ 10˗7 lbm/scf], at a specified temperature and pressure.
Sulfur Content
This limits the concentration of sulfur compounds to prevent corrosion, toxicity, and odor when the
gas is burned. Typical sulfur specifications are shown in Table 2.6.
The specifications in Table 2.6 assume the gas is sold in the residential heating market. Gas sold to
industrial buyers, particularly for power generation, may not require such low sulfur levels.
The specification of the allowable sulfur content in a “sweet” gas is often misunderstood. The gas
is sweet only in the sense that there is no detectable, obnoxious odor on burning and it is not corrosive if
the pipeline is free of liquids. If the pipeline contains liquids like water, glycol, amine, and the like, this
“sweet” gas can be corrosive. So, in wet systems, meeting the specification is no assurance that corrosion
or deposition of corrosion products will not occur.
Non-hydrocarbons
Nitrogen is an important non-hydrocarbon component. Its concentration is usually limited to less
than 2-3 mol%. Where produced concentrations are higher, the seller sometimes negotiates higher N2 allow-
ances.
Carbon dioxide is often specified separately because of its corrosive nature in the presence of water.
A maximum value of 2-3 mol% is typical, but for dedicated buyers (not on a large transmission system) the
CO2 specification is often negotiable.
Oxygen is seldom present in natural gas; however, most contracts explicitly set out an oxygen limit
due to its corrosivity in a wet environment. Specifications vary, but a typical value is 0.1-0.2 mol% .
Mercury has not been typically addressed in gas contracts although that is changing. If the gas is
sold to an LNG plant or other low temperature processing facility, it is the buyer’s facilities that are at risk,
and the buyer usually takes responsibility for mercury removal, but when specified a typical specification
value is 10 ng/Nm3.
Delivery Point, Pressure, and Temperature

The delivery point is usually the valve on the meter run containing the buyer’s meter. The contract
then specifies the operation and testing of this meter run. The required delivery pressure is normally the

maximum anticipated line pressure. This varies with the gas customer requirements. For gas transmission
systems, it is typically 7000-8000 kPa [1000-1150 psia]. For gas-turbine-based power plants, the delivery
pressure is 3500-4100 kPa [500-600 psia].
A maximum delivery temperature at the transfer point may be specified to protect the integrity
of the protective coatings of the pipeline. It is often about 49°C [120°F].
Liquid Hydrocarbon Products

The liquid produced from gas contains many different components. Liquid produced by simple
separation at ambient temperature is a mixture whose composition is fixed by equilibrium, as discussed in
Chapter 5. This is sometimes called a “field condensate” and consists mainly of C5+ components.
Other liquid products are a result of a process (typically refrigeration) to extract components from
the gas stream. These are commonly called “natural gas liquids” (NGLs). This product mixture is then
fractionated into its component parts based on composition.
The amount of processing done at the production site depends on the amount of liquids present in
the gas stream, available transportation to market, and local conditions. Offshore, swamps, jungle, or arctic
type locations limit the feasibility of complicated systems. The focus is on providing minimum processing
necessary at the site to transport the gas to more favorable locations for further processing.
One or more of the following NGL products may be specified. Table 2.8 shows various NGL products
and their associated markets.
Table 2.8(2.2)
NGL Product and Markets
NGL Component Market Use

Ethane (C2 ) Petrochemical feedstock for manufacture of ethylene
Propane (C3 )* Petrochemical feedstock for manufacture of propylene

Residential and commercial fuel in areas with no access to natural gas. Also
transportation fuel.
Isobutane (iC4 ) Refinery feedstock to alkylation unit. Fuel use as LPG.
Normal butane (nC4 ) Gasoline (petrol) blending, petrochemical feedstock for manufacture of light
olefins
Fuel use as component in LPG
Sometimes isomerized to i-C4
Natural Gasoline (C5+)** Refinery feedstock to reformer or isomerization unit

Petrochemical feedstock for manufacture of light olefins
* Often sold as liquefied petroleum gas (LPG). LPG can be C3, C3-C4 mix, or predominantly C4.
** Natural gasoline is a North American term, also referred to as light naphtha or condensate in other regions.
NGL Mixtures. An “NGL mix” product typically consists of a mixture of unfractionated C2+
hydrocarbon liquids (often referred to as “Y-grade” in the USA), or C3+ liquids in locations where ethane
recovery is not warranted. These mixture products are typically transported by pipeline to a separate facility
for fractionation into “commercial” products, i.e., ethane, propane, butane, LPG. There are no standard
specifications on such mixtures, although the methane and CO2 content are often limited. Product specifica-
tions for these products can be found in Appendix 2A.
CHAPTER 2 33
In some areas where recovery of NGLs is not economically viable due to lack of market or
transportation infrastructure, NGL liquids have been “spiked” into crude oil. The quantity of NGLs which
can be sold this way is limited by the crude oil vapor pressure specification. If the vapor pressure specifica-
tion is atmospheric pressure or below, the NGL recovery is typically limited to pentanes and heavier and
perhaps a small quantity of butanes. Higher vapor pressure specifications allow higher recovery of butanes
and possibly some propane. NGLs are also sometimes used to lower the viscosity of the crude for transpor-
tation purposes. Since NGLs tend to be substantially paraffinic; they can cause asphaltene deposition in the
crude oil and this is should be considered in the planning of the production facility.
GAS PROCESSING SCHEMES

The actual processes that are used to condition and process a natural gas stream depend on the feed
gas composition, temperature, pressure, and the sales specifications (composition, delivery temperature, and
pressure) for both the gas and liquid products. The following discussion provides descriptions of the processes
used.
Gas Conditioning
Figure 2.4 shows an example block flow diagram for a gas processing facility. Each block represents
a process unit that may be present. Not shown are the pumps, compressors, valves and fittings, and lines
necessary to move, control, and contain the fluids flowing between processing units.
Tail Gas
Sulfur Product
SRU/TGU
H2S & Other CO2 to Vent

S Compounds or Reinjection
He and N2
Natural Gas Sales
Natural Gas to LNG
Natural Gas to GTL

Produced
Gas Stream NGL
Conditioning
Extraction
Fuel
Recompression
Hg NGL Sales or
H2O Stabilization / Product Condensate
Disposal
Fractionation Treating
Conditioning NGL Extraction Stabilization/ Product Treating

Fractionation
1. Sweetening 1. Adsorption (SGU) 1. Demethanizer 1. Sweetening
2. Dehydration 2. Absorption (Lean Oil) 2. Deethanizer a. H2S, COS, CS2, RSH
3. Mercury Removal 3. Condensation 3. Depropanizer b. CO2
a. Valve 4. Debutanizer 2. Dehydration
b. Turboexpander
c. Refrigeration
Figure 2.4 Example Gas Processing Facility Block Flow Diagram

The conditioning unit is typically installed at the inlet of the gas processing plant. It is generally
designed to remove some or all of the following contaminants from the gas:
1. H2O
2. Sulfur compounds: H2S, CS2, COS, mercaptans (RSH ), et.al.,
3. CO2
4. N2
5. O2
6. Hg
7. Solids: hydrates, asphaltenes, dust, scale, etc.
Sweetening
“Gas sweetening” is a general term used to describe the removal of sulfur compounds from the gas:
hydrogen sulfide (H2S) and other sulfur species that may be present, including mercaptans (RSH), carbonyl
sulfide (COS), and carbon disulfide (CS2 ). Technically, carbon dioxide (CO2 ) is not a “sour” component
but is often removed from the gas in a “sweetening” unit. Together, H2S and CO2 are often referred to as
“acid gas” components because they dissolve in water to form a weak acid. While generally considered to
be relatively weak acids, they can be quite corrosive to carbon steel metallurgy. Acid gas removal and sulfur
recovery are discussed in more detail in Chapter 19.
There are several processes that can be used to remove these components from natural gas. Many
of these are proprietary and require a license. The following processes are the most common:
1. Chemical Absorption: This is the most common process used for H2S and CO2 removal.
Amines are water-soluble, organic, nitrogen compounds that form a basic solution in water.
They react reversibly with acid-gas components to form a water-soluble salt. The acid/base
reaction is reversed in the regenerator at low-pressure, high-temperature conditions. The acid
gas is removed at the regenerator overhead while the amine solution is removed from the bot-
tom and is recirculated to the absorber. Some of the common amines used are:
a. Monoethanol amine (MEA)
b. Diethanol amine (DEA)
c. Methyl diethanol amine (MDEA)
d. Diglycol amine (DGA)
e. Diisopropanol amine (DIPA)
With the exception of MDEA, amines are generally not selective and will remove both CO2
and H2S from the gas. MDEA will preferentially absorb H2S over CO2 due to faster reaction
time. Amines frequently are “engineered” to increase selectivity and/or absorption capacity. Most
amine solutions are ineffective in removing other sulfur species such as mercaptans and COS.
2. Physical absorption: Physical solvents absorb acid-gas components by solubility in the
solvent (i.e., no chemical reaction). In general, physical solvents are used in applications where
the partial pressure of the acid-gas components in the feed gas is high and/or removal of other
sulfur species is required. Relative to amines, physical solvents are less corrosive and require
less energy to regenerate but tend to coabsorb heavy hydrocarbons. In almost all cases, physical
solvents are proprietary processes and require a licensing agreement.
3. Fixed bed: H2S and other sulfur species can be removed from gas by adsorption or reaction
with a solid material such as a molecular sieve or a metallic oxide. These processes are limited to
sulfur-removal applications and, in general, are applied when the amount of sulfur to be removed
is small, for example less than 100-200 kg/day [220-440 lbm/day].
CHAPTER 2 35
4. Membranes: Membranes are used widely for the removal of CO2 from natural gas. They are
generally not effective for the removal of H2S and other sulfur species because of the very low
outlet concentrations required.
5. Other: Several other process schemes can be used to remove acid-gas components from natural
gas. These processes include the removal of H2S (liquid scavengers from the removal of H2S and
other sulfur species) and removal of CO2. These schemes may be the optimal choice in a specific
application but, in general, represent a small percentage of total acid-gas removal installations.
Acid Gas
In amine, physical solvent, and membrane processes, the acid gas is recovered as a low-pressure
gas stream. If this stream is CO2 and contains no sulfur compounds, it is either vented to atmosphere or
compressed and re-injected. In miscible-flood projects, such as those in the Permian Basin in the U.S., the
CO2 is recovered and re-injected into the producing reservoir to increase oil recovery.
When the recovered acid gas stream contains sulfur compounds, venting or flaring typically is not
an option. In these cases, the acid gas can be re-injected for disposal or sequestration. When the acid gas
stream is substantially H2S, it is frequently sent to a Sulfur Recovery Unit (SRU ), followed by a Tail Gas
Unit (TGU), where the sulfur species are converted to sulfur.
Dehydration
Gas dehydration is the most commonly used process in the midstream sector. Water removal is
necessary to meet the requirements of water content specifications contained in the sales gas contracts. The
purpose of these specifications are:
1. Prevention of hydrates in gas transmission and distribution facilities
2. Prevention of corrosion due to the presence of free water
3. Prevention of multiphase flow related problems associated with the presence of free water
In addition to sales gas specification requirements, it is often necessary to remove water to prevent
hydrate/freeze-up problems in other processing operations, in particular low-temperature hydrocarbon
liquids recovery and nitrogen removal operations.
There are three main gas dehydration processes:
1. Absorption: This process almost always refers to glycol dehydration. The most common solvent
is triethylene glycol. Glycol dehydration is used widely for gas dehydration in production and
pipeline applications, but is also used in process applications where the minimum processing
temperature is –34 to –40°C [–30 to –40°F]. Glycol dehydration is covered in detail in Chapter 17.
2. Adsorption: This process is most common when the outlet water concentration must be extreme-
ly low, <1 ppmv. It is the dominant dehydration process in deep recovery NGL extraction plants,
as well as LNG facilities. Typically the desiccant is a molecular sieve, but silica gel sometimes is
used in HCDP applications. Adsorption dehydration is discussed in detail in Chapter 18.
3. Inhibition and Condensation: This process dehydrates the gas by condensing water due to tem-
perature reduction and is integrated with the refrigeration system used in gas conditioning or
NGL extraction processing. Hydrate formation is prevented by the injection of an inhibitor, typi-
cally monoethylene glycol (MEG) or methanol. The water-inhibitor solution is separated from
the condensed hydrocarbons, regenerated, and re-injected into the feed gas, typically upstream
of a heat exchanger. Inhibition and condensation are discussed in detail in Chapters 6 and 15.
4. Other – CaCl2: Calcium chloride can be used to dehydrate natural gas. The CaCl2 will combine
with water to form a brine, which is removed for disposal. Use of this process is typically limited
to small-volume, remote locations.
5. Membranes: Membranes can be used to remove water from natural gas based on the higher
permeability of water through the membrane relative to methane. Only a few membrane dehy-
dration units have been installed to date.

Mercury Removal
Removal of mercury from natural gas (or less commonly liquid products) is typically performed in
order to protect aluminum components, mainly heat exchangers, often found in cryogenic gas processing
facilities from corrosion damage. Although the concentration of mercury in the feed gas is small, localized
accumulation of mercury under certain conditions can occur over time. Mercury can attack aluminum
components via two main mechanisms:
1. Amalgam corrosion is a self-propagating reaction that involves the formation of a mercury-
aluminum “amalgamation”, a type of liquid metal solution, in the presence of small amounts of
water.
2. Liquid metal embrittlement (LME) involves the liquid diffusion of mercury along grain bound-
aries in the base metal (aluminum) which can lead to rapid initiation and propagation of cracks.
A secondary problem associated with mercury is accumulation in equipment, which can result in
health-related exposure risks to personnel during maintenance activities. The two most common methods
for removal of mercury from plant feed gas are:
1. Sulfur-impregnated carbon or alumina beds, Table 2.9
normally installed downstream of the molecu- Example Mercury Concentration Levels in
Produced Natural Gas(2.3, 2.4)
lar sieve dehydration units in a cryogenic gas
plant of LNG liquefaction facility. Concentration
Location Range μg/Nm3
2. Metallic sulfide beds which can be provided
in the oxide form and converted to the active North America 0.005-20
sulfide via sulfur removed from the feed gas or South America 1-119
supplied pre-sulfided. The metal sulfide adsor- North Europe 0.01-180
bent can be used to treat wet gas streams which North Africa 0.3-130
allows them to be installed farther upstream in Middle East 1-10
the process flow scheme which has some ad-
East Asia 10-2000
vantages.
Both of these processes are non-regenerable. Table 2.9 provides some regional examples of mercury
levels in natural gas.
Gas Processing / NGL Extraction

As discussed previously, NGL extraction is typically justified to: (1) meet a gas sales hydrocarbon
dewpoint specification or (2) upgrade the market value of the produced gas stream by the extraction and
sale of NGLs. With the former, minimal extraction levels are required and removal of the iC5+ compo-
nents is usually satisfactory. With the latter, the processor takes advantage of the price differential between
a pure NGL product and its value as a natural gas constituent. The value of NGL product as a natural gas
constituent is termed the “ shrinkage value.” It represents revenue foregone by the extraction of the NGL
from the gas. NGL extraction is often economically viable when the price of crude oil is high relative to the
price of natural gas. This is because NGL product prices are often related to crude prices.
Figure 2.5 provides a schematic that shows the range of NGL extraction that can occur in gas condi-
tioning and processing facilities.
Uplift is the increase in the value of the plant product streams as a result of NGL extraction in
comparison to only producing sales gas. To be profitable, this uplift in value must be greater than the capital
and operating costs associated with NGL extraction, including transportation, fractionation, and storage
plus taxes.
CHAPTER 2 37
Minimal Liquids Recovery LPG Recovery with No Ethane Deep NGL Extraction
C5+ Removal 80+ % C2 Removal
95+ % C3 Removal
Increasing Extraction Levels
Level of extraction set by HCDP specification Level of extraction limited by economics

and minimum HHV specification
Figure 2.5 Range of NGL Extraction in Gas Conditioning and Processing Facilities
Example 2.2: Determine the value of propane in $/tonne [$/U.S. gal] as a component in a natural
gas stream if the sales price for the gas is $6.00/GJ [$6.33/MMBtu]. The market
price for LPG is $800/tonne [$1.50/U.S. gal].
Determine gross profit on the sale of LPG.
SI Solution:
From Figure 2.6a, the shrinkage value for C3 is $300/tonne. The gross profit is
$500/tonne.
FPS Solution:
From Figure 2.6b, the shrinkage value for C3 is $0.58/U.S. gal. The gross profit is
$0.92/U.S. gal.
Figure 2.6a and b provide the shrinkage value of an NGL product as a function of natural gas price.
900
800
C2
iC5+
700
Shrinkage Value, $/tonne
600
500
400
300
200
100
0
0 2 4 6 8 10 12 14 16
Gas Price, $/GJ
Figure 2.6a Shrinkage Value of NGL Components as a Function of Gas Price – SI Units

2.00
1.60
iC5+
1.60
nC4
iC4
1.40
C3
Shrinkage Value, $/US gal
1.20
1.00 C2
0.80
0.60
0.40
0.20
0.00
0 2 4 6 8 10 12 14 16
Gas Price, $/MMBTU
Figure 2.6b Shrinkage Value of NGL Components as a Function of Gas Price - FPS Units
Economic justification of an NGL extraction facility requires that the market value of the NGL
product be sufficient to cover all costs associated with its extraction. These costs include:
1. Shrinkage
2. Fuel
3. Maintenance and operating expense
4. Transportation and fractionation
5. Storage
6. Taxes, royalties, etc.
7. Capital costs
Common NGL extraction and HCDP processes can be classified as: condensation, absorption,
adsorption.
The most common NGL-extraction processes involve refrigeration of the gas. These processes are
discussed in detail in Chapter 15.
Mechanical Refrigeration
Mechanical (or external) refrigeration involves the use of a refrigerant to chill the gas to low
temperatures for the purpose of condensing the NGLs (and possibly water). This process is used widely in
gas-conditioning applications (e.g., HCDP control), but it is also used in NGL-recovery applications as the
primary refrigeration option or in conjunction with another refrigeration option. The most common refriger-
ant is propane. In general, the minimum processing temperature is limited to the atmospheric boiling point
of the refrigerant, –40°C [–40°F].
CHAPTER 2 39
Valve Expansion
This process relies on the cooling from a Joule-Thomson (J-T) expansion of the natural gas and
often is referred to as a J-T plant. Other terms applied to the process are low-temperature separation (LTS)
and low-temperature extraction (LTX). The advantages of this process are simplicity and low cost. The
primary drawback is the pressure drop that occurs across the valve, which often ranges from 2070 to
6900 kPa [300-1000 psia]. This process typically is used in HCDP-control applications on high-pressure,
non-associated gas in which the flowing tubing pressures are sufficiently high to eliminate the need for
compression downstream of the process.
Expansion Turbines (Turboexpanders)

Turboexpanders are single-stage, radial-inflow expansion turbines that theoretically approach a

constant-entropy expansion (rather than constant-enthalpy expansion that occurs across valves). Lower
outlet temperatures are achieved for the same pressure drop compared to a J-T expansion. These are the
most common processes used worldwide for deep NGL extraction, with minimum temperatures below
–101°C [–150°F] achieved routinely. In addition, this process is used for gas-conditioning applications
(HCDP control). In HCDP applications, the required pressure drop across the expander is substantially less
than that required across a J-T valve, which can result in lower compression costs over the life of the field.
Absorption
Prior to 1970, the refrigerated lean-oil process was the dominant NGL extraction process in North
and South America. This process uses a gasoline-like solvent to absorb NGLs from the gas at low tempera-
tures. High recoveries of C2 and C3 are possible. A few lean-oil plants are still used in the U.S. and Canada,
but they have been largely replaced by turboexpander plants.
Adsorption
Silica gel has an affinity for C5+ hydrocarbons as well as for water. It can be used to meet water and
hydrocarbon dewpoint specifications simultaneously. This process is frequently referred to as a “hydrocar-
bon recovery unit” (HRU), or a “short cycle unit” (SCU). Common applications include conditioning of
gas withdrawn from gas-storage reservoirs and conditioning of high pressure gas for which phase behavior
limits the effectiveness of the refrigeration process. Additional information on hydrocarbon adsorption can
be found in Chapter 18.
Stabilization / Fractionation
Once the NGL has been extracted from the gas, it must be stabilized to meet sales specifications.
These specifications can vary significantly depending upon the end markets and transportation method. In
some cases, the NGL product is a stabilized condensate consisting only of C5+ having a vapor pressure less
than 101 kPa [14.7 psia]. In other cases, the NGL product is a C4+ mixture that can be “spiked” into a crude
oil stream for sale. In deep NGL extraction plants, the NGL product is more likely a C2+ or C3+ product that
may be transported to a fractionation plant for product separation, sale, and distribution.
The stabilization of the extracted NGL is typically accomplished by distillation. The distillation
process may be refluxed or non-refluxed. In some cases, particularly where the NGL product is a C5+ stream
with a vapor pressure less than 1 atm, flash stabilization can be used. Distillation is covered in detail in
Chapter 16.

Liquid Product Treating

NGL must meet certain specifications regarding contaminant levels prior to sale. Contaminants of
interest include CO2, sulfur compounds, and water. In many cases these contaminants are removed from the
gas in the conditioning process unit upstream of NGL extraction and are therefore not present in the NGL
product. In some cases, however, these contaminants will be present in the NGL and must be removed. The
most common applications of product treating involve the removal of:
1. CO2 from a C2 or C2+ NGL product
2. Sulfur compounds from LPG and C5+ products
A typical CO2 specification for ethane is 100 ppmw. This is set by the petrochemical buyer. CO2 is
not easily fractionated from ethane since CO2 and ethane form an azeotrope. The most common method for
removing CO2 from ethane is absorption with an amine solution, typically DEA.
Sulfur compounds that may be present in LPG and C5+ include H2S, COS, CS2, and mercaptans
(RSH). These are typically present in low concentrations, less than 100 ppmw, and are often removed by
adsorption on a molecular sieve, reaction with a caustic solution, or amine treating.
Nitrogen Rejection and Helium Recovery

Naturally occurring nitrogen is present at elevated levels in certain gas fields around the world.
High levels of nitrogen in produced gas may also be caused by utilization of nitrogen injection for reservoir
pressure maintenance. In either case, it is often necessary to remove nitrogen from produced gas in order to
meet sales gas specifications, which typically limit nitrogen content to 2-3 mol%.
Three typical processes used to achieve this are:
1. Cryogenic separation
2. Membranes
3. Pressure swing adsorption
It is common to achieve nitrogen rejection as an “add-on” processing unit integrated into a low
temperature NGL extraction plant, where it is fractionated from the methane in a distillation column.
Operating temperatures vary with pressure but can be as low as –185°C [–300°F].
The concentration of helium in most gas fields is typically less than 0.1 mol %, though a few fields
have concentrations as high as 8-9 mol%. Helium is often substantially more valuable than natural gas. A
helium concentration higher than 0.4 mol% is normally necessary to make helium recovery from natural
gas economically viable. Helium recovery is typically achieved via an “add-on” processing unit attached
to a low temperature NGL extraction plant using a distillation column or membranes to separate the helium
from the nitrogen.
Helium has many uses including controlled atmospheres for semiconductor manufacture, cryogen-
ics, welding, pressure/purge where an inert gas is required, balloons, etc.
CHAPTER 2 41
PRODUCTION FACILITIES
Crude Oil
Crude oil is usually treated to meet specifications for:
1. BS&W (Basic Sediment and Water)
2. Vapor pressure
3. Salt
4. Sulfur content (H2S)
The BS&W specification is essentially an entrained water specification. It limits the amount of
free water carried with the crude. It often varies from 0.3% to 3.0% by volume, with the lower number
applied to light crudes and the higher number to heavy crudes (< 20° API). This specification is typically
met by gravity separation. Heat, electricity chemicals, and mechanical coalescers may be used to
enhance this process generally referred to as “crude oil dehydration.”
The vapor pressure specification limits the volatility of the crude oil. If the crude oil is stored or
transported at or near atmospheric pressure, this specification will be less than 101.3 kPa [14.7 psia]
at the system temperature. This specification can be stated in terms of a True Vapor Pressure (TVP) or
a Reid Vapor Pressure (RVP). Chapter 5 provides an expanded discussion of vapor pressure specifications.
Salt specifications can be met in the production facility or in the refinery. Salt is present in the
produced water that is entrained in the crude and is removed by mixing the crude with fresh water and
removing the resultant brackish water in a crude oil dehydration process unit. The amount of salt in the
product crude oil depends on the salinity of the entrained water and the BS&W specification. A typical salt
specification is 30g/m3 of crude [10 lbm/1000 bbl of crude].
Most of the sulfur in the crude oil is organic sulfur tied up in large molecules. Organic sulfur is
almost always removed in the refinery. In production facilities the main concern is volatile sulfur compounds
such as H2S and mercaptans. These are typically removed by flash stabilization and/or gas stripping. A
common H2S specification is 30 ppmw.
Produced Water
Produced water must be treated in order to meet reinjection or disposal specifications for:
1. Hydrocarbons
2. Free solids
3. Dissolved solids e.g., CaCO3, NaCl, BaSO4, etc.
4. Soluble organics
5. Heavy metals
The hydrocarbon specification is particularly important if the produced water is discharged to the
sea. In most offshore locations, the hydrocarbon content specification is 10-40 ppmw. This specification is
typically met by gravity separation, flotation units, centrifugal separation (hydrocyclones), or a combina-
tion thereof. Historically most of the test methods have focused on measuring “dispersed” or “free” oil.
Free solids may require removal if the produced water is to be re-injected into the reservoir.
Removal methods include gravity separation, filtration, and centrifugal separation. Dissolved solids must
be analyzed to assess their compatibility with the existing water in the reinjection zone or with reinjection
water from other sources, such as seawater. In this case, specifications can only be established by detailed
sampling and testing of the streams involved. Figure 2.7 provides a flowsheet of an integrated production
facility which includes crude oil and produced water handling and treatment.

Figure 2.7 Example Integrated Production Facility
PROCESS SELECTION & DESIGN BASIS

The most critical phase of project development occurs at or near the very beginning. At this point a
series of philosophical guidelines must be applied to all calculations.
If the input is from a petroleum reservoir, future performance is uncertain. The reservoir engineer-
ing does not dictate how the reservoir will perform in the future; current analyses and flow conditions will
certainly change with time. A series of questions like the following must be answered:
1. What is the probable forecast of reservoir performance? What is the trend, magnitude, and
timing of fluid analyses, gas-oil ratios, etc.?
2. What are the magnitude and timing of enhanced recovery techniques?
3. Based on the above, what modifications of current analytical data are desirable?
4. Are current data from tests, samples, and analyses indicative of current reservoir characteristics?
Do such data reflect equilibrium reservoir performance? If production is to be from more than one
zone, have all such zones been tested and sampled?
5. Is the reservoir likely to produce solids at the flow rates anticipated?
6. What amount of water must be handled, now and in the future?
7. If water and/or gas is being injected, when and how will breakthrough occur? Is a gas lift
system anticipated? What will the impact be on the surface system?
8. What is the market for the natural gas and associated liquids?
CHAPTER 2 43
There are many cases where natural gas is found in remote areas, distant from existing gas markets.
A common term for this gas is “stranded gas.” Alternatives for bringing the gas to market include:
1. Long distance pipeline
2. LNG
3. Chemicals (ammonia or methanol)
4. Gas-to-liquids (GTL)
If the transportation distance is less than about 1500-2500 km [900-1500 mi] pipeline transpor-
tation to the market is generally the most economical alternative. This of course depends on the terrain,
cost of right-of-way, sub-sea water depth, etc. For longer distances, LNG may be the preferred alternative.
Exporting natural gas as a chemical product, e.g., methanol or ammonia, is often not attractive for large
volumes of gas because market size for these products is limited.
Gas-to-liquids is a technology which has received considerable attention over the past few years
and may be economically attractive when oil prices are high relative to natural gas prices. Natural gas can
be converted to liquid hydrocarbons via partial oxidation and Fischer-Tropsch synthesis. The range of
hydrocarbons produced depends on synthesis reactor temperature and residue times. The major drawback
to this option is a high capital cost and poor conversion efficiency of around 60% on an energy basis.
SUMMARY
The philosophical discussions in these first two chapters have been included to emphasize that
engineering is a science whose proper application depends to a large degree on human judgment. Since we
can now out-compute our real knowledge, the calculation itself is no longer the primary challenge.
In spite of this, correct and meaningful calculations are still important. As we discuss the principles,
laws, correlations, and equations that have proven useful, please remember: calculations solve equations
and models—but not problems. Only people solve problems.
REFERENCES
2.1 Cannon, R., “The Gas Processing Industry: Origins and Evolution”, Gas Processors Association (1993).
2.2 Hubbard, R., “The Role of Gas Processing in the Natural-Gas Value Chain”, Journal of Petroleum Technology (Aug. 2009).
2.3 Carnell, P., Foster, A., J. Gregory, “Mercury Matters”, Hydrocarbon Engineering, (Dec. 2005).
2.4 Eckersley, N., “Advanced Mercury Removal Technologies”, Hydrocarbon Processing, (Dec. 2010.)

APPENDIX 2A – EXAMPLE NGL SPECIFICATIONS
*LV%=Liquid Volume Percent
Table 2A.1
Example Propane / Butane and Propane Butane Mix Specifications
Product Designation
Product Commercial Commercial Commercial B-P
Characteristics Propane Butane Mixtures Propane HD-5
Composition Predominantly Predominantly Predominantly Not less than 90

propane and/or butanes and/or mixture of butanes liquid volume percent
propylene butylenes and/or butylenes propane; not more
with propane and/or than 5 liquid volume
propylene percent propylene
Vapor Pressure
at 100°F, psig max 208 70 208 208
37.8°C, kPa max 1434 483 1434 1434
Volatile Reside
Temp @ 95% –37°F [–38.3°C] 36°F [2.2°C] 36°F [2.2°C] –37°F [–38.3°C]
evap 2.5 — — 2.5
butane + LV% — 2.0 2.0 —
pentane+LV%
Total Sulfur, ppmw 185 140 140 123
Table 2A.2
Example Butane and Natural Gasoline Specifications
Product Product Designation

Characteristic Field Butanes i-Butane n-Butane Natural Gasoline
Composition LV%
Propane 2.5-3.0 max 2.5-3.0 max
Propane/i-Butane 3.0 max — —
n-Butane 65 min 4.0 max 95 min
i-Butane 20 min 95 min 4.0 max
Pentanes/n-Butane 3.0 max — —
Pentanes 3.0 max
Specific Gravity 60/60°F 0.570 min 0.560 min 0.580 min
0.585 max 0.570 max 0.588 max
API Gravity 79.7 min
@ 60°F 91.3 max
Vapor Pressure, psig 37 min 56 min —
@ 100°F 48 max 60-62 max 43 max
Reid Vapor Pressure, 12.0 min
@ 100°F 14.2 max
Sulfur, gr/100 scf 10 10 10 10
Corrosion Copper Strip No. 1 No. 1 No. 1
Dryness No Free Water No Free Water No Free Water No Free Water
Distillation Temp 36°F 31°F 36°F —
@ 95% 25% min
% Dist. @ 140°F 85% max
% Dist. @ 275°F 90% min
Endpoint 375°F
CHAPTER 2 45
Table 2A.3
Example Y-Grade, Ethane and Ethane Propane Mix Specifications
Product Designation
Product Characteristic Y-Grade Ethane E-Grade E-P Mix G Grade
Composition LV%
Methane 0.5-1.5 max 1.5 max —
C1/C2 1.5 max — 1.5 max
Carbon dioxide 1.0 Max 1.0 max —
CO2/C2 0.35 max — 1.0 max
Ethane — 94.0 min 70 min˗90 max
Ethylene/Ethane — — 10.0 max
Propane — 3.5 (C3+) max 30 (C3+) max

Propylene — — 0.5 max
Butane — 3.0 max
Aromatics 1.0
Aromatics/C5+ 10 max
Olefins 1.0 max
C4=/C4 0.1 max
Fluorides 1 ppmv max
Vapor Pressure psig @ 100°F 600 max

14 min
Temperature
>50 mol% C2 90°F max
<50 mol% C2 110°F max
Sulfur gr/100 scf 10 10 10
Corrosion Copper Strip No. 1 No. 1 No. 1
Dryness No Free Water @ 34°F 20 ppmw No Free Water
Distillation Temp. end point 280-375°F
Table 2A.4
Natural Gasoline Basic Specifications
Reid vapor pressure @ 38°C [100°F] 70-235 kPa [10-34 psi]

Percentage evaporated at 60°C [140°F] 25-85%
Percentage evaporated at 135°C [275°F] not less than 90%
End point not higher than 190°C [375°F]
Corrosion not corrosive by specified test
Doctor test negative
Color not less than plus 25 (Saybolt)
Water content as specified

3
PHYSICAL PROPERTIES OF
HYDROCARBON SYSTEMS
A reliable estimate of physical properties is required in order to obtain reliable calculations.
For single component systems, data are readily available. Table 3A.1(a) and Table 3A.1(b) in Appendix
3A provide physical property data for selected hydrocarbons and non-hydrocarbon components. Refer-
ences 3.1-3.3 may be used to estimate properties of pure paraffins heavier than decane.
Most hydrocarbon streams are mixtures of the hydrocarbon species summarized in Chapter 1.
Many contain water and varying quantities of contaminants like sulfur compounds (primarily hydrogen
sulfide), carbon dioxide, and nitrogen. The physical and chemical properties depend on pressure, tempera-
ture, and composition.
The basic philosophy of physical property correlations, described later in this chapter, depends
on some understanding of the molecular character of the mixture. The primary factors involved are
pressure, temperature, size and shape of individual molecules, their distance apart, the degree and nature
of their attractive and repulsive forces, and the relative amount of each species present. These are not all
independent variables, so correlations for mixtures are approximations of varying accuracy.
Each of the homologous series of hydrocarbons exhibit similar behavior through molecules
with up to about six carbon atoms. Shape and mass have a greater effect on behavior as the molecules
become larger. As a general rule, correlations for light hydrocarbons do not accurately model mixtures
containing a significant quantity of heavier hydrocarbons.
Mixtures containing molecules with similar physical character result in orderly behavior. A single
component system composed entirely of a simple, relatively spherical and non-polar molecule like methane
behaves in a predictable, correlatable manner. There are no absolute rules of behavior but, in general, the
accuracy of the calculation decreases as you go down the following list:
1. Single component system
2. Mixture of molecules from the same homologous series
3. Mixture of molecules from different homologous series
4. Hydrocarbon mixtures containing sulfur compounds and/or carbon dioxide
5. Hydrocarbon mixtures containing water, methanol, glycols, etc.
Properties for single component systems can be accurately correlated as a function of temperature
and pressure. For mixtures a P-V-T equation of state (EOS) is typically used, along with what is usually
called a “combination or mixing rule.” The EOS is simply an equation which relates the volumetric proper-
ties of the mixture to temperature, pressure and composition. The constants in the EOS are generally a
CHAPTER 3 47
PHYSICAL PROPERTIES OF HYDROCARBON SYSTEMS
function of the critical properties of the components in the mixture. The mixing rules provide the ability to
modify or “tweak” the constants based on actual experimental data. The accuracy of the EOS and accom-
panying mixing rules is tied to the quantity and accuracy of the underlying data and the complexity of the
system.
The principle of the combination rule is that the total mixture property is a type of summation of
the properties of the molecular components in the mixture. The simplest combination rule is to assume
that the contribution of individual molecules is proportional to their relative quantity in the mixture. This
is never strictly true but serves as a reasonable approximation in selected applications.
The more dissimilar the molecules, the less accurate the prediction becomes. For this reason, hydro-
carbon mixtures containing sulfur compounds and/or carbon dioxide are particularly difficult to model. For
these systems, the difference between the model prediction and actual data can exceed 20% depending on
the property being estimated and system conditions. This uncertainty should be incorporated in design or
operational calculations.
It is not practical, or even possible, to build a theoretical EOS-based property correlation that will
accurately handle all compositions, temperature and pressures. No matter how complex they may appear,
all P-V-T equations of state are empirical. Their application outside of the range of data on which they
were developed can lead to significant inaccuracies.
No mention of water has been made, even though water in liquid or vapor form is present to
some degree in all of the systems discussed here. Liquid water is essentially immiscible in hydrocarbons.
For moderate to high-pressure systems, water often represents a trivial percentage of the total mass
present (seldom more than 0.1 to 0.2 wt%) in the vapor phase. Nonetheless, water introduces a great
deal of complexity into mixture behavior. For this reason water is often dealt with using special correlations
separate from the EOS. Some of these will be introduced in subsequent chapters.
As mentioned earlier, EOS use critical properties (T, P and V) to calculate correlation constants
in the EOS. A widely used principle in physical and thermodynamic correlations is pure components that
exist at the same reduced temperature and pressure will exhibit similar behavior. The reduced temperature
and reduced pressure are simply the actual temperature and actual pressure of the system divided by the
critical temperature and pressure, respectively, of the component(s) in the system. This is referred to as the
Principle of Corresponding States and is an important tool in these correlations. It will be discussed in more
detail later in this chapter.
The following correlations are used commonly for hydrocarbon systems and are suitable for use in
future calculations in this book.
GAS PROPERTIES – EQUATIONS OF STATE

Ideal Gas Law
Any equation correlating P, V, and T is called an “equation of state.” The simplest EOS begins with
the Boyle-Charles Laws, which states that P times V is proportional to T. The addition of a proportionality
constant (R), normally called a “universal gas constant", leads to the ideal gas Equation (3.1).
PV = nRT (3.1)
Where: P = absolute pressure
V = volume
n = number of mols of gas of volume V at P and T
T = absolute temperature

If “n” is set at 1.0 (i.e., one mol) Equation (3.1), then “V” is the molar volume, designated “v” in
this text. If “V” is a mass specific volume (reciprocal of density), then “n” is the reciprocal of molecular
weight.
For most gas mixtures, Equation (3.1) is valid up to pressures of about 400 kPa [60 psi]. As pressure
increases above this level, the accuracy decreases and the system should be considered a non-ideal gas. light
gases, e.g., methane, exhibit ideal gas behavior at higher pressures than heavier gases, e.g., propane, butane.
Compressibility Factor and Nonideal P-V-T Equations

Because of its simplicity, Equation (3.1) is often corrected by a compressibility factor, z.
PV = znRT (3.2)
Where z represents the deviation from ideal volumetric behavior due to molecular interactions, i.e.,
attractive and repulsive forces.
Equation (3.2) may be written in terms of density at the system P and T:
(P)(MW)
t= zRT
(3.3)
The units for the terms in Equations 3.1 thru 3.3 are provided in the table below.
P V T R t
kPa m3 K 8.314 kPa.m3/kmol.K kg/m3
MPa m3 K 0.008 31 MPa.m3/kmol.K kg/m3
bar m3 K 0.083 14 bar.m3/kmol.K kg/m3
psi ft3 °R 10.73 psia-ft3/lb-mol.°R lbm/ft3
lb/ft2 ft3 °R 1545 psfa-ft3/lb-mol.°R lbm/ft3
Figure 3.1a thru Figure 3.4b present several graphs showing the compressibility factors for various
hydrocarbon gas mixtures plotted as a function of temperature and pressure (3.8). The Benedict-Webb-
Rubin-Starling equation of state [BWRS] was used to estimate “z,” and the gas compositions represent
natural gas mixtures with relative densities of 0.60, 0.65, 0.70, and 0.80. The compositions are for
mixtures of paraffin hydrocarbons and include no non-hydrocarbon components such as CO2, H2S,
and N2. The compressibility factors for gases containing non-hydrocarbon components will generally be
higher than the values in Figure 3.1a thru Figure 3.4b.
An easy way to determine the properties of a gas at different conditions from a known state using
the corrected ideal gas equation is provided in Equation (3.4):
P1 V1 P2 V2
z1 T1 = z 2 T2 (3.4)
CHAPTER 3 49
Figure 3.1a Compressibility Factors for Low Molecular Weight Natural Gas, MW = 17.40 (SI)
(Reproduced with permission from GPA)
Figure 3.1b Compressibility Factors for Low Molecular Weight Natural Gas, MW = 17.40 (FPS)

CHAPTER 3 51

CHAPTER 3 53
Example 3.1: Calculate the density at 25°C [77°F] and 7000 kPa [1015 psia] of a gas with a rela-
tive density of 0.6 and a gas with a relative density of 0.8.
SI Units
For γ = 0.6, T = 25°C, and P = 7000 kPa, from Figure 3.1a; z = 0.86
MW = (0.6) ´ 29 kg/kmol = 17.4 kg/kmol
(P)(MW) (7000 kPa)(17.4 kg/kmol) kg

t = (z)(R)(T) = = 57 3
(0.86) a8.314 kmol K k (298 K)
3
kPa m m
For γ = 0.8, from Figure 3.4a; z = 0.69
(7000 kPa)(23.2 kg/kmol) kg

t = = 95 3
(0.69) c8.314 kmol K m (298 K)
3
kPa m m
FPS Units:
For γ = 0.6, T = 77°F, P = 1015 psia, from Figure 3.1b; z = 0.86
(1015 psia)(17.4 lbm/ lb - mol ) lbm

t= 3 = 3.6 3
(0.86) d10.73 - n (537 %R )
psia ft ft
lb mol %R
For γ = 0.8, from Figure 3.4b; z = 0.69
(1015 psia)(23.2 lbm/ lb - mol lbm

t= = 5.9 3
psia ft3
(0.69) d10.73 - n(537 cR)
ft
lb mol %R
In sections that follow, selected correlations for z are presented that have proven useful for natural
gas. A large number of P-V-T equations have been developed to describe non-ideal, real gas behavior. Each
is empirical in that it correlates a specific set of data using one, or more, empirical constants. There can be
as many such equations as there are people who correlate data. The following equations are some of the
most common. The inclusion, or exclusion, of an equation is not a reflection of the worth of an equation.
It merely reflects degree of recognition in this industry. The Katz correlation and Kay’s rule are provided
in Appendix 3B. This is a simple hand calculation method for estimating z for sweet natural gases. The
Wichert-Aziz(3.4) method provided in Appendix 3C provides a modification to the Katz correlation for sour
natural gases.
van der Waals:
RT a
P= – (3.5)
v – b v2
Where: a&b = correlation constants
v = molar volume
The “a” represents the intermolecular forces and “b” represents the molecular size.

Benedict-Webb-Rubin (BWR):
2
P = RTt + (B o RT - A o - C o /T 2) t 2 + (bRT - a) t3 + aat6 + (ct3 /T 2) (1 + ct 2) e - ct (3.6)
Where: P = absolute pressure

T = absolute temperature
1
t = molar density = v
Ao, Bo, Coa, b, c,  & g = correlation constants

Soave-Redlich-Kwong (SRK):
RT a
v – b v ^v + b h
P= – (3.7)
Peng-Robinson (PR):
RT a
P = v-b - (3.8)
v (v + b) + b( v - b)
Where: a, & b = correlation constants

v = molar volume
The constant “a” in the SRK and PR EOS is a function of temperature and acentric factor.
The van der Waals equation is the “grandfather” of P-V-T equations. It is seldom used today but
serves as a basis for many concepts used in the correlation of mixture properties.
Equations (3.5), (3.7), and (3.8) are called cubic equations of state because they are cubic
when written in terms of volume. The constants a and b are a function of the critical properties Tc
and Pc and a third parameter, usually the acentric factor, ~. For mixtures, mixing rules are necessary to
determine the values of a and b.
A number of modifications to these equations of state have been published and are used in
the oil and gas industry. The purpose of the modifications is to improve the validity of the model. An
example of this is the Starling modification to the BWR equation (BWRS).
The previous equations are used primarily as a basis for computer solutions. They tend to offer
more precision, but the real accuracy of the results may be no better than the simpler methods when
one considers the quality of the P, T, and composition data available.
As discussed earlier, no correlation is equally good for all gas mixtures. Like all empirical
relationships, equations of state can be extrapolated beyond the compositions, T and P on which they were
based, but only with an inherent loss of accuracy.
CHAPTER 3 55
Corresponding States Concept

The corresponding states concept
states that physical and thermodynamic
properties, e.g., density, viscosity, vapor 10 000
pressure, etc., which depends on intermolec-
ular forces are related to the critical properties
1000
ne
Pressure, kPa
in a universal way. Mathematically, another
tha
way of stating this concept is to say that if
Me
an equation of state for any fluid is written 100
ne
pa
in terms of reduced properties, that equation
Pro
is also valid for any other fluid. Reduced
properties are defined as: 10
T P v
Tr = T , Pr = P , vr = v (3.9)
c c c 1
-200 -150 -100 -50 -0 50 100
(a) Temperature, °C
Where the subscript “r” denotes a
reduced property and “c” a critical property. 1.0
Critical properties for several natural gas
components may be found from Table
3A.1(a) and Table 3A.1(b). 0.1
The corresponding states concept is

only partially valid for real fluids, nonethe- 0.01
Pr
ne
less it is a powerful correlation tool. As you tha
ne
Me
would expect, it is most accurate for mixtures
pa
Pro
of similar molecules exhibiting little interac- 0.001
tion. It is illustrated in Figure 3.5.
The vapor pressure curves for methane 0.0001
0.20 0.40 0.60 0.80 1.00
and propane are shown in Figure 3.5(a). The (b) Tr
terminus of each curve represents the critical
point for that substance. Figure 3.5(b) shows Figure 3.5 Vapor Pressure (a) and Reduced Vapor Pressure
the same curves plotted on reduced coordi- (b) of Methane and Propane
nates (Tr, Pr). These curves terminate at Pr
and Tr = 1.0, which is the critical point.
Notice how the two reduced vapor pressure curves are almost identical. If the corresponding
states theory were perfectly valid, these curves would be identical.
Third Parameters
The corresponding states concept says that fluid properties can be predicted from the relationship:
property, e.g., density = f (Pr , Tr) (3.10)
As we have seen above, the corresponding state concept is not entirely valid. To improve the
accuracy and generality of an equation of state, a third parameter may be added to the corresponding states
concept so that:
property = f (Pr , Tr third parameter) (3.11)
where the third parameter is a term capable of characterizing fluid behavior.

A number of third parameters can be used in Equation (3.11). The following two are used most
commonly.
Acentric Factor (~). This was developed by Pitzer to describe the deviation of a fluid from
simple fluid behavior, or its nonconformity with the corresponding states principle. For the simple,
noble gases like argon and zenon, ~ is equal to zero. Acentric factor increases with molecular size, shape
and polarity. For example, from Table 3.1, methane has an acentric factor of 0.0104 while n-pentane has
an acentric factor of 0.2514.
Table 3.1
Physical Constants
Compound Molecular Weight zc Acentric Factor w

C1 16.043 0.29 0.0104

C2 30.070 0.29 0.0979
C3 44.097 0.28 0.1522
iC4 58.124 0.28 0.1852
nC4 58.124 0.27 0.1995
iC5 72.151 0.27 0.2280
nC5 72.151 0.27 0.2514
nC6 86.178 0.26 0.2994
nC7 100.205 0.26 0.3494
nC8 114.232 0.26 0.3977
nC9 128.259 0.25 0.4445
nC10 142.286 0.25 0.4898
N2 28.016 0.29 0.0372
CO2 44.010 0.28 0.2667
H2S 34.076 0.28 0.0948
O2 32.000 0.29 0.0216
H2 2.016 0.30 –0.2202
H2O 18.015 0.235 0.3443
The parameter ~ is defined by the equation:
~ = - log Pr - 1 (3.12)
Where: Pr = P*/Pc; P* is the vapor pressure at T = 0.7 Tc
This parameter is widely used as a correlating device. It is the third parameter used in the SRK and
PR equations of state. It can be visualized from Figure 3.5(b). It is a measure of the difference between the
reduced vapor pressure of a component at Tr = 0.7 and the reduced vapor pressure of an ideal molecule at
Tr = 0.7 which is Pr = 0.1.
Critical Compressibility (zc). In Table 3.1 it may be noted that each component has a different zc.
This parameter has been used as a basis for z factor correlations designed for manual calculations. A chart
of z versus Pr and Tr is prepared for different values of zc. With the growth of computer usage, this approach
is not employed now as commonly as in the past, although it is a legitimate approach.
The relationship of zc to ~ may be approximated using Equation (3.13):
z c = 0.291 - 0.088~ (3.13)
CHAPTER 3 57
Mixture Combination Rules

Tc and Pc for a mixture cannot be read from a table. They must be calculated in some manner if Pr
and Tr are to be used to calculate a property like z. Likewise, the values of the parameters a, b, c, etc., in
Equations (3.5)-(3.8) must be determined in a special way for mixtures. As discussed earlier, any equation
or series of equations used to obtain mixture parameters is called a “combination rule” or “mixing rule.” The
calculation, regardless of its exact form, is based on the premise that the properties of a mixture are a type of
weighted average summation of the properties of the individual molecules comprising that mixture.
The mixing rules used in cubic equations of state (i.e., van der Waals, Soave-Redlich-Kwong,
Peng-Robinson) are:
a m = / / x i x j (a i a j)1/2 (1 - k ij) ; b m = / x i b i (3.14)
Where: am and bm = the a and b parameters for the mixture

ai, aj, bi = a and b parameters for any components in the mixture
xi, xj = composition (mol fraction) for any two components in the mixture
kij = binary interaction parameter
Once am and bm have been determined, the equation of state computations proceed as though a and
b were for a pure component. With cubic equations of state, the mixing rules sum the properties based on
binary pairs. For example, a 4-component mixture would consist of 6 binary pairs.
The binary interaction parameter, kij, has no theoretical basis. It is empirical and is used to overcome
deficiencies in the corresponding states theory or the basic model (equation of state). Binary interaction
parameters are regressed from experimental data for a specific model and should be applied in that model
only.
A number of different mixing (or combination) rules are used in property correlations. Each property
correlation is designed for use with the given combination rule that was used to derive it from actual data.
Like kij’s, these two go together and cannot be mixed. The same is true for the multiple constant equations
of state. The constants obtained apply only with the combination rule used to obtain them.
The critical values found from a combination rule are not necessarily true values; thus, they are
called “pseudocriticals.” Remember: the word pseudo means “fake” or “not real.” Thus, a pseudocritical
value is not a point on the phase curve; it is merely a correlating parameter that uses the concept of corre-
sponding states. In this book a pseudocritical will be written with a “prime” Tc' and Pc'.
Approximate Correlation for Tc’ and Pc’

Often density calculations are required when very little information is available.
Figure 3.6 can be used to estimate pseudocritical temperature and pressure if no analysis is
available. This is an approximate correlation and is applicable to gases with less than 5 mol percent CO2
and H2S. For gases, Equation (3.15) and (3.16) can be used to estimate Pc' and Tc'.

700
Pc' = 5.218 - 0.90328 c - 0.0248 c 2 (3.15)
4.8
Miscellaneou
650 Condensa
s Gases 4.6
Tc' = 94.00 + 194.2c - 41.1c 2 (3.16)
P’c, MPa
te Well
P’c, psia
Fluids 4.4
4.2
600
4.0 Where: Pc' = pseudocritical pressure, MPa
550
300
Tc' = pseudocritical temperature, K
s γ = relative density of the gas
500 G ase 280
us
eo
an
ell 260
isc
Other Correlations for z
T’c’ °R
T’c’ K
450
240
ids
l Flu
400 te Wel 220In general, equations of state methods are
s a
den
Con the most widely used correlations for the determi-
200
350
180
nation of gas density (t). They are not necessarily
300 the most accurate. Empirical correlations developed
0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 for a specific mixture or a narrow range of mixtures
Gas Relative Density, g (Air = 1.0) provide better accuracy but are often less general.
An example would be the Katz correlation, which is
Figure 3.6 Approximate Pseudo-Critical Properties of
Sweet Natural Gas(3.5) quite good when applied to “sweet” pipeline quality
gases but less reliable for gases containing signifi-
cant amounts of H2S, CO2, and/or N2.
To extend the validity of empirical correlations, third parameters and more sophisticated mixing
rules are required. This added complexity typically makes the calculation too tedious to perform manually,
so a computer method is required.
A final word about compressibility factor accuracy is warranted. Compressibility factor is a
dimensionless, surrogate measure of gas density. Its primary applications are in equipment sizing,
gas flow measurement, and performance testing, e.g., centrifugal compressors. The latter two applications,
gas flow measurement in particular, require a very accurate determination of compressibility factor. The
methods outlined in this chapter would not generally be used in these applications. A highly accurate
compressibility factor is not critical to the sizing of most equipment, especially when the uncertainties
in other process variables are considered.
For fiscal metering of natural gas, an accurate experimental database has been developed, and
compressibility factor correlations with uncertain-
ties generally within ±0.2% have been published z
in the industry standards, AGA Report No. 8 and Katz 0.80
ISO 12213. Reference 3.6 provides a summary of Katz w/ Wichert and Aziz correction 0.83
some common “z” correlations and their effect on gas
measurement accuracy. SBV 0.83
For comparative purposes, the compress- Appendix 3A 0.80

ibility factor, z, has been calculated for the gas in SRK equation of state 0.85
Example 3.1 using several correlations. The calculated PR equation of state 0.81
values are summarized in the table to the right. The
results should be viewed as an indication of the range BWRS equation of state 0.84
of possible outcomes encountered, not as an indication AGA Report No. 8 Correlation Eqn. 0.83
of the inherent accuracy (or inaccuracy) of any one
method.
CHAPTER 3 59
Gas Viscosity
Since the intermolecular Temperature, °F
forces are a function of the distance 100 150 200 250 300 350
0.045
between molecules, viscosity depends
on whether the fluid is a liquid or gas
at system temperature and pressure. 0.040
The viscosity of a liquid is much P=
55.
2 MP
higher than that for a gas at the same a [8
000
psia
0.035 ]
conditions of pressure and tempera-
ture. As with density, it is convenient P=
41.
4 MP
a [6
to consider liquid and gas viscosities 0.030
0 00
psia
]
P=
separately. 34.4
MPa
[500
0 psi
Viscosity, cp
a]
In general, gas viscosity 0.025 P=

27.6
MPa [
is used in fluid flow pressure drop 4000 p
sia]
calculations, detailed heat exchanger P = 20

.7 MPa [300
0 psia]
calculations, and droplet settling calcu- 0.020
P = 17.2 MPa [2500 psia]
lations for separation. The accuracy of P = 13.8 MPa [2000 psia]
gas viscosity values in facilities work 0 psia]

P = 10.3 MPa [150
]
0.015
6. 9 M Pa [1000 psia
is generally not critical. For hydrocar- P=
P a [ 20 0 psia]
P = 1.4 M
bon gases, a good general assumption
for viscosity is 0.013 cp. Figure 3.7 0.010
can be used to estimate natural gas Gas MW = 19.7

viscosities.
0.005
30 55 80 105 130 155 180
The Equations (3.17)-(3.20) Temperature, °C
are used in the Lee Correlation used to
estimate the viscosity of hydrocarbon Figure 3.7 Lee et al. Equation for Hydrocarbon Gas Viscosity (µg)(3.7)
gases.
n g = L1 exp ;L 2 c A m E
t g L3
(3.17)
(7.77 + 0.0063 (MW))T 1.5

L1 = 10–4 (3.18)
[122.4 + 12.9 (MW) + T]
1914.5
L 2 = 2.57 + T
+ 0.00095 (MW) (3.19)
L3 = 1.11 + 0.04 L 2 (3.20)
SI FPS
Where: μg = gas viscosity cp cp
tg = gas density kg/m3 lbm/ft3
MW = molecular weight of gas kg/kmol lbm/lb-mol
A= conversion factor 1000 62.4
T= absolute temperature 1.8 K oR

LIQUID PHYSICAL PROPERTIES

Liquids are relatively incompressible compared to gases. However, the calculation of the properties
of liquid mixtures is complicated by two factors: (1) the presence of high vapor pressure components like
methane and ethane and (2) the shrinkage in volume upon mixing two hydrocarbon liquids.
Both effects can be understood by remembering that liquid is made up of molecules of different
sizes and shapes, possessing different amounts of energy.
The size and shape of the molecules affect all properties. If liquid molecules were magnified, a
series of shapes and sizes with space between them would be observed. The size depends on the molecular
weight. The larger paraffin molecules would be shaped somewhat like a sausage. The aromatic (ring)
molecules would be more circular. The small molecules like methane and ethane would be rather spherical.
The energy of molecules in moving around is somewhat relative to vapor pressure, which in turn is
related to molecular weight. Molecules like methane are very active, and this movement clears more space
between molecules as collisions occur. The large molecules are more lethargic.
The properties are dependent on size, shape, and energy. In a container full of large rocks, there
are spaces between the rocks that can accommodate smaller-sized objects like gravel and sand. In a similar
way liquids containing molecules of different sizes experience shrinkage on mixing, as smaller molecules
occupy voids between the bigger ones; i.e., the volumes are not additive.
All of this says that the physical properties of a mixture are dependent on factors that are measures
of energy, size, and shape. Density is one of these factors. It is not only needed for basic calculations but
correlates with properties like viscosity, energy content, boiling points, etc.
Liquid correlations can be divided into two general categories: (1) natural gas liquids (NGL), where
an analysis showing most of the components is available and (2) undefined liquids (like crude oil), where
a detailed analysis is not feasible. If the NGL is recovered from the gas after reservoir fluids have been
separated, the concentration of components heavier than decane will be trivial and NGL correlations will
suffice. If reservoir liquids are involved, some form of characterization is often used. The distillation charac-
teristics of the heavier components are one of the basic analytical methods employed.
When the liquid is composed of butane and heavier molecules, their energy is low enough that
relatively simple correlations may suffice. Some correction for pressure and temperature is required in many
cases. Molecular energy increases with increasing temperature, thus reducing density and other physical
properties. Increasing pressure has the opposite effect, since it “squeezes” the molecules closer together.
Distillation Characteristics
Two types of distillation are used commonly: (1) ASTM and (2) true boiling point (TBP). Both are
batch distillations. The ASTM apparatus is a non-refluxed, single-stage unit. The temperature at which the first
droplet of liquid is collected overhead is recorded as the initial boiling point (IBP). The temperature is raised
at a steady rate and recorded when several mass or volume percentages of the sample have been recovered.
The end point temperature is recorded, usually when 95% of the sample volume has been distilled overhead.
The TBP is the preferred approach. The apparatus usually contains ten or more equivalent stages. A
high reflux rate is used to obtain a sharper separation between the fractions distilled.
The average boiling point often is used. This may be the 50% point of the distillation found from
a combination rule or by a correlation. In addition to the correlations shown herein, further information is
available from references, 3.8 , 3.9 and 3.26.
CHAPTER 3 61
Figure 3.8 shows some representative TBP curves. The one on the left is based primarily on oil
samples from North and South America. The one on the right is based on 85 samples from the Middle East
and North Africa.
Average of North America Average of Mid-East and

and South America Samples North Africa Samples
Figure 3.8 Some Representative TBP Distillation Curves
Sulfur affects the shape of TBP curves. Most sulfur occurs in the highest boiling or residual parts
of the oil. Thus, the primary effect of sulfur is to steepen the slope of the higher boiling parts of the curve.
Without sulfur, the curves for the lower API gravity oils would be flatter.
If the quantity of the liquid sample is sufficient, properties such as density and molecular weight
of each distillation fraction may be measured. It is relatively common to measure density, less common
to measure MW. Correlations are available to estimate the critical properties and acentric factor of each
fraction based on measured properties. For purposes of predicting physical and thermodynamic proper-
ties, each fraction may now be treated as an individual component. The fraction actually consists of many
different types of molecules (perhaps hundreds) and is referred to as a pseudo-component. Reference 3.29
provides an excellent summary of this procedure.
Characterization Parameters
Gas chromatography was briefly discussed in Chapter 1. One method of presenting the composition
of C6+ components is by equivalent carbon number based on a chromatographic analysis. You will remember
from the discussion in Chapter 1 that these carbon numbers, C6, C7, C8, etc., are not pure components but
mixtures.
(3.25)
Table 3.2 presents average properties (BP, MW, g) from several crude oil/condensate systems.
These properties can be used to characterize C6+ fractions when distillation data is unavailable. The use
of the parameters in Table 3.2 is preferable to assuming that each carbon number component is a normal
paraffin.
Figure 3.9 and Figure 3.10 show the relationships “MW vs. relative density” and “BP vs. relative
density,” for the characterization parameters in Table 3.2 based upon the Watson, Kw, method. The properties
of n-paraffins are included for comparative purposes along with the properties of naphthenic and aromatic
hydrocarbon mixtures.

1.00
1<111
re
: s
1 0: 1<0K<wK<w
eus
0.95
ic iMxtiuxrt 12
iactM KK <<12
oAr
moamt
t u
r r
ese:s1: 1 1<< w w
0.90 Ar icMM ixitxu
ehneinc
Relative Density, L
t
h
apap
h h
t ≈ 11.9
0.85 NN b le 3.2: K w
m Ta
a fro
Dat 2 < K<w1<313
0.80 n -P
a r ranffis:n1s2: 1< K w
aaffi
n -P
0.75
0.70
0.65
0.60
0 100 200 300 400 500 600 700
Molecular Weight
Figure 3.9 Relative Density vs. MW for Generalized Hydrocarbon Fractions
1.00
< 11
10 < K w
0.95 ures:
ic Mixt
mat
Aro 12
0.90 K <
11 < w
Relative Density, L
e s :
tur 11.9
Mix Kw≈
0.85 h enic 3 .2 :
ht le
Nap rom Tab
a f
0.80 Dat 13
≤ Kw ≤
ffin s: 12
ra
0.75 n-Pa
0.70
0.65
0.60
0 100 200 300 400 500 600
Boiling Point, °C
Figure 3.10 Relative Density vs. Boiling Point for Generalized Hydrocarbon Fractions
It should be emphasized that the parameters in Table 3.2 are default values to be used
only when analytical information is unavailable. These parameters are based on crude oil and condensate
systems, which are often substantially paraffinic.
CHAPTER 3 63
Table 3.2 (3.25)

Generalized Properties of Petroleum C6+ Groups
Hydrocarbon Boiling Range Average Boiling Point Density Molecular

Group °C °F °C °F (g/ml) Weight
C6 36.5 to 69.2 97.9 to 156.7 63.9 147.0 0.685 84

C7 69.2 to 98.9 156.7 to 210.1 91.9 197.5 0.722 96
C8 98.9 to 126.1 210.1 to 259.1 116.7 242.1 0.745 107
C9 126.1 to 151.3 259.1 to 304.4 142.2 288.0 0.764 121
C10 151.3 to 174.6 304.4 to 346.4 165.8 330.5 0.778 134

C11 174.6 to 196.4 346.4 to 385.5 187.2 369.0 0.789 147
C12 196.4 to 216.8 385.5 to 422.2 208.3 407.0 0.800 161
C13 216.8 to 235.9 422.2 to 456.7 227.2 441.0 0.811 175
C14 235.9 to 253.9 456.7 to 489.2 246.4 475.5 0.822 190
C15 253.9 to 271.1 489.2 to 520 266 511 0.832 206
C16 271.1 to 287.3 520 to 547 283 542 0.839 222
C17 287 to 303 547 to 577 300 572 0.847 237
C18 303 to 317 577 to 603 313 595 0.852 251
C19 317 to 331 603 to 628 325 617 0.857 263
C20 331 to 344 628 to 652 338 641 0.862 275
C21 344 to 357 652 to 675 351 664 0.867 291
C22 357 to 369 675 to 696 363 686 0.872 305
C23 369 to 381 696 to 717 375 707 0.877 318
C24 381 to 392 717 to 737 386 727 0.881 331
C25 392 to 402 737 to 756 397 747 0.885 345
C26 402 to 413 756 to 775 408 766 0.889 359
C27 413 to 423 775 to 793 419 784 0.893 374
C28 423 to 432 793 to 810 429 802 0.896 388
C29 432 to 441 810 to 826 438 817 0.899 402
C30 441 to 450 826 to 842 446 834 0.902 416
C31 450 to 459 842 to 857 455 850 0.906 430
C32 459 to 468 857 to 874 463 866 0.909 444
C33 468 to 476 874 to 888 471 881 0.912 458
C34 476 to 483 888 to 901 478 895 0.914 472
C35 483 to 491 901 to 915 486 908 0.917 486

Watson Characterization Factor

This factor is defined by the following equation:
A(T b)1/3
Kw = c
(3.21)
SI FPS
Where: Tb = average boiling point or NBP K oR
γ = relative density (sp. gr.)

A = conversion factor 1.22 1.0
The Watson characterization factor, referred to commonly as the “UOP Watson Factor,” is an
important parameter used to correlate properties of hydrocarbon mixtures.
For most hydrocarbon mixtures the value of Kw will vary from 10-13. The low end of the range
is indicative of substantially aromatic mixtures while the high end is indicative of paraffins. Naphthenic
mixtures fall in between.
Figure 3.9 and Figure 3.10
indicate the given correlations for the
(PNA) paraffin, naphthene, and aromatic
family groups. Each curve represents the
correlation of mixture specific gravity
(or relative density) vs. NBP, or MW for
a discrete range of Kw. The atmospheric
distillation data shown in Table 3.2 yield
a Kw of 11.9, indicating that the C6+
fractions are predominately paraffins. (i.e.,
Hexane). Beyond this value, the occur-
rence of naphthenes and/or aromatics may
be detected.
Figure 3.11(3.10) shows the
relationship between various fluid
property parameters. Knowing any two of
the parameters allows estimation o f the
others. For example, a 40° API crude with
a Watson Characterization factor of 11.9
will have an estimated molecular weight
of 209 and an average boiling point of
255°C [491°F]. The carbon-to-hydrogen
weight ratio varies with molecule size
and type. It is another way to charac-
terize the oil properties. Paraffin series
molecules all possess a C-H weight ratio
less than 6.0. Thus, any value above 6.0
indicates other “families” are present.
The weight ratio is sometimes used in
combustion calculations.
Figure 3.11 Correlations Relating Various Characterization
Variables and Liquid Properties
CHAPTER 3 65
Liquid Density
Prediction of liquid density is a fundamental calculation. The complexity of this calculation
depends on the presence of methane, ethane, CO2, sulfur compounds, and non-paraffins.
Pan and Maddox(3.11) present a series of useful equations for calculating both physical and thermo-
dynamic properties of saturated liquids and vapors.
A thorough presentation was made by Whitson for liquids containing only heptanes and heavier
molecules based on data available from a TBP distillation of this liquid.(3.12) A number of properties are
addressed, but the following equations are provided for estimating molecular weight and density.
MW = (1.66 ´ 10–4)(Tb)2.20(c)–1.02 t = (9.84 ´ 102)(Tb)0.002(c)1.006 (3.22)
Where: MW = molecular weight, kg/kmol

Tb = average boiling point, K
c = relative density at 15.5°C [60°F]
t = liquid density, kg/m3
Units of Density
Wherever practical, liquid density is presented as relative density throughout this book to simplify
unit conversions. Specific gravity, by definition, is the density of a liquid divided by the density of pure
water. In SI standards, specific gravity is replaced by the term relative density.
At 15°C [59°F], the density of water is 1.000 95 g/cm3; for engineering calculations, 1.0 g/cm3 will
suffice at any ambient air temperature. As a practical matter, the error in using 1.0 g/cm3 is trivial. For this
case, the density, t, for any liquid is:
t = c(g/cm3) , t = 1000 c(kg/m3) , t = 62.4c(lbm/ft3) (3.23)
API Gravity
The density of crude oil, condensates, and petroleum products is sometimes shown in °API. This
term is defined by the equation:
141.5 %API = 141.5 - 131.5
c= (3.24)
131.5 + %API c
Notice that API gravity is inversely proportional to the relative density of the liquid. In general, oils
fall into the following categories based upon their API gravity values in Table 3.3.
Table 3.3
General API Gravity Ranges for Liquid Hydrocarbons
Oil Type API Gravity Relative Density Liquid Density - kg/m3 Liquid Density - lbm/ft3
Condensate 70-45 0.7-0.80 700-800 44-50
Light Oil > 30 < 0.88 < 876 < 55
Medium Oil 30-21 0.88-0.93 876-928 55-58
Heavy Oil 20-10 0.93-1.00 934-1000 58-62
Extra Heavy Oil < 10 > 1.00 > 1000 > 62

API Barrel
The word barrel traditionally refers to the term API barrel. By definition, 1 API barrel = 42
U.S. gallons. The reference temperature for an API barrel is 15.5°C [60°F].
If a density term is used where the volume is expressed in barrels (bbl), the following conver-
sion factors are useful:
1 API bbl = 42 U.S. gallons = 35 U.K. Imperial gallons = 5.61 ft3 = 0.159 m3 = 159 liters
General Correlations
A series of liquid density correlations are available that are suitable for most routine applica-
tions and can be performed manually.

One simple approach is to use the Law of Ideal Solutions, which says that the properties of a
mixture are the sum of the properties of its individual parts (components). An equation like Kay’s
Rule can be used for this purpose. This approach is fine for finding apparent molecular weight but has more
limited application when the liquid contains substantial quantities of methane and ethane. The density of
liquids containing these components are lower than predicted by the ideal solution law and by correla-
tions developed for liquids containing primarily propanes and heavier hydrocarbons.
The law of ideal solutions, called Amagat’s Law, is given by Equation (3.25):
vmix = / x i vi (3.25)
Where: vmix = molar volume of the mixture
xi = mol fraction of each component
vi = molar volume of each component
The accuracy required for the density calculation depends on the use. From an energy viewpoint,
a liquid can be regarded as incompressible with pressure; pressure has little effect on the liquid energy
level. For custody transfer, the effect of P and T on density is important. In most engineering calcula-
tions, the order of magnitude effects of P and T are important, but a high degree of precision is not. The
correlations that follow have proven useful for the type of systems discussed herein.
General Nomographs
There is a useful series of nomographs available which are useful for predicting the density of
liquids containing no significant amounts of methane and ethane. They apply primarily for crude oils
separated at low pressure or for natural gas liquids that have been deethanized or separated at ambient
temperatures at 3.5 MPa [500 psia] or below. These nomographs will usually yield results that are within
3-5% for the liquids described above, provided the temperature is below 0.9 Tc.
Two such nomographs are shown in Figure 3.12 and Figure 3.13. Figure 3.12(3.8) may be used to
estimate the density of hydrocarbon mixtures over a range of pressures and temperatures. A point on the
middle grid is located easily from the intersection of any two lines. In most cases, Kw and API gravity are
used. The example is for a liquid with a Kw of 11.0 and an API gravity of 33 (relative density of 0.86) at
7500 kPa [1088 psia] pressure. The result is 0.63-0.64. At atmospheric pressure, the result would be
0.58-0.59. Thus, the pressure has increased relative density.
Figure 3.13 is a simple correlation for estimating the density of a saturated paraffin hydrocarbon
liquid. Since a liquid leaving a gas-liquid separation is saturated (i.e., at its bubblepoint), at the temperature
and pressure of the separation, this correlation is useful. It should be used with caution if the liquid contains
significant amounts of aromatics and/or naphthenes.
CHAPTER 3 67
550
1000 1.05
1.05
Example:
500
A at 300°C an Oil with Relative Density of 0.86
900
B at 15°C and 101.325 kPa (abs), and KW = 11.0
1.00
C has a Relative Density of 0.636 at 7500 kPa (abs)
450
1.00
800
[(Mean Average Boiling Point, °C + 273.15) x 1.8]1/3 0.95
400 KW =
Relative Density at 15°C and 101.325 kPa (abs)
700 0.95
350
0.90
1 .0 .04 .06
55 00
1 1
5
0
600
0.90
Temperature, °C
300 A
0. 0.98 .00 2
45
0.85
0
40
t, °C
Boilin Average
92 94 96
Relative Density
500
Temperature, °F
0.85
35
g Poin
250
0
0.
Mean
30
0.
0.80
sity 15°C
5 kPa (abs)
0
0.9
0
25
8
0.8 0.80
0
400
200 6
0.8
Relative Den
20
and 101.32
0
4 0.75
15 0.8
0 2
0.8 0.75
B 0
150 300 10 0.8
0 8
0.7
0.70
50 0.76
0.70
0.74
100
200 0 0.72
0.65
0.70 0.65
.5
0.68
10
.0
0.66 C
11
12 .5
50
11
K 0.64 0.60
0.60
12 .0
100 W
.5
0.55
0.55
0
0.50
0.50 0.45
10 000 kPa (abs) [1450 psia] 0.40
7500 k Pa (abs) [1088 psia] 101.325 kPa (abs)
Adapted to SI by GPSA from Rutter, Lenoir, 5000 kPa (abs) [725 psia] [14.7 psia]
and Schweppe, Petroleum Refiner, 1958 2500 kPa (abs) [360 psia]
Figure 3.12 Relative Density of Liquid Hydrocarbon Mixtures

275
130 0.75
Example:
120 250
A a Paraffin Mixture at 103°C
110
B with a Molecular Weight of 82.3
A
C has a Relative Density of 0.564
100
200
90
80 0.70
70
150
60
50 125
100
95
40 90
100 0.65
85
Relative Density at Bubblepoint Pressure

30 80
B
75 75
20
70
Temperature, °C
Temperature, °F
10 50 65
60 0.60
0
55
-10
Molecular Weight
50
-20
45
-30 C
40 0.55
-40
-50 35
-50
30
-60
0.50
-70
-100 25
-80
-90 0.45
20
-100 -150
18
0.40
-110
16
0.35
-120
0.30
-200 0.25
Figure 3.13 Relative Density of Paraffin Hydrocarbon Mixtures at their Bubblepoint Pressure
CHAPTER 3 69
Corresponding States Methods

Several corresponding states models have been proposed for prediction of liquid densities. Three
methods widely used in the industry are:
1. API Method(3.10)
2. Modified Rackett Equation(3.13)
3. Hankinson-Brobst-Thomson [COSTALD] provided in Appendix 3D(3.14, 3.15)
Of these, only the API method readily lends itself to hand calculation. Figure 3.14 is a plot of C, a
density factor, as a function of Pr and Tr. The density factor is used to correct the known density, t , at
1
one T and P to a density, t , at another T and P using the following equation.
C
t 2 = t1 d C2 n (3.26)
1
Figure 3.14 Effect of Temperature and Pressure on the Density of Hydrocarbon Liquids(3.15)

In Figure 3.14 and Equation (3.26), the critical (or pseudocritical) properties are used to find the
reduced T and P at conditions (1) and (2). Values of C1 and C2 are then found from Figure 3.14. The
quantity t1 could be found from the Law of Ideal Solutions or one of the nomographs previously discussed.
The critical-values could be found from Table 3A.1a or Table 3A.1b for a pure substance or from Kay’s rule
for a mixture.
The API method can be used to predict densities of hydrocarbon liquid mixtures when the mixture is
composed of molecules of similar size and shape, e.g., C3-C4, C5-C6, etc. It is less accurate for mixtures
containing a wider range of molecules, e.g., C1-C7.
The modified Rackett equation can be used to estimate the density of saturated liquids. For pure
components, the equations are fairly simple and can be done by hand. For mixtures, the mixing rules for the
determination of Tc are quite complex and require computer solution.

The Hankinson-Brobst-Thomson method is sometimes referred to as the “COSTALD method”
(Corresponding States Liquid Densities). Special mixing rules are used to determine the primary variables
used for the mixture. These are too complex to permit hand calculation. Binary interaction parameters have
been used to improve the accuracy on specific mixtures.(3.16, 3.17)
Example 3.2: Estimate the density of an EPmix (80% mol C2, 20% mol C3 ) at 10 000 kPa
[1450 psia] and 10°C [50°F] using Figure 3.14 and Equation (3.25).
Step 1. Determine the density at reference (saturated) conditions using Equation (3.25).
Pure component densities may be found from Table 3A.1(a) and Table 3A.1(b).
From Table 3A.1a
cC2 = 0.358 tC2 = 358 kg/m3

cC3 = 0.508 tC3 = 508 kg/m3
From Equation (3.25)

MWi x i
vmix = / vi x i = / ti
(30)(0.8) (44)(0.2)
vmix = + = 0.084 m3 /kmol
358 508
MWmix = (30)(0.8) + (44)(0.2) = 32.8 kg/kmol
MW
t mix = d v mix n = a 0.084 k = 390 kg/m3
32.8
mix
Step 2. Find C1 – Apply Kay’s rule to determine Pc' and Tc'

Pc' = (0.8)(4.87) + (0.2)(4.24) = 4.74 MPa
Tc' = (0.8)(305) + (0.2)(370) = 318 K
Reference conditions at 15°C and saturation
Pr = saturated liquid
CHAPTER 3 71
Example 3.2 (Cont'd):

288
Tr = 318 = 0.91
From Figure 3.14, C1 = 0.71
Step 3. Find C2
10.0
Pr2 = 4.74 = 2.1
283
Tr2 = 318 = 0.89
From Figure 3.14, C2 = 0.78

C
t 2 = t1 d C2 n = 390 a 0.71 k = 430 kg/m3
0.78
1
For comparison purposes, the density of this liquid using other methods is shown
below:
tCOSTALD = 456 kg/m3

t Rackett = 451 kg/m3
For these types of mixtures, the COSTALD error is less than 0.5% in comparison to experimental
data, so the actual density calculated in Example 3.2 would be close to 456 kg/m3.
Summary of Liquid Density Correlations

In general, liquid density correlations can be placed in the following three categories:
1. Empirical P and T correlations
2. Corresponding States Methods
3. Equations of State
Empirical P and T correlations are used to correct a known density to actual process conditions.
They are frequently used on crude oils and condensates for which no analysis is available, but for which
a stock-tank density or API gravity may be known. Figure 3.12 and Figure 3.13 fall into this category.
Corresponding States Methods are also empirical and designed to correct a known density to actual
process conditions using the corresponding states principle. In the API method, the “known” density is
either measured or calculated from Amagat’s Law. In both the Rackett and COSTALD methods, the
“known” density is essentially the critical density. These methods require a liquid composition.
EOS methods may also be used to estimate liquid densities. In general, cubic equations of
state (SRK, PR) are less accurate than the corresponding states models. The BWRS equation of state is
considered more accurate for liquid density predictions.
For liquids of known composition, the COSTALD method is probably the most general and the
most accurate of the methods presented. Errors for the COSTALD method are generally less than 1%. For
crude oils and condensates, Figure 3.12 provides acceptable results for most engineering calculations.

Liquid Viscosity
Liquid viscosity is used
in fluid flow calculations, vapor/
liquid separator sizing, detailed heat
exchanger calculations, distillation
and absorber column calculations,
and for highly viscous liquids in
the sizing of pumps. The predic-
tion of liquid viscosity is somewhat
analogous to the prediction of
density. You can use P-V-T equations

of state and combination rules
or general correlations based on
physical parameters like molecular
weight. Many of the former are not
suitable for manual calculations.
References 3.18-3.24 present such
methods and those not included in
the discussion herein.
Figure 3.15 shows the
viscosity at atmospheric pressure for
common light paraffin hydrocarbons,
as a function of temperature. Most
natural gas liquids have a viscosity in Figure 3.15 Viscosity of Pure Paraffin Hydrocarbons
the range of 0.08 to 0.5 cp.
The viscosity of crude oils is more difficult to estimate. Crude oil viscosities vary significantly
depending on composition, i.e., paraffinic, aromatic, and naphthenic. Figure 3.16 shows the kinematic
viscosity of selected crudes from around the world. It can be used as a guide to the range of viscosities
encountered in crude oil systems. The crude oil pour point is important as well. The pour point is the
temperature below which the crude oil becomes “plastic” or partially solid. The pour point is determined
from the ASTM D92-12 test method, and it is likely the crude oil will no longer flow in the pipeline at these
conditions.
Correlations for prediction of the viscosity of liquids with known composition possess a general
reliability of 13-15%. This range offers no particular practical problem in the type of calculations where
viscosity is used. For crude oils, the viscosity should be determined by laboratory test, particularly for
separator design. Note in Figure 3.16 that the sampling of 35 different crude oils results in a wide range of
viscosities and is not a correlation on the liquid density alone, as is demonstrated in Example 3.3.
Example 3.3: From Figure 3.16, compare the physical properties and viscosities of crude oil sam-
ples 13 and 25 at 25°C.
Crude Oil API Gravity Sulfur Pour Point Viscosity
Content °C cSt
13 35.4 0.42 –21 7.5
25 35.4 0.11 –3 4.9
CHAPTER 3 73
Selected Crude Oil Properties Temperature, °F

API Sulfur Pour Point 0 50 100 150 200
Gravity Content % °C 50 000
1 39.2 0.78 -6 10 000

2 28.4 2.9 <-33 5000
3 33.2 1.7 <-30 2000 22
10
4 38.2 0.41 9 1000
5 13.2 2.7 -9 500
300 5
6 38.0 0.31 9 35
200
7 39.0 0.05 34
8 28.2 0.08 -6 100
26
9 39.6 0.14 30 50
10 09.3 5.0 17 40 19
30 27 24 30
Kinematic Viscosity, mm2/s (cSt)

11 38.6 0.26 3
20 17 20
12 30.6 0.30 <-36
15
13 35.4 0.42 -21 13
14 44.5 0.12 -19 10 1
16
8 32
15 37.2 0.31 0 2
16 31.5 0.11 30 6
28
5 12 21
17 34.8 0.24 -24
4
18 33.4 0.07 27 8 3
29 7
29
19 31.1 1.70 -6 3 15 4 23
20 34.0 1.4 -15 2.5 34
11 6
21 31.1 2.5 -21
2 1825
22 14.8 2.3 -18 33
33
23 39.4 0.03 18 31 9
14 31
1.5
24 22.5 3.4 -18
25 35.4 0.11 -3
Fr
26 25.5 0.27 -30 es
h
1 W
27 34.4 0.95 <-30 at
0.9 er
28 41.3 1.20 -9 ( no
0.8 sa
29 37.8 0.16 21 lt)
30 25.0 0.99 18 0.7
31 34.8 0.06 6
32 38.6 0.24 -3 0.6
33 33.8 0.08 27
0 25 50 75 100
34 38.6 0.28 6
35 11.9 2.7 3 Temperature, °C
Figure 3.16 Kinematic Viscosity vs. Temperature, and Other Properties, for a Wide Range of Traditional Crude Oils
USEFUL CONVERSION FACTORS FOR CHAPTER 3

Density of water . 1.0 g/cm3 . 1000 kg/m3 . 62.4 lbm/ft3
density of liquid 141.5
c (liquid) = density of water (at a specified P and T) =
(131.5 + %API)
(mol wt gas) MW gas density of gas
c (gas) = (mol wt air) = 28.96 = density of air (at standard P and T)

Density of air at 60°F and 1 atm (14.7 psia) = 0.0764 lbm/ft3
1 cp = 0.01 dyne·s/cm2 = 0.001 N·s/m2 = 0.001 kg (m·s) = 0.000 672 lbm/(ft-sec)
1 centistoke = cp/t (where t is in g/cm3) = 0.01 cm2/s = 10–6 m2/s = 1 mm2/s

REFERENCES
3.1 Fisher, C. H., Chem. Engr. (Jan. 11, 1982), p. 107.
3.2 Ibid. (Sept. 20, 1982), p. 111.
3.3 Yaws, C. L., Ibid. (May 12, 1975), p. 89.
3.4 Wichert, E. and K. Aziz, Hydr. Proc. (May 1972), p. 119.
3.5 Brown, G.G., Katz, D.L., Oberfell, G., Alden, R.C., “Natural Gasoline and Volatile Hydrocarbons”, NGAA, Tulsa, OK,
(1948).
3.6 Hannisdal, N-E., “Gas Compression Equations Evaluated,” Oil & Gas J. (May 4, 1987), p. 38-41.
3.7 Lee, A. L., Gonzalez, M.H., and B.E. Eakin, “The Viscosity of Natural Gases”, J. Pet. Tech. (Aug. 1966) 997-1000; Trans.,
AIME (1966) 234.
3.8 GPSA, Engineering Data Book, 12th Ed. (2012).

3.9 Nelson, W. L., Petroleum Refinery Engineering, McGraw-Hill, New York.
3.10 API Technical Data Book (1980).
3.11 Pan, W. P. and R. N. Maddox, Chem. Engr. (Nov. 1981), p. 79.
3.12 Whitson, C. H., SPE Jour. (Aug. 1983), p. 683.
3.13 Spencer, C.F. and R.P. Danner, J. Chem. Eng. Data, Vol. 1 (1973), p. 230.
3.14 Hankinson, R. W. and G. H. Thomson, AIChE J., Vol. 2S (1979), p. 653.
3.15 Buxton, T.S., and Campbell, J.M., SPE Journal (March 1967), p. 80.
3.16 Teja, A.S., Chem. Eng. Sci., Vol. 33 (1978), p. 609.
3.17 Teja, A.S. and S.I. Sandler, AIChE J., Vol. 26 (1980), p. 341.
3.18 Chew, Ju Nam and C. A. Connally, Trans. AIME, Vol. 216 (1959), p. 23.
3.19 Lohrenz, J., Bray, B. G. and C. R. Clark, Ibid., Vol. 231 (1964), p. 1171.
3.20 Houpert, A. H. and M. B. Thelleiz, SPE Paper No. 5057, presented at Annual Meeting, (Oct. 6-9, 1974).
3.21 Gonzalez, M. H. and R. F. Bukacek, Trans. AIME, Vol. 240 (1967), p. 75.
3.22 Beal, C., Ibid., Vol. 165 (1964), p. 94.
3.23 Eakin, B. E. and R. T. Ellington, Ibid., Vol. 228 (1963), p. 210.
3.24 Little, J. E. and H. T. Kennedy, Ibid., Vol. 243 (1968), p. 157.
3.25 Katz, D. L. and A. Firoozabadi, “Predicting Phase Behavior of Condensate/Crude Oil Systems Using Methane Interaction
Coefficient,” Petr. Tech (Nov. 1978), p. 1649-1655.
3.26 Robinson, D. F., et al., Trans. AIME, Vol. 219 (1960), p. 54.
3.27 Satter, A. and J. M. Campbell, SPE Jour. (Dec. 1963), p. 333.
3.28 Allahwala, S. A., Ibid. (Sept. 1981), p. 271.
3.29 Maddox, R. N. and J. H. Erbar, "Gas Conditioning and Processing:, Vol. 3, Campbell Petroleum Series, Norman, Oklahoma
(1981).
CHAPTER 3 75
APPENDIX 3A – PHYSICAL CONSTANTS OF APPENDIX

HYDROCARBONS

Table 3A.1(a)
Physical Properties of Select Fluids - SI(3.8)
(Adapted from GPSA Engineering Data Book, 13th Ed., 2012, Reproduced with permission)
Critical Constants Density of Liquid (101.325 kPa,
15 °C)
Pressure, kPa(abs)
Freezing Point °C
(mass in vacuum)
101.325 kPa(abs)
101.325 kPa(abs)
Relative Density,
(specific gravity)
Boiling Point °C
Temperature, K
Vapor Pressure
Volume, m3/kg
kPa(abs) 40°C
Molar Mass
(Molecular
15°C/15°C
Formula
m3/kmol
Number
Weight)
kg/m3
Compound
1 Methane CH4 16.042 -161.48 (35000.) -182.47 4599 190.56 0.00615 (0.3) (300.) (0.05)
2 Ethane C2H6 30.069 -88.6 (6000.) -182.8 4872 305.33 0.00484 0.3583 358.0 ----
3 Propane C3H8 44.096 -42.07 1369.9 -187.63 4244 369.77 0.00455 0.50812 507.67 0.08686
4 Isobutane C4H10 58.122 -11.62 530.1 -159.61 3640 407.82 0.00446 0.56357 563.07 0.10322
5 n-Butane C4H10 58.122 -0.51 379.4 -138.36 3798 425.12 0.00439 0.58466 584.14 0.0995
6 Isopentane C5H12 72.149 27.84 151.4 -159.89 3381 460.4 0.00427 0.62511 624.54 0.11552
7 n-Pentane C5H12 72.149 36.1 115.6 -129.72 3370 469.7 0.00422 0.63162 631.05 0.11433
8 Neopentane C5H12 72.149 9.51 269.8 -16.57 3196 433.7 0.00431 0.59681 596.29 0.121
9 n-Hexane C6H14 86.175 68.73 37.3 -95.31 3012 507.5 0.00429 0.66448 663.89 0.1298
10 2-Methylpentane C6H14 86.175 60.24 50.71 -153.67 3010 497.5 0.00426 0.65839 657.8 0.131
11 3-Methylpentane C6H14 86.175 63.25 45.74 -162.89 3120 504.4 0.00426 0.66946 668.86 0.12884
12 Neohexane C6H14 86.175 49.72 73.45 -99.83 3080 488.7 0.00417 0.65416 653.57 0.13185
13 2,3-Dimethylbutane C6H14 86.175 57.97 55.37 -128.53 3130 499.9 0.00415 0.66646 665.86 0.12942
14 n-Heptane C7H16 100.202 98.41 12.336 -90.56 2736 540.3 0.00426 0.6886 687.98 0.14565
15 2-Methylhexane C7H16 100.202 90.03 17.23 -118.27 2730 530.1 0.00420 0.68369 683.08 0.14669
16 3-Mehtylhexane C7H16 100.202 91.85 16.16 ---- 2810 535.2 0.00403 0.69211 691.49 0.14491
17 3-Ethylpentane C7H16 100.202 93.47 15.27 -118.58 2890 540.5 0.00415 0.70333 702.7 0.1426
18 2,2-Dimethylpentane C7H16 100.202 79.17 26.32 -123.78 2770 520.4 0.00415 0.6787 678.09 0.14777
21 Triptane C7H16 100.202 80.86 25.41 -24.56 2950 531.1 0.00397 0.69474 694.12 0.14436
22 n-Octane C8H18 114.229 125.67 4.14 -56.76 2487 568.8 0.00420 0.70737 706.73 0.16163
23 Diisobutyl C8H18 114.229 109.11 8.417 -91.16 2490 550 0.00422 0.69846 697.83 0.16369
24 Isooctane C8H18 114.229 99.24 12.97 -107.35 2570 543.9 0.00410 0.69668 696.05 0.16411
25 n-Nonane C9H20 128.255 150.78 1.349 -53.49 2280 594.7 0.00433 0.72224 721.59 0.17774
26 n-Decane C10H22 142.282 174.11 0.4876 -29.66 2100 617.7 0.00439 0.73442 733.76 0.19391
27 Cyclopentane C5H10 70.133 49.23 73.99 -93.87 4508 511.6 0.00371 0.75033 749.66 0.09355
28 Methylcyclohexane C6H12 84.159 71.83 33.75 -142.43 3784 532.8 0.00379 0.75399 753.31 0.11172
29 Cyclohexane C6H12 84.159 80.78 24.64 6.69 4073 553.5 0.00366 0.78395 783.24 0.10745
30 Methylcyclohexane C7H14 98.186 100.94 12.21 -126.56 3471 572.2 0.00375 0.77435 773.66 0.12691
31 Ethene (Ethylene) C2H4 28.053 -103.73 (8700) -169.16 5040 282.3 0.00466 ---- ---- ----
32 Propene (Propylene) C3H6 42.080 -47.69 1653 -185.26 4665 365.6 0.00448 0.52348 523.01 0.08046
33 1-Butene (Butylene) C4H8 56.106 -6.23 455 -185.36 4043 420 0.00426 0.60108 600.54 0.09343
34 cis-2-Butene C4H8 56.106 3.72 337.9 -138.90 4243 435.6 0.00417 0.62813 627.56 0.0894
35 trans-2-Butene C4H8 56.106 0.88 366.1 -105.57 3964 428.6 0.00424 0.61076 610.21 0.09195
36 Isobutene C4H8 56.106 -6.91 463 -140.34 4000 417.9 0.00425 0.60128 600.74 0.09339
37 1-Pentane C5H10 70.133 29.96 141.65 -165.22 3513 464.8 0.00421 0.64654 645.96 0.10857
38 1,2-Butadiene C4H6 54.090 10.63 274.9 -136.19 4520 452.2 0.00435 0.65829 657.7 0.08224
39 1,3-Butadiene C4H6 54.090 -4.53 436.2 -108.92 4277 425.2 0.00408 0.6278 627.24 0.08624
40 Isoprene C5H8 68.117 34.06 123.8 -145.95 4010 479.2 0.00415 0.68657 685.96 0.0993
41 Acetylene C2H2 26.037 -83.82 ---- -80.8 6139 308.3 0.00433 ---- ---- ----
42 Benzene C6H6 78..112 80.06 24.36 5.53 4898 562.2 0.00332 0.8851 884.3 0.08833
43 Toluene C7H8 92.138 110.61 7.891 -94.94 4106 591.8 0.00343 0.87226 871.48 0.10573
44 Ethylbenzene C8H10 106.165 136.16 2.865 -94.96 3606 617.2 0.00352 0.8721 871.31 0.12184
45 o-Xylene C8H10 106.165 144.42 2.043 -25.17 3734 630.3 0.00348 0.88492 884.12 0.12008
46 m-Xylene C8H10 106.165 139.09 2.547 -47.84 3536 617.1 0.00354 0.86922 868.44 0.12225
47 p-Xylene C8H10 106.165 138.33 2.647 13.26 3511 616.2 0.00357 0.86597 865.19 0.12271
48 Styrene C8H8 104.149 145.26 1.917 -30.64 4053 645.9 0.00333 0.91131 910.49 0.11439
49 Isopropylbenzene C9H12 120.192 152.37 1.469 -96.01 3209 631.1 0.00355 0.86695 866.17 0.13876
50 Methyl Alcohol CH4O 32.042 64.54 35.44 -97.66 8097 512.6 0.00368 0.79672 796.0 0.04025
51 Ethyl Alcohol C2H6O 46.068 78.29 17.9 -114.05 6148 513.9 0.00362 0.79443 793.72 0.05804
52 Carbon Monoxide CO 28.010 -191.52 ---- -205.02 3494 132.8 0.00329 0.79258 791.87 0.03537
53 Carbon Dioxide CO2 44.010 -78.4 ---- -56.56 7377 304.13 0.00214 0.81707 816.33 0.05391
54 Hydrogen Sulfide H2S 34.082 -60.29 2867 -85.45 9008 373.6 0.00288 0.80014 799.42 0.04263
55 Sulfur Dioxide SO2 64.065 -9.98 629 -75.45 7884 430.64 0.00190 1.39376 1392.5 0.04601
56 Ammonia NH3 17.0306 -33.33 1555 -77.65 11333 405.4 0.00444 0.61805 617.49 0.02758
57 Air N2+O2 28.9586 -194.25 ---- ---- 3805 132.61 0.00286 0.87594 875.16 0.03309
58 Hydrogen H2 2.0159 -252.76 ---- -259.19 1315 33.2 0.03320 0.07086 70.8 0.02847
59 Oxygen O2 31.9988 -182.962 ---- -218.79 5043 154.58 0.00229 1.1422 1141.2 .02804
60 Nitrogen N2 28.0135 -195.795 ---- -210 3396 126.19 0.00319 0.80681 806.09 0.03475
61 Chlorine Cl2 70.9054 -34.03 1146 -100.98 7700 417 0.00175 1.42561 1424.33 0.04978
62 Water H2O 18.0153 99.974 7.3849 0 22064 647.1 0.003106 1.0000 999.1 0.01803
63 Helium He 4.0026 -268.92 ---- -270.97 227.5 5.2 0.01436 0.12485 124.73 0.03209
64 Hydrogen Chloride HCl 36.4606 -85 6639 -114.18 8310 324.69 0.00222 0.85532 854.56 0.04267
(Adapted from GPSA Engineering Data Book, 13th Ed. 2012 © Gas Processors Suppliers Association, Tulsa, Oklahoma)
Please refer to the GPSA Engineering Data Book for relevant notes associated with the data provided.
CHAPTER 3 77
Table 3A.1(a) (cont’d)

Physical Properties of Select Fluids - SI(3.8)
Specific Heat Flammability
Combustion Ideal Gas

Heat of Vaporization
Boiling Point, kJ/kg

Ideal Gas 101.325 Capacity 101.325 Limits, vol% in
101.325 kPa(abs) at
m3 (air)/ m3 (gas)
Air Required for
kPa(abs), 15°C kPa(abs), 15°C Heating Value, 15°C Air Mixture
Cp kJ/kg °C Net Gross
Specific Vol-
ume m3/kg
Ratio gas/
(liquid in
Ideal Gas,
vacuum)
Formula
Ideal gas,
Number
kPa(abs)
kPa(abs)
vacuum)
Volume
(mass in
Higher
101.325
101.325
Lower
MJ/m3,
MJ/m3,
MJ/m3
Liquid
Liquid
MJ/kg
Ideal Gas Liquid Compound
1.4739 (442.) 2.2062 ---- 33.949 ---- 37.707 ---- 511.3 9.542 5 15 CH4 Methane 1
0.7864 281.51 1.7094 4.511 60.429 47.162 66.067 18471 489.2 16.698 2.9 13 C2H6 Ethane 2
0.5362 272.22 1.6292 2.6131 86.419 45.957 93.936 25377 425.5 23.855 2 9.5 C3H8 Propane 3
0.4068 229.06 1.6218 2.3552 112.008 45.211 121.404 27609 365.6 31.011 1.8 8.5 C4H10 Isobutane 4
0.4068 237.63 1.6577 2.3745 112.396 45.343 121.792 28719 386.9 31.011 1.5 9 C4H10 n-Butane 5
0.3277 204.68 1.6014 2.2458 138.088 44.899 149.363 30349 343.7 38.168 1.3 8 C5H12 Isopentane 6
0.3277 206.81 1.6256 2.275 138.381 44.974 149.656 30712 359.2 38.168 1.4 8.3 C5H12 n-Pentane 7
0.3277 195.41 1.6351 2.313 137.485 44.74 148.761 28881 315.9 38.168 1.3 7.5 C5H12 Neopentane 8
0.2744 182.16 1.6178 2.2314 164.399 44.734 177.554 32094 335.1 45.324 1.1 7.7 C6H14 n-Hexane 9
0.2744 180.49 1.6047 2.203 164.077 44.664 177.231 31755 323 45.324 1.18 7.0 C6H14 2-Methylpentane 10
0.2744 183.52 1.5792 2.1699 164.187 44.691 177.342 32306 326 45.324 1.2 7.7 C6H14 3-Methylpentane 11
0.2744 179.33 1.5968 2.1499 163.649 44.572 176.803 31490 305.4 45.324 1.2 7.0 C6H14 Neohexane 12
0.2744 182.7 1.5657 2.1499 163.983 44.647 177.138 32132 316.4 45.324 1.2 7.0 C6H14 2,3-Dimethylbutane 13
0.2360 162.34 1.6123 2.2083 190.388 44.557 205.422 33095 318.1 52.481 1 7 C7H16 n-Heptane 14
0.2360 161.19 1.5978 2.1816 190.095 44.504 205.128 32823 307.5 52.481 1.0 7.0 C7H16 2-Methylhexane 15
0.2360 163.17 1.5865 2.1487 190.239 44.535 205.272 33249 309 52.481 (1.01) 6.6 C7H16 3-Mehtylhexane 16
0.2360 165.82 1.6166 2.1501 190.322 44.554 205.356 33801 310.5 52.481 (1.0) 6.5 C7H16 3-Ethylpentane 17
0.2360 160.01 1.6169 2.1608 189.625 44.417 204.659 32524 292.1 52.481 (1.09) 6.8 C7H16 2,2-Dimethylpentane 18
0.2360 163.79 1.5796 2.0871 189.685 44.435 204.719 33306 289.5 52.481 (1.08) 6.8 C7H16 Triptane 21
0.2070 146.29 1.6073 2.1961 216.372 44.419 233.285 33866 302.4 59.637 0.8 6.5 C8H18 n-Octane 22
0.2070 144.45 1.5736 2.1338 215.792 44.331 232.705 33379 283.8 59.637 (0.92) 6.3 C8H18 Diisobutyl 23
0.2070 144.08 1.5948 2.1634 215.727 44.341 232.64 33301 269.4 59.637 0.95 6 C8H18 Isooctane 24
0.1844 133.03 1.6036 2.1842 242.398 44.32 261.19 34481 290.1 66.794 0.7 5.6 C9H20 n-Nonane 25
0.1662 121.94 1.6009 2.1784 268.393 44.236 289.064 34979 278.2 73.95 0.7 5.4 C10H22 n-Decane 26
0.3371 252.74 1.1363 1.7617 131.108 43.787 140.504 35200 390.6 35.782 (1.48) 8.3 C5H10 Cyclopentane 27
0.2810 211.64 1.2595 1.8425 156.753 43.657 168.029 35273 348.8 42.939 1 8.35 C6H12 Methylcyclohexane 28
0.2810 220.05 1.215 1.811 156.032 43.438 167.307 36504 355.8 42.939 1.2 8.35 C6H12 Cyclohexane 29
0.2408 186.31 1.3366 1.8413 181.566 43.359 194.72 35996 318.9 50.095 1.1 6.7 C7H14 Methylcyclohexane 30
0.8429 ---- 1.5013 ---- 55.964 ---- 59.723 ---- 484.2 14.313 2.7 36 C2H4 Ethene (Ethylene) 31
0.5619 293.88 1.4952 2.3961 81.46 45.384 87.098 25393 440 21.469 2 11.7 C3H6 Propene (Propylene) 32
0.4214 253.09 1.4889 2.2458 107.463 44.91 114.98 28873 392.4 28.626 1.6 10 C4H8 1-Butene (Butylene) 33
0.4214 264.47 1.3951 2.2078 107.178 44.759 114.694 30077 416.2 28.626 1.6 10 C4H8 cis-2-Butene 34
0.4214 257.16 1.5316 2.2149 107.022 44.703 114.539 29212 406.6 28.626 1.6 10 C4H8 trans-2-Butene 35
0.4214 253.17 1.5539 2.2923 106.764 44.61 114.281 28702 387.1 28.626 1.6 10 C4H8 Isobutene 36
0.3371 217.78 1.5057 2.1711 133.457 44.621 142.853 30870 360.2 35.782 1.3 10 C5H10 1-Pentane 37
0.4371 287.5 1.4398 2.2634 104.117 45.075 109.755 31266 450.2 26.24 (1.62) 10.3 C4H6 1,2-Butadiene 38
0.4371 274.19 1.4344 2.2395 101.914 44.146 107.551 29236 415 26.24 2 12.5 C4H6 1,3-Butadiene 39
0.3471 238.11 1.467 2.1718 127.328 43.804 134.845 31837 380.6 33.397 (1.12) 8.5 C5H8 Isoprene 40
0.9081 ---- 1.6585 ---- 53.157 ---- 55.036 ---- 821.7 11.927 1.5 100 C2H2 Acetylene 41
0.3027 267.68 1.0139 1.7144 134.053 40.138 139.69 37003 394.2 35.782 1.2 8 C6H6 Benzene 42
0.2566 223.64 1.0871 1.6757 159.54 40.523 167.057 36996 361.7 42.939 1.2 7.1 C7H8 Toluene 43
0.2227 194.06 1.1632 1.7202 185.550 40.922 194.946 37480 336.6 50.095 1 8 C8H10 Ethylbenzene 44
0.2227 196.91 1.2144 1.7413 185.091 40.809 194.487 37930 345.3 50.095 1 7.6 C8H10 o-Xylene 45
0.2227 193.42 1.1485 1.6898 185.018 40.8 194.414 37250 340.7 50.095 1 7 C8H10 m-Xylene 46
0.2227 192.69 1.1495 1.6825 185.052 40.81 194.448 37119 338.6 50.095 1 7 C8H10 p-Xylene 47
0.2270 206.71 1.1 1.723 180.328 40.506 187.845 38434 357.1 47.71 1.1 8 C8H8 Styrene 48
0.1967 170.4 1.2828 1.7585 211.325 41.192 222.6 37601 309.1 57.252 0.8 6.5 C9H12 Isopropylbenzene 49
0.7379 587.4 1.3598 2.4749 28.605 19.912 32.363 18058 1121.9 7.156 5.5 44 CH4O Methyl Alcohol 50
0.5133 407.38 1.3873 2.3569 54.038 26.802 59.676 23570 846.6 14.313 3.28 19 C2H6O Ethyl Alcohol 51
0.8442 668.46 1.0357 ---- 11.965 ---- 11.965 ---- 215.1 2.385 12.5 74.2 CO Carbon Monoxide 52
0.5373 438.59 0.8316 ---- 0 ---- 0 ---- 573.3 ---- ---- ---- CO2 Carbon Dioxide 53
0.6938 554.61 0.9967 2.1698 21.905 14.738 23.784 12698 545.3 7.156 4.3 45.5 H2S Hydrogen Sulfide 54
0.3691 513.94 0.6166 1.378 0 ---- 0 ---- 388.9 ---- ---- ---- SO2 Sulfur Dioxide 55
1.3884 857.32 2.0792 4.7087 13.391 ---- 16.21 ---- 1369.5 3.578 15.5 27 NH3 Ammonia 56
0.8165 714.57 1.0045 ---- 0 ---- 0 ---- 201.9 ---- ---- ---- N2+O2 Air 57
11.7293 830.38 14.245 ---- 10.223 ---- 12.102 ---- 445.5 2.385 4 74.2 H2 Hydrogen 58
0.7389 843.25 0.9166 ---- 0 ---- 0 ---- 213.1 ---- ---- ---- O2 Oxygen 59
0.8441 680.38 1.0395 ---- 0 ---- 0 ---- 199.2 ---- ---- ---- N2 Nitrogen 60
0.3335 474.97 0.4757 ---- ---- ---- ---- ---- 287.6 ---- ---- ---- Cl2 Chlorine 61
1.3125 1311.3 1.862 4.1888 ---- ---- ---- 0 2256.5 ---- ---- ---- H2O Water 62
5.9074 736.84 5.1931 ---- ---- ---- 0 ---- 20.8 ---- ---- ---- He Helium 63
0.6485 554.18 0.7969 ---- ---- ---- ---- ---- 447.2 ---- ---- ---- HCl Hydrogen Chloride 64

Table 3A.1(b)
Physical Properties of Select Fluids - FPS(3.8)
Density of Liquid
Critical Constants
(14.696 psia, 60◦F)
Vapor Pressure, psia
◦F 14.696 psia (abs)
lbm/gal (weight in
(specific gravity)
Temperature, ◦F
Relative Density
Molecular Mass
(◦F, 14.696 psia)
Volume, ft3/lbm
Freezing Point,
Pressure, psia
Boiling Point
60◦F/60◦F
gal/lbmol
(mol wt.)
Formula
vacuum)
Number
100◦F
(abs)
Compound
1 Methane CH4 16.042 -258.67 (5000)* -296.45 667.0 -116.66 0.09850 (0.3)* (2.5)* (6.4172)
2 Ethane C2H6 30.069 -127.48 (800)* -297.04 706.6 89..92 0.07750 0.35643 2.9716 10.1190
3 Propane C3H8 44.096 -43.72 188.7 -305.73 615.5 205.92 0.07280 0.50738 4.2301 10.4240
4 Isobutane C4H10 58.122 11.08 72.48 -255.3 527.9 274.41 0.07150 0.56295 4.6934 12.3840
5 n-Butane C4H10 58.122 31.09 51.68 -217.05 550.9 305.55 0.07030 0.58408 4.8696 11.9360
6 Isopentane C5H12 72.149 82.11 20.46 -255.80 490.4 369 0.06850 0.62460 5.2074 13.8550
7 n-Pentane C5H12 72.149 96.98 15.76 -201.50 488.8 385.8 0.06760 0.63113 5.2618 13.7120
8 Neopentane C5H12 72.149 49.12 36.7 2.17 463.5 321 0.06900 0.59624 4.9710 14.5140
9 n-Hexane C6H14 86.175 155.72 4.961 -139.56 436.9 453.8 0.06880 0.66404 5.5363 15.5660
10 2-Methylpentane C6H14 86.175 140.44 6.773 -244.6 436.6 435.8 0.06820 0.65794 5.4853 15.7100
11 3-Methylpentane C6H14 86.175 145.84 6.103 -261.20 452.5 448.3 0.06820 0.66902 5.5777 15.4500
12 Neohexane C6H14 86.175 121.49 9.865 -147.69 446.7 420 0.06670 0.65371 5.4501 15.8120
13 2,3-Dimethylbutane C6H14 86.175 136.34 7.41 -199.35 454.0 440.2 0.06650 0.66603 5.5528 15.5190
14 n-Heptane C7H16 100.202 209.13 1.6203 -131.01 396.8 512.9 0.06820 0.68819 5.7375 17.4640
15 2-Methylhexane C7H16 100.202 194.05 2.273 -180.87 396.0 494.5 0.06730 0.68327 5.6966 17.5900
16 3-Mehtylhexane C7H16 100.202 197.33 2.13 ---- 407.6 503.7 0.06460 0.69170 5.7668 17.3760
17 3-Ethylpentane C7H16 100.202 200.25 2.012 -181.44 419.2 513.2 0.06650 0.70291 5.8603 17.0990
18 2,2-Dimethylpentane C7H16 100.202 174.50 3.494 -190.80 401.8 477.1 0.06650 0.67828 5.6550 17.7190
21 Triptane C7H16 100.202 177.54 3.376 -12.21 427.9 496.3 0.06360 0.69433 5.7887 17.3100
22 n-Octane C8H18 114.229 258.21 0.5366 -70.17 360.7 564.2 0.06730 0.70698 5.8942 19.3800
23 Diisobutyl C8H18 114.229 228.39 1.102 -132.09 361.1 530.3 0.06760 0.69806 5.8199 19.6270
24 Isooctane C8H18 114.229 210.62 1.709 -161.23 372.7 519.4 0.06560 0.69628 5.8050 19.6780
25 n-Nonane C9H20 128.255 303.40 0.17003 -64.28 330.7 610.8 0.06930 0.72186 6.0183 21.3110
26 n-Decane C10H22 142.282 345.40 0.06160 -21.39 304.6 652.2 0.07030 0.73406 6.1200 23.2490
27 Cyclopentane C5H10 70.133 120.61 9.917 -136.96 653.8 461.2 0.05940 0.74985 6.2516 11.2180
28 Methylcyclohexane C6H12 84.159 161.29 4.491 -224.38 548.8 499.4 0.06070 0.75353 6.2823 13.3960
29 Cyclohexane C6H12 84.159 177.40 3.267 44.03 590.7 536.6 0.05860 0.78349 6.5321 12.8840
30 Methylcyclohexane C7H14 98.186 213.69 1.609 -195.81 503.4 570.3 0.06000 0.77394 6.4525 15.2170
31 Ethene (Ethylene) C2H4 28.053 -154.72 ---- -272.50 731.0 48.5 0.07460 ---- ---- ----
32 Propene (Propylene) C3H6 42.080 -53.85 227.9 -301.47 676.6 198.4 0.07170 0.52265 4.3574 9.6570
33 1-Butene (Butylene) C4H8 56.106 20.79 62.07 -301.65 586.4 296.2 0.06830 0.60046 5.0062 11.2070
34 cis-2-Butene C4H8 56.106 38.70 45.93 -218.02 615.4 324.4 0.06670 0.62754 5.2319 10.7240
35 trans-2-Butene C4H8 56.106 33.59 49.84 -158.03 574.9 311.9 0.06790 0.61017 5.0871 11.0290
36 Isobutene C4H8 56.106 19.56 63.17 -220.61 580.2 292.6 0.06810 0.60066 5.0078 11.2040
37 1-Pentane C5H10 70.133 85.93 19.12 -265.4 509.5 376.9 0.06740 0.64600 5.3859 13.0220
38 1,2-Butadiene C4H6 54.090 51.14 37.23 -213.14 655.6 354.3 0.06960 0.65773 5.4836 9.8640
39 1,3-Butadiene C4H6 54.090 23.85 59.46 -164.05 620.3 305.6 0.06540 0.62718 5.2289 10.3450
40 Isoprene C5H8 68.117 93.30 16.68 -230.71 581.6 402.9 0.06650 0.68606 5.7199 11.9090
41 Acetylene C2H2 26.037 -118.87 ---- -113.44 890.4 95.3 0.06930 ---- ---- ----
42 Benzene C6H6 78.112 176.10 3.222 41.96 710.4 552.2 0.05310 0.88458 7.3749 10.5920
43 Toluene C7H8 92.138 231.10 1.0322 -138.89 595.5 605.6 0.05490 0.87182 7.2686 12.6760
44 Ethylbenzene C8H10 106.165 277.09 0.3705 -138.93 523.0 651.3 0.05640 0.87169 7.2674 14.6080
45 o-Xylene C8H10 106.165 291.96 0.2632 -13.3 541.6 674.9 0.05570 0.88453 7.3745 14.3960
46 m-Xylene C8H10 106.165 282.35 0.3291 -54.12 512.9 651 0.05670 0.86882 7.2435 14.6570
47 p-Xylene C8H10 106.165 280.99 0.3422 55.86 509.2 649.5 0.05720 0.86557 7.2164 14.7120
48 Styrene C8H8 104.149 293.47 0.2467 -23.15 587.8 703 0.05340 0.91088 7.5942 13.7140
49 Isopropylbenzene C9H12 120.192 306.27 0.1884 -140.81 465.4 676.3 0.05680 0.86655 7.2246 16.6360
50 Methyl Alcohol CH4O 32.042 148.17 4.631 -143.79 1174.0 463.1 0.05900 0.79626 6.6386 4.8266
51 Ethyl Alcohol C2H6O 46.068 172..91 2.313 -173.29 891.7 465.4 0.05810 0.79402 6.6199 6.9590
52 Carbon Monoxide CO 28.010 -312.73 ---- -337.04 506.7 -220.63 0.05270 0.79265 6.6085 4.2385
53 Carbon Dioxide CO2 44.010 -109.12 ---- -69.81 1070.0 87.76 0.03430 0.82203 6.8534 6.4216
54 Hydrogen Sulfide H2S 34.082 -76.52 395.5 -121.81 1306.5 212.81 0.04620 0.80269 6.6922 5.0928
55 Sulfur Dioxide SO2 64.065 14.04 85.31 -103.81 1143.0 315.48 0.03050 1.39241 11.6090 5.5186
56 Ammonia NH3 17.0306 -27.99 212.0 -107.77 1644.0 270.1 0.07120 0.81730 5.1466 3.3091
57 Air N2+O2 28.9586 -317.64 ---- ---- 551.9 -220.97 0.04580 0.87603 7.3036 3.9649
58 Hydrogen H2 2.0159 -422.97 ---- -434.55 190.7 -399.9 0.53190 0.07087 0.5908 3.4120
59 Oxygen O2 31.9988 -297.332 ---- -361.82 731.4 -181.43 0.03670 1.14230 9.5236 3.3599
60 Nitrogen N2 28.0135 -320.431 ---- -346 492.5 -232.53 0.05110 0.80687 6.7270 4.1643
61 Chlorine Cl2 70.9054 -29.25 157.3 -149.73 1117.0 290.93 0.02800 1.42410 11.8730 5.9720
62 Water H2O 18.0153 211.953 0.95051 32 3200.1 705.1 0.04975 1.00000 8.3372 2.1608
63 Helium He 4.0026 -452.06 ---- -455.75 33.0 -450.32 0.23000 0.12486 1.0409 3.8452
64 Hydrogen Chloride HCl 36.4606 -121.00 921 -173.52 1205.0 124.77 0.03560 0.85120 7.0970 5.1375
CHAPTER 3 79
Table 3A.1(b) (cont’d)

Physical Properties of Select Fluids - FPS(3.8)
Specific Heat Capacity Heating Value, 60◦F Flammability
Combustion Ideal Gas

(14.696 psia, 60◦F)
14.696 psia at Boiling

Heat of Vaporization
Ideal Gas Limits, vol% in
◦
(14.696 psia, 60 F) Btu/(lbm-◦F) Net Gross Air Mixture
Air Required for
ft3 (air)/ft3(gas)
Point, Btu/lbm
Ration ft3 gas/
Btu/ft3, Ideal
Btu/ft3 Ideal
Gas, 14.696
gas, 14.696
gal Liquid
(weight in
ft3 gas/lb
vacuum)
Formula
Number
Btu/lbm
Specific
Volume
Volume
Btu/gal
Higher
Liquid
Liquid
Lower
C p, C p,
psia
psia
Ideal Gas Liquid Compound
23.6550 (59.138)* 0.52725 — 909.4 — 1010.0 — 219.8 9.542 5.00 15.00 CH4 Methane 1
12.6200 37.503 0.40880 1.09000 1618.7 20277 1769.7 65916 210.3 16.698 2.90 13.00 C2H6 Ethane 2
8.6060 36.404 0.38970 0.62530 2314.9 19758 2516.2 90905 182.9 23.855 2.00 9.50 C3H8 Propane 3
6.5291 30.644 0.38798 0.56330 3000.4 19437 3252.0 98935 157.2 31.011 1.80 8.50 C4H10 Isobutane 4
6.5291 31.794 0.39649 0.56790 3010.8 19494 3262.4 102926 166.3 31.011 1.50 9.00 C4H10 n-Butane 5
5.2598 27.390 0.38311 0.53700 3699.0 19303 4000.9 — 147.7 38.168 1.30 8.00 C5H12 Isopentane 6
5.2598 27.676 0.38882 0.54390 3706.9 19335 4008.7 108789 154.4 38.168 1.40 8.30 C5H12 n-Pentane 7
5.2598 26.146 0.39126 0.55340 3682.9 19235 3984.8 110094 135.8 38.168 1.30 7.50 C5H12 Neopentane 8
4.4036 24.380 0.38696 0.53350 4403.8 19232 4756.0 103509 144.1 45.324 1.10 7.70 C6H14 n-Hexane 9
4.4036 24.155 0.38391 0.52680 4395.2 19202 4747.4 115060 138.8 45.324 1.18 7.00 C6H14 2-Methylpentane 10
4.4036 24.562 0.37782 0.51880 4398.1 19214 4750.3 113838 140.2 45.324 1.20 7.70 C6H14 3-Methylpentane 11
4.4036 24.000 0.38202 0.51410 4383.7 19162 4735.9 115819 131.3 45.324 1.20 7.00 C6H14 Neohexane 12
4.4036 24.453 0.37465 0.51410 4392.7 19195 4744.9 112890 136 45.324 1.20 7.00 C6H14 2,3-Dimethylbutane 13
3.7872 21.729 0.38566 0.52790 5100.0 19156 5502.5 115198 136.7 52.481 1.00 7.00 C7H16 n-Heptane 14
3.7872 21.574 0.38225 0.52160 5092.1 19133 5494.7 — 132.2 52.481 1.00 7.00 C7H16 2-Methylhexane 15
3.7872 21.840 0.37957 0.51370 5096.0 19147 5498.5 118654 132.9 52.481 (1.01) 6.6 C7H16 3-Mehtylhexane 16
3.7872 22.194 0.38669 0.51410 5098.2 19155 5500.8 117678 133.5 52.481 (1.00) 6.5 C7H16 3-Ethylpentane 17
3.7872 21.417 0.38687 0.51670 5079.6 19096 5482.1 119206 125.6 52.481 (1.09) 6.8 C7H16 2,2-Dimethylpentane 18
3.7872 21.923 0.37797 0.49910 5081.2 19104 5483.7 116499 124.5 52.481 (1.08) 6.8 C7H16 Triptane 21
3.3222 19.582 0.38446 0.52500 5796.0 19097 6248.9 119996 130 59.637 0.80 6.50 C8H18 n-Octane 22
3.3222 19.334 0.37652 0.51030 5780.5 19059 6233.3 119410 122 59.637 (0.92) 6.3 C8H18 Diisobutyl 23
3.3222 19.285 0.38154 0.51720 5778.8 19063 6231.6 — 115.8 59.637 0.95 6.00 C8H18 Isooctane 24
2.9588 17.807 0.38358 0.52210 6493.2 19054 6996.4 121428 124.7 66.794 0.70 5.60 C9H20 n-Nonane 25
2.6671 16.323 0.38294 0.52070 7189.5 19018 7743.0 119675 119.6 73.950 0.70 5.40 C10H22 n-Decane 26
5.4109 33.827 0.27199 0.42140 3512.0 18825 3763.6 119396 167.9 35.782 (1.48) 8.3 C5H10 Cyclopentane 27
4.5091 28.328 0.30142 0.44060 4199.0 18769 4500.9 123634 149.9 42.939 1.00 8.35 C6H12 Methylcyclohexane 28
4.5091 29.454 0.29084 0.43310 4179.7 18675 4481.6 125424 153 42.939 1.20 8.35 C6H12 Cyclohexane 29
3.8650 24.939 0.31989 0.44030 4863.7 18641 5215.9 126195 137.1 50.095 1.10 6.70 C7H14 Methylcyclohexane 30
13.5270 — 0.35897 — 1499.1 — 1599.8 126465 208.2 14.313 2.70 36.00 C2H4 Ethene (Ethylene) 31
9.0182 39.296 0.35759 0.57290 2182.1 19512 2333.0 130880 189.2 21.469 2.00 11.70 C3H6 Propene (Propylene) 32
6.7637 33.860 0.35613 0.53700 2878.6 19308 3079.9 129063 168.7 28.626 1.60 10.00 C4H8 1-Butene (Butylene) 33
6.7637 35.387 0.33368 0.52800 2871.0 19243 3072.3 — 178.9 28.626 1.60 10.00 C4H8 cis-2-Butene 34
6.7637 34.408 0.36630 0.52930 2866.8 19219 3068.1 — 174.8 28.626 1.60 10.00 C4H8 trans-2-Butene 35
6.7637 33.871 0.36689 0.54800 2859.9 19179 3061.2 90951 166.4 28.626 1.60 10.00 C4H8 Isobutene 36
5.4109 29.143 0.36017 0.51910 3575.0 19184 3826.5 103472 154.9 35.782 1.30 10.00 C5H10 1-Pentane 37
7.0158 38.472 0.34433 0.54110 2789.0 19379 2940.0 107798 193.6 26.240 (1.62) 10.3 C4H6 1,2-Butadiene 38
7.0158 36.685 0.34316 0.53560 2730.0 18980 2880.9 104694 178.4 26.240 2.00 12.50 C4H6 1,3-Butadiene 39
5.5711 31.866 0.35092 0.51930 3410.8 18832 3612.1 102861 163.6 33.397 (1.12) 8.5 C5H8 Isoprene 40
14.5750 — 0.39647 — 1423.9 — 1474.3 110652 353.3 11.927 1.50 100.00 C2H2 Acetylene 41
4.8582 35.829 0.24266 0.40980 3590.9 17256 3741.9 112072 169.5 35.782 1.20 8.00 C6H6 Benzene 42
4.1186 29.937 0.26014 0.40060 4273.7 17422 4474.9 104780 155.5 42.939 1.20 7.10 C7H8 Toluene 43
3.5745 25.977 0.27833 0.41130 4970.4 17594 5222.0 114131 144.7 50.095 1.00 8.00 C8H10 Ethylbenzene 44
3.5745 26.360 0.29052 0.41630 4958.1 17545 5209.7 — 148.5 50.095 1.00 7.60 C8H10 o-Xylene 45
3.5745 25.892 0.27480 0.40400 4956.1 17541 5207.7 — 146.5 50.095 1.00 7.00 C8H10 m-Xylene 46
3.5745 25.795 0.27506 0.40230 4957.1 17545 5208.6 132671 145.6 50.095 1.00 7.00 C8H10 p-Xylene 47
3.6437 27.671 0.26320 0.41190 4830.5 17415 5031.8 132658 153.5 47.710 1.10 8.00 C8H8 Styrene 48
3.1573 22.811 0.30697 0.42040 5660.8 17710 5962.7 134394 132.9 57.252 0.80 6.50 C9H12 Isopropylbenzene 49
11.8430 78.624 0.32504 0.59180 766.2 8561 866.9 136016 482.4 7.156 5.50 44.00 CH4O Methyl Alcohol 50
8.2374 54.531 0.33176 0.56400 1447.5 11523 1598.5 133572 364 14.313 3.28 19.00 C2H6O Ethyl Alcohol 51
13.5480 89.533 0.24738 — 320.5 — 320.5 133102 92.5 2.385 12.50 74.20 CO Carbon Monoxide 52
8.6228 59.095 0.19875 — 0.0 — 0.0 137819 246.5 — — — CO2 Carbon Dioxide 53
11.1350 74.514 0.23811 0.51910 586.8 6337 637.1 134831 234.4 7.156 4.30 45.50 H2S Hydrogen Sulfide 54
5.9235 68.764 0.14735 0.32930 0.0 — 0.0 — 167.2 — — — SO2 Sulfur Dioxide 55
22.2830 114.680 0.49679 1.12560 358.7 — 434.2 64744 588.8 3.578 15.50 27.00 NH3 Ammonia 56
13.1040 95.710 0.23992 — 0.0 — 0.0 84511 86.8 — — — N2+O2 Air 57
188.2500 111.220 3.40270 — 273.8 — 324.2 — 191.5 2.385 4.00 74.20 H2 Hydrogen 58
11.8590 112.940 0.21894 — 0.0 — 0.0 — 91.6 — — — O2 Oxygen 59
13.5470 91.128 0.24829 — 0.0 — 0.0 46156 85.6 — — — N2 Nitrogen 60
5.3520 63.544 0.11365 — — — — — 123.6 — — — Cl2 Chlorine 61
21.0646 175.620 0.44476 1.00030 — — 0.0 0.0 970.12 — — — H2O Water 62
94.8100 98.692 1.24040 — — — 0.0 — 8.9 — — — He Helium 63
10.4100 73.900 0.19033 — — — — — 192.3 — — — HCl Hydrogen Chloride 64

APPENDIX 3B – THE KATZ CORRELATION AND KAY’S RULE
This is one of the simplest methods for calculating compressibility factor z. It assumes that
Equation (3.10) is valid. Figure 3B.1 is the correlation prepared by Katz, et al., for lean, sweet natural
gas.
The values of Pc' and Tc' for use with Figure 3B.1 may be found from Kay’s Rule. This rule states that:
Pc' = / y i Pci and Tc' = / y i Tci (3B.1)

Where: yi = mol fraction of each component in the mixture

Tci and Pci = critical values for each component found from Tables 3.1 or 3A.1
Dividing the actual absolute temperature and pressure by the corresponding critical values
gives the necessary reduced values.
Kay’s Rule is also used to calculate the effective molecular weight of a mixture, as shown in
Example 3B.1. Kay’s rule is a molar weighted average.
CHAPTER 3 81
1.1
re, T’ r
duced Temperatu
Pseudo-re 3.00
2.80
1.0 2.60 05
1.
2.40
0
1.1
2.20
2.00 0 1.20
1.5 1.30
1.90
0.9 1.80
1.70 0
1.4
1.60
0.8
1.50
Compressibility Factor, z
1.45
1.40
0.7
1.35
1.30
0.6 5
1.2
0
1.2
5
1.1
0.5
0
1.1
05
1.
0.4
0.3
0.25
0 1 2 3 4 5 6 7 8
Pseudo-reduced Pressure, P’r
Figure 3B.1 Katz Compressibility Factor Chart

Example 3B.1: Calculate the compressibility factor for the gas shown in the table below at 13.94
MPa [2021 psia] and 331 K [595°R] using both Kay’s Rule and Figure 3B.1.
FPS SI ΣMW
Comp. yi Pc Pc′ Tc Tc′ Pc Pc′ Tc Tc′ MW MW’
N2 0.0046 493 2.3 227 1.00 3.40 0.02 126 0.6 28.016 0.13
CO2 0.0030 1071 3.20 548 1.60 7.38 0.02 304 0.9 44.010 0.13
H2S 0.1438 1300 186.9 672 96.60 8.96 1.29 373 53.6 34.076 4.90
C1 0.8414 666 560.40 343 288.6 4.60 3.87 191 160.7 16.043 13.50
C2 0.0059 707 4.20 550 3.2 4.88 0.023 305 1.8 30.070 0.18
C3 0.0008 617 0.50 666 0.5 4.25 negl. 370 0.3 44.097 0.04
iC4 0.0003 528 0.20 734 0,2 3.65 negl. 408 0.1 58.124 0.02
nC4 0.0002 551 0.10 765 0.2 3.80 negl. 425 0.1 58.124 0.01
5.23
1.0000 758 psia 392°R MPa 218 K MW = 18.90
P 13.94 P ' 2021

Pr' 2.67 = 2.67
P c'
r
P c' 5.23 758
SI: T FPS:
331 T 585
Tr' = 218 = 1.52 = '
= = 1.52
Tc'
r
Tc' 392
From Figure 3B.1, z = 0.80. The actual density of the gas can be found from Equation (3B.1).
(13.94)(18.90)
SI: t = (0.80)(0.008 31)(331) = 120 kg/m3
(2021)(18.90)
FPS: t = (0.80)(10.73)(595) = 7.5 lbm/ft3
Example 3B.2: Rework Example 3B.1 assuming only the molecular weight of the gas is known.
From Example 3B.1, MW = 18.90
The relative density of this gas is 18.90/28.97 = 0.65 from Figure 3.6
P ' = 4.62 MPa [670 psia]
c and T ' = 208 K [375 %R]
c
P 13.94 T 331
SI: P r' = = =
4.62 3.02 T r' = = = 1.59
P c' '
Tc 208
P 2021 T 595
FPS: P r' = ' =
670
= 3.02 T r' = ' = = 1.59
Pc T c 375
From Figure 3B.1, z = 0.825
(13.94)(18.90)
SI: t = (0.825)(0.008 31)(331) = 116 kg/m3
(2021)(18.90)
FPS: t = (0.825)(10.73)(595) = 7.25 lb/ft3
CHAPTER 3 83
APPENDIX 3C – WICHERT AZIZ METHOD FOR SOUR NATURAL GASES
Since many people use the Katz compressibility factor correlation for hand calculations, the
question is often asked how it may be extended to gases containing H2S and CO2. One method available for
this application is the Wichert and Aziz approach. This method is a reasonable estimation for gas composi-
tions that do not exceed a total of 5 mol % of sour gases (H2S and CO2 ).
The Wichert and Aziz(3.4) approach utilizes an adjustment of the Pc' and Tc' which is found from
Kay’s combination rule and used to prepare the Katz chart. It uses a correction parameter, ɛ , found from
Figure 3C.1.
This correction parameter is used to adjust the pseudocriticals found from Kay’s Rule. The adjusted
values are then used to find the reduced pressure and temperature for use with Figure 3B.1.
The equations for making the adjustment are:
P c' T c"
T c" = T c' - 0.556 f , P c" = (3C.1)
T c' + B (1 - B)( f) (0.556)
SI:
Pc Tc
FPS: T c = T c - f , P c" = ' (3C.2)
T c + B(1 - B)( f)
Where: Tc" & Pc" = adjusted critical values for use in Figure 3B.1
Tc' & Pc' = pseudocriticals from Kay’s Rule, e is from Figure 3C.1
B = mol fraction H2S in the gas
Figure 3C.1 can be estimated by the equation(3.28):
f = 120 (A 0.9 - A1.6) + 15 (B 0.5 - B 4) (3C.3)

Where: f = correction factor in °R (to obtain in K, divide by 1.8 or multiply by 0.556)
A = mol fraction H2S plus CO2 in the gas
B = mol fraction H2S in the gas

Figure 3C.1 Correction Factor Chart for Sour Gases (3.27)
Example 3C.1: Rework Example 3B.1 using Figure 3C.1 correction. From Figure 3C.1, ɛ = 21.0
T c" = 218 - (0.556)(21) = 206.3 K

SI:
(5.23)(206.3)
P c" = = 4.92 MPa
218 + (0.1438)(0.8562)(21.0)(0.556)
T c" = 392 - 21 = 371%R

FPS:
(758)(371)
P c" = = 713 psi
392 + (0.1438)(0.8562)(21.0)
Then Prꞌꞌ = 2.8, Trꞌꞌ = 1.6, and Z = 0.83
^13.94h^18.90h
= 115 kg/m3
^0.83h^0.008 31h^331h
t=

^2021h^1890h
= 7.2 lbm/ft3
^0.83h^10.73h^595h
t=
CHAPTER 3 85
APPENDIX 3D – (COSTALD)
The Hankinson and Thomson Corresponding state liquid density equation is shown below:
* = v R ^1 – ~SRK v R h
vs ^0h ^dh
Where: vs = molar volume at saturated liquid T

v* = an empirical constant which is typically within 1-4% of vc
wSRK = SRK acentric factor

vR and vRd = reduced volume factors which depend upon Tr
vR(0) = 1 – 1.52816(1 – Tr)1/3 1.43907(1 – Tr)2/3 – 0.81446(1 – Tr) + 0.190454(1 – Tr)4/3
vR(d) = –0.296123 + 0.386914Tr – 0.0427258T r2 – 0.0480645T r3

Tr – 1.00001
Values for v*, wSRK can be found in the following reference: R. W. Hankinson, G. H. Thomson,
AIChE J. 25 (1979) 653-663.
The COSTALD Mixing Rule equations are provided below:
N
SRK = / x SRKi
i=1
` x i V i* + 3 ` / x i ^V i*h j` / x i ^v*i h jj
1 /N N
2/3
N
1/3
V m* =
4 i=1 i=1 i=1
1 /N N
cm = *
/ xi x j V* T *
Vm = =

4
QUALITATIVE PHASE BEHAVIOR
The energy possessed by any substance depends on its phase. There are three different familiar
phases: solid, liquid, and gas (vapor), which are easily identified by sight.
A solid possesses a definite shape and is hard to the touch. It is composed of molecules with very low
energy that stay in one place even though they vibrate. There is space between these molecules, so a solid is
not impenetrable.
A liquid has a definite volume but no definite shape. It will assume the shape of the container in which
it is placed but will not necessarily fill that container. The molecules of which the liquid is composed possess
more energy than in a solid, enough energy to move from place to place. By virtue of this energy, there is more
space between molecules. So, with few exceptions, a substance is less dense in the liquid form than in the solid
form.
A vapor has no definite volume or shape and will fill a container in which it is placed. The molecules
have more energy than in the liquid form. In fact, they are very active. Vapor density usually is low enough
that you can see through a vapor. As might be expected, the density of a given substance is lower in the vapor
phase than in the liquid phase.
One of our objectives is to understand the difference in energy level between phases. Energy must be
added to melt a solid to form liquid. If enough additional energy is added, the liquid can be vaporized.
It is important to know the phase or phases that exist at given conditions of pressure, volume, and
temperature in order to ascertain the corresponding energy level. To do this, substances are separated into two
classifications: pure substances (single component systems) and mixtures of substances (multi-component
systems).
SINGLE COMPONENT SYSTEMS

The word component refers to each of the molecular or atomic species present in the substance. A
single-component system is composed entirely of one kind of atoms or molecules. We often use the word pure
to describe a single-component system; for example, 100% methane or 100% propane.
Figure 4.1 is a typical three-dimensional phase diagram for a pure substance. It has three axes: P, V,
and T. It is composed of a series of plane surfaces, each of which represents a given phase or a mixture of
phases. We are particularly interested in the two-phase planes: BDHG—solid plus liquid, FGIJ—solid plus
vapor, and an irregular-shaped plane HCI for the liquid plus vapor. All of these planes are perpendicular to
the temperature axis.
The liquid-only plane is the “cliff” to the left of plane HCI and adjacent to plane BDHG. The vapor-
only plane is the “slope” to the right of plane HCI.
CHAPTER 4 87
The critical temperature, Tc, can be located

E
Tc
on the temperature axis and is shown as a dashed line.
T1 It passes through the critical point “c” and is tangent
a to the phase envelope HCI. The temperature lines
C
B D
between line HC and CI inside the phase envelope
A
occur at constant pressure. This is a basic character-
P
P11
Solid Liquid Liquid istic of all such diagrams for pure substances.
+ + q
Liquid Vapor
Solid
b Vapor
Although all planes are of interest, we are
Pressure
primarily concerned with plane HCI, the vapor-

Pressure
d
n o
m liquid region of the phase diagram.
PP11
G H I e
Solid + Vapor Tc A three-dimensional phase diagram like
F
raret
ur
e
Figure 4.1 is awkward to use, so we normally draw a
etu
J mpra
Teempe projection of this diagram. Both P-T and P-V projec-
TT1 T
1
K tions are important.
Specific Volume
Specific Volume
Since all of the two-phase planes in Figure
4.1 are perpendicular to the T axis, they appear as
Figure 4.1 P-V-T Diagram for a Single Component System single lines in a P-T projection like Figure 4.2.
P-T Plot for Single Component Systems

Figure 4.2 provides a typical pressure-temperature (P-T) diagram for a single component. Lines
HD, HC, and FH are the equilibrium lines, i.e., combinations of pressure and temperature at which the
adjoining phases are in equilibrium. At equilibrium, a phase change can occur at constant pressure and
temperature by simply adding or removing energy from the system. Point H, the triple point, is the only
combination of pressure and temperature at which all three phases can exist together.
Along line FH, no liquid phase is ever present and solid sublimes to vapor. The use of “dry ice”
for cooling is an example of this. Line HD is the equilibrium line between solid and liquid. Ice water at
0°C [32°F] and atmospheric pressure occurs on this line. Line HD can have a positive or negative slope
depending on whether the liquid expands or contracts on freezing. The energy change occurring along line
HD is called the heat of fusion. At any P and T along this line the system can be all solid, all liquid, or a
mixture of the two, depending on the energy level.
Dense Fluid This line could be called the “solid-liquid satura-
D f g
C tion” or “solid-liquid equilibrium” line.
Line HC is the saturation or equilibrium
P1 m n o b d h curve between vapor and liquid. It starts at the triple
Superheated point and terminates at the critical point “C.” The
Vapor or Gas
pressure and temperature conditions at this latter
Liquid
point are known as critical temperature (Tc) and
Pressure
Solid Vapor critical pressure (Pc). At this point the properties of

the liquid and vapor phases become identical. For
H a pure substance the critical point can be defined
Triple Point as that point above which liquid cannot exist as a
F unique, separate phase. Above Pc and Tc the system
Temperature is often referred to as a dense fluid (or super critical
fluid) to distinguish it from normal vapor and liquid.
Figure 4.2 P-T Diagram for a Single Component System

In Figure 4.2, consider a process starting at pressure P1 and proceeding at constant pressure. From
“m” to “n” the system is entirely solid. The system is all liquid for the segment o-b. At “b,” the system is a
“saturated liquid”—any further addition of energy will cause vaporization at constant pressure and temper-
ature. At “d,” the system is in the saturated vapor state. At temperatures above “d,” it is a “superheated”
vapor.
Line HC is thus known by many names: equilibrium, saturated, bubblepoint, dewpoint, and vapor
pressure. For a pure substance, these words all mean the same thing.
At the pressure and temperature represented by HC, the system may be all saturated liquid, all
saturated vapor, or a mixture of vapor and liquid. The exact phase condition of the system depends on the
energy level at the P and T involved.
The rectangle “bfghd” illustrates another important phase property that is confirmed experimentally.
Suppose a liquid is placed in a windowed cell at condition “b” and illuminated it so it is easily visible. The
pressure is then increased at constant temperature (isothermally). As the system moves toward point “f,” the
color will begin to fade. At some point, the color disappears completely. The cell now contains what looks like
a vapor, but no bubble of vapor was ever seen to form.
At “f” (above the critical pressure), the system is in a fourth phase that cannot be described by the
senses. It is usually called “dense phase fluid” or “super critical fluid.” The word fluid refers to anything that
will flow and applies equally well to gas and liquid.
This fluid at “f” looks like a gas but possesses different properties from regular gas found to the
right of line HC and below the critical pressure. It is denser than regular gas but is more compressible than a
regular liquid. Gas type correlations are used but must be modified to reflect the different behavior patterns
of this dense phase fluid.
From “f,” the temperature is increased at constant pressure (isobaric) to “g”. The pressure is then
reduced isothermally to “h,” and then the temperature is reduced isobarically to “d.” The phase condition
has changed from saturated liquid to saturated vapor without encountering any discernible change of phase,
or “boiling”.
The system could move from “b” to “d” directly by just adding energy to the liquid at constant
pressure. In the cell, bubbles of vapor would be observed, and an interface would develop between gas and
liquid. As energy input continued, the liquid level would fall until the liquid phase disappeared. No tempera-
ture change would occur in going from “b” (saturated liquid) to “d” (saturated vapor).
Vapor Pressure of Hydrocarbons

Figure 4.3 is a vapor pressure plot for light paraffin hydrocarbons. The lines shown are curve HC
in Figure 4.2. They have been straightened artificially by using a non-linear reciprocal temperature scale on
the abscissa and log scale on the ordinant. Figure 4.4 is a corresponding vapor pressure chart for paraffinic
hydrocarbon mixtures and applies to pure or narrow boiling point petroleum fractions based on their normal
boiling point. Figures such as these are often referred to as Cox charts.
The Antoine equation can also be used to estimate the vapor pressure of hydrocarbon liquids. Antoine
equation constants can be found in References 4.1 and 4.2.
Although the true vapor pressure curve of a pure component must terminate at its critical point, the
line often is extrapolated above that point in the calculation of mixture properties. This pseudo value may
be used to estimate the contribution of that molecular species to total mixture properties.
CHAPTER 4 89
Figure 4.3 Vapor Pressure Chart for Paraffin Hydrocarbons
Figure 4.4 Vapor Pressure Chart for Normal Paraffin Hydrocarbons Based on Normal Boiling Point(4.3)

MULTI-COMPONENT SYSTEMS
For a multi-component system, composition must be added to the phase diagram since the location of
the phase boundaries depends on composition.
For a pure substance, the phase envelope HCI (Figure 4.1) is a plane surface parallel to the tempera-
ture axis and appears as a line in the P-T projections. For multi-component mixtures, this phase envelope is
not a plane; it has thickness. Composition is the variable that reflects this thickness.
Figure 4.5 shows the phase envelope for a natural gas mixture. This figure is a projection showing
only the liquid-vapor portion of the phase envelope.
There are several terms used to define the location of various points on the phase envelope.
Cricondenbar – the maximum pressure at which liquid and vapor may coexist in equilibrium
(Point N).
Cricondentherm – the maximum temperature at which liquid and vapor may coexist in equilib-
rium (Point M).
Retrograde Region – Two retrograde regions exists. The blue area represents isothermal retrograde
condensation, where liquid condenses when pressure decreases. The green shaded area repre-
sents isobaric retrograde vaporization. In this area liquid condensation occurs as temperature
increases.
Quality Lines – these lines show constant molar percentages of liquid or vapor which intersect at
the critical point (C) and are essentially parallel to the bubblepoint and dewpoint curves. The
bubblepoint curve represents 0% vapor and the dewpoint curve 100% vapor.
Bubblepoint – the temperature at a given pressure where the first bubble of vapor will form. To
the left of this curve the fluid is all liquid. To the right, the fluid has two phases (vapor and
liquid). It can also be defined as the pressure at a given temperature where the first bubble of
vapor forms.
Dewpoint – this represents the temperature at constant pressure where the first drop of liquid will
form. The phase behavior along this line is more complex than for the bubblepoint. To the right
of the cricondenbar the dew point line represents the phase boundary between all vapor and a
two-phase system. Liquid condenses on a reduction in temperature. To the left of the cricon-
denbar the boundary is between a dense phase with vapor-like properties and a two-phase
system. Along this line, liquid condenses on an increase in temperature (see the isobaric retro-
grade vaporization discussion above).
Critical Point – the point located at the intersection of the bubble and dewpoint lines. As the
critical point is approached, the properties of the vapor and liquid phases become equal,
resulting in a single phase at the critical point: a homogenous critical fluid.
Line ABDE represents a typical isothermal retrograde condensation process similar to that occurring
in a gas condensate reservoir. Point A represents the single phase fluid outside the phase envelope. As
pressure is decreased condensation begins at Point B. This is referred as the upper dewpoint. As pressure is
further decreased, more liquid forms because of the change in the slope of the quality lines. Maximum liquid
condensation occurs at point D. As the process continues below point D, the condensed liquid re-vaporizes
until the lower dewpoint is reached (Point E). Below E no liquid forms.
CHAPTER 4 91
Cricondenbar
N A
Isobaric
Retrograde B
Region
De
wp
oin
Critical C
t
Point
Isothermal
Retrograde
Pressure
D Region
t
oin
e
Lin
lep
bb
uid
e
Bu
Lin
Liq
M
e
%
uid
Lin
Cricondentherm
25
Liq
uid
0%
e
1
Liq
oint
Lin
5% ui
d
wp
Liq
1%
De
E
Temperature
Figure 4.5 Typical Phase Diagram for a Multi-Component Natural Gas Mixture
Based upon experience, the critical point has always occurred to the left of the cricondenbar for
naturally occurring hydrocarbon gas mixtures. It is not, however, necessarily in the position shown. It may
be further down on the phase curve or closer to the cricondenbar. Location of “C” is most important, for it
fixes the shape of the quality lines, which in turn governs the vapor-liquid ratio at a given temperature and
pressure within the phase envelope.
Note that the pseudocritical values calculated in Chapter 3 are not point “C” on Figure 4.5 except
by coincidence.
Effect of Composition
Figure 4.6 shows a T-P-x diagram for binary mixtures of C2-nC7. The third axis is the composition
axis and represents the mol fraction of nC7 in the mixture.
Figure 4.7 is a pressure-temperature projection of Figure 4.6 and shows the effect of composition
on the shape and location of the phase envelope for the C2-nC7 binary system. The two curves that bound
Figure 4.7 are the vapor pressure curves for C2 and nC7, which terminate at their critical point.
Three phase envelopes are shown for different compositions of C2 and nC7. This illustrates the fact
that the shape and location of the phase envelope depend on composition.
The dashed line is the critical locus drawn tangent to all possible phase envelopes, at the critical
point on each curve. It starts at the critical point of C2 and ends at the critical point of nC7. From the shape of
this curve, you can deduce that the critical point location on each phase envelope varies with composition.
For systems dominated by the heavy components, the critical point may occur to the right of the
cricondenbar. This characteristic is exhibited in most crude oil systems.
Note too that the critical pressures of mixtures are not a linear function of composition.
This means that a reliable analysis is important to obtain representative phase behavior predictions.
The accurate prediction of bubble and dewpoint conditions is important to the design and/or operation of
processing facilities. The accuracy of liquid recovery predictions depends on the corresponding quality of
the phase data. Chapter 5 will clarify the calculations.

P, kPa
8000
6000
4000
2000
-100
0 0
1.0
Te
100 0.9
m
0.7 0.8
pe
0.6
200 0.5
ra
0.4
tu
0.3
0.2 Fra ction
re
300 0.1 nC 7, mol

,°
0.0
C
Figure 4.6 T-P-x Diagram for C2-nC7 System
Effect of C6+ Characterization

As discussed in chapters 1 and 3, the analysis and/or characterization of the C6+ or C7+ fraction in
a natural gas mixture are routinely performed. It has a significant effect on the shape of the phase envelope.
This is illustrated in Figure 4.8.
Temperature, °F
-200 -100 0 100 200 300 400 500
10 000
9000
1250
8000
7000 1000
Pressure, psia
Pressure, kPa
6000
C2
l%
mo
750
5000
60
2
C
%
ol
m
40
4000
ne
Etha
500
C2
3000 l%
mo
20
2000
250
ne
a
e pt
1000 n -H
0 0
-150 -100 -50 0 50 100 150 200 250 300
Temperature, °C
Figure 4.7 Effect of Composition on Phase Envelope, Ethane and n-Heptane Binary
CHAPTER 4 93
Figure 4.8 presents phase envelopes for 4 different characterizations of the C6+ fraction: nC7, nC9,
nC11, and full characterization based on a distillation analysis of the C6+.
Special gas chromatographic techniques can identify individual components heavier than C6-C7
(see Chapter 1). This is called an extended analysis. If the phase behavior of the gas has a significant effect
on the system design, it is highly recommended that an extended analysis be performed. If an extended
analysis is not available, predictive characterization techniques may be used. These are summarized in
Chapters 3 and 5.
For lean natural gases, the C6+ characterization has a significant effect on the dewpoint line. The
effect on the location of quality lines is less significant.
It should be noted that quantitative measurement of the C6+ components in natural gas streams may
not be accurate. Therefore, the calculation of hydrocarbon dewpoint from a chromatographic analysis is
uncertain. For custody transfer purposes, it is advisable to insist on direct measurement of the hydrocarbon
dewpoint rather than calculation from an analysis.
Temperature, °F
-300 -250 -200 -150 -100 -50 0 50 100 150 200 250 300
18 000
2500
N2 0.93
16 000 CO2 11.68

C1 73.77 2250
C11
11
C2 8.20
14 000 C3 3.23 Characterization based
on TBP analysis of C6+
C6+ 2000
iC4 0.28
nC4 0.78 C9
12 000 iC5 0.24 1750
nC5 0.18
C6+ 0.71 1500
Pressure, psia
Pressure, kPa
10 000 100.00
1250
8000 C7
1000
6000
750
4000
500
2000
250
0 0
-200 -150 -100 -50 0 50 100 150
Temperature, °C
Figure 4.8 Effect of C6+ Characterization on Phase Envelope for Non-Associated Gas

Effect of Impurities
Hydrocarbons are frequently produced with non-hydrocarbon impurities. The most common
include water, carbon dioxide, hydrogen sulfide, and nitrogen. Since water has a low vapor pressure and is
virtually immiscible in the hydrocarbon liquid phase, it does not have a significant effect on the shape of
the hydrocarbon phase envelope except at high temperatures and low pressures. Knowing where the water
dewpoint line is in relation to the hydrocarbon phase envelope is important. This is discussed in Chapter 6.
The effects of CO2, H2S, and N2 on the phase behavior of an example reservoir fluid are shown
in Figures 4.9 (a)-(c). Both CO2 and H2S lower the cricondenbar of the mixture. If sufficient quantities of
the CO2 and H2S components are added to a reservoir fluid and the reservoir pressure is kept above the
phase envelope, a single dense fluid phase exists. Although the actual mechanism is more complex, it is
this solubility that is the primary driving force behind miscible flood enhanced oil recovery projects. NGL
components such as ethane, propane, and butane have a similar effect.
Nitrogen, on the other hand, raises the cricondenbar and decreases miscibility. It is sometimes used
for reservoir pressure maintenance.
Temperature, °F
-200 -100 0 100 200 300 400 500 600 700 800 900
45 6500
= Critical Point 6000
O22
40 l% C 2
Mo
0m CO 2
l% 5500
Mo
m
10 2
35 CO 2
l% 5000
0 Mo
m
2 CO 2
2
M
m ol % 4500
30 40 2
CO 2
M
mol %
60 4000
Pressure, MPa
Pressure, psia
25
3500
20 3000
2500
15
2000
10 1500
1000
5
500
0 0
-150 -100 -50 0 50 100 150 200 250 300 350 400 450 500
Temperature, °C
Figure 4.9a Effect of CO2 on Volatile Oil Phase Behavior(4.5)
CHAPTER 4 95
Temperature, °F
-200 -100 0 100 200 300 400 500 600 700 800 900
45 6500
= Critical Point
S 6000
40 H 22S
l%
Mo
0m SS 5500
HH 22
%
M ol
35 10
m
5000
SS
HH 22
%
M ol 4500
m
30 20
SS
4000
Pressure, MPa
Pressure, psia
HH 22
25 ol
%
M
m 3500
40
SS 3000
20 H 22
%
ol
M
m 2500
60
15
2000
10 1500
1000
5
500
0 0
-150 -100 -50 0 50 100 150 200 250 300 350 400 450 500
Temperature, °C
Figure 4.9b Effect of H2S on Volatile Oil Phase Behavior (4.5)
Temperature, °F
-500 -400 -300 -200 -100 0 100 200 300 400 500 600 700 800 900
160
22 000
= Critical Point
140
20 000
Mol% N22
60 mol%
18 000
120
16 000
100
14 000
Pressure, MPa
Pressure, psia
Mol% N22
40 mol% 12 000
80
10 000
60
N2
8000
Mol%
20 m
Mol% N22
10 m 6000
40
Mol% N22
0 mo
4000
20
2000
0 0
-300 -200 -100 0 100 200 300 400 500
Temperature, °C
Figure 4.9c Effect of N2 on Volatile Oil Phase Behavior (4.5)

APPLICATION OF PHASE ENVELOPES

Proper assessment of many petroleum systems requires knowledge of at least a portion of the phase
envelope. Several examples are summarized to illustrate some of these applications.
Reservoir Behavior
The reservoir is the “warehouse” from
Vo
which fluid is withdrawn for production and process- l
at
ile
ing operations. Knowledge of the phase behavior is
O il
essential to the intelligent development of the field.
Bla
Pressure
ck
Oi
Ga
Figure 4.10 provides example phase l
sC
ond
envelopes for dry gas, wet gas, gas condensate,
ensate
W
volatile oil and black oil reservoirs. The phase
et
D
G
as
ry G
envelopes for each type of reservoirs are different due
as
to the different compositions. This is reflected in
Figure 4.10.
Temperature
Figure 4.11 provides an example phase
Figure 4.10 Characteristic Phase Envelopes for Five
envelope for a black oil reservoir (low gas oil ratio Reservoir Types
(GOR)). The initial reservoir pressure is shown. The
Temperature, °F
vertical dashed line represents reservoir pressure -200 -100 0 100 200 300 400 500 600 700 800 900 1000
40
decline at constant temperature. The curved line Initial Reservoir
Conditions
5500
35
represents pressure and temperature changes that 5000
occur in the wellbore and through the choke. The %30 Critical
4500
80
point labeled Separator Conditions represents the Point 4000
Pressure, MPa
Pressure, psia
25 %
60
inlet to the first stage production separator.
3500
20 3000
The reservoir temperature is significantly

%
2500
40
15
2000
less than the critical temperature. At initial reservoir
%
20
10 1500
conditions the reservoir is undersaturated. No vapor
1000
will form in the reservoir until the pressure reaches 5
Separator 500
Conditions
the bubblepoint. Any additional pressure decline 0 0
-150 -100 -50 0 50 100 150 200 250 300 350 400 450 500 550
will cause vapor to form in the reservoir. Temperature, °C
An example phase envelope for a volatile oil Figure 4.11 Black Oil Reservoir
reservoir (higher GOR) is provided in Figure 4.12.
Like the black oil reservoir, the reservoir temperature Temperature, °F
-200 -100 0 100 200 300 400 500 600 700 800 900
is also less than the critical temperature. The oil may 40
Initial Reservoir
Initial Reservoir 5500
be lighter in color but color is not a reliable indicator 35
Conditions
Conditions 5000
of the reservoir type. Once again, no vapor forms in 30 80% 4500

Pressure, MPa
4000
the reservoir until the bubblepoint pressure is attained,
Pressure, psia
25
%
3500
50
even though vapor forms in the wellbore as shown. 20 3000
2500
%
An example phase envelope for a gas-conden-

30
15
2000
sate reservoir is shown in Figure 4.13. The reservoir 10 1500
1000
temperature falls between the critical and criconden-
%
5 Separator 10
500
therm temperatures. When the reservoir pressure
Conditions
0 0
-150 -100 -50 0 50 100 150 200 250 300 350 400 450 500
reaches the dewpoint, retrograde condensation will Temperature, °C
occur. Initially most of this condensation occurs near
the wellbore since that is where most of the reservoir Figure 4.12 Volatile Oil Reservoir
CHAPTER 4 97
pressure drop occurs. Much, if not all, of this liquid will be unrecoverable, as it is held in the rock pores by
capillary forces. In addition, as the amount of condensed liquid increases it can reduce gas production. Both
gas and liquid flow will be influenced by the relative
Temperature, °F
-200 -150 -100 -50 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
50
permeability of the rock which in turn is a function of
45 Initial Reservoir
7000
6500
rock properties as well as gas and liquid saturation.
40
Critical
Point
Conditions
6000 Gas condensate reservoirs are sometimes cycled to
5500 maximize liquids recovery prior to blowdown to
35
recover the gas. Cycling refers to the process of
5000
Pressure, MPa
Pressure, psia
4500
reinjecting the separator gas back into the reservoir to

30
4000
25
3500
10% 5% maintain the reservoir pressure above the dewpoint.
20 3000
15% The decision to cycle or blowdown a gas condensate
2500
15 20% 2000 reservoir is an economic one. In general, the leaner
10 1500
1000
the reservoir fluid composition (less C7+) the more
5 Separator
Conditions
500 likely the development decision will be to blowdown
0
-150 -100 -50 0 50 100 150 200 250 300 350 400
0
the reservoir.
Temperature, °C
Two example phase envelopes for true gas
Figure 4.13 Gas Condensate Reservoir
reservoirs are shown in Figure 4.14. The reservoir
Temperature, ˚F
temperature is greater than the cricondentherm
18
-300 -250 -200 -150 -100 -50 0 50 100 150 200 250 300
2600 temperature. No liquid hydrocarbon will form in the
16
Initial
Reservoir 2400 reservoir at any pressure. If the separator conditions
Wet Gas Conditions 2200
14
Reservoir are inside the phase envelope some liquid will form
2000
1800
in the wellbore and appear at the surface. If no liquid
12
Pressure, MPa
Pressure, psia
1600 hydrocarbon exists in the production separator these

10
1400
reservoirs are often referred to as “dry gas” reser-
voirs. If liquid hydrocarbons exist in the separator the
8 Dry Gas 1200
Reservoir
Dry Gas 1000
Critical Point
6
Wet Gas 800 term “wet gas” reservoirs is often used.
Critical Point
4 600
Separator
Conditions 400 For a black oil reservoir, a section of the
2
200
bubblepoint curve is all that is required to evaluate
0 0
-200 -150 -100 -50 0 50 100 150 development options. For reservoirs that might be
Temperature, ˚C
volatile oil or gas condensate, gas characterization
Figure 4.14 Dry Gas Reservoir of the upper section of the phase envelope, including
the critical point, the cricondenbar, and criconden-
50 000 therm may be necessary. One of the most common
Wet Retrograde Volatile Black
mistakes is failure to obtain representative reservoir
Initial producing gas-oil ratio, scf/STB
Dry gas Gas Gas Oil Oil

40 000 fluid samples and subsequently base development
plans on incorrect information.
30 000
Another indicator of the reservoir type is
the concentrations of heptanes plus in the reservoir
20 000
fluid and the initial producing gas-oil ratios, as
Dewpoint
shown in Figure 4.15(4.4). The red and blue shaded
10 000 Bubblepoint regions indicate which phase boundary is crossed as
the reservoir pressure declines (dewpoint or bubble-
0 point).
0 5 10 15 20 25 30
Heptanes plus in reservoir fluid, mol%
Figure 4.15 The Effect of Composition on Initial Producing

GOR (4.4)

Facility Phase Behavior

For facilities work and equipment troubleshooting, it is important to understand where the process is
operating relative to the phase envelopes. Often this can help determine the cause of a problem, or how to
avoid the problem in the first place. The following examples highlight a few applications of phase envelopes
to facilities work.
Pump Suction Head
We often pump commercially pure liquids like
ethane and propane at their bubblepoint. It is important that
no vapor form in the pump suction to prevent cavitation. Point Liquid
A in Figure 4.16 represents the condition in the storage tank

B
(saturated). Point B represents the pressure at the pump inlet
Pressure
ve
C ur
flange due to the head of liquid in the suction piping. Point C C ssu
re
Pre
represents the pressure inside the pump at the impeller eye. A or Vapor
Vap
Pressure drop B-C occurs in the pump suction. Point

C must be above the saturation curve to prevent cavitation. If
the pressure drop B-C is greater than the head A-B, cavitation Temperature
may occur. Figure 4.16 Pump Suction Pressure Conditions

Refrigeration Processes
Refrigeration is frequently used to cool a gas in order to meet a hydrocarbon dewpoint (HCDP)
specification. When the refrigeration takes place at high pressure, it is important to have an accurate descrip-
tion of the phase behavior. Figure 4.17 shows the phase envelope for a lean gas typical of that found in
the southern North Sea or Gulf of Mexico. The cricondentherm of this gas is 30°C [86°F] and occurs at a
pressure of 3000 kPa [435 psia].
Temperature, °F
-200 -150 -100 -50 0 50 100
11 000
Required Hydrocarbon 1500
Operating Operating
10 000 Pressure Temperature Dewpoint
Specification
kPa psia °C °F (-3°C [26.6°F])
9000 3000 435 -3.0 26.6 A
5000 725 -7.2 19.04 1250
7000 1015 -19.4 -2.92
8000 7500 1088 -25.1 -13.18 B
7900 1145 -34.0 -29.2 B Feed Gas
7000 1000
Pressure , psia
Pressure , kPa
6000 Processed Gas
750
5000
4000
500
Chricondentherm Temperature
3000 of Processed Gas = -3°C [26.6°F] A
2000
250
1000
0 0
-150 -100 -50 0 50
Temperature, °C
Figure 4.17 Effect of Pressure on Dewpoint Control Processing Temperatures
CHAPTER 4 99
Assume that this gas is to be processed in a mechanical refrigeration plant to meet a HCDP speci-
fication of –3°C [27°F]. If the processing pressure is 3000 kPa [435 psia], the gas must be cooled to at least
–3°C [27°F] (point A) to meet the specification. However, if the processing pressure is 7500 kPa [1088
psia], the gas must now be cooled to –25°C [–13°F] (point B). The table in Figure 4.15 shows the maximum
processing temperature required to meet the HCDP specification at various pressures.
The cricondenbar of the processed gas is
8000 kPa [1160 psia]. Above this pressure this gas
could not be processed in a mechanical refrigera-
tion plant to meet the HCDP specification. For feed
A gas pressures above the cricondenbar pressure to
meet the specification, an expansion process (valve

Pressure
B
or expander), or an adsorption process would be
required.
Cooling in Facility Piping

In a number of gas conditioning processes, it
Temperature is important to remove the hydrocarbon liquids from
the inlet gas stream to prevent solvent contamination
Figure 4.18 Cooling of a Gas in Facility Piping
or degradation of adsorbents. If liquid hydrocarbons
Sweet Gas To Dehydration are present in the production separator the gas leaving
the separator (and entering the processing facility)
Lean Amine will be at its dewpoint. Any cooling occurring in the
piping between the separator and the process will
result in liquid condensation. If the feed gas pressure
Amine Contactor
is above the cricondentherm pressure, additional
Distance = L
liquid may be formed due to retrograde condensation
To Amine Level
Control Valve associated with pressure drop in the piping. This is
illustrated in Figure 4.18. In addition the gas leaving
the separator may also contain a small amount of
Sour Gas
Rich Amine liquid hydrocarbon due to separator carryover.
Inlet Filter To Closed Drain The presence of this liquid is the reason
Coalescer
that installation of a properly sized filter coalescer
Figure 4.19 Process Flow Diagram for an Amine System upstream of the process unit is recommended, as
Inlet
shown in Figure 4.19 for an amine unit. In some
cases, the filter coalescer is installed at a consider-
able distance from the contactor. When this happens,
K the condensation illustrated in Figure 4.18 can lead
L to solvent contamination and operating problems.
Contamination is also an issue in glycol dehydration
Pressure
and adsorption systems.

I
J Dense Phase Pipelines
Consider Figure 4.20. Suppose the solid blue
line represents the phase envelope of the gas entering
the pipeline, and points I and J represent the inlet and
Temperature outlet conditions of the pipeline. When line I-J crosses
Figure 4.20 High Pressure Pipeline Phase Envelope
the dewpoint curve, liquid will condense in the line.
From that point on, two-phase flow exists.

Liquid formation can be prevented by removing sufficient heavy components to change the shape
and position of the phase envelope, as illustrated by the dashed envelope in Figure 4.20.
For dense phase pipelines (K-L case), the primary concern is the cricondenbar of the gas. If the
pipeline pressure drops below the cricondenbar pressure liquid condensation may occur. If the receiving
facilities connected to the pipeline are not designed to handle two phase flow (which is likely the case), then
significant operating problems may be the result.
Accurate determination of the dewpoint curve and quality lines is essential for design of dense
phase pipelines.
Operation Near the Critical Region

Near the critical point, all properties of the vapor and liquid in the system converge to the same
value. This region is not well predicted by equation of state models.
The properties of the vapor and liquid are strongly affected by small changes in temperature and
pressure near the critical point, which makes operation under these conditions inherently unstable. The
most common examples of near-critical operation are low temperature expander-type gas processing plants
and de-ethanizers.
Practical Suggestions
As indicated in the previous examples, accurate knowledge of phase behavior is essential to the
design and operation of processing facilities. The cost of obtaining good data is usually trivial compared to
the economic benefits obtained.
Here are some guidelines that should be followed:
1. Obtain good samples using experienced samplers.

2. Handle the samples carefully.
3. Analyze the samples in a reputable laboratory.
4. Develop all, or that portion needed, of the phase envelope. Above about 14 MPa [2000 psi],
calculated points are suspect no matter how sophisticated the correlation. The results should
be regarded as estimates only. If an estimate is good enough, fine. If not use experimental data
from a reliable laboratory. In many cases, a few laboratory points supplemented by calculations
will suffice.
4.1 Linstrom, P.J. and W.G. Mallard, Eds., NIST Chemistry WebBook, NIST Standard Reference Database Number 69, National
Institute of Standards and Technology, Gaithersburg MD, 20899, http://webbook.nist.gov, (retrieved July 24, 2013).
4.2 Poling, B., Prausnitz, J., and O’Connell, J.,“ The Properties of Gases and Liquids”, 5th Edition, McGraw-Hill, (2001).
4.3 Lee, B. I. and M. G. Kesler, Hydr. Proc. (July 1980), p. 163.
4.4 Whitson, C. H., SPE Jour. (Aug. 1983), p. 683.
4.5 Moshfeghian, M., http://www.jmcampbell.com/tip-of-the-month/2012/05/impact-of-non-hydrocarbons-on-the-reservoir-
fluids-phase-envelope/
CHAPTER 4 101
102
5
VAPOR-LIQUID EQUILIBRIUM BEHAVIOR
Many production/processing operations involve control of the phases present. Selected components
must be vaporized or condensed to achieve specified goals. For a given mixture’s fluid composition, the
phase envelope defines the vapor, liquid, and two-phase regions. Determination of the bubble and dewpoint
curves fixes the extent of the two-phase region. Within the two-phase region, it is necessary to predict
vapor-liquid ratio and the composition of both phases. The latter involves the concept of equilibrium.
“Equilibrium” is commonly used to describe a state wherein the progression of time has no effect
on system behavior. In a phase behavior context, the composition of the vapor and liquid in contact will
remain constant with time.
It takes time to reach equilibrium. In a typical hydrocarbon system, up to several minutes of contact
is required. Since the fluids are often intimately mixed in the piping upstream of the separator, it is usually
assumed that a separator should be treated as an equilibrium process.
In absorption and fractionation calculations, no true equilibrium exists because the vapor and liquid
are not in contact for a sufficient period. The assumption of equilibrium (made for convenience) must be
corrected by an efficiency factor.
The concept of equilibrium in a two-phase system does not mean that the system is static. There is
still a continuous transfer of molecules between phases. The rate of vaporization and condensation of all
molecular species is equal. Thus, no net change in composition occurs.
EQUILIBRIUM VAPORIZATION RATIO

It is convenient to represent equilibrium with an equilibrium vaporization ratio, Ki. This is defined by:
y
Ki = xi (5.1)
i
Where: Ki = equilibrium vaporization ratio of the component “i”

yi = concentration of the component “i” in the vapor phase
xi = concentration of the component “i” in the liquid phase
This Ki may be incorporated into a material balance around a separator (see Figure 5.1). Values
of zi, xi and yi are specified or found from sampling and the resultant analyses. Values of F, V, and L are
specified or measured (for an existing system).
CHAPTER 5 103
V, yi
Where: zi = mol fraction of any component
“i” in the feed stream to the
Overall Material separator
Balance: yi = mol fraction of any component
F=V+L “i” in the vapor phase
F, zi xi = mol fraction of any component
Component
“i” in the liquid phase
Material Balance:
Ki = equilibrium vaporization ratio
Fzi = Vyi + Lxi of the component “i” (equilib-
yi rium constant) = yi/xi
And: Ki = x
i F = total mols of feed
V = total mols of vapor
L, xi L total mols of liquid
Figure 5.1 Separator Equilibrium Vaporization
Partial Pressure Concept

At pressures up to about 400 kPa [60 psia], where ideal gas concepts apply, vapor pressure may be
used to find equilibrium behavior.
At equilibrium, the rate of vaporization of all components must
equal the rate of condensation so that no change occurs in vapor or liquid
composition. For this to occur, the driving force in both directions must
be equal. This driving force may be represented by a partial pressure (pp).
Dalton’s Law assumes the vapor phase is an ideal gas:
pp (vapor phase) = P yi
Where: P = operating pressure of the separator, or total pressure P yi
Assume the liquid phase is an ideal solution:

pp (liquid phase) = Pvixi
Where: Pvi = vapor pressure of any component at the P and T of
Pv xi
the separator
Assuming the vapor in equilibrium with the liquid is an ideal gas

(Dalton’s law) and the liquid and gas phases are both ideal solutions at
Figure 5.2 Partial Pressure
equilibrium results in Raoult’s law: Schematic
Pv
P y i = Pvi x i or Ki = P i (5.2)
Equation (5.2), applies anywhere within the phase envelope. It does not apply for the liquid water
phase in a hydrocarbon system, since water is essentially immiscible with liquid hydrocarbons (Chapter
6 will discuss this in detail). Equilibrium calculations for the hydrocarbon portion of the system are not
influenced to a measurable degree by the presence of water except at low pressures and high temperatures.

Equation (5.2) is a convenient way to estimate K at pressures below 300-400 kPa [45-60 psia].
Vapor pressure, Pvi, may be found from pure component vapor pressure data.
Fugacity Derived K Values

The term fugacity (f) is a conceptual term related to free energy and other basic thermodynamic
concepts. It has the units of pressure. Since it is one way to correct for non-ideal behavior and may be
related to compressibility factor z, it is sometimes referred to as a “corrected pressure.” Some correlations
are developed using fugacity coefficient (f/P), a convenient dimensionless term.
For a two-phase mixture at equilibrium, the fugacity of a component in the vapor is equal to the
fugacity of the component in the liquid because of the equality of partial Gibbs free energy, thus:
fiv = fiL (5.3)

Where: fiv = fugacity of component “i” in the vapor mixture
fiL = fugacity of component “i” in the liquid mixture
Fugacity is a thermodynamic property similar to enthalpy or entropy. Because it is a function of P,

T, and V it can be calculated from an EOS. For pure components, fugacities are often available in tabular
format as a function of P and T.
If the liquid and vapor fugacities are assumed to be proportional to the mol fraction of component
“i” in the phase, then:
fiv = y i f %iv (5.4)
f iL = x i f iL% (5.5)
Where: f iv% = fugacity of component “i” in the pure vapor state

f%
iL = fugacity of component “i” in the pure liquid state
These two assumptions are equivalent to saying that both the vapor and liquid phases of the mixture
are ideal solutions.
From substitution, Equations (5.3), (5.4) and (5.5) reduce to:
y i f iv% = x i f%iL (5.6)

Rearranging Equation (5.6):
y i f iL%
=
x i f iv% = K i (5.7)
Equation of State Method

As previously indicated, fugacity is a thermodynamic property that is related mathematically to P,
V, and T. Fugacity coefficients, {i and {i , are used, where {iL = fiL xi/P and {iv = fiv yi/P at equilibrium:
L v
{ (5.8)
fiv = fiL so K i = {iL
iv
CHAPTER 5 105
Fugacity coefficients can be calculated from Equation (5.9) where the P, V, T relationships are
provided by an Equation of State (PR, SRK, BWRS, etc.).
3
;a 2n k - V E dV - ln z
l 2P RT
ln{ i = RT # T,V,n j
(5.9)
v
This is the most common method of determining K values for hydrocarbon mixtures.
Activity Coefficients
A K value is a function of pressure, temperature, and composition. Of the two phases present,
liquid composition is the most critical. One difference between correlations is the method chosen to find the
coefficients used to characterize the liquid phase.
Equation of state methods, generally do a reasonably good job of determining vapor phase fugac-
ities. The liquid phase is more difficult, especially when the liquid contains dissimilar molecules. Polar
molecules like H2S, H2O, alcohols, and glycol are not easily handled. In these situations, the liquid phase
fugacity may be calculated from Equation (5.10).
fiL = f%iL x i c iL (5.10)
Where the activity coefficient, iL, is an empirically determined correction factor.

Standard thermodynamics may be used to relate the effect of temperature and pressure on activity
coefficient. The effect of composition is not so easy. The activity coefficient (iL ) of a component approaches
unity as the concentration of that component approaches 100%. It is expressible by the Margules, van Laar,
Wilson, or Renon type equations. The Hildebrand equations may be used to estimate activity coefficients
for nonpolar mixtures. The K value is then determined from Equation (5.11).
y f i% c i
K i = x i = PL{ (5.11)
i iv
The Chao Seader method is an example of a K value correlation that utilizes activity coefficients.
Stated simply, there is no one magic correlation or equation of state that works equally well for
all mixtures. The choice must be made by one who has experience with the use of a given calculation and
knows the kind of fit to be expected so adjustments can be made. This is not an area for those who know
how to use the computer and are only interested in obtaining output. Most problems resulting from the
use of K values result more from the persons developing and using them than from the weaknesses of the
calculations themselves.
There is only one true criterion for evaluating K values. How well do they match experimental or
field operating data? The first alternative is to use laboratory data for similar mixtures at similar conditions
(temperature and pressure) and compare the K values calculated from the data sets to the correlation K
values. Alternatively, for field operating data, analyze the vapor and liquid stream compositions. Calculate
the K values from the data and compare the operating K values with the correlation K values. This analysis
can be used to modify the correlation or develop alternative correlations to improve accuracy.
K Value Charts
The K value of any component depends on pressure, temperature, and the composition of the total
fluid. Many plots of log K versus P and T have been proposed. The effect of composition may be ignored
by making the plot for a specific group of components, with the exception of methane, at pressures less than
6.9 MPa [1000 psia]. The effect of composition on K usually is not significant considering other uncertain-
ties in the data.

A set of K values are summarized in the appendix at the end of this chapter. Appendix 5A is a series
of computer-generated charts using SRK equations. The values shown are useful particularly for the calcu-
lation of systems discussed in this book wherein liquid is being condensed from gas systems.(5.1)
The values in Appendix 5A will be used in all examples in this book to achieve internal consistency.
K Values for C6+ Fractions

Proper characterization of the C6+ (or C7+) fractions is important for accurately estimating the
phase behavior of hydrocarbon fluids. This was illustrated in Figure 4.8. The K values for these fractions are
typically calculated from an EOS using the approach summarized in this chapter. The C6+ (or C7+) fractions
are characterized using pseudocomponents based on the methods discussed in Chapter 3.
The number of pseudocomponents used to characterize the heavy fraction varies with the calcula-
tion application; e.g., design, debottlenecking, performance testing, etc., as well as the fluid composition and
system temperature and pressure. For low pressure, low GOR (gas-oil ratio) crude oil separation where gas
handling is minimal, one or two pseudocomponents may be satisfactory. For high pressure gas condensate
or volatile oil systems, as many as 15 to 20 pseudocomponents have been used. Fewer pseudocomponents
are required for design calculations than performance testing. In general, the number should be the smallest
amount necessary to adequately characterize system behavior. Uncertainties in flowrate, temperature, and
pressure often have a greater effect on the calculations than the number of pseudocomponents.
When provided with only a C6+ or C7+ lumped fraction with no detailed information about boiling
points, relative densities, or MWs of the subfractions, several techniques have been proposed for creating a
pseudo analysis of this lumped fraction to better predict K values.(5.2-5.6) The simplest approach assumes a
logarithmic distribution of the heavy molecules using carbon number cuts and attributing properties to each
cut, based on the parameters in Table 3.2, or less accurately, n-paraffin properties.
The calculation of the K value for the C6+ or C7+ fraction(s) will usually be done by computer, but
it is often useful to check the value for consistency using a manual, graphical method. These may also be
used for consistency checks on VLE data collected from separation vessels such as test separators. In these
applications, K can be calculated from measured data (Ki = yi/xi ). The empirically determined K values can
then be plotted against various parameters to check for consistency. Three methods are outlined below.
Ln K vs. Tc2
This plot is linear for almost all of the available hydrocarbon VLE data. This relationship serves two
practical purposes: (1) checking K values for internal consistency and (2) extrapolating pure component K
values to obtain the K of the heaviest fractions.(5.7)
Figure 5.3 is an example of the chart used. The abscissa is really Tc2 (where Tc is the critical tempera-
ture of a component in absolute units) but has been drawn to reflect the component and the molecular
weight of the heaviest fraction. It is used as follows:
a. Plot K values for each pure component at the equilibrium P and T of the system.
b. Draw the best straight line through the points for propane through hexane components.
c. If any K value points are not on the line, use the line values for any calculation.
d. Find the K value of the C7+ fraction from its molecular weight and the extrapolation of the line
from step b.
If the K values come from a computer program, the values may be converted into a straight line by
regression analysis since the equation of the straight line is log K = a + bTc2.
CHAPTER 5 107
Figure 5.3 Plot of ln K vs. Tc2
Example 5.1: Table 5.1 provides compositional data collected from a test separator on a gas well.
The separator conditions are at 1170 kPa nd 27.8°C [169.7 psia and 82°F]
* The vapor phase mol fraction of the C10 Decanes provided in Table 5.1 is actually
for the C10+ components.
The normal boiling points for the sample were not provided in the sample analysis,
so the values from Table 3.2 were used as estimates. In this case, this is acceptable as
the MW and specific gravities from the data are not significantly different than those
provided in Table 3.2.
The reservoir fluid analysis shown in Table 5.1 was determined based upon a separator
recombination analysis using the compositions and flow rates of the vapor and liquid
phase. The recombination analysis is not shown for Example 5.1, but an example of
the recombination procedure is provided in Example 5.8.
The critical constants for the pseudocomponents C6-C12 were calculated from a
process simulator.


Determine if the data is consistent using the ln K vs. Tc2 method.
Table 5.1
Test Separator Data
Data from
Reservoir Test Data Table 3.2
Component Separator Separator (Feed) K-Value
Gas Liquid Fluid NBP, NBP, Pc, Pc, from
(Symbol / Name) (mol%) (mol%) (mol%) MW sp. gr. °C °F Tc, °C Tc, °F kPa psia Test Data
N2 Nitrogen 0.665 0.027 0.624 28.0 24.6
CO2 Carbon Dioxide 2.769 0.299 2.612 44.0 9.26

H 2S Hydrogen Sulfide 0.000 0.000 0.000 34.1
C1 Methane 71.305 4.107 67.028 16.0 –161.5 -258.7 –82.6 –116.7 4599 667.0 17.4
C2 Ethane 12.067 3.477 11.520 30.1 0.364 –88.6 -127.5 32.3 90.1 4880 707.8 3.471
C3 Propane 6.361 5.026 6.276 44.1 0.507 –42.1 -43.73 96.6 205.9 4240 615.0 1.266
iC 4 i-Butane 1.034 1.756 1.080 58.1 0.563 –11.8 10.78 134.7 274.4 3640 527.9 0.589
nC 4 n-Butane 2.332 5.410 2.528 58.1 0.584 –0.5 31.08 151.9 305.5 3784 548.8 0.431
iC5 i-Pentane 0.783 3.616 0.963 72.2 0.624 27.8 82.11 187.2 369.0 3381 490.4 0.217
nC5 n-Pentane 0.903 4.536 1.134 72.2 0.631 36.1 96.9 196.5 385.7 3365 488.1 0.199
C6 Hexanes 0.680 8.277 1.164 86.0 0.664 63.9 147 231.0 447.8 3065 444.5 0.082
C7 Heptanes 0.583 10.656 1.224 95.2 0.701 91.9 197.5 261.8 503.2 2781 403.3 0.055
C8 Octanes 0.324 12.395 1.092 108.6 0.724 116.7 242 288.9 552 2575 373.5 0.026
C9 Nonanes 0.069 7.600 0.548 121.7 0.750 142.2 288 320.9 609.6 2461 357.0 0.009
C10 Decanes* 0.125 6.591 0.537 141.5 0.762 165.8 330.5 344.2 651.6 2267 328.8
C11 Undecanes 4.583 0.292 147 0.781 187.2 369 369.6 697.3 2183 316.6
C12 Dodecanes 3.357 0.214 161 0.792 208.3 407 390.6 735.1 2044 296.4
C13 Tridecanes 3.071 0.195 175 0.803 227.2 441
C14 Tetradecanes 2.505 0.159 190 0.814 246.4 475.5
C15 Pentadecanes 2.009 0.128 206 0.824 266.1 511
C16 Hexadecanes 1.477 0.094 222 0.831 283.3 542
C17 Heptadecanes 1.261 0.080 237 0.839 300.0 572
C18 Octadecanes 1.146 0.073 251 0.844 312.8 595
C19 Nonadecanes 0.989 0.063 263 0.849 325.0 617
C20 Eicosanes 0.737 0.047 275 0.854 338.1 640.5
C21 Heneicosanes 0.612 0.039 291 0.859 351.1 664
C22 Docosanes 0.529 0.034 305 0.864 363.3 686
C23 Tricosanes 0.460 0.029 318 0.869 375.0 707
C24 Tetracosanes 0.421 0.027 331 0.873 386.1 727
C25 Pentacosanes 0.373 0.024 345 0.876 397.2 747
C26 Hexacosanes 0.308 0.020 359 0.880 407.8 766
C27 Heptacosanes 0.273 0.017 374 0.884 417.8 784
C28 Octacosanes 0.248 0.016 388 0.887 427.8 802
C29 Nonacosanes 0.212 0.014 402 0.890 436.1 817
C30+ Triacontanes Plus 1.656 0.105 528 0.917
Total 100.0 100.0 100.0
Molecular Weight 24.22 123.31 30.54
CHAPTER 5 109

To simplify the chart, divide the Tc2 term by 100 000. Please note that the critical
temperatures must be in absolute units. The FPS solutions of the graphical valida-
tion methods for K values are not provided. The solution steps are the same as those
presented for the SI units.
From the data provided generate the graph as shown in Figure 5.4.
100.000
2
Tc /100 000 SI [FPS] K Values
C1 0.36 [1.2] 17.4

C1 C2 0.93 [3.0] 3.47
C3 1.37 [4.4] 1.27
10.000 iC4 1.66 [5.4] 0.589
nC4 1.81 [5.9] 0.431
C22
iC5 2.12 [6.9] 0.21
nC5 2.20 [7.1] 0.19*
Vapor Equilibrium K Values
C3
C6 2.54 [8.2] 0.080*
1.000 C7 2.86 [9.3] 0.030*
iC44
nC44
C8 3.16 [10.2] 0.022*
iC55 C9 3.53 [11.4] 0.009

nC5 *K Values from linear fit
C6
0.100
C77
C8
C9
0.010
0.001
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Tc2/100 000
Figure 5.4 ln K vs. Tc2 for Data from Example 5.1
Notice the plotted K values are linear which indicates that the data provided is of
consistent quality.
Example 5.2: Using Figure 5.4, estimate the K values for C10, C11, and C12.
SI Solution:
Calculate the Tc2/100 000 values for C10, C11, and C12:
C10 = 3.81 C11 = 4.13 C12= 4.40
Plot Tc2/100 000 values on figure to determine K values.

100.000
2 2
Tc /100 00 Tc /100 000 K Values
C1
C10 3.81 K 12.3 °R 0.005
10.000 C11 4.13 K 13.4 °R 0.002
C22 C12 4.40 K 14.3 °R 0.001

Vapor Equilibrium K Values
C3
1.000 iC44
nC44
iC55
nC55
nC6
0.100
nC77
nC8
nC9
0.010
CC1010
C11
11
C12
0.001
0.0 0.5 1.00
1.0 1.5 2.0 2.50
2.5 3.0 3.50
3.5 4.0 4.5 5.0
Tc2/100 000 [deg K]
Figure 5.5 ln K vs. Tc2 to Determine C10-C12 K-values
Using this approach the K values of the C10-C12 components can be estimated for
process calculations.
As demonstrated in Example 5.1 and Example 5.2, this method can be used to validate the data from
laboratory samples. This approach can also be used to validate compositional data from test separators. If the
data does not produce a linear relationship there is reason to suspect the data quality.
Use of a KP Plot
In this method, the relationship ln (KP) vs. b [(1/Tb ) – (1/T)] is plotted for those components for
which K values are known. This method can be used to check the validity of empirical data and to estimate
K values of heavy components. The boiling point for a given fraction may be estimated from Table 3.2, or
Figure 5.7. The value of “b” is found from the equation:
A 61n(Pc) - 1n (B)@
b= (5.12)
_1 Tbi - _1 Tci
Where: Pc = critical pressure kPa, [psia]
B= 100 kPa [or 14.50 psia]
A= 1.8 when T is in K
= 1.0 when T is in °R
Tb = boiling point K, °R
Tc = critical temperature K, °R
CHAPTER 5 111
Example 5.3: Develop the KP Plot for the data from Example 5.1.
Estimate the K values for C10, C11, and C12.
SI Solution:
Calculate b, b[(1/Tb ) – (1/T)] for C10, C11, and C12. Plot values of b[(1/Tb ) – (1/T)]
for C10, C11, and C12 on the KP Plot to determine ln(KP). Refer to Figure 5.6.
Table 5.2
KP Plot
Comp. b b[(1/Tb)-(1/T)] Comp. b b[(1/Tb)-(1/T)]
C1 1854 10.5 C6 6259 -2.2
C2 3259 6.8 C7 6878 -4.0

C3 4151 4.2 C8 7434 -5.6
iC4 4704 2.4 C9 7958 -7.3
nC4 4967 1.7 C10 8530 -8.9
iC5 5505 0.0 C11 8999 -10.4
nC5 5724 -0.5 C12 9517 -11.9
From the ln(KP) values provided from Figure 5.6, calculate K values for C10, C11 & C12:
e1n (KP)
K= =
P , where P 1170 kPa
Table 5.3
K-Values
ln(KP) K
C10 1.83 0.005
C11 1.22 0.003
C12 0.60 0.002
Notice that the KP Plot results in a linear relationship which indicates the data quality is good.
12.0
b[(1/Tb) – (1/T)] In(KP) K
C10 -8.9 1.83 0.005
C11 -10.4 1.22 0.003
10.0
C12 -11.9 0.60 0.002
8.0
ln[KP] – SI Units
6.0
4.0
2.0
-8.9
-10.4
-11.9
0.0
-15.0 -10.0 -5.0 0.0 5.0 10.0 15.0
b[(1/Tb) – (1/T)] – SI Units
Figure 5.6 KP Plot Used to Estimate C10-C12 K-Values (SI Units)

As demonstrated in Example 5.3, this is Atmospheric Boiling Point, °F

another method that can be used to validate the 50 100 150 200 250 300 350 400 450 500 550
data from laboratory samples or compositional 0.90
Liquid Relative Density, L (Water = 1.0)

data from test separators. If the method applied
to the data does not produce a linear relationship 0.85
then there is reason to suspect the quality of the

0.80
data.
0.75
Ln K vs. (1/Tb) 180
200
220
160
This is approximately a straight line 0.70
140
t
120
for the heavier components. It is simple to use eigh
lar W
0.65
100 lecu
Mo
although it has been superseded by methods 1 80 90
and 2. It may be extrapolated to the Tb of the
70
0.60
heaviest fraction, where Tb is the boiling point 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
in absolute units at atmospheric pressure. Atmospheric Boiling Point, °C
Figure 5.7 Another Correlation for Estimating

Hydrocarbon Boiling Point
VAPOR-LIQUID EQUILIBRIUM (VLE) CALCULATIONS

Three different calculations are required to define vapor-liquid phase behavior: (1) a bubblepoint
calculation to define that portion of the phase envelope, (2) a dewpoint calculation for the remaining portion,
and (3) a flash calculation at any P and T inside the phase envelope.
In the discussion that follows, the K values from Appendix 5A will be used in all examples.
Bubblepoint
The bubblepoint may be defined as that condition at which the system is all liquid with one (infinites-
imally small) bubble of vapor present. The composition of the liquid is essentially equal to the composition
of the total system. By definition, the sum of the mol fraction of all components must add up to unity in both
vapor and liquid. It follows that at equilibrium:
/ K i x i = / y i = 1.0 (5.13)
The procedure to determine the bubblepoint for a system of known composition is:
1. Assume a temperature for the known pressure (or assume pressure if temperature is known).
2. Find Ki at pressure and temperature from Step 1.
3. Multiply Ki from Step 2 by corresponding xi.
4. If summation of values from Step 3 is 1.0, the correct pressure or temperature was assumed. If
not, repeat Steps 1-3 until ΣKixi = 1.0.
Note: You can use mol percent instead of mol fraction for xi, in which case Equation (5.13)
sums to 100 instead of 1.0.
CHAPTER 5 113
Example 5.4: Determine the bubblepoint temperature of the mixture shown at 4.0 MPa [580 psia],
assuming that the C7+ fraction has the properties of C8.
Comp. xi Ki K i xi = yi This solution shows the final

CO2 1.25 1.50 1.88 iteration at T = –14°C [7°F].
Since percentages rather than
H 2S 0.50 0.41 0.21
mol fractions are used, the right-
C1 21.36 3.48 74.33 hand column should sum to 100.
C2 36.78 0.58 21.33
C3 10.21 0.16 1.63

iC4 6.38 0.063 0.40
nC4 9.84 0.043 0.42
iC5 2.63 0.017 0.04
nC5 4.01 0.012 0.048
C6 3.90 0.0036 0.014
C7+ 3.14 0.000 33 0.001
R K ixi = 100.30
The composition used in Example 5.4 is predominately NGL components. The methane concentra-
tion is low. Notice that in spite of this, methane is the largest number in the bubblepoint Kixi column. The
concentration of the lightest components have the greatest effect on bubblepoint calculations.
This calculation is iterative and tedious for hand-calculations, which are seldom done today.
Equations of state use the same principles in determining the bubblepoint of the fluid.
The primary application of the bubblepoint calculation is to estimate the bubblepoint pressure (vapor
pressure) of a hydrocarbon mixture. This is frequently done in the evaluation of fractionation and product
storage systems.
Dewpoint
The dewpoint is defined as an all-vapor system except for one small droplet of liquid. In this case, the
system composition, zi, is equal to that of the vapor, yi. So,
/ (y i K i) = / x i = 1.0 (5.14)
Example 5.5 shows the results of a dewpoint calculations for the hydrocarbon mixture in Example
5.4.
Notice, the heptanes plus have the largest effect on the dewpoint calculation. This quantity is the least
accurate, both with respect to composition and properties. A dewpoint calculation is therefore inherently less
accurate than a bubblepoint calculation, particularly for lean gases containing only a small quantity of these
heavy components.
The primary application of a dewpoint calculation is to estimate the point at which liquid hydrocar-
bons will condense from a vapor. This is frequently done in gas pipelines, heat transfer, and fractionation
calculations.

Example 5.5: Determine the dewpoint temperature of the mixture shown at 4.0 MPa [580 psia],
assuming the C7+ fraction has the properties of C8.

Comp. yi Ki yi /K i = xi
The solution shows the final
CO2 1.25 4.83 0.26 iteration at a temperature of
H 2S 0.50 2.38 0.21 153°C [307°F].
C1 21.36 6.36 3.36
C2 36.78 2.84 12.95

C3 10.21 1.57 6.50
iC4 6.38 1.02 6.25
nC4 9.84 0.86 11.44
iC5 2.63 0.55 4.78
nC5 4.01 0.49 8.18
C6 3.90 0.28 13.93
C7+ 3.14 0.097 32.37

R yi/K i = 100.23
Flash Calculation
The purpose of the flash calculation on a two-phase system is to establish the amounts of vapor
and liquid, and the composition of each phase. Figure 5.1 shows a schematic of an equilibrium separation.
Overall Material Balance F = V+L (5.15a)

Component Material Balance Fz i = Vy i + Lx i (5.15b)
For convenience, F = 1 and L and V are liquid and vapor fractions. Equation (5.15b) becomes
zi = yiV + xiL by definition of the equilibrium constant, yi = Kxi. Substituting accordingly and rearranging
the terms results in the following equations:
z zi
xi = + i , yi = (5.16a)
L VK i V + (L K i)
The sum of all the mol fractions in any stream must equal 1. Thus, algebraically,
zi zi
/ xi = / = 1.0 , / y i = / = 1.0
L + VK i V _L K ii
+ (5.16b)
By assuming an L or V, you may solve Equations (5.16b) or (5.16b) iteratively. Convergence is

obtained in when Σxi or Σyi = 1.0. Thus, the compositions of the streams as well as the quantities may be
calculated.
Another objective function is (Σyi – Σxi) = 0. This results in Equation (5.17).
z i (K i - 1)
/ yi - / xi = / =0 (5.17)
V(K i - 1) + 1
CHAPTER 5 115
Equation (5.17) is the most common objective function used in computer programs.
The basic calculation procedure for a flash is:
1. Find K at the pressure and temperature of the two-phase system (separation conditions).
2. Assume V or L.
3. Solve the flash equation (Equations (5.16a), (5.16b) or (5.17)).
4. If the objective function is satisfied, calculation is complete. If not, repeat Steps 2-4.
5. Calculate xi and yi from Equations (5.16a) or (5.16b).
Example 5.6 shows the results of a flash calculation.
Example 5.6: Calculate the analyses and quantities of vapor and liquid for a flash at 4.0 MPa
[580 psia] and 100°C [212°F]. Use the K values in Appendix 5A.
Comp. zi Ki Syi – Sxi xi yi
CO2 1.25 4.050 1.139 0.373 1.512
H 2S 0.50 1.740 0.236 0.319 0.554
C1 21.36 5.950 21.974 4.439 26.413’
C2 36.78 2.160 22.535 19.427 41.962
C3 10.21 1.030 0.299 9.979 10.279
iC4 6.38 0.600 –3.688 9.220 5.532
nC4 9.84 0.490 –8.264 16.203 7.940
iC5 2.63 0.280 –4.250 5.903 1.653
nC5 4.01 0.240 –7.348 9.668 2.320
C6 3.90 0.120 –10.646 12.098 1.452
C7+ 3.14 0.031 –11.987 12.370 0.383
Σ 0.000 100.000 100.000
The first step is to assume a V or L. This table reflects the final iteration for
V = 0.770.
Accuracy of Equilibrium Calculations

The accuracy of calculations involving K values depends on the reliability of the sampling, the
compositional analysis of that sample, and on the K value correlation used.
Different equations of state yield different K values. A VLE calculation involves solving equations
of state, which requires the use of combination rules. Binary interaction parameters are determined by
fitting the equation of state to mixture vapor-liquid equilibrium data. Thus, the accuracy of an equation
of state applied to a fluid composition is dependent upon the underlying data. As with z, H, S, and other
quantities, there is no one correlation that fits all systems equally well.
So as long as the molecules involved are similar, the problem of fitting is relatively routine.
Predicted values for the normal paraffins (ethane through decane) are usually quite reliable. Methane poses

a problem because of its high vapor pressure and unusual behavior in the liquid phase. Nitrogen poses a
similar problem. One can likewise correlate values for the aromatics and napthenes. Hydrogen sulfide,
water, and carbon dioxide act differently from hydrocarbons because of their polarity.
If you have a mixture containing many, or all, of the previous components, the behavior is rather
complex. As noted in Chapter 3 for other properties, special correlations are necessary for some mixtures.
All K values are sensitive to composition, particularly volatile components like nitrogen, methane
and ethane. In correlations like those shown in Appendixes 5A, the potential error in K for nitrogen and
methane may be large.
For design purposes, several models may be used to determine a range of results. This range, rather
than one set of numbers, is then used to specify equipment. The name of the game is flexibility. It is unlikely
the composition, flow rates, temperature and pressures used as the design basis will occur.
It is important that the K values be internally consistent. This can be checked with the methods
outlined earlier in this chapter.
Table 5.4 shows a comparison of results from a low temperature calculation using several K value
correlations. Other comparisons can be found in the literature.(5.8) Comparisons like these should be made
for your specific systems to establish a range of possible conditions.
Table 5.4
Comparison of Experimental and Predicted Liquefaction
Weight % Condensed
Total Total Total Total Total Total
Liquid Ethane Propane Liquid Ethane Propane
–48°C & 6895 kPa [–55°F & 1000 psia] –57°C & 6895 kPa [–70°F & 1000 psia]
Experimental 17.12 25.6 45.3 33.8 44.6 57.1
BWRS 18.16 28.0 47.4 32.5 44.1 57.7
Peng-Robinson 18.67 29.2 51.1 31.0 44.7 62.2
GPA SRK 19.01 29.9 52.0 31.2 45.1 63.0
–51°C & 6210 kPa [–60°F & 900 psia] –73°C & 3450 kPa [–100°F & 500 psia]
Experimental 19.02 30.9 56.4 23.23 52.1 85.4
BWRS 19.57 32.3 56.5 24.7 55.5 86.7
Peng-Robinson 19.66 32.8 58.9 24.9 56.6 87.9
GPA SRK 19.83 33.3 60.2 24.5 56.1 88.2
STAGE SEPARATION
Flash stabilization is the most common method
V1 V2 V3
of stabilizing crude oil and condensate.
F1 F2 F3 Several stages of separation are often used as
Stock
Tank shown in Figure 5.8. This is classified as either two-stage
or three-stage separation, depending on whether the
L1 L2 L3 stock tank is considered a stage. Most systems consist of
Figure 5.8 Two-Stage (or Three-Stage) Separation two-separator stages, but three or more may be used in
selected instances. Increasing the number of intermedi-
CHAPTER 5 117
ate separation stages increases total liquid production, although the increase may be relatively small beyond
three stages. It also increases system complexity and capital cost.
The first-stage pressure is normally fixed by well inflow performance considerations and/or sales
gas requirements. It is seldom greater than 13.8 MPa [2000 psia]. The stock tank pressure will be at, or near,
atmospheric pressure and is fixed by temperature and crude oil vapor pressure specification. Intermediate
stage pressures can be adjusted to yield maximum liquid recovery at stock tank conditions.
Intermediate pressures can be optimized by a series of flashes. The flash in stage one (High Pressure
Separator) fixes the analysis and quantity of liquid leaving, which is the feed to stage two (Medium Pressure
Separator). A corresponding flash on stage two gives stock tank feed if a three stage system is being used.
The “stock tank” can actually be an atmospheric tank or an enclosed, low pressure separation vessel.
A flash is normally performed on this vessel; however, for atmospheric, fixed-roof tanks, the actual process
is some combination of differential vaporization, weathering and breathing losses.
10
Export Gas
Cooler
Gas Export
Scrubber
MP Suction
Scrubber
MP Flash Gas LP Suction

2 Scrubber
Compressor
MP
1 Compressor
Suction Cooler
60˚C LP Flash Gas
[140˚F] Compressor LP Compressor
HP Suction Cooler
Separator
7000 kPa
[1015 psia] 4
3
MP
Separator
6 ST Flash Gas
60°C Compressor
[140°F] 5
LP
2500 kPa Separator
[363 psia]
8
58°C
[136°F] 7
ST
600 kPa Separator
[87 psia]
HP = High Pressure 9
MP = Medium Pressure 52°C
[125°F]
LP = Low Pressure 132 kPa
ST = Stock Tank [19 psia] Crude Oil
Product
Figure 5.9 Stage Separation System

Another important factor to consider in optimizing stage separation pressures is compression ratio.
In virtually all crude oil stabilization systems today, flaring is not allowed. As a result, separator flash gas
(in many cases this includes the stock tank vapors) must be compressed. Compression ratio is limited
by compressor type and gas properties. Generally, the maximum compressor discharge temperature is
150-160°C [302-320°F]. For hydrocarbon gases with a relative density of 0.6 to 0.7 and a suction tempera-
ture of 40°C, the compression ratio is limited to about 3.0-3.5. For heavier MW gases, typical of those
flashing from the low pressure separators, the maximum compression ratio may approach 5.0.
The disposition of the compressor scrubber liquids is another consideration in the design of stage
separation systems. As the flash gas from each separator is compressed and subsequently cooled, liquids
condense from the gas. These liquids are frequently recycled back to a lower pressure separation stage
which is the simplest way of handling the disposition of these liquids. However, due to the scrubber liquids
recycle, the compression power increases over that required without recycle because a portion of these
scrubber liquids flash to gas and must be re-compressed. Depending on the crude oil vapor pressure speci-
fication and the gas export conditions (T, P), propane and butane molecules often are “trapped” in the
recycle loop. This effect can significantly increase compression power. Figure 5.9 shows a 4-stage separa-
tion system including recycle of compressor scrubber liquids. Separator temperatures and pressures are also
shown. In the 4-stage example considered here, recycling scrubber liquids increases the compressor power
to 3720 kW [5000 hp] from 3068 kW [4150 hp], or 21%. Table 5.5 provides an example material balance
for the system shown in Figure 5.9.
Another consideration in recycle systems is the cooling effect of the scrubber liquids as they are
flashed into a separation stage. This may require additional heating on the Stock Tank Separator (4th Stage
Separator) to meet the crude oil vapor pressure specification. Figure 5.10 provides example phase envelopes
for the 4-stage separation system shown in Figure 5.9.
CHAPTER 5 119
Table 5.5
Summary Material Balance for 4-Stage Separation System Shown in Figure 5.9
Vapor Streams Liquid Streams

1 2 4 6 8 10 3 5 7 9
HP MP LP ST Export HP MP LP ST
Mol % Feed Vapor Vapor Vapor Vapor Gas Mol % Liquid Liquid Liquid Liquid
N2 0.522 0.956 0.481 0.121 0.008 0.794 N2 0.097 0.017 0.001 0.000
CO2 0.948 1.291 1.806 2.072 0.797 1.438 CO2 0.612 0.365 0.112 0.010
C1 50.395 83.518 74.456 41.819 6.673 76.709 C1 17.936 6.270 0.895 0.032
C2 5.279 6.309 9.780 15.584 9.717 7.925 C2 4.270 3.143 1.438 0.211
C3 5.944 4.574 8.097 22.452 32.616 7.872 C3 7.286 7.155 6.100 2.244
iC4 0.978 0.496 0.861 2.873 6.598 0.936 iC4 1.450 1.580 1.732 1.051
nC4 3.476 1.454 2.508 8.646 22.565 2.713 nC4 5.457 6.097 7.033 4.923
iC5 1.439 0.375 0.597 1.998 6.487 0.562 iC5 2.481 2.880 3.444 3.116
nC5 1.638 0.364 0.566 1.851 6.248 0.498 nC5 2.886 3.374 4.004 3.815
C6* 2.138 0.234 0.324 0.933 3.373 0.228 C6* 4.004 4.767 5.376 5.800
C7* 3.968 0.293 0.387 1.064 3.859 0.248 C7* 7.569 9.051 10.011 11.090
C8* 3.700 0.080 0.088 0.214 0.732 0.051 C8* 7.247 8.718 9.444 10.688
C9 * 2.853 0.028 0.028 0.062 0.201 0.015 C9 * 5.621 6.767 7.323 8.288
C10* 2.211 0.014 0.013 0.027 0.083 0.007 C10* 4.364 5.254 5.685 6.433
C11* 1.646 0.006 0.005 0.010 0.029 0.002 C11* 3.253 3.916 4.238 4.794
C12* 1.325 0.002 0.002 0.003 0.009 0.001 C12* 2.621 3.155 3.415 3.862
C13* 1.326 0.001 0.001 0.001 0.003 0.000 C13* 2.624 3.158 3.417 3.865
C14* 1.119 0.000 0.000 0.000 0.001 0.000 C14* 2.215 2.666 2.885 3.263
C15+* 9.095 0.000 0.000 0.000 0.000 0.000 C15+* 18.008 21.666 23.447 26.515
Total 100.0 100.0 100.0 100.0 100.0 100.0 Total 100.0 100.0 100.0 100.0
MW 74.80 20.44 22.97 33.92 52.45 22.14 MW 128.1 149.5 160.6 175.1
Flowrate Flowrate
106 std 5.675 2.81 0.49 0.34 0.29 3.88 m3/d 21 841 19 209 18 355 17 390
m3/d
MMscfd 200 99.42 17.44 11.97 10.22 137.44 bpd 137 379 120 826 115 451 109 383
Temperature Temperature
oC 60 60 60.5 58 52 45 oC 60 60.5 58 52
oF 140 140 140.9 136 125 113 oF 140 140.9 136 125
Pressure Pressure
kPa 7000 7000 2500 600 133 7000 kPa 7000 2500 600 133
psia 1015 1015 363 87 19 1015 psia 1015 363 87 19
Note: * indicates modeled as pseudo components.
Note: 1 The standard volumetric flowrate of stream 1 includes both the vapor and liquid rates on an overall
molar basis

Temperature °F
-200 -100 0 100 200 300
14 000 2000
MP Sep Vapor
12 000 1750
HP Sep Vapor LP Sep Vapor 1500

10 000
HP Sep Op Point
MP Sep Op Point 1250
Pressure, psia
Pressure kPa
8000 LP Sep Op Point

ST Sep Op Point
1000
6000 ST Vapor
750
4000
500
2000
250
0 0
-150 -100 -50 0 50 100 150 200
Temperature °C
Figure 5.10 Example Phase Envelopes for 4-Stage Separation System
Figure 5.11 shows the crude production and compressor power requirements plotted against the
number of separation stages for the system shown in Figure 5.9.
Note on Figure 5.11 that liquid production increases with the number of separation stages and
compression power decreases. On the other hand, both capital cost and system complexity increase with
the number of stages. How many stages would be used in this example? The answer would be 3 or 4,
depending on equipment costs, operating costs, facility location, and value of liquid product.
The optimum number of stages required for separation is a function of the inlet separator (High
Pressure Separator) pressure. Table 5.6 provides some general guidelines for the number of stages of
separation for a given inlet pressure range.
30 000 18 000
Table 5.6
Stage Separation Guidelines Production with uids
ber Liq
Stabilized Crude Production, m3/d
25 000
Recycle of Scrub
17 500
(excluding Stock Tank) u t
t
o u
Compression Power, kW
tiioonn w witithhobeerr LLiiqquuiids

ds
20 000
duucct Sccrruubbb 17 000
Inlet Separator Inlet Separator Number of PPrroodyyccllee ooff S
Pressure, kPa Pressure, psia Stages RReecc
15 000 16 500
175-850 25-125 1
Power Required with
850-3500 123-508 2 10 000 Recycle of Scrubber Liquids 16 000
3500-6900 508-1000 3
5000 15 500
Greater than Greater than 4 Power Required without
6900 1000 Recycle of Scrubber Liquids
0 15 000
1 2 3 4
Separation Stages
Figure 5.11 Liquid Production and Compression Power

vs. Number of Separation Stages
CHAPTER 5 121
CONVERSION CALCULATIONS
In making equilibrium calculations, it is often necessary to convert or combine quantities when
performing VLE calculations.
Conversion Between Liquid, Mol or Mass

Analyses are given normally in mol percent, but it is sometimes necessary to convert to mass
percent or liquid volume percent. NGL product specifications are often written in mass or liquid volume
units. In addition, product prices are seldom stated in mol units. The procedure is illustrated in Example 5.7.
Example 5.7:
(1) (2) (3) (4) (5) (6) (7)
Liquid
Comp. Mol % MW (1) × (2) Mass % Liq Rel. t (3)/(5) Vol. %
C1 5.40 16.04 86.6 0.74 0.3 289 1.78
C2 6.98 30.07 209.9 1.80 0.3564 589 3.63
C3 12.54 44.10 553.0 4.74 0.5057 1090 6.72
iC4 5.38 58.12 312.7 2.68 0.563 555 3.42
nC4 6.42 58.12 373.1 3.20 0.5841 639 3.94
C5+* 63.28 160 10 125 86.83 0.775 13 064 80.51
R = 100.00 R = 11 660 100.00 R = 16 226 100.00
* MW = 160, gL = 0.775
Column (3) is the mass (in kg or lbm) corresponding to the mols in Column (1). Column (4)
is simply each entry in Column (3) divided by the total of that column. Column (6) is each mass entry
in Column (3) divided by relative density to find the equivalent volume. Each entry in Column (6)
divided by its total gives the values shown in Column (7).
Well Stream Test Separator Recombination

A common way to sample a two-phase stream is to use a test separator. The compositions and flow
rates of both the liquid and vapor streams are measured. These results may then be recombined to form a
composite (or total) stream analysis.
Flow rates should be expressed in mass units before they can be added. Since no chemical reaction
is occurring, the mol is a convenient mass unit. Example 5.8 illustrates the procedure.

Example 5.8: A well stream test separator operates at the conditions shown below:
SI FPS
Gas flowrate = 67 800 std m3/d 2.40 MMscfd
Pressure = 6.9 Mpa 1000 psia
Temperature = 46°C 115°F
GOR = 2335 std m3/m3 13 140 scf/Bbl
Relative density of separator liquid = 0.7
MW of separator liquid = 80.6
Using composition in the table below calculate the well stream composition.
Component Vapor mol% Liquid mol%

C1 89.46 20.22
C2 5.41 6.56
C3 3.10 11.16
iC4 0.55 4.45
nC4 0.78 7.08
iC5 0.22 4.65
nC5 0.12 3.37
C6 0.26 10.33
C7 0.10 32.18
R = 100.00 100.00
Basis
SI units 1 000 000 sm3 Liquid rate = 1 000 000/2335 = 428 m3 = (428)(700)/80.6 = 3717 kmol
FPS units 1 000 000 scf Liquid rate = 1 000 000/13140 = 76.1 Bbl = (76.1)(350)(0.7)/80.6 =
231 lb-mol
SI Units:
(3) (5)
(1) (2) kmol (4) kmol liquid (6) = R(3)+(5) (7)
Comp. Mol % Gas 10 6 std m 3 Mol % Liq. 10 6 std m 3 Well Stream Mol %
C1 89.46 37 843 20.22 752 38 595 83.86
C2 5.41 2288 6.56 244 2532 5.50
C3 3.10 1311 11.16 415 1726 3.75
iC4 0.55 233 4.45 165 398 0.87
nC4 0.78 330 7.08 263 593 1.29
iC5 0.22 93 4.65 173 266 0.58
nC5 0.12 51 3.37 125 176 0.38
C6 0.26 110 10.33 384 494 1.07
C7 0.10 42 32.18 1196 1239 2.69
100.00 42 300 100.00 3717 46 021 100.00
CHAPTER 5 123
FPS Units:
(3) (5)
(1) (2) lb - mol vapor (4) lb - mol liquid (6) = R(3)+(5) (7)
Comp. Mol % Gas MMscf Mol % Liq. MMscf Well Stream Mol %
C1 89.46 2357 20.22 47 2404 83.87
C2 5.41 143 6.56 15 158 5.50
C3 3.10 82 11.16 26 108 3.75
iC4 0.55 14 4.45 10 25 0.86

nC4 0.78 21 7.08 16 37 1.29
iC5 0.22 6 4.65 11 17 0.58
nC5 0.12 3 3.37 8 11 0.38
C6 0.26 7 10.33 24 31 1.07
C7 0.10 3 32.18 74 77 2.69
100.00 2635 100.00 231 2866 100.00
The SI tabulation and the corresponding FPS unit tabulation are based on the same principle. Columns
(2) and (4) are the gas and liquid analyses from sampling. Multiplying each number in Column (2)
by 42 300 gives the number of mols of each component per million std cubic meters of gas shown in
Column (3). Multiplying each number in Column (4) by 3717 kmol oil/million std cubic meters gives
the numbers shown in Column (5).
Cols. (3) and (5) may now be added (for they are on the same basis) to obtain Col. (6). Dividing each
entry in Col. (6) by its total gives the desired mol fraction analysis of the well stream.
Basic Conversion Factors

SI UNITS 100 000 N/m2 = 100 000 Pa = 1.02 kg/cm2 = 100 kPa = 1 bar
Standard Conditions: 15°C and 101.325 kPa
1 000 000 std m3 = 106 std m3 = 42 300 kmol
There are 23.64 std m3/kmol and 42 300 kmol/106 std m3 (@ 15°C and 101.325 kPa)
Density of gas at 15°C and 101.325 kPa = (γg)(1.22)
1 m3 = 1000 liters; 1 liter = 1000 cm3
1 g/cm3 = 1000 kg/m3
FPS UNITS Standard Conditions: 60°F and 14.696 psia (This Text)
1 000 000 std cu ft = 1 MMscf = 2635 lb-mol
There are 379.5 std ft3/lb-mol at 60°F and 14.696 psia
Density of air at 60°F and 14.7 psia = 0.076 4 lb/ft3
1 ft3 = 7.48 U.S. gal = 6.23 U.K. gal
1 bbl = 42 U.S. gal = 35 U.K. gal = 5.61 ft3
CONVERSIONS BETWEEN UNITS
1 std ft3 (@ 60°F and 14.696 psia) = 0.028 25 std m3 (@ 15°C and 101.325 kPa)
1 std m3 (@ 15°C and 101.325 kPa) = 35.4 std ft3 (@ 60°F and 14.696 psia)
1 bbl = 159 L = 0.159 m3
1 m3 = 35.31 ft3 liquid = 264 U.S. gal = 220 U.K. gal = 6.29 bbl
1 L = 0.264 U.S. gal = 0.22 U.K. gal = 0.0353 ft3

LIQUID PRODUCT VAPOR PRESSURE SPECIFICATIONS

For crude oil, condensate and C5+ NGL mixtures the vapor pressure specification, with few excep-
tions, is at or below one atmosphere at a specified temperature. If stage separation (similar to that in Figure
5.9) is used the temperature and pressure of the final separation stage will determine the vapor pressure
of the product. If a crude oil or condensate stabilizer is used, the vapor pressure of the product will be
determined by the stabilizer column bottom conditions. Likewise, if the product is a C5+ NGL mixture the
vapor pressure will be determined by the debutanizer bottom conditions.
The purpose of a “near atmospheric” vapor pressure specification is to facilitate the storage and
transportation of the product due to pressure and emission limitations on storage tanks, rail cars and marine
tankers. Vapor pressure specifications are typically stated in one of two ways:
1. True Vapor Pressure (TVP): the true vapor pressure is the actual vapor pressure of the product
at a specified temperature and is measured with a sample cylinder as shown in Figure 5.13.
TVP specifications must always be referenced to a temperature, which frequently falls be-
tween 30-50°C [86-122°F]. TVP is difficult to measure and depends on the ratio of the vapor to
liquid, V/L, in the measurement device. If V/L = 0, the vapor pressure is essentially equivalent
to the bubblepoint of the mixture which is the highest vapor pressure value for the liquid. As
V/L increases, i.e., a small amount of vapor exists at the point of measurement, the measured
vapor pressure will decrease. The relationship between the measured TVP and V/L depends on
the composition of the mixture. For “near pure” component mixtures, V/L has little effect on
the measured vapor pressure. For mixtures with a large composition range, such as crude oil or
condensate, the effect of V/L on the measured vapor pressure can be significant. The following
standards are used for vapor pressure measurement:
TVP Measurement Standards:
ISO 8973:1997, Liquefied petroleum gases — Calculation method for density and
vapour pressure
ISO 4256:1996, Liquefied petroleum gases — Determination of gauge vapour pressure
— LPG method
ASTM D1267 — 12, Standard Test Method for Gage Vapor Pressure of Liquefied
Petroleum (LP) Gases (LP-Gas Method)
ASTM D6377 — 10, Standard Test Method for Determination of Vapor Pressure of
Crude Oil: VPCRx (Expansion Method)
ASTM D6897 — 09, Standard Test Method for Vapor Pressure of Liquefied Petroleum
Gases (LPG) (Expansion Method)
ASTM D4953 — 06(2012), Standard Test Method for Vapor Pressure of Gasoline and
Gasoline-Oxygenate Blends (Dry Method)
ASTM D5482 — 07(2013), Standard Test Method for Vapor Pressure of Petroleum
Products (Mini Method—Atmospheric)
2. Because of the difficulty in accurately measuring TVP, an alternative method of measuring
vapor pressure is frequently used. This is the Reid Vapor Pressure or RVP. The RVP is a stan-
dard test set out in ISO 3007:1999, Petroleum products and crude petroleum – Determination
of vapour pressure – Reid method. Another standard that applies to RVP is: ASTM D323 – 08,
CHAPTER 5 125
Standard Test Method for Vapor Pressure of Petroleum Products (Reid Method). The vapor
pressure is measured in a RVP Sample Cylinder shown in Figure 5.12. The RVP test is appli-
cable for crude oils, condensates, and petroleum products such as gasoline (petrol) mixtures.
A liquid sample is collected in the lower 20% chamber. The 80% chamber, which is filled with
air at atmospheric pressure, is connected to the 20% chamber. The connecting valve is opened
and the cylinder is inserted into a water bath at 37.8°C [100°F]. The pressure indicated on the
gauge is the RVP.
Figure 5.14 provides a conversion for RVP to TVP for motor gasoline (petrol) and natural
gasoline (C5+ NGLs) at various temperatures. Figure 5.15(5.8) is a nomograph that shows the
approximate relationship between RVP and TVP for crude oil. It is commonly used for convert-
ing RVP to TVP at custody transfer points where the vapor pressure specification for the oil is
a TVP, but the actual vapor pressure measurement is an RVP.
Example 5.9: A gas processing plant recovers a stabilized C5+ NGL product. It has been determined
that the product should have a TVP less than 96.5 kPa [14 psia] at 40°C [104°F] which
is the maximum expected temperature in a storage vessel. What RVP specification is
equivalent to the TVP specification?
From Figure 5.14a & b the RVP is 83 kPa [12 psi].
Certified Test Gauge Certified Test Gauge
TVP Bleed Valve
RVP Cylinder LPG Cylinder
80% Air Chamber 80% Air Chamber
20% Liquid
Sample Chamber
20% Chamber
Figure 5.12 Schematic of an RVP Sample Cylinder Figure 5.13 Schematic of an LPG Sample Cylinder
Figure 5.15 is a nomograph for crude oils that has been modified from one issued by the API. It is
used commonly for accepting crude oil shipments. Many purchasers have specifications on such a shipment to
prevent loss of liquid in storage tanks. The temperature and RVP of the oil are measured at the transfer point.
Figure 5.15 is then used to determine true vapor pressure to ascertain if that shipment fulfills contract specifi-
cations. Tanker imports of crude oil must often have an RVP limit of 69-76 kPa [10-11 psi].

Temperature, °C
-15 -10 -5 0 5 10 20 30 40 50 60 70 80 90
100
90 600
80
70 500
60 400
Natural Gasolines
50
300
40
30 i]
ps i] 200
3 4 s
a [ 0 p i]
kP a [3 6 ps i]
4 s
23 6 kP a [2 2 p i]
P
Motor Gasolines
20 9 k a [2 ps
20 17 2 k P [ 18
a i]
15 kP ps
4 1 4
d 12 a[
ho kP
eitd
True Vapor Pressure, psia
True Vapor Pressure, kPa

RMe 9 100
iyd
]Reb 90
b°Fy
1°0F0] 80
0[ i]
C0 ps
10 8[°1
°3C [ 8 psi]
70
9 3=8 a
kP a [7 psi
]
tT =T 55 kP [6
60
8 eat
a si]
urer 48 kPa [5 p
ssus 41 kPa 50
7 eres
rPPr
or 34
6 ppo
Va 40
5
30
4
90 kPa [13 psi]
83 kPa [12 psi]
3 76 kPa [11 psi]
20
69 kPa [10 psi]
62 kPa [9 psi]
10
9
8
1 7
0 10 20 30 40 50 60 70 80 90 100 120 140 160 180 200
Temperature, °F
Figure 5.14 Vapor Pressures vs. Temperature for Typical C5+ NGLs
CHAPTER 5 127
Figure 5.15 Reid Vapor Pressure vs. True Vapor Pressure for Crude Oil

Example 5.10: From Figure 5.15, estimate the RVP of the product crude from the Summary Mate-
rial Balance for 4-Stage Separation System presented in Table 5.5. The stock tank
operating conditions are:
T = 52ºC [125ºF], P = 133 kPa [19 psia]
SI Solution:
On Figure 5.15, locate 52ºC on the right temperature axis. Locate 133 kPa on the left
pressure axis. Draw a straight line between the operating conditions and read a RVP
of 69 kPa.
FPS Solution:
On Figure 5.15, locate 125ºF on the right temperature axis. Locate 19 psia on the left
pressure axis. Draw a straight line between the operating conditions and read a RVP
of 9.9 psia.
REFERENCES
5.1 Maddox, R. N., private communication.
5.2 Lohrenz, J., et al., Trans. AIME, Vol. 228 (1963), p. 1233.
5.3 Jacoby, R. H. and V. J. Berry, Ibid., Vol. 213 (1958), p. 59.
5.4 Lohrenz, J. and B. Bray, Ibid., Vol. 231 (1964), p. 1171.
5.5 Erbar, J., GPA Report RR-13 (1976).
5.6 Whitson, C. H., SPE Jour. (Dec. 1984), p. 685.
5.7 Galimberti, M. and J. M. Campbell, Proc. GPA (1969).
5.8 White, W., et al., Oil and Gas J. (May 4, 1970), p. 121.
CHAPTER 5 129
APPENDIX
APPENDIX 5A – K VALUE CHARTS 5A – K VALUE CHARTS
This appendix contains K value charts for carbon dioxide, hydrogen sulfide, nitrogen, and the
paraffin hydrocarbons methane through decane. Both SI and FPS unit charts are included.
As discussed in the text, the K value is a function of temperature, pressure and composition. The
effect of composition on K values is difficult to show graphically. Historically, the concept of convergence
pressure has been used to adjust K values for the effect of composition. The K values in the following charts
are based upon a convergence pressure of 3000 psia which is consistent with compositions found in oil
and gas production facilities. These charts should not be used in applications such as low temperature gas
processing, NGL fractionation systems, etc.
Example phase behavior calculations for bubblepoints, dewpoints, and flash calculations shown for
the gas composition given in Example 5.4, 5.6, 5.7 and 5.8 were generated using the Hadden-oriented K
values contained in this Appendix for the sake of consistency. However, the composition of these Examples
are outside the range shown above. The SRK equation of state would be a much better choice to determine
the K values of those Examples.

40 40
Carbon Dioxide Carbon Dioxide
CHAPTER 5
30 30
20 20
Temperature, °C Temperature, °F
40
0
20 10
10 5
15
0
30
0
10
5
7 80 7
0 0 0
95
0
60
22 18 14 10
0
70
5 40 5 20 160 12
K 50 K
0
4 4
80
15
30 60 40
5
20
3 3
-1
0
0
-2
0
-2
0
2 2
-3
0
-4
0
-4
0
1.0 1.0
0.7 0.7
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000

Pressure, MPa Pressure, psia
131
132
20 20
Hydrogen Sulfide Hydrogen Sulfide
10 10
7 7
5 5
40
20 0
4 5 4 30
15 0
0 20
3 3 0
22
10 0
5 16
0
95 18
80 0
K 2 K 2 12
0
70 14
0
60
50 80
10
40 0
30
1.0 1.0 60
15
40
5
0.7 0.7 20
-10
0.5 0
-20 0.5
0.4 -30 0.4 -20
0.3 -40 0.3 -40
0.2 0.2
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000

100 100
70 Nitrogen 70 Nitrogen
CHAPTER 5
50 50
40 40
30 30
20 20
10 10
K K
7 7
5 5
4 4
3 3 100
40
40
5
20
-10
2 2 0
-30 -20
1.0 1.0
-40
0.7 0.7
-40
0.5 0.5
1 2 3 4 5 7 10 20 100 200 300 500 1000 2000
133
134
40 40
30 Methane 30 Methane
20 20 Temperature, °F
30
Temperature, °C 0
15
10 0 60
10
30
40
15
7 7 20
5
K -1 K 0
5 0 5
-2 -2
0 0
4 4
-3
0 -4
0
3 -4 3
0
200
95 180
2 80 2 160
70 140
60 120
50 100
40 80
1 1
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000


20 20
Ethane Ethane
CHAPTER 5
10 10 Temperature, °F
40
0
7 Temperature, °C 7
30
0
5 205 22
05 5 0
15 20
0 0
4 4 18
10
5 0
16
3 95 3 0
80 14
0
70
12
K 2 60 K 2 0
50 10
0
40 80
30
60
1.0 15 1.0 40
5
20
0.7 -10 0.7
-20 0
0.5 0.5
-30 -20
0.4 0.4
-40 -40
0.3 0.3
1.0 0.2
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000
135
136
10 10
Propane Propane
7 7
5
5
4 4
3 3
40
25 0
0
2 15 2 30
0
0
22
10
5 18 0
0
20
95 0
1.0 80 1.0
160
70
K K 140
60
0.7 0.7 120
50
40 100
0.5 0.5
30 80
0.4 0.4
15 60
0.3 0.3
5 40
0.2 20
0.2 -10
0
-20
-20
-30
0.1 0.1
-40 -40
0.07 0.07
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000


7 7
5 Iso-Butane Iso-Butane
CHAPTER 5
5
4 4
3 3
2 2
20 40
5 0
15
0 30
0
1.0 1.0
10
5 22
0.7 0.7 0
95 20
0
80 1 80
0.5 0.5
70 160
K 0.4 60 K 0.4 140
0.3 50 120
0.3
40 100
0.2 30 0.2 80
15 60
5 40
0.1
0.1
20
-10
0.07 0.07
0
-20
0.05 0.05
0.04 -30 -20
0.04
0.03 -40 0.03 -40
0.02 0.02
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000
137
5 5
138
4 N-Butane 4 N-Butane
3 3
2 2 40
0
20
5
30
0
1.0 15 1.0
0
22
0
0.7 0.7 20
10
5 0
95 18
0.5 0.5 0
16
0.4 80 0.4 0
70 14
0
0.3 60 0.3 120
K 50 K 100
0.2 40 0.2
80
30
60
0.1 15 0.1
40
5
0.07 0.07
20
-10
0.05 0.05
0.04 0.04 0
-20
0.03 0.03
-30 -20
0.02 0.02
-40
-40
0.01 0.01
1 2 3 4 5 7 10 20 100 200 300 500 700 1000 2000

4 4
3 Iso-Pentane 3 Iso-Pentane
2 2
220 40
055 0
1.0 1.0
30
15 0
0.7 0 0.7
0.5 0.5
10 22
0.4 5 0.4 0
95 20
0
0.3 0.3 18
0
80
16
70 0
0.2 0.2
60 140
K K
50 120
0.1 40 0.1 100
30
0.07 0.07 80
0.05 15 0.05 60
0.04 0.04
5 40
0.03 0.03
20
0.02 -10 0.02
0
-20
0.01 0.01 -20
-30
0.007 0.007
-40
0.005 -40
0.005
1 2 3 5 7 10 20 100 200 500 1000 2000

CHAPTER 5 139
4 4
N-Pentane N-Pentane
2 2 400 Temperature, °F
Temperature, °C
1.0 1.0 300
205
0.8 0.8
0.6 150 0.6

22
0
0.4 0.4 20
0
105 18
0
95 16
0
0.2 80 0.2 14
0
K 70 K 12
0
60
0.1 50 0.1 100
0.08 40 0.08
80
0.06 30 0.06
60
0.04 0.04
15
40
5
0.02 0.02 20
-10
-20 0
0.01 0.01
0.008 -30 0.008
0.006 0.006 -20
-40
0.004 0.004
-40
0.002 0.002
1 2 3 4 6 10 20 100 200 400 600 1000 2000

2 2
N-Hexane N-Hexane
20 Temperature, °C 40
Temperature, °F
1.0 5 1.0 0
0.8 0.8
0.6 15 0.6
0 30
0
0.4
0.4
10 22
5 0
0.2 95 0.2 20
0
80 18
0
0.1 70 0.1 160
0.08 60 0.08
140
0.06 0.06
50
120
0.04 40 0.04
K K 100
30
0.02 0.02 80
15 60
0.01 0.01
5 40
0.008 0.008
0.006 0.006
20
-10
0.004 0.004
-20 0
0.002 0.002
-30 -20
0.001 0.001
0.0008 0.0008
-40
0.0006 0.0006 -40
1 2 3 5 7 10 20 100 200 300 500 1000 2000

CHAPTER 5 141
1.0 1.0
0.8 N-Heptane 0.8 N-Heptane
205 400
0.6 0.6
0.4 0.4
300
150
0.2 0.2
0.1 105 0.1 220

0.08 0.08 200
95
0.06 0.06
180
80
0.04 0.04 160
70
60 140
0.02 0.02
50
50 120
K 40 K 100
0.01 0.01
0.008 30 0.008
0.006 80
0.006
0.004 15 0.004 60
5 40
0.002 0.002
20
-10
0.001 0.001
0.0008 0.0008
0
0.0006 -20 0.0006
0.0004 0.0004
-30
-20
0.0002 0.0002
-40 -40
0.0001 0.0001
1 2 4 6 10 20 100 200 300 500 1000 2000

1.0 1.0
0.8 N-Octane 0.8 N-Octane
0.6 0.6 400
0.4 205 0.4
0.2 0.2 300

150
0.1 0.1
0.08 0.08
0.06 220
0.06
105
200
0.04 0.04
95
180
80
0.02 0.02 160
70
140
0.01 60 0.01
0.008 0.008 120
50
0.006 0.006
40 100
0.004 0.004
K K
30 80
0.002 0.002
60
15
0.001 0.001
0.0008 0.0008 40
5
0.0006 0.0006
0.0004 0.0004 20
-10
0.0002 0.0002
0
-20
0.0001 0.0001
0.00008 -30 0.00008 -20
0.00006 0.00006
0.00004 0.00004
-40
-40
0.00002 0.00002
1 2 3 5 7 10 20 100 200 500 1000 2000
CHAPTER 5 143
0.5 0.5
0.4 N-Nonane 0.4 N-Nonane
400 Temperature, °F
205 Temperature, °C
0.2 0.2
0.1 0.1
300
0.08 150 0.08
0.06 0.06
0.04 0.04
220
105
0.02 0.02
200
95
180
0.01 0.01
80
0.008 0.008
160
70 0.006
0.006
0.004 60 0.004 140
K K
50 120
0.002 0.002
40
100
0.001 30 0.001
0.0008 0.0008 80
0.0006 0.0006
15
0.0004 0.0004 60
5 40
0.0002 0.0002
0.0001 -10 0.0001 20

0.00008 0.00008
0.00006 0.00006
0
-20
0.00004 0.00004
0.00002 -30 0.00002 -20
0.00001 0.00001
1 2 3 5 7 10 20 100 200 500 1000 2000

0.4 0.4
N-Decane N-Decane
0.2 0.2
205 400
0.1 0.1
0.08 0.08
0.06 0.06
300
150
0.04 0.04
0.02 0.02
220
105
0.01 0.01
0.008 95 0.008 200
0.006 0.006
180
0.004 80 0.004
160
K 70 K
0.002 0.002 140

60
0.001 50 0.001 120

0.0008 0.0008
40
0.0006 0.0006 100
0.0004 30 0.0004
80
0.0002 0.0002
15 60
0.0001 0.0001
0.00008 0.00008
5 40
0.00006 0.00006
0.00004 0.00004
-10 20
0.00002 0.00002
1 2 3 5 7 10 20 100 200 500 1000 2000
CHAPTER 5 145
146
6
WATER-HYDROCARBON PHASE BEHAVIOR
Water and hydrocarbons are natural companions. Hydrocarbons are formed in a water environment
and are in equilibrium with water at reservoir conditions.
Liquid water and hydrocarbons are essentially immiscible in each other. Their slight mutual
solubility is important for hydrate prediction but has no measurable effect on their vapor-liquid equilibrium
behavior. At 25°C [77°F] and atmospheric pressure the mol fraction of a paraffin like n-pentane in water
is about 3.5 × 10-6. In general, the solubility of paraffin hydrocarbons in water decreases with increasing
carbon number. The mutual solubility of aromatic and naphthenic hydrocarbons and water is substantially
higher than for paraffins.
If both liquid water and hydrocarbons—and gas—are present in a system there will be two liquid
phases. The amount of water vapor in the gas will be governed by gas composition and the vapor pressure
of the liquid water phase.
Two calculations are primary to the water-hydrocarbon gas system: calculation of the water content
of the gas and prediction of the conditions under which hydrates will form. Prevention of hydrates by
dehydration or inhibition is important in oil and gas operations.
WATER CONTENT OF GASES

The water content of a gas depends on system pressure and temperature and the composition of the
water containing gas. The published record in this area goes back to the work of Poynting in 1881. Current
methods of calculation include the use of:
1. Partial pressure and partial fugacity relationships.
2. Empirical plots of water content versus P and T.
3. Corrections to (2) for the presence of contaminants like hydrogen sulfide, carbon dioxide and
nitrogen.
4. Equations of state.
Partial Pressure and Fugacity

If Raoult’s Law (discussed in Chapter 5) is applied to water, it can be written:
Px
y w = vP w (6.1)
Where: P = absolute system pressure

yw = mol fraction water in the vapor phase
Pv = vapor pressure of water at system temperature
xw = mol fraction water in the liquid water phase (= 1.0)
CHAPTER 6 147
The liquid mol fraction can be taken as 1.0 because of the immiscibility of the liquid phases.
Thus, for a known pressure and water vapor pressure the mol fraction water in the vapor phase is
found from Equation (6.1).
However, this equation is valid only at low pressure where the ideal gas law is valid. Equation (6.1)
is recommended for system pressures up to about 400 kPa [60 psia].
Empirical Water Content Charts

Figure 6.1a & b show the water content of natural gas plotted against temperature for selected
pressures. These charts were developed based on data from several sources.(6.1-6.4) The water content shown
is the maximum the gas can hold at the P and T of the system. The gas is fully saturated, its relative humidity
is 100% or, stated another way, the temperature is the water dewpoint temperature of the gas at the concen-
tration and pressure shown.
The concentrations in mass per unit standard volume are related to mol fraction of water, yw, as:
kg water/106 std m3 = (y w) (18) (42 300) = 761 400y w (6.2)
lbm water/MMscf = (y w) (18) (2635) = 47 430y w (6.3)

Where: 18 = molecular weight of water
42 300 = kmol gas/106 std m3 [@ 15°C and 101.325 kPa]
2635 = lbmol gas/MMscf [@ 60°F and 14.7 psia]
Comparison of the water content at various points in the system serves many purposes. One is to
determine the water loading for dehydration. Another is to establish how much water has been condensed
as liquid at any point in the system.
Suppose at one point in a system the water content (from a correlation) is 200 kg/106 std m3
[13 lbm/MMscf ]. At some point downstream the same correlation gives a maximum water content of 100
kg/106 std m3 [6.5 lbm/MMscf ]. What is the conclusion? If no water has been withdrawn, there is 100
kg of liquid water in the system per 106 std m3 [6.5 lbm/MMscf ] of gas flowing. This water is available
to form hydrates, unless it is removed or inhibited. It also is a primary source of corrosion-erosion
problems. The purpose of dehydration is to prevent such water condensation.
Figure 6.1a & b are satisfactory for most applications involving lean, sweet natural gas. The likely
error of 6-10% probably is more accurate than the underlying data used to develop the correlation. In
general, the water content of natural gas is a weak function of composition except for the components CO2
and H2S. It is good practice to make a correction for these contaminants even though it may be small when
concentrations and pressures are low.

10 0000
80 000
60 000
50 000
40 000
30 000
20 000
Water Content of Sweet Natural Gas, kg/106 std m3 (at 101.325 kPa and 15 ˚C)
10 000
Pa
0k
8000
Pa
10
0k
20
6000
Pa
0k
5000
40
Pa
0k
Pa
4000
70
M
1.0
3000
Pa
M
Pa
2.0
M
Pa
0
2000 M a
3.
. 0 MP a
4 0 P
5. .0 M Pa
7 M a
.0 P
10 0 M
5 . Pa
1 M
1000 . 0
30 Pa
800 M
.0
70
600
500
400
300
200
100
80
60
50
40
30
20
JMC, 1983
10
-40 -20 0 20 40 60 80 100
Water Dewpoint, ˚C
Figure 6.1a Water Content of Sweet, Lean Natural Gas (SI Units)
CHAPTER 6 149
10 000
8000
6000
5000
4000
3000
2000
Water Content of Sweet Natural Gas, lbm/MMscf (at 14.7 psia and 60 ˚F)
1000
sia
p
.7
800
ia
14
ps
600 25
ia
ps
500
50
sia
0p
400
10
sia
0p
300
50 00 p sia
20
0p
80 00 psia a
6 0 si
30
200
sia i
0 p ps
4
ia
ps a
0 0 psi a
i
10 500 ps a
1 00 si
2 00 p sia
0
100 0
3 00 p
sia
80 50 0p
0 0
10
60
50
40
30
20
10
8
6
5
4
3
JMC, 1983
1
-40 0 40 80 120 160 200 240
Water Dewpoint, ˚F
Figure 6.1b Water Content of Sweet, Lean Natural Gas (FPS Units)

Water Content of Sour Gases

There are several available methods for estimating the water content of gases containing H2S and
CO2 .(6.5-6.7)
Figure 6.2a & b(6.7) is a correlation for estimating sour gas water content that is reasonably
accurate and simple to use. The charts shown were calculated from the SRK equation of state assuming
that the hydrocarbon portion of the gas is methane. It is assumed that CO2 has 70% of the water content of
H2S at the same T and P. Multiply the percent CO2 by 0.70 and add the result to the percent H2S to get the
“equivalent H2S” content.
H2 S (equiv.) = % H2 S + 0 .70 (% CO2) (6.4)
To use Figure 6.2a & b, enter the lower portion of the graph at the system temperature. Proceed
horizontally to the equivalent H2S concentration. Proceed vertically to the system pressure then horizontally
to the y-axis. The “water content ratio” factor should be multiplied by the sweet water content (at the same
T & P) to obtain the water content of the sour gas.
The method is limited to an H2S equivalent of 50 mol % and applicable for temperatures from
10-177°C [50-350°F] and pressures from 1379 kPa to 69 MPa [200 to 10 000 psia]. In comparison
with 70 data points covering natural gas mixtures with up to 50% equivalent H2S concentrations from
38-107°C [100-225°F] and 1379 kPa to 41 MPa [200 to 6000 psia], the error for the this method was
randomly distributed with an average absolute error of 10% and a maximum of 37%.(6.8)
Example 6.1: Estimate the water content of a natural gas containing 5% H2S and 20% CO2 at 60°C
and 10 000 kPa [140°F and 1450 psia].
SI Units
a. Figure 6.1a (sweet natural gas)
W = 2050 kg/106 std m3

b. Equiv. H2S conc. = 5% + (0.70)(20%) = 19%
From Figure 6.2a Factor = 1.1
W = (2050)(1.1) = 2255 kg/106 std m3
FPS Units
a. Figure 6.1b (sweet natural gas)
W = 130 lbm/MMscf
b. Equiv. H2S conc. = 5% + (0.70)(20%) = 19%
From Figure 6.2b, Factor = 1.1
W = (130)(1.1) = 143 lbm/MMscf
In Example 6.1 the water content from Figure 6.2a & b is greater than that from Figure 6.1a & b.
This is expected for the sour gas in question. In this case the acid gas components increase the water content
by about 10%.
CHAPTER 6 151
Figure 6.2a Water Content Ratios — Sour Gas (SI Units)
Figure 6.2b Water Content Ratios — Sour Gas (FPS Units)

Effect of Nitrogen and Heavy Hydrocarbons on Water Content

Nitrogen will hold less water than methane. At pressures to about 7.0 MPa [1000 psia] the
water content of nitrogen is about 6-9% less than for methane. This deviation increases with pressure.
Thus, including nitrogen as a hydrocarbon is practical and offers a small safety factor. The presence of
heavier hydrocarbons tends to increase the water content of the gas. Once again the deviation is relatively
small at normal system pressures. The nitrogen and heavy end effects tend to cancel out each other in
many production systems.
Water Content Applications

Water content correlations are used primarily for dehydration calculations and to determine how
much water (if any) will condense from the gas. The latter involves considerations of disposal, corrosion/
erosion and hydrate inhibition.
For most high pressure natural gas systems, the amount of condensed water is small, relative to the
total stream rate. The real danger is underestimating the quantity. Estimates should err to the “safe” side of
the possible range of values. The additional capital expenditure normally will be trivial. There is a tendency
to predict flowing temperatures lower than they turn out to be. Notice in Figure 6.1a & b that the water
content is a log scale. A change in temperature of only 5°C [9°F] in the ambient range causes about a 25-30%
increase in water content. A common cause of poor dehydrator performance is under-prediction of the water
loading.
Example 6.2: Water is separated in an inlet scrubber upstream of a compressor at 7.0 MPa and
35°C [1015 psia and 95°F]. The gas is then compressed to 14.0 MPa [2030 psia] and
cooled to 50°C [122°F ] before entering a dehydrator. Is the gas saturated as it enters
the dehydrator?
SI Units
From Figure 6.1a, water content at 7.0 MPa and 35°C = 824 kg/106 std m3
From Figure 6.1a, water content at 14.0 MPa and 50°C = 1070 kg/106 std m3
FPS Units
From Figure 6.1b, water content at 1015 psia and 95°F = 52 lbm/MMscfd
From Figure 6.1b, water content at 2030 psia and 122°F = 68 lbm/MMscfd
The gas in this example is capable of holding 1070 kg/106 std m3 [68 lbm/MMscf ]
downstream of the compressor aftercooler, but contains only 824 kg/106 std m3
[52 lbm/MMscf ] which is set by the conditions at the suction scrubber. Therefore, the
gas is not saturated. There is less than the maximum amount of water to be removed
in the dehydrator.
In most cases the maximum water content of the gas downstream of the system will be less than
that upstream. In these cases water must condense in the system. A water content correlation may be used
to estimate the amount of liquid water present.
If no separation occurs between the wellhead and a processing facility, such as a gas dehydra-
tion unit, it is reasonable to assume that the gas is saturated at the reservoir pressure and temperature for
purposes of estimating the amount of liquid water in the system. Of course, in many cases the well stream
will also contain liquid water from the reservoir in addition to the water in the vapor phase.
CHAPTER 6 153
Saturated Water Content in Equilibrium with Hydrates

Figure 6.1a & b are based on the assumption that the condensed water phase is a liquid. However, at
temperatures below the hydrate temperature of the gas, the “condensed” phase will be a solid (hydrate). The
water content of a gas in equilibrium with a hydrate will be lower than equilibrium with a metastable liquid.
Hydrate formation is a time dependent process. The rate at which hydrate crystals form depends
upon several factors including gas composition, presence of crystal nucleation sites in the liquid phase,
degree of agitation, etc. During this transient “hydrate formation period” the liquid water present is termed
“metastable liquid.” Metastable water is liquid water that, at equilibrium, will exist as a hydrate.
References 6.9-6.11 and 6.51 present experimental data showing equilibrium water contents of
gases above hydrates. Data from Reference 6.10 is presented in Figure 6.3. For comparative purposes, the
“metastable” water content of a sweet gas from Figure 6.1a & b is also shown. The water content of gases
in the hydrate region is a strong function of composition. Figure 6.3 should not be applied to other gas
compositions.
Temperature, °F
-40 -30 -20 -10 0 10 20 30 40
100
1000
10
Water Content, kg/106 std m3
Water Content, lbm/MMscf

100
ia]
0 ps 1
a [30
10 206 8 kP
ia]
0 0 ps
a [15
42 kP
10 3 0.1
1
Hydrate
Metastable
0.01
0.1
-40 -35 -30 -25 -20 -15 -10 -5 0 5
Temperature, °C
Figure 6.3 Water Content of 5.31% C3 — 94.69% C1 Gas in Equilibrium with Hydrate and Metastable Liquid
When designing dehydration systems, particularly TEG systems to meet extremely low water
dewpoint specifications, it is necessary to determine the water content of the dried gas in equilibrium with
a hydrate using a correlation like that presented in Figure 6.3. If a metastable correlation is used, one will
overestimate the saturated water content of the gas at the dewpoint specification. This, in turn, may result
in a dehydration design which is unable to achieve the required water removal. Where experimental data is
unavailable, utilization of an EOS-based correlation that has been tuned to empirical data can provide an
estimate of water content in equilibrium with hydrates.

WATER DEWPOINT ANALYZERS

Measurement of the water content of gas is a normal part of the gas conditioning process. There
are many instruments on the market for this purpose, in a wide price range. The choice is not routine. Some
may not be sufficiently robust to be used in severe environments.
The grandfather of this family of instruments is the Bureau of Mines Dewpoint Tester, or commonly
referred to as a “chilled mirror” device. It consists of a polished mirror that can be cooled at a steady rate.
When the first drops of liquid “dew” appear visually on this mirror the technician records the temperature
and pressure. This is a direct measurement of the water dewpoint temperature, not the water content of
the gas. The measured water dewpoint temperature needs to be converted into a water content value using
a correlation such as Figure 6.1a and Figure 6.1b. It is simple and rugged. But, it depends on the visual
judgment of the technician, and the exact point at which condensation begins is not visible to the eye, hence,
different operators will get different results.
Another problem is the fact that hydrocarbons, and contaminants such as alcohols or glycols, often
condense at a higher temperature than water and flood the mirror. One solution for this is to place an
activated carbon chamber in the sample line upstream of the tester. Carbon has little affinity for water. Once
it has been saturated the gas leaving will be representative of the gas being tested.
A more sophisticated form of the chilled mirror uses a gold plated mirror bonded to a copper
thermocouple holder. As this assembly is cooled an optical sensing bridge detects the change in light level
that occurs when dew forms on the mirror. The optical sensor makes the measurement less ambiguous than
a visual measurement, but it does not have the capability to make the distinction between the type of fluid
that has condensed.
Many gas pipeline companies use the color tube indicator, also referred to as the “Draeger tube”
or “stain tube” to quickly get an estimate of the water content of natural gas. The tube is manually exposed
to the pipeline gas for a given length of time. The chemical within the tube reacts with the water and the
color of the chemical changes. The final color of the tube indicates the amount of water that was present in
the natural gas. The tubes are calibrated by the manufacturer, but these measurements are directly related to
exposure time, flow rate, and sampling method. Variation in the sampling method and duration can result
in errors that can be as high as 25%. Draeger tubes will read the presence of methanol in the gas as water
vapor, which can lead to erroneous results. In many cases, Draeger tubes are well suited for infrequent
approximate estimations of water content.
One of the better (and more expensive) of the wetted sensor type instruments uses quartz crystal
sensors. The sensor has two hygroscopically coated quartz crystal oscillators that vibrate at 9 MHz. Water
vapor is alternately adsorbed and desorbed on each crystal. The mass change involved is reflected by changes
in frequency, which is compared electronically. Each crystal is exposed alternately to the moist sample gas
for 30 seconds while the other is exposed to a dry reference gas. Self-calibrating units are available, which
include a moisture generator and software diagnostics. A sample conditioning/filtration system can be used
to prevent contamination of the crystal sensors.
Another instrument uses an aluminum oxide type sensor. The sensor has an anodized aluminum
strip providing an aluminum oxide layer on which a thin layer of gold has been deposited. Two conduc-
tors are used. When water adsorbs on the oxide surface it changes the dielectric properties. The impedance
is measured and converted to water content in equilibrium with the sensor. It takes time for the water
molecules to enter and exit the aluminum oxide pores resulting in “wet-up” and “dry-down” time delays.
Corrosive materials and contaminants can damage and clog the pores, which results in a “drift” in the
calibration. Glycols and methanol can deactivate the sensor, thus an effective sample filtration system is
recommended.
CHAPTER 6 155
Impedance ceramic moisture sensors are also available. Water vapor absorbs onto a porous
non-conducting “sandwich” between two conductive layers built on top of a base ceramic substrate. The top
porous conducting layer and the active sensor layer are very thin which allows rapid water vapor adsorp-
tion. This type of sensor will not have the “wet-up” and “dry-down” delays that are experienced with the
aluminum oxide sensors. These sensors should be used with the proper sample conditioning and filtration
to prevent contamination of the ceramic sensor.
There are many variations of the electrolytic moisture analyzer available. The exact system varies
with the manufacturer. One type consists of a glass tube with two platinum wires wound in a double helix
on the inside surface. The space on this surface, between the wires, is coated with phosphorous pentoxide
(P2O5 ). When moisture wets the P2O5 an electrolysis current is produced as a potential and is applied to the
wires. The magnitude of this current is used to indicate water content.

You also can measure water content in a chromatograph. In one method the gas is passed through
calcium carbide. The water reacts, producing equivalent amounts of acetylene, which can be measured
in the chromatograph. Another chromatographic method measures the water content using two identical
columns coated with glycerol.
Laser-based analyzers are well accepted and very common in the natural gas industry today.
These analyzers are based upon tunable diode laser adsorption spectroscopy. At certain frequencies water
molecules will absorb light energy, while at other frequencies they absorb minimal amounts of light energy.
By measuring the laser light intensity with a photodetector, the instrument can measure the partial pressure
of water by the correlation of laser light lost to the incident light. The gas continuously flows through the
sample cell. At one end of the sample cell is an optical window, behind which is located the tunable diode
laser and photodetector. These are in a sealed housing. At the other end of sample cell is a mirror. The
laser light is transmitted through the optical window into the cell and is reflected off of the mirror then is
measured by the photodetector. Since only light comes in contact with the process gas, it is not subject to
becoming contaminated with glycol, methanol, amines, H2S, etc. These instruments have become very
reliable and require little maintenance, often making them the water content analyzer of choice.
Many of the instruments that were briefly described may be satisfactory in a given case. None are
perfect. Some require calibration, which at best is a nuisance. If you have sour gases the choice becomes very
limited and none may be truly satisfactory. The electrolytic cells are particularly susceptible to poisoning.
GAS HYDRATES
Gas hydrates are a form of clathrate first discovered by Sir Humphrey Davy in 1810. Villard, in
1888, presented performance data on hydrocarbon hydrates. Thus, the scientific study of these physical
compounds has been very extensive.
A clathrate is any compound wherein guest molecules are entrapped in a cage structure composed
of host molecules. With the natural gas hydrate the lattice is formed by water molecules as shown in Figure
6.4. The circles represent water molecules and the lines hydrogen bonds. Contained within each lattice
is a series of cavities or cages that must be occupied by sufficient guest molecules to stabilize this lattice
crystal. Hydrates can form in systems with free water present at ambient temperatures typically less than
27°C [80°F], and at moderate pressures generally greater than 600 kPa [87 psia].
X-ray diffraction analysis shows the gas hydrate crystal structure to be a derivative of the pentago-
nal dodecahedron, a twelve-sided structure whose faces have five edges. Since the bonding angle is 108°
and that of ice is 109.5°, the structure was long thought to be the probable basic hydrate building structure;
yet, no orderly packing arrangement can be made with the regular pentagonal dodecahedron. Claussen
proposed two separate crystal lattices of modified dodecahedron configurations designated as Structures I
and II.

Structure I (8 gas molecules + 46 water molecules)
2 6
Hydrate Formers
N2
512 512 62
CO2
H2S
Structure II (24 gas molecules + 136 water molecules) CH4
C2H6
C3H8
16 8
iC4H10
512 512 64 nC4H10
C6H14*
(Neohexane)
Structure H (6 gas molecules + 34 water molecules)
C7H14*
(Cycloheptane)
3 2 1 *Form structure H only
512 435663 512 68
Figure 6.4 Schematic of Natural Gas Hydrate Lattices
The basic lattice of Structure I (sI) has a 512 structure (pentagonal dodecahedra), because there are 12
faces of pentagonally bonded water molecules for each cavity. Within these cavities, small guest molecules
are entrapped within the water molecule structure. The guest molecules have limited translation motion,
but have substantially more rotation and vibration ability. These building block structures are joined either
through either the vertices (sI), or through the faces (sII). All of these structures must fill the space within
their cavities to prevent hydrogen-bond strain and breakage. For sI hydrates, there are 46 water molecules
present for each crystal structure. There are two small pentagonal dodecahedral voids (512), and six larger
voids for the sI hydrate. The larger voids of the sI hydrate are comprised of five pentagonal faces, and two
hexagonal (51262).
A second crystal form, Structure II (sII ), designated as a pentagonal dodecahedral-diamond lattice,
is formed in the presence of hydrocarbons larger than ethane. For this structure, a unit cell having 136
water molecules is present. There are sixteen small pentagonal dodecahedral voids and eight larger voids.
The large voids, termed hexakaidecahedron, have four hexagonal and twelve pentagonal faces (51264 ).
Entrapment of propane, n-butane, and isobutane occurs in these structures as well as possible entrapment
of ethane and methane. It can be surmised that the absence of propane and heavier molecules would cause
only sI hydrates to be formed, while the presence of both ethane and propane would result in both. This is
possible since the availability of excess water and hydrocarbons during hydrate formation may be limited.
A third hydrate structure, structure H hydrate, which has three cavity sizes, has also been
proposed(6.12-6.15). The smallest cavity of this hydrate is similar in size to the small cavity of sI and sII, but
the largest cavity is bigger than either sI or sII. This large cavity can accommodate larger guest molecules
(in the presence of a smaller “help” molecule) including molecules such as benzene, cyclopentane, and
cyclohexane. In addition, recent work(6.13) has indicated that the larger cavity in sII hydrates may also
accommodate some of these larger molecules.
CHAPTER 6 157
Are H hydrates of concern in hydrate modeling? It is certainly true that the addition of a sH former,
such as neohexane, increases the hydrate formation temperature at a given pressure; however, the addition of
the same amount of propane to methane increases the temperature even more. It has been confirmed that for
naturally occurring gas and gas condensate compositions sII hydrates will form preferentially to sH(6.14), thus
sH hydrates are not common in natural gas systems. It is necessary to have all three sizes of cages relatively
full in order to stabilize the lattice.
It is apparent from the above that molecular size is an important factor. A second important factor
is gas solubility. Solubility primarily affects the rate of clathration since it governs the statistical probability
that a given molecule will be present when the lattice is closing. Hence, the greater the solubility of a given
component, the faster a hydrate will form.
It is believed that the guest molecule dictates which type of structure will be formed, and its solubil-
ity governs the rate of formation. Size also affects the formation rate. This may be seen from the hydrate
behavior of methane, hydrogen sulfide, and propane. At a given temperature the pure methane hydrate
requires a higher pressure to form than the propane hydrate, although its solubility in water is considerably
greater than that of propane. It is much easier for a small molecule to avoid entrapment as the cage is closing
than a larger one. There are more methane molecules present, but their more active, random movement,
and smaller size make clathration more difficult. The similarly sized hydrogen sulfide molecule is far more
soluble than methane, forms in the same structure, and requires about one-twentieth the time to hydrate.
The actual imprisonment conditions are considered satisfied when the gas molecule is properly
oriented within the water structure such that the aggregation of water and gas molecules have best utilized
the available space. This corresponds to the state of lowest potential energy for the aggregation such that
attractive, repulsive, rotational, and bonding forces are as much in equilibrium as possible. Once formed,
the hydrogen-bonded structure will not be broken until these forces become so unbalanced that the strength
of the hydrogen bond is exceeded and fracturing occurs.
The guest molecules provide stability to the lattice structure in the same manner that liquid in the
pores of subsurface sand prevents subsidence. Not all cages must be full. Therefore, there is no specific
formula for hydrates.
The following is representative of typical hydrate crystals formed by a given component.(6.15)
Structure I: CH4 5.9 H2O ,

 C2H6 8.2 H2O , H2S 6.1 H2O ,
  CO2 6.0 H2O 
Structure II: N2 6.0 H2O ,

 C3H8 17.0 H2O , iC4H10 17.0 H2O
 
The number of water molecules in the hydrate crystal structure is called the hydrate number. The
hydrate number is a function of pressure. Normal butane can form a hydrate but it is unstable. With the
exception of neopentane all paraffin hydrocarbons larger than the butanes are non-hydrate formers.
A natural gas mixture forms hydrates more readily than any pure component.
Individual hydrate crystals form in the liquid water phase. For all practical purposes, only in the
liquid phase does one have the necessary concentration and energy level to allow hydrogen atom bonding.
These crystals are very small. But, they can grow by sharing the faces composed of 5- and 6-membered
water molecules. It is only when this growth continues to form a plug are hydrates a known problem.

Hydrate Equilibrium
Figure 6.5(6.16) shows the hydrate forming characteristics of common natural gas components.
Below and to the right of the line no hydrates can form. At some temperature the hydrate formation line
becomes vertical for pure components. This happens at the point where the hydrate formation line intersects
the vapor pressure curve of that component. If no vapor is present, pressure has little effect on the hydrate
formation temperature.
Temperature, °F
30 40 50 60 70 80 90
70.0 10 000
50.0 7000
5000
20.0 3000
a ne
M eth 2000
10.0
7.0 1000
5.0 700
Pressure, MPa
Pressure, psia
500
3.0
2.0 CO 2 300
ane
Eth 200
1.0
0.7 100
H 2S
0.5 70
e
an
50
op
0.3
Pr
0.2 30
20
i-Butane
0.1 n-Butane
10
-5 0 5 10 15 20 25 30 35
Temperature, °C
Figure 6.5 Hydrate Forming Conditions for Natural Gas Components
Temperature, °F As shown in Figure 6.6, below 0°C [32°F]

0 10 20 30 40 50
1.0 145 both ice and hydrate are present above the curve;
0.9 Liquid
0.8 Hydrate Propane
+ + only vapor and ice are below. Above the freezing
0.7 Water Water 100
0.6 90
80
point, hydrate is the only solid phase to the left of
0.5 70 the hydrate forming curve. At the intersection of the
r 60
0.4 Vapo vapor pressure and hydrate curves the latter becomes
ane
Prop C v
u r e 50
sure
Pressure, MPa
Pressure, psia
0.3 Pres essentially vertical. This intersection establishes the

40
maximum hydrate forming temperature for pure
30
0.2 components.
Hydrate + Ice e
urv
nC
matio 20 Figure 6.6 illustrates the general behavior
For
yd rate Vapor + Water
H for a propane-water system.
0.1
0.09
0.08 Vapor + Ice
0.07 10
9
0.06 8
0.05 7
-20 -15 -10 -5 0 5 10
Temperature, °C
Figure 6.6 Phase Behavior of Propane-Water System
CHAPTER 6 159
The same general behavior occurs for a gas mixture, as shown in Figure 6.7. Line FEGC is the
hydrocarbon dewpoint line for the mixture. The slope of the hydrate curve (FGH) becomes increasingly
vertical along the quadruple line (FG). The slope of the quadruple line is dependent upon the amount of
hydrocarbon liquid in the system. Increasing amounts of liquid steepen the slope. If the quadruple line
intersects the phase envelope to the left of the critical point ( bubble point line) the hydrate curve will be
essentially vertical in the liquid hydrocarbon phase region.
The general procedure for hydrate prediction
involves the following basic steps: Hydrate Water
Curve Dewpoint Line
H
1. Use a suitable correlation to establish the
position of the dewpoint line FEGC. C
G
2. Use a suitable correlation to find the water P Hydrocarbon

dewpoint at point E, and estimate the wa- Bubble Point Line
ter dewpoint line. E

3. Use a suitable correlation to find hydrate
Hydrocarbon
curve FGH. F Dewpoint Line
The first step was covered in Chapter 5. The T

correlations that follow may be used for Step 2. The
water content charts provided in Figure 6.1a & b can Figure 6.7 General Hydrate Formation Characteristics
of a Gas Mixture
be used to determine the water dewpoint line, or these
values can be determined using an appropriate EOS correlation.
HYDRATE PREDICTION CORRELATIONS

All basic hydrate prediction correlations are for a system containing only gas and water in a static test
cell that was sufficiently agitated to ensure equilibrium. In most cases the data shown are the hydrate melting
conditions, a more reproducible data point than the formation point, and more reliable for calculation use.
Temperature, °F
40 50 60 70
5000
30
4000
20 3000
2000
10
Pressure, MPa (abs)
8
Pressure, psia
1000
6
800
5
4 600
500
3
400
2 300
Methane
Relative Density 0.6
Relative Density 0.7 200
1 Relative Density 0.8
100
0 5 10 15 20 25
Temperature, °C
Figure 6.8 Conditions for Formation of Natural Gas Hydrates(6.16)

Early correlations showed hydrate forming curves as a function of gas relative density. Figure 6.8
is a graph of this type, and is based upon the Katz correlation. Although they are simple to use and can give
a quick estimate of the hydrate conditions, they are not recommended for engineering calculations. This
particular graph should not be used for gas compositions containing H2S, CO2, and N2. The C2+ composition
for higher molecular weight gases can change the hydrate formation temperature significantly. It is not recom-
mended to extrapolate Figure 6.8 for natural gases with relative densities greater than 0.8.
Vapor Solid Equilibrium Constants

Katz and his co-workers developed a set of vapor-solid equilibrium constants (Kv-s ) values for
hydrate prediction.(6.17-6.20) These are presented in Figure 6.9-Figure 6.13 and are the Kv-s charts for this
method as redrafted by the GPSA and modified for use herein. Figure 6.12 replaces the figure in the original
work.(6.21)
In spite of some theoretical flaws in the method it has proven reliable up to about 7 MPa [1000 psia].
Some of the curves do not exceed this pressure. With others the accuracy begins to decrease as the values
converge to Kv-s = 1.0.
In the original work it was assumed that nitrogen was a non-hydrate former and that n-butane
had the same Kv-s value as ethane. Later work has shown these to be technically incorrect. A Kv-s curve is
now provided for n-butane. Nitrogen is a hydrate former, and it is likely that some nitrogen may end up
in the hydrate lattice in typical natural gas production systems. However, it is not a factor in determining
hydrate formation conditions unless you are working with mixtures of nitrogen and methane which are
sometimes found in coalbed methane production. In these cases the N2-CH4 mixture will have a lower
hydrate formation temperature than pure methane. As a practical matter using Kv-s = infinity for nitrogen
gives satisfactory results for typical natural gas mixtures.
This method should only be applied to gases that have minimal amounts of sour components
(CO2 and H2S), as it was developed to predict the hydrate formation conditions of “sweet” natural gas.
A dewpoint-type calculation is made using the Kv-s values shown. The term “yi” is the mole fraction
of each component in the gas. Kv-s equals infinity for all non-hydrate formers present.
/ (y i /K v - s) = 1.0 (6.5)
This is an iterative calculation around T or P. To calculate the hydrate formation temperature an
initial temperature is assumed and Kv-s values are obtained from Figure 6.9 thru Figure 6.13 at the assumed
temperature and the system pressure. If Equation (6.5) does not sum to 1.0, then a new temperature is
assumed and the calculation repeated. Example 6.3 shows a hydrate calculation using Equation (6.5).
Example 6.3: Find the hydrate formation temperature of the gas below at 2.0 MPa [290 psia].
At 10°C [50°F] At 9.4 °C [49°F]

Component yi Kv-s yi /Kv-s Kv-s yi /Kv-s
Nitrogen 0.094  0.000  0.000
Methane 0.784 2.04 0.384 2.03 0.386
Ethane 0.060 0.82 0.073 0.75 0.080
Propane 0.036 0.125 0.288 0.11 0.327
Iso-Butane 0.005 0.047 0.106 0.04 0.125
n-Butane 0.019 0.21 0.090 0.19 0.100
CO2 0.002 2.91 0.001 2.64 0.001
1.000 Σyi/Kv-s = 0.94 Σyi/Kv-s = 1.0
CHAPTER 6 161
Temperature, °F
35 40 45 50 55 60 65 70 75 80 85
4.0
700 kPa (abs)
1000
3.0 Methane
1500
2000
2500
Kv-s
2.0
3000
3500
4000
5000
5500
7000
10 000 15 000
20 000
1.0
0 5 10 15 20 25 30
Temperature, °C
Temperature, °F
35 40 45 50 55 60 65 70 75 80 85
2.0
000 000
30 0
1.5
00
)s)
000
000
0000 000 000 00

40 00
000
bbs
700 10 15 00 0000
25
0
(a(a
000
15
000
35
000
Paa
000 2
50
20
10
kkP
55
0
70
1.0
0.9 Ethane
0.8
0.7
0.6
0.5
Kv-s
0.4
Pressure
kPa psia
0.3 700 100
1000 145
1500 220
2000 290
2500 360
0.2 3000 435
3500 510
4000 580
5000 725
5500 800
7000 1015
10 000 1450
15 000 2175
20 000 2900
0.1
0 5 10 15 20 25 30
Temperature, °C
Figure 6.9 Vapor-Solid K Values for Methane and Ethane

Temperature, °F Temperature, °F
35 40 45 50 55 60 65 70 75 80 85 25 30 35 40 45 50 55 60 65 70 75 80 85
1
0
1
0
0
0
0.9
0 0
CHAPTER 6
15 00
0.8
2
0.8
700
25 00
s)
000
0.7
ab
1000
1000
0.6
10
1500
3500
2000
3000
700 kPa (abs)

2500
4000
0.6
Pa (
k
0
0.5
7000 5000
0.5
400
150
0
0.4
2500
200
0.4
0
0.3
Propane iso-Butane
350
0
0.3
550
0.2
000
10
0.2
0.1
0.08
Pressure Pressure
0.1
kPa psia
Kv-s
0.06 kPa psia
Kv-s
0.09
0.08 700 100 0.05 400 60
1000 145 700 100
0.07 1500 220 0.04 1000 145
0.06 2000 290 1500 215
2500 360 2000 290
3000 435 0.03
0.05 2500 360
3500 510 3500 500
0.04 4000 580 5500 790
5000 725 0.02 10 000 1430
7000 1015
0.03 10 000 1450
15 000 2175
20 000 2900
25 000 3625
0.01
0.02
0.008
0.006 Adapted to SI by GPSA

Adapted to SI by GPSA Original from University
Original courtesy AIME 0.005
of Alberta, 1975
0.01 0.004
0 5 10 15 20 25 30 -5 0 5 10 15 20 25 30
Temperature, °C Temperature, °C
Figure 6.10 Vapor-Solid K Values for Propane Figure 6.11 Vapor-Solid K Values for iso-Butane
163
Temperature, °F
30 35 40 45 50 55
3.0
Carbon Dioxide a
0 kP
130 Pa
2.0
0 0k
20 kP
a
0
2 50 Pa
0 0k
35 a
1.0 0 kP
0.9 4 00
Pa
0.8 0k
Kv-s
0.7 600 Pa
0 0 0k Pressure
0.6 7
kPa psia
0.5 1300 190
2000 285
0.4 2500 360
3500 500
0.3 4000 575
6000 860
7000 1000
0.2
-2.5 0 2.5 5 7.5 10 12.5 15
Temperature, °C
Temperature, °F
30 40 50 60 70 80 90
1.00
0.80 Hydrogen Sulfide
0.70
0.60
a
0.50 0 kP
70 a
0.40 0 kP
1 00 a
kP
0.30 3 00 Pa
1
0 0k
20
0.20 a
kP
a
kP
0 0
Kv-s
30
00
kPa
Pressure
50
000
kPa psia
700 100
15
0.10 1000 145

0.08 1300 190
0.07 2000 290
3000 435
0.06 5000 725
0.05 15 000 2175
0.04
0.03
-5 0 5 10 15 20 25 30 35
Temperature, °C
Figure 6.12 Vapor-Solid K Values for CO2 and H2S

Temperature, °F
25 30 35 40 45 50 55 60 65
0.50
0.40
0.30
L1
0.20
V Line
L1 L2 H
0.10 0
20
0.09
0.08
00
Kv-s
0.07
-15
500
400
350
0
0
600
25
30
0.06
700
Pressure, psia
0.05
0.04 Pressure
Transition Zone
kPa psia
about 13-16°C [55−61°F] or
0.03 1380 200 10 340−13 800 kPa [1500−2000 psia]
1725 250
2070 300 At low concentrations of nC4 (1 mol%)
2415 350 Kv-s goes to infinity at low end of
0.02 2760 400 transition zone range.
3450 500 At high concentrations of nC4 (6 mol%)
4140 600 Kv-s goes to infinity at high end of
4830 700
transition zone range.
6895 1000
0.01
-5 0 5 10 15 20
Temperature, °C
Figure 6.13 Vapor-Solid Equilibrium Constants for n-Butane
The preceding approach may also be applied using a different source of Kv-s values. Sloan,
et al.(6.22) present
Kv-s values which are dependent upon composition and type of hydrate structure (I or II).
Trekell-Campbell
The Katz method possesses pressure limitations and fails to adequately address the hydrate depres-
sion effects of molecules too large to fit into the cavities. The Trekell-Campell correlation(6.23), presented
in Appendix 6A, addresses these issues.
McLeod-Campbell Method
This work(6.24) is for use with high pressure gases above about 35-40 MPa [5000-6000 psia].(6.25)
Early work indicated erroneously that gas hydrate forming curves approach the pure methane curve at these
high pressures. This work proves that said curves are parallel to the methane curve and have essentially the
same slope for all gas mixtures.
A specific correlation was prepared from 41.4-69 MPa [6000-10 000 psia] using a modified
Clapeyron equation to describe the energy of phase transformation. Using available data this was reduced
to Equation (6.6).
CHAPTER 6 165
T = A(C') 0.5 (6.6)

SI FPS
Where: T = hydrate forming temperature K °R
A = correlation factor 2.16 3.89
C' = composite component factor calculated from values in — —
Table 6.1
Table 6.1
McLeod-Campbell Component Factors
Pressure C Values
MPa psia C1 C2 C3 iC4 nC4

41.4 6000 18 933 20 806 28 382 30 696 17 340
48.3 7000 19 096 20 848 28 709 30 913 17 358
55.2 8000 19 246 20 932 28 764 30 935 17 491
62.1 9000 19 367 21 094 29 182 31 109 17 868
69.0 10 000 19 489 21 105 29 200 30 935 17 868
In using Equation (6.6) you express the gas composition in terms only of the relative quantity of
methane through n-butane. All heavier molecules are ignored. Multiply this pseudo mol fraction by each
component’s “C” value from the table to find a composite value, C’, for substitution into Equation (6.6).
Example 6.4: Calculate the hydrate forming temperature of a gas at 41.4 MPa [6000 psia] with the
pseudo analyses shown.
Component Pseudo Mol Fr. C C’

C1 0.906 18 933 17 153
C2 0.066 20 806 1373
C3 0.018 28 382 511
iC4 0.005 30 696 153
nC4 0.005 17 340 87
Total 1.000 19 277
From Equation (6.6), T = (2.16)(19 277)0.5 = 300 K = 27 °C

T = (3.89)(19 277) 0.5 = 540 °R = 80 °F
Reference 6.25 presents hydrate data for a lean natural gas at pressures to 100 MPa [14 500 psia].
Hydrate Predictions for High Sour Content Gases

The methods presented previously provide reasonable results for sweet natural gases at a range of
pressures. The Katz method is not applicable for gases that contain significant amounts of H2S and CO2
even though Kv-s values are available. Hydrate formation conditions for sour gas content streams can vary
significantly from those composed solely of hydrocarbons. The hydrate formation temperature of a natural
gas stream is generally increased with the presence of H2S.
Baille and Wichert(6.26) developed a method for predicting the hydrate formation temperature of
high H2S content gases, shown in Figure 6.14a & b. Example 6.5 demonstrates the use of this method.

Figure 6.14a Hydrate Chart for Gases Containing H2S SI Units (Courtesy of GPSA)
CHAPTER 6 167
Figure 6.14b Hydrate Chart for Gases Containing H2S FPS Units (Courtesy of GPSA)

Example 6.5: For the following gas composition at 3800 kPa [563 psia], determine the hydrate
formation temperature using Figure 6.14a & b.
Component Mol %
H 2S 10.00
C1 87.00
C2 2.25
C3 0.50
iC4 0.25
MW 18.4
γ 0.64
SI Solution:
Step 1. Enter the bottom chart in Figure 6.14(a) at 3800 kPa. Proceed horizontally to the H2S
concentration curve (10.0%).
Step 2. From this intersection point, proceed down vertically to the relative density of the gas
line. (γ = 0.64).
Step 3. Follow the diagonal guide line to the temperature at the bottom of the graph.
T = 20°C.
Step 4. Apply the C3 correction using the insert titled C3 Adjustment. Enter the left hand side
of the figure at the H2S concentration and proceed to the C3 concentration line. From
this intersection, proceed down vertically to the system pressure and read the tempera-
ture correction on the left hand scale. T = –2.1°C. Note that the temperature correction
is negative when the propane concentrations are low (left hand side of graph), and
positive when the propane concentrations are high (right hand side of graph).
Step 5. Calculation of the hydrate formation temperature:
TH = 20 – 2.1 = 17.9°C
FPS Solution:
Step 1. Enter the bottom figure of the chart at 563 psia. Proceed to the H2S concentration
curve (10.0%).
Step 2. From this intersection point, proceed down vertically to the relative density of the gas
line. (γ = 0.64).
Step 3. Follow the diagonal guide line to the temperature at the bottom of the graph.
T = 68 °F.
Step 4. Apply the C3 correction using the insert titled C3 Adjustment. Enter the left hand side
of the figure at the H2S concentration and proceed to the C3 concentration line (0.5%).
From this intersection, proceed down vertically to the system pressure and read the
temperature correction on the left hand scale. T = –3.8°F. Note that the temperature
correction is negative when the propane concentrations are low (left hand side of graph),
and positive when the propane concentrations are high (right hand side of graph).
Step 5. Calculation of the hydrate formation temperature:
TH = 68 – 3.8 = 64.2°F
CHAPTER 6 169
In Example 6.5 the calculated hydrate formation temperature is 17.9°C [64.2°F]. Using the Katz
method on the same composition, the calculated hydrate formation temperature is 14.8°C [58.6°F]. This is
a good illustration of why using the Katz method for gases containing H2S is not recommended.
The impact of CO2 addition to the hydrate formation temperature of a gas varies with the gas
hydrocarbon composition. The hydrate formation temperature for pure methane at a fixed pressure will
slightly increase with the addition of CO2. For a typical “sweet” natural gas composition, the addition of
CO2 often decreases the hydrate formation temperature. For gases containing a significant amount of CO2
and/or H2S it is often recommended to use an equation of state method validated by experimental data to
more accurately predict the hydrate formation temperature of the gas stream.
Equation of State Calculations

A series of EOS-based solutions have been developed for prediction of hydrate forming condi-
tions.(6.8,6.27- 6.37) In general, these are preferred to the empirical correlations shown here. This is particularly
true for gases containing non-hydrocarbon components, and for systems where liquid hydrocarbons may
be present. As stated earlier, empirical data is based on the measurement of the hydrate melting point
(often referred to as the hydrate dissociation point). The actual hydrate formation temperature will be
lower than the dissociation temperature. Regardless of the methodology used to predict hydrate formation
conditions, it should be recognized that the accuracy of the correlations is at best plus or minus 1°C [2°F]
for normal systems and several degrees greater than this for systems where the aqueous phase contains salt
or a hydrate inhibitor such as methanol or glycol. Accuracy also decreases with increasing pressure and
when the gas composition includes significant amounts of H2S and CO2.
HYDRATE PREVENTION
Remember that hydrates can form only when the gas is saturated with water. This assumption is
implicit in any hydrate correlation.
In addition, when using the correlations presented in this text it is assumed that no liquid hydrocar-
bon or ice is present in the system. (Small amounts of liquid hydrocarbon have little effect on the hydrate
temperature.)
Hydrates are a problem only if they are allowed to agglomerate to a degree where they restrict or
stop flow. Turbulent flow with liquid hydrocarbons present, coupled with straight piping runs containing a
minimum of elbows, tees, reducers, strainers, etc., will often reduce the observed hydrate point below that
calculated. In a multi-phase pipeline the liquid can sometimes keep the hydrates from attaching themselves
and growing. The same is true of wellbore flow. In many production systems the design case for hydrate
mitigation is at shut-in conditions.
There are three main approaches to hydrate prevention.
1. Dehydrate the gas.
2. Control the temperature and/or the pressure of the gas to be outside of the hydrate formation
conditions. Options include a heater and/or insulation.
3. Inhibit the system with chemicals.
The most effective method of preventing hydrates (and corrosion) is to keep the lines and equipment
“dry”, i.e., free of liquid water. Often it is not economically practical to dehydrate the gas. This results in
the requirement to operate a system (pipeline or processing facility) with liquid water present in the system.
It may not be feasible to provide line heaters and insulation to maintain the system temperature above the
hydrate condition. If this is the case, and the minimum system temperature is below the hydrate forming

temperature, then inhibition of this water is necessary. There are two main types of chemical inhibitors:
1. Thermodynamic Inhibitors
2. Low Dosage Hydrate Inhibitors (LDHI)
Thermodynamic inhibitors (glycols or methanol) lower the hydrate formation temperature. Usually
methanol, monoethylene glycol (MEG) or diethylene glycol (DEG) are used. All may be recovered and
recirculated, but in many cases the economics of methanol recovery may not be favorable. LDHIs are either
kinetic hydrate inhibitors (KHIs), or antiagglomerants (AAs). LDHIs do not lower the hydrate formation
temperature. KHIs increase the time it takes hydrates to form. AAs do not prevent hydrates from forming,
but inhibit the agglomeration of small hydrate crystals.
Methanol may be used effectively at any temperature. It is not generally recommended to use DEG
below about –10°C [14°F] because of its viscosity and the difficulty of separation if liquid hydrocarbons
are present. Above –10°C [14°F] it might be preferred because there is less vaporization loss than MEG or
MeOH.
The total injection rate is that required to provide the necessary inhibitor concentration in the liquid
water plus that inhibitor which enters the vapor phase, and the hydrocarbon liquid phase if present. Any
inhibitor in the vapor phase has little effect on hydrate formation conditions.
Equation (6.7)(6.38) developed by Hammerschmidt in 1934 has been found reliable for prediction
of the inhibitor concentration necessary in the water phase to suppress the hydrate forming temperature a
given amount.
(d)(MWinhib) (6.7)
X R = K + (d)(MW (100)
i inhib)
SI FPS
Where: d = depression of hydrate point °C °F
XR = weight percent inhibitor in the liquid water phase — —
(rich inhibitor concentration)
MWinhib = molecular weight of inhibitor — —
Ki = constant 1297 2335
Equation (6.7) can also be written in terms of d.

Ki XR
d = MW (100 (6.8)
inhib – X R)
Equation (6.7) is a simplification of the actual thermodynamic relationship between hydrate

depression (d) and inhibitor concentration (XR). However, when using the constants shown above, Equation
(6.7) does an excellent job of matching laboratory equilibrium data for hydrate suppression with methanol
solutions up to about 25 wt% and MEG to about 50 wt%.
Some references have suggested a range of Ki values of 1297-2222 [2335-4000] for glycols. Higher
values of Ki result in lower concentrations of rich (diluted) glycol (XR in Equation (6.7)) which, in turn,
suggests a lower inhibitor injection rate. Experimental data from GPSA Research Reports (6.39-6.40, 6.54)
suggests Ki = 1297 [2335] is the correct constant as illustrated in Figure 6.15. However, in some systems
hydrate formation has been prevented with glycol concentrations corresponding with Ki values as high as
2222 [4000].
CHAPTER 6 171
140 250
Hammerschmidt
K i = 2222 [4000]
120
Hammerschmidt
K i = 1297 [2335]
200
100
Nielsen & Bucklin
150
80 85 wt%
d, °F
d, °C
MeOH RR -106
60 73.7 wt%
MeOH RR -106 100
40 25 wt% MEG RR -92 65 wt% MeOH RR -106

70 wt% MEG RR - 205 50
20 50 wt% MeOH RR -106

50 wt% MEG RR -92 50 wt% MeOH RR -92
25 wt% MeOH RR -92
0 0
0 10 20 30 40 50 60 70 80 90
Inhibitor Concentration, mol%
Figure 6.15 Hydrate Suppression vs. Inhibitor Concentration in Mol %, Comparison of Correlation and Data
In truth, no one value of Ki applies to all systems because it is affected by system dynamics,
configuration, location and method of injection, etc. It is good practice to design a system using a Ki of
1297 [2335]. Once the system is operating most experienced operators will adjust the injection rate to the
minimum required to prevent hydrate formation.
Correlations other than Equation (6.5) have been proposed. For methanol concentrations up to
about 80 wt% and MEG concentrations to about 70 wt% the following equation by Nielsen and Bucklin(6.41)
is more representative of empirical data.
d = Aln ^1 – x mh or
(6.9)
x m = 1 – e d/A
SI FPS
Where: d = depression of hydrate point °C °F
xm = mol fraction of inhibitor in the liquid water phase – –
A = constant –72 –129.6
Note that the inhibitor concentration in Equation (6.9) is expressed as a mol fraction rather than a
weight percent. Equations (6.10) and (6.11) can be used to convert molar concentrations to mass concentra-
tions. In addition, Figure 6.16 may be used in lieu of the equations.
e o
wt% inhib
MWinhib
mol% = (100) (6.10)
wt% inhib _100 – wt% inhib i
> H
MWinhib + 18
_ mol% inhib i_MWinhib i
7((mol% inhib) (MWinhib) + 18 (100 - mol% inhib))A
wt% = (100) (6.11)
Where: MW of methanol = 32
MW of MEG = 62

100% The quantity “d” is found by first

predicting the hydrate forming temperature
90%
at the maximum pressure in the system. The
80% minimum flowing temperature is then estimated.
70% EG The quantity “d” is the difference between these
M
l two numbers. In the absence of a more defini-

60% no
ha tive number, 4-10°C [39-50°F] may be used as
et
wt %
M
50%
a reasonable minimum flowing temperature for
40% buried lines and lines at the bottom of a body of
30%
water over 30-40 m [100-130 ft] deep. In ultra-
deep water, the minimum flowing temperatures
20%
may be 0°C [32°F], or slightly lower.
10%
The inhibitor injection rate to satisfy the
0%
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
required aqueous phase inhibitor concentration is
mol % found from the Equation (6.12):
Figure 6.16 Molar Percent to Weight Percent

Conversions for MEG and MeOH
X
m I = m w d X –RX n (6.12)
L R
SI FPS
Where: mI = mass flow of inhibitor solution kg/d lbm/day
mW = mass flow of liquid water kg/d lbm/day
XR = rich inhibitor concentration wt%
XL = lean inhibitor concentration wt%
The lean inhibitor concentration, XL, is almost always 100% for methanol and typically varies from
60-80% for glycols. The rich inhibitor concentration, XR, is determined from Equation (6.7) for field and
pipeline inhibition. For inhibition in gas processing plants, the ability to adequately mix the inhibitor and
gas in the piping or exchanger is the primary concern. In these cases, the rich inhibitor concentration is set
based on two criteria: 1) hydrate depression and 2) mixing. The mixing requirement usually dominates and
often results in a specified dilution (XL to XR ) of 10% or less. The concentrations of both the lean and rich
glycol must be kept in the non-freezing region (see Figure 6.20).
Table 6.2 lists useful properties of common inhibitors.
Table 6.2
Inhibitor Properties
MeOH MEG DEG

Molecular Weight 32 62 106
Density: g/cm3 0.80 1.11 1.12
kg/m3 800 1110 1120
lbm/ft3 49.7 69.4 69.6
lbm/U.S. gal 6.64 9.27 9.30
lbm/bbl 279 389 390
CHAPTER 6 173
Inhibition in the Presence of Salts in Produced Water

Most produced water contains dissolved inorganic salts. These salts can lower the hydrate formation
temperature both with and without the presence of an equilibrium inhibitor such as methanol and glycol.
Reference 6.42 provides experimental
Hydrate Formation Temperature, °F
data for three salts, NaCl, CaC12 and KC1 both 35 40 45 50 55 60 65
11000 1600
alone and in the presence of methanol. NaC1 10000
Pure Water
20% NaCI 1400
and CaC12 have similar inhibition characteristics, 9000 20% MeOH
i.e., for the same mass concentration the hydrate 8000
5% MeOH 15% NaCI 1200
5% MeOH 5% NaCI
suppression is the same. This is because the 7000
Pressure, psia
Pressure, kPa
1000
normality of the solution is similar for NaC1 and 6000

800
CaC12 for equivalent mass concentrations. KC1 5000
is less effective since it has a lower normality. 4000 600
3000
400
In general, both NaC1 and CaC12 have 2000
a slightly larger hydrate suppression effect than 1000
200
methanol. Equations (6.7) and (6.8) can be used 0 0

0 4 8 12 16 20
to estimate the hydrate suppression effect of these Hydrate Formation Temperature, °C
salts, if Ki is changed to 2500 [4500]. The appli-
cable range is limited to concentrations less than Figure 6.17 Hydrate Inhibition with Methanol and NaCl(6.41)
about 20-25 wt%.
Figure 6.17 shows the inhibition effect of mixtures of methanol and NaCl in the aqueous phase.
Inhibitor Losses to the Hydrocarbon Phase

Inhibitor may be lost due to its solubility in the hydrocarbon liquid and vapor phases. For glycol
systems these losses are small. Table 6.3 provides useful guidelines.
Table 6.3
Glycol Losses
Glycol Losses
Vapor 3.5 L/106 std m3 0.23 lbm/MMscf
Liquid nil nil
It should be recognized that entrainment of glycol in both the hydrocarbon vapor and liquid phases
can be substantial, especially in systems where the performance of the separation equipment is inefficient.
Methanol losses are more significant, particularly vapor phase losses.
Figure 6.18a & b can be used to estimate methanol losses to the vapor phase. It is based on data
from references 6.43-6.46, 6.53.
At the system pressure and temperature read the methanol K-value from the y-axis. The mass of
methanol in the vapor phase can then be calculated from the Equations (6.13a) and (6.13b):
SI: (kg MeOH/106 std m3) = 1.35 # 106 (K)(x) (6.13a)

FPS: lbm MeOH/MMscf = 84 300 (K)(x) (6.13b)
Where x is the mol fraction of methanol in the water phase.

0.0500
25° 37.8°C RR 149 -3.9°C RR 149 Extrapolation
C
20°C 20°C RR 117 -3.9°C Jacoby
11°C RR 149 -10°C RR 117
15°C
4.4°C Jacoby
10°C
MeOH K-Values, K = y/x
5°C
0.0100
0°C
-5°C
-10
°C
0.0010
0.0005
0.6 1.0 10 30
Pressure, MPa
Figure 6.18a Methanol K-Values in Natural Gas, SI Units(6.55)(6.56)
0.0500
Extrapolation
100°F RR 149 25°F RR 149
68°F RR 117 25°F Jacoby
70° 51.8°F RR 149 14°F RR 117
F
60° 40°F Jacoby
F
50°F
MeOH K-Values, K=y/x
0.0100 40°F
30°F
20°
F
10°F
0.0010
0.0005
100 1000 4000
Pressure, Psia
Figure 6.18b Methanol K-Values in Natural Gas, FPS Units(6.55)(6.56)
Methanol losses to the hydrocarbon liquid phase are more difficult to predict. Solubility is a strong
function of both the water phase and hydrocarbon phase compositions(6.57). Figure 6.19 shows solubility
of methanol in various hydrocarbon liquids: paraffin and mixtures of paraffins and toluene. The y-axis is
a distribution coefficient which is the mol fraction of methanol in the aqueous phase divided by the mol
fraction of methanol in the hydrocarbon phase. Lower values for the distribution coefficient indicate higher
hydrocarbon solubility. The use of a distribution coefficient to estimate methanol losses to the hydrocarbon
liquid phase is shown in Example 6.6.
CHAPTER 6 175
Temperature, °F
-50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140
)Mol fraction MeOH in Hydrocarbon Phase
Mol fraction MeOH in Aqueous Phase
1000
No Toluene
28 - 33 Mol% Toluene
100
10
(
Distribution of methanol between aqueous and

Distribution Ratio
hydrocarbon phases, data from various sources.

Hydrocarbon phases includes various alkane and
cycloalkane compounds. Data shows the variation
of distribution with changes in the amount of
toluene in the hydrocarbon phase.
1
-50 -40 -30 -20 -10 0 10 20 30 40 50 60
Temperature, °C
Figure 6.19 Liquid-Liquid Distribution Ratios for Methanol and Hydrocarbons(6.57)
Calculation Summary
The inhibition calculation procedure may be summarized as follows:
1. Determine the hydrate formation temperature of the gas.
2. Establish the lowest temperature expected in the system.
3. Compute the amount of liquid water present at the temperature in Step 2, using a suitable
water content correlation. This will be the sum of the condensed water plus any liquid water
entering the system.
4. Use Equation (6.7) to solve for “XR.” In the equation “d” is the temperature in Step 1 minus
that in Step 2. Calculate the weight of inhibitor from Equation (6.12), using XR from Equation
(6.7). (Note, if Equation (6.9) is used to calculate xm, it must be converted to a weight percent,
XR, before being used in Equation (6.12).)
The volume rate of injection of solution will be the weight of inhibitor per unit time divided
by its density, after correcting for concentration.
5. If methanol is used, one must correct for that amount lost to the hydrocarbon vapor and liquid
phases using Figure 6.18a & b, and Figure 6.19.
6. Total injection rate equals that found from Step 5 plus that from Step 4. This is the rate of
inhibitor solution.

Example 6.6: 3.5 × 106 std m3/d [124 MMscfd] of natural gas leaves an offshore platform at 40°C
[104°F] and 8000 kPa [1160 psia]. The hydrate formation temperature of the gas is
17°C [63°F]. The gas arrives onshore at 5°C [41°F] and 6500 kPa [943 psia]. Associ-
ated condensate production is 60 m3/106 std m3 [10.7 bbl/MMscf]. The condensate
relative density is 0.78, and MW = 140.
Calculate the amount of methanol and 80% MEG inhibitor required to prevent hydrate
formation in the pipeline. Use 1100 kg/m3 [9.19 lbm/U.S. gal] for the density of the
80wt % MEG solution
SI Solution (Methanol):
Step 1. Hydrate formation temperature = 17°C.

Step 2. Lowest temperature in system = 5°C, therefore; d = 17 – 5 = 12°C.
Step 3. Water content at inlet of pipeline @ 40°C and 8000 kPa = 1000 kg/106 std m3
Water content at outlet of pipeline @ 5°C and 6500 kPa =160 kg/106 std m3
3.5 # 106 std m3 kc (1000 - 160)kg m =
Water condensed a d 2940 kg H 2 O/d
106 std m3
Step 4. Calculate inhibitor concentration from Equation (6.7).
(12) (32) (100)
X R = 1297 + (12) (32) = 23 wt%
Calculate mass of inhibitor required in water phase from Equation (6.12).

(2940) (23)
mI = = 880 kg/d
(100 - 23)
Step 5. Determine methanol losses to the hydrocarbon phases.
Vapor losses: From Figure 6.18a determine methanol K-value.
K-value at 6500 kPa and 5°C = 0.0020
From Figure 6.16, 23 wt % = 14 mol %
From Equation (6.13a),
MeOH kg 6 kg
6 3 = (1.35 # 10 ) (0.002)(0.14) = 380
10 std m 10 std m 3
6
3 a
380 kg 3.5 # 106 std m3 k = 1330 kg
Losses per Day: 6
10 std m d d
Liquid hydrocarbon phase losses:
From Figure 6.19 at 5°C, and assuming a substantially paraffinic hydrocarbon

liquid,
mol frac. MeOH in aqueous phase

distribution coefficient = 110 mol frac. MeOH in hydrocarbon phase
MeOH in hydrocarbon phase =
mol frac. MeOH in aqueous phase 0.14
Dist. coefficient = 110 = 0.0013 mol frac. MeOH
CHAPTER 6 177

780 kg kmol
Mols MeOH per m3 cond. = ^0.0013hc mc m kmol MeOH
m3 140 kg = 0.0072 m3 cond.
kmol MeOH a
Mass MeOH per m3 cond. = a0.0072 k 32 kmol k = 0.23 3
kg kg MeOH
m3 m cond.
Total MeOH losses in hydrocarbon liquid phase per day:
c
0.23 kg
mc 60 m
3
cond. ma 3.5 # 106 std m3 k = 50 kg MeOH
m MeOH 10 std m3
3 6 d d
Total losses per day = 1330 kg/d + 50 kg/d = 1380 kg/d

(vapor phase) (liquid phase)
Total MeOH injection rate

= 880 kg/d + 1380 kg/d = a kd m na 1 d k = 0.12 m3 /h
2260 kg 3
(water phase) (losses) d 800 kg 24 h
SI Solution (MEG):
For 80% MEG solution calculate XR from Equation (6.7).

(12)(62)(100)
X R = 1297 + (12)(62) = 36.5 wt%
Calculate the mass of inhibitor required in the water from Equation (6.12).
(2940)(36.5) kg
mI = - = 2470 d
(80 36.5)
Total MEG inhibitor injection rate:
a kc m ma 1 d k = 0.094 m
2470 kg 3 3
d 1100 kg 24 h h
FPS Solution:
Step 1. Hydrate formulation temperature = 63°F.

Step 2. Lowest temperature in system = 41°F, therefore d = 63 – 41 = 22°F
Step 3. Water content at inlet of pipeline at 104°F and 1160 psia = 63 lbm/MMscf
Water content at outlet of pipeline at 41°F and 943 psia = 9.5 lbm/MMscf
124 MMscf ka (63 - 9.5) lbm k

Water condensed = a day MMscf = 6640 lbm/day
Step 4. Calculate inhibitor concentration from Equation (6.7).

(22)(32)(100)
X R = 2335 + (22)(32) = 23 wt%
Calculate mass of inhibitor required in water phase from Equation (6.12).

(6640)(23)
mI = = 2000 lbm/day
(100 - 23)


Step 5. Calculate losses to the hydrocarbon phases.
Vapor losses: From Figure 6.18b determine methanol K value at 41°F and 943 psia.
K = 0.0020
From Figure 6.16, 23 wt % = 14 mol %
lbm MeOH = 23.6 lbm MeOH
From Equation (6.13b), MMscf (84 300)(0.002)(0.14) = MMscf
Methanol vapor losses per day:
a 23.6MMscf
lbm MeOH kc
124 day m = 2930
MMscf lbm MeOH
day
Methanol hydrocarbon liquid losses:
From Figure 6.19 at 41°F, and assuming a substantially paraffinic hydrocarbon

mol frac. MeOH in aqueous phase
liquid, the distribution coefficient = 110 mol frac. MeOH in hydrocarbon phase
Concentration of MeOH in liquid hydrocarbon phase =
a 0.14
110 k = 0.0013 mol frac. MeOH
Determine the density of the condensate in lbm/bbl:
(0.78) ^350 lbm/bblh = 273 bbl

lbm
a (0.0013) lb- mols MeOH ka273 lbm ka lb - mol k = 0.0025 lb- mol MeOH
lb-mol condensate bbl 140 lbm bbl
Mass MeOH per bbl condensate =
a 0.0025 lb - mol MeOH ka 32 lbm k = 0.08 lbm MeOH

bbl - lb mol bbl cond.
MeOH liquid phase losses per day =
c 124 MMscf ma 10.7 bbl ka 0.08 lbm MeOH k = 110 lbm MeOH
day MMscf bbl cond. day
Total methanol losses per day = 2930 + 110 = 3040 lbm/day MeOH
Total injection rate = (2000 + 3040) lbm MeOH/d
MeOH ma 1 U.S. gal ka 1 day k =

= c5040 lbmday 6.64 lbm 1440 min 0.53 U.S. gpm
^0.53h^1440h 18 bbl
=
42 day
CHAPTER 6 179

FPS Solution – MEG
For 80% MEG solution – calculate XR from Equation (6.7).

(22)(62)(100)
X R = (2335) + (22)(62) = 36.9 wt%
Calculate mass of inhibitor required in the water from Equation (6.12).

(6640)(36.9)
mI = = 5700 lbm/d MEG solution
(80 - 36.9)
Total MEG inhibitor injection rate:
a 5700 lbm ka ka 1 day k =

1 gal
=
day 9.19 lbm 1440 min 0.43 U.S. gpm 15 bbl/day
Example 6.7: Compare the Neilsen and Bucklin method inhibitor injection requirements for both
methanol and MEG with the Hammerschmidt results presented in Example 6.6.
SI Solution:
Determine the required inhibitor concentration (applies both the MeOH and MEG)
from Equation (6.9).
From Example 6.6:
d = 12oC and the water condensed = 2940 kg H2O/d
From Equation (6.9):
xm 1 – e ((12)/(–72)) 0.154 = 15.4 mol%

FPS Solution:
Determine the required inhibitor concentration (applies both the MeOH and MEG)
from Equation (6.9).
From Example 6.6:
d = 22oF and the water condensed = 6640 lbm H2O/d
From Equation (6.9):
xm = 1 – e((22)/(–129.6)), xm = 0.154 = 15.4 %
A comparison of the results from Neilsen Bucklin method with the Hammerschmidt
Method for this example is shown:


Neilsen Bucklin Hammerschmidt (Example 6.6)
MeOH
wt % MeOH in water phase 24.4% 23%
Mass MeOH in water phase 950 kg/d [2140 lbm/day] 880 kg/d [2000 lbm/day]
MeOH vapor phase losses 1460 kg/d [3220 lbm/day] 1330 kg/d [2930 lbm/day]
MeOH hydrocarbon liquid 53 kg/d [120 lbm/day] 50 kg/d [110 lbm/day]
phase losses
Total Required MeOH 2463 kg/d [5480 lbm/day] 2260 kg/d [5040 lbm/day]
injection rate
MEG
wt% MEG in water phase 39% 36.5%
Total required MEG 2800 kg/d [6300 lbm/day] 2470 kg/d [5660 lbm/day]
injection rate
The Nielsen Bucklin method results in a 9% increase in the MeOH injection rate,
and a 13% increase MEG injection rate as compared to the Hammerschmidt method.
Crystallization (Freezing) of Glycols

Glycols do not freeze solid but form a “mushy” solution that nevertheless does not flow very well.
The concentration must be such that this is avoided.
Figure 6.20 shows the “freezing
point” for MEG water solutions. The 0 32
curve goes through a minimum. At a given

temperature the concentration should be
kept between the lines. A value of about -10 14
60-70 wt % glycol is safe at any likely

temperature.
-20 -4
If the minimum system tempera-
ture is below –10°C [14°F], the injection
Temperature, °C
Temperature, °F
rate must satisfy Figure 6.20 and Equations
(6.7) and (6.12). Typically the lean MEG -30 -22
solution injected will contain 20-30 wt %

water.
-40 -40
Inhibitor Selection
Hydrate inhibition with methanol = RR -205 (Ref. 6.54) Experimental Data
or MEG is common in pipeline applica- -50
Note: Shaded region represents range
of experimental data where freezing -58
may have been observed.
tions, as well as in gas processing facilities.
The choice of inhibitor for a specific
application is influenced by a number of -60 -76
0 20 40 60 80 100
factors. A few of these are listed in Table
wt% MEG in Aqueous Solution
6.4:
Figure 6.20 Freezing Points of MEG-Water Solutions
CHAPTER 6 181
Table 6.4
Comparison of MeOH and MEG Advantages and Disadvantages
Comparison MeOH MEG

Advantages 1. Relatively inexpensive 1. Low vapor phase losses
2. Very low freezing point (low vapor pressure)
3. Requires lower concentrations in the 2. High flash point (not as flammable as MeOH)
aqueous phase 3. Can be easily regenerated
4. Lower viscosity than MEG 4. Less toxic than MeOH
5. Transported in the vapor phase after 5. Generally not considered a contaminant in hy-
injection point which can be helpful for drocarbon vapor and liquid products
disassociating hydrates in downstream 6. Provides corrosion inhibition for “top of line cor-
piping rosion” in pipeline
6. Can inhibit to –100°C [–148°F] 7. Can inhibit to –40°C [–40°F]
Disadvantages 1. High losses in vapor phase 1. Relatively expensive (roughly three times the
2. MeOH contamination of hydrocarbon cost of MeOH)
vapor and liquid phases 2. Contaminants in water phase of produced fluids
3. More toxic than MEG are concentrated in the MEG phase during
regeneration which requires special regeneration
4. Flammable (low flash point) designs
5. Regeneration more complex 3. Higher viscosity makes separation from hydro-
carbon liquid phase more difficult
4. Requires higher concentrations in the aqueous
phase
5. Transported in the liquid phase once injected
which makes it less effective for disassociating
hydrates in downstream piping
Figure 6.21 provides a comparison of

H H H the important physical property comparison
H C OH HO C C OH
between methanol and MEG.
Applications that require continu-
H H H
ous inhibition typically use MEG. Methanol
Methanol Monoethylene Glycol is generally used in applications that have
MW = 32 MW = 62 intermittent inhibition requirements, such as
sp. gr. = 0.80 sp. gr. = 1.11 start-ups and shutdowns, or during periods
NBP = 65°C [149°F] NBP = 198°C [388°F] of cold weather. Methanol contamination
Pv at 0°C [32°F] = 29.8 mmHg Pv at 0°C [32°F] = < 0.1 mmHg
resulting from the high vapor and liquid phase
Viscosity at 0°C [32°F] = 0.79 cP Viscosity at 0°C [32°F] = 33.5 cP
Flash Point = 4°C [39°F] Flash Point = 127°C [261°F]
losses has become a more significant issue due
Freezing Point = –93.9°C [-137°F] Freezing Point = –11.5°C [11.3°F] to increasingly stringent contaminant specifi-
cations for natural gas, NGLs, and condensate
Figure 6.21 Comparison of Physical Properties of Pure MeOH products.
and MEG

Inhibition in Refrigeration Systems

Figure 6.22 shows a flow diagram for a typical MEG injection system in a refrigeration process. The
process shown is a mechanical refrigeration system but glycol injection is also used in LTS and expander
processes. In these facilities, the glycol inhibitor is sprayed into the gas upstream of heat exchangers,
expansion valves or expanders. The exchanger type can be shell and tube, plate or brazed aluminum. As
water condenses, the inhibitor is present to mix with the water and prevent hydrates. Injection must be in a
manner to allow good distribution in the gas flow path. It is common practice to inject 2 to 3 times the glycol
rate calculated using the methodology presented earlier in this chapter. The additional cost of overdosing
with MEG is low because the circulation rates are small relative to the process flows and in a well-designed
system virtually all of the glycol can be recovered.
The viscosity of MEG and its aqueous solutions increases significantly as temperature decreases.
This effect must be considered in the design and rating of exchangers in low temperature gas processing
facilities.
The inhibitor and condensed water mixture is separated from the gas stream along with a separate
liquid hydrocarbon stream. Experimental data(6.47) suggests that the water dewpoint of the gas will be
somewhat lower than the cold separator temperature. For a 50 wt % MEG solution at typical cold separator
pressures, 2.5-5.0 MPa [362-725 psia], the metastable water dewpoint of the vapor in equilibrium with
the MEG-water solution is approximately 5°C [9°F] lower than the actual separator temperature. For a 70
wt% MEG solution the equilibrium metastable dewpoint was about 11°C [20°F] lower the than separator
temperature. For higher pressures, 10-20 MPa [1450-2900 psia], typical of those encountered in high
pressure long haul pipelines, the dewpoint suppression was 1-2°C [2-4°F] less than at lower pressure condi-
tions. It is important to note that these are metastable dewpoints not hydrate dewpoints. As discussed earlier
in this chapter, hydrate dewpoints will be higher (warmer) than metastable dewpoints and the difference is
a function of both composition and pressure.
Glycol-water solutions and liquid hydrocarbons can emulsify when agitated or when expanded
from a high pressure to a lower pressure, e.g., J-T expansion valve or expander. It is critical that the low
temperature separator be properly designed to ensure efficient separation between the two liquid phases.
Careful separator design normally allows nearly complete recovery of the diluted glycol for regeneration
and reinjection. The regenerator in a glycol injection system should be operated to produce a regenerated
lean glycol solution that will have a freezing point (see Figure 6.20) below the minimum temperature
encountered in the system. This is typically 75-80 wt %.
Inhibitor Regeneration
An integral part of an inhibition system is the regeneration (sometimes referred to as reconcentra-
tion) of the inhibitor. Glycol is almost always regenerated due to its high purchased cost. Methanol may or
may not be regenerated depending on the rate of injection, whether it is continuous or intermittent, and local
environmental discharge regulations.
CHAPTER 6 183
184
Dry Residue Gas
Steam to
Atmosphere
Wet Inlet Gas

Propane Liquid
Vapor to Propane
Injection Refrigerant Refrigerant Cooling
Nozzle Compressor Supply Medium
Packed
Gas/Gas Exchanger Stripper
Column
Injection
Nozzle Flashed TIC
Hydrocarbon Heat
Vapor Medium
FI FI Supply
Gas Chiller and
Reboiler Return
LI
Lean Glycol
Surge Tank
Rich Glycol
Flash Tank
NGLs to Flow
Stabilizer Control
Cold Bypass
Separator Filter Valve
Rich Glycol Lean Glycol Glycol
Injection
Lean/Rich EG Pump
Exchanger
Figure 6.22 Typical Mechanical Refrigeration Plant with MEG Injection System (for Rich Wet Inlet Gas)

For MEG, regeneration temperatures range from 121-127°C [250-260°F]. The maximum regenera-
tion temperature is approximately 164°C [327°F] due to thermal decomposition of the glycol. The relative
volatility of water to MEG is about 30, so the regeneration requires only a few theoretical stages. Reboiler
heat is provided by hot oil, fire tube combustion, steam or electric coils.
Regeneration of methanol (distillate product) by fractionation is more difficult. The relative volatility
of methanol to water at atmospheric pressure is about 2.5. Methanol is regenerated to very high concentra-
tions, typically 99 wt %. Further, the required methanol concentrations in the water (bottom product) are
quite low to avoid methanol losses and to meet local environmental standards. As a result, the distillation
column can be tall; 20-30 m [66-100 ft] is not unusual. The tower operates near atmospheric pressure and
the typical reboiler temperature is 100-105°C [212-221°F].
Two points should be emphasized about methanol injection. First, due to methanol’s high vapor
pressure, losses to the vapor phase are not insignificant and can represent a sizeable portion of the facility
operating cost, especially in those applications where the cold separator temperature is warmer than
–10-0°C [14-32°F]. Second, methanol solubility in the hydrocarbon liquid stream often necessitates water
washing of the hydrocarbon liquid in order to meet sales specifications. This is usually accomplished by
a static mixer followed by a coalescer. If the hydrocarbon liquid stream is an NGL product, dehydration
downstream of the water wash may be required.
MEG Regeneration in Production Systems(6.47)

MEG is often used to inhibit flow lines in production facilities both onshore and offshore. In these
applications the aqueous phase will contain dissolved salts, mainly NaCl. Salt is not a major problem in
methanol injection systems since it leaves with the bottom product (water). However, in conventional MEG
regeneration units with a reboiler and still column, the salt accumulates and precipitates, causing severe
problems with fouling, corrosion and MEG thermal degradation. Additional equipment to remove the salt
via a separate MEG Reclamation Unit, or integrated MEG Regeneration and Reclamation Unit, (“MRU”)
becomes necessary. There are two typical concepts for doing this:
1. Full Reclamation — rich MEG is regenerated and reclaimed in one integrated package. This
is often done on offshore platforms to save space; however, the size and cost of the reclama-
tion equipment can be high. In addition, significant heat is required in the process, although in
many facilities waste heat from gas turbine exhaust may be available.
2. Slipstream Reclamation — rich MEG is regenerated to produce salty lean MEG and a “slip-
stream” portion of the lean MEG is sent to a separate MEG reclamation package. This is a
typical arrangement in onshore facilities. Lean MEG delivery systems can tolerate the presence
of some dissolved salt with 20-30 g/L [0.17-0.25 lb/U.S. gal] being a typical design limit. This
makes it unnecessary to produce totally salt-free lean MEG, which in turn can substantially
reduce the size and cost of the reclamation equipment.
Modern, large MRU units utilize flash vaporization where all the feed is immediately flashed under
vacuum on contact with a large flow of heated recycle fluid (see Figure 6.23a). The flashing and vapor
liquid separation occur inside the Flash Separator, which typically operates at 10-40 kPa [1.5-6 psia], and a
temperature below 145oC [293oF].
The salt precipitates and accumulates in the liquid pool in the lower part of the Flash Separator,
while MEG/water vapor exits the top and is fed to a rectification unit (regenerator) where the MEG is
separated from the water. For rich MEG reclamation, the MEG-water stream leaving the Flash Separator is
not condensed and the regeneration unit requires no additional heat.
CHAPTER 6 185
Non-Condensables
MEG + Water e.g., Light Hydrocarbons
Rich MEG Feed
Recycle
Liquid
Rectifier Water
(Regenerator)
Clean
Flash Separator MEG
Salt, Contaminated MEG + Heavy Hydrocarbons
Figure 6.23a Example MEG Reclamation Unit
Clean MEG Clean MEG
Rich MEG Feed Rich MEG Feed
Liquid
Recycle
Settling Tank
Filter,
Flash Separator Centrifuge
Flash Separator
Salt Cake or Slurry
Salt Slurry
Salt Extracted from Flash Separator Salt Extracted from Recycle Circuit
(Method shown in Fig 6.23a) (older design)
Figure 6.23b MEG Reclamation Unit Salt Extraction Options
The liquid leaving the bottom of the flash separator is concentrated, salt-laden MEG including any
other high boiling point components in the feed such as heavy hydrocarbons. It is heated and recirculated
to the Flash Separator at rates as high as 50-60 times the volumetric flow of the feed. The recycle liquid
feed is tangential to promote mixing with the rich MEG feed and high internal velocities to minimize salt
deposition. The heat exchanger is typically a spiral exchanger.

The recycle liquid contains salt crystals. In most units a slipstream of the recycle liquid is sent to a
solids removal unit which can be a settling tank, filter, or centrifuge. In newer designs solids separation is
done internally in the Flash Separator which reduces the salt content of the liquid recycle stream. Some MEG
is lost in the solids removal process. These losses depend on the wetness of the solids which in turn depends
on the solids removal scheme selected. Both of these salt extraction options are shown in Figure 6.23b.
Several aspects of the salt removal and MEG recovery elements of MRU designs on the market are
proprietary and protected by patents.
Calcium salts, e.g., calcium chloride (CaCl2 ) are problematic because they do not precipitate from
the recycle solution. This sometimes requires the injection of a precipitant such as sodium carbonate to
facilitate precipitation.
Thermal degradation of MEG and corrosion are both greatly accelerated if oxygen is present.
The MRU operates under vacuum, which demands care to avoid leakage at flanges, valve packing, etc.
Dissolved oxygen can also enter the system in the chemical injection solutions. To guard against these risks
it is standard practice to dose the MRU with oxygen scavenger. Sodium sulphite or similar is well suited for
this because the scavenging by-products, e.g., sulphates, can be removed with the other salts.
Low Dosage Hydrate Inhibitors (LDHIs)

Historically hydrates have been inhibited by the use of equilibrium (or thermodynamic) inhibitors
such as methanol and glycol. These lower the hydrate formation temperature by decreasing the chemical
activity of water. As we have seen from previous calculations the inhibitor concentrations required for
inhibition in producing and transportation systems can vary from 20-50 wt % depending on the inhibitor
used and the required hydrate suppression.
Figure 6.24 shows the P-T path for the formation of a hydrate in a laboratory cell.
The initial cell conditions start at point A.
Hydrate May The cell is cooled while being continuously mixed
Form Here
Start of Hydrate until hydrate formation is observed at point B, which
Formation A
n
coincides with an abrupt drop in the cell pressure (as
Metastable Regio
B gas molecules are trapped in the hydrate structure).
Cooling E Thermodynamic
Pressure
Point C represents the point where all of the water in

Hydrate Formation
Point
n
the cell has been converted to hydrate. At this point

io
iat
the cell is heated and at point D the hydrate begins

oc
iss
eD
to melt or dissociate. Finally at point E the hydrate

at
dr
Heating Hy is fully dissociated.

C D Start of Dissociation
Equilibrium hydrate models such as those
Temperature put forward in this chapter as well as those in most
commercial simulators identify “E” as the hydrate
Figure 6.24 Hydrate Formation
formation point. But, you can see from Figure 6.24
that a metastable region exists between E and B. This represents a region where hydrates may form given
sufficient time. The amount of sub-cooling necessary to trigger the formation of hydrates (TE – TB) varies
with several factors such as rate of cooling, degree of agitation, and presence of nucleation sites in the
water, but can be 10-15°C [18-27°F]. It is this metastable region and the associated kinetics of hydrate
formation that have spawned the development of low dosage hydrate inhibitors.
To date low dosage hydrate inhibitors (LDHIs) have fallen into two general categories—kinetic
hydrate inhibitors (KHIs) and antiagglomerants (AAs).
CHAPTER 6 187
LDHIs inhibition dosage concentrations range from 0.1 to 1.0 wt % polymer in the free water phase
depending upon the hydrate suppression requirements. This significantly reduces the required injection
rates as compared to thermodynamic inhibitors. Other significant benefits of LDHIs include:
1. Low vapor pressure (low vapor phase losses)

2. Low solubility in the liquid hydrocarbon phase (less than 10% partition)
3. Lower toxicity as compared to methanol or MEG
4. Reduced capital costs through decreased injection rate requirements, and decreased chemical
storage
5. Ideal for offshore applications where weight and space are critical to facility capital costs
6. Reduced operating costs (decreased chemical consumption and delivery frequency)
7. Where flowline or inhibitor injection capacity is limited, use of LDHIs may increase produc-
tion rates
Kinetic Hydrate Inhibitors

Kinetic hydrate inhibitors (KHIs) were Temperature, °F
40 50 60 70 80 90 100 110
designed to inhibit hydrate formation in subsea and 11 000
With 1550
Hydrates Pipeline
cold-weather environments. They have been success- 10 000
Inhibitor
In
1450
fully used in the southern North Sea since 1996. 1350
9000
Pressure, psia
Thermodynamic Equilibrium
Pressure, kPa
(6.48-6.49) Typical process applications for KHIs include

Inhibitors (MEG and Methanol) 1250
pipelines, flowlines, and downhole equipment. Note 8000

lower hydrate formation
temperature by freezing point 1150
depression.
that KHIs do not alter the thermodynamic hydrate 1050
7000
formation conditions as shown in Figure 6.25. They Out
950
inhibit hydrate formation by significantly reducing 6000 850
the rate of hydrate nucleation and growth. This 5000 750
mechanism is different from thermodynamic inhibi- 0 5 10 15 20 25 30 35 40 45
Temperature, °C
tors (methanol and MEG) which depress the hydrate
formation temperature. Figure 6.25 Hydrate Prevention with Thermodynamic Inhibitor
KHIs performance is limited to a minimum operating temperature. This minimum operating temper-
ature is determined by the difference of the process temperature and the equilibrium hydrate formation
temperature and is referred to as “subcooling”. For gas systems without acid gas components, current KHI
inhibition capabilities are up to 15.5°C [28°F] of subcooling. For gas systems that have sour components,
the limit is less than 11°C [20°F] of subcooling. The subcooling achievable with KHIs is time and flow
dependent. In flowing systems, shorter time periods at the subcooled conditions allow for higher subcool-
ing values. In non-flowing systems, the time that the inhibitor remains effective is often too short to allow
for pipelines to restart without other intervention, such as, temporary glycol and methanol injection or a
temporary decrease in pipeline pressure. These conditions must be maintained until adequate re-distribution
of KHI throughout the pipeline has occurred. It is important to note that the design subcooling must be
consistent with the expected system residence time.
Mixed inhibition (combination of KHI and methanol or glycol) has proven to be helpful in some
cases. The mixed inhibitor reduces the hydrate equilibrium temperature, but not below the operating
temperature of the pipeline. This, in effect, reduces the subcooling compared to pure KHI inhibition.
KHI-methanol and KHI-glycol injection schemes are useful where the operating temperature of the pipeline
results in subcooling that is outside the range of KHI performance, or where methanol only injection is not
desirable due to limited storage volumes or injection rate capabilities.

Antiagglomerant Inhibitors
Antiagglomerant inhibitors (AAs) were Temperature, °F
developed to extend the range of subcooling for 30 40 50 60 70 80 90 100 110
11 000
LDHIs beyond the capabilities of KHIs. These Pipeline 1550
AAs KHIs Hydrates In
10 000 1450
inhibitors are surface active molecules, often
1350
Pressure, psia
Pressure, kPa
with long oleophilic (oil loving) tails, which 9000
1250
keep the hydrate particles dispersed in the 8000 1150
hydrocarbon phase. AAs may not be effective 7000
1050
Out 950
in systems that have high water cuts. These
6000 850
inhibitors allow hydrates to form, but keep them
5000 750
suspended in the liquid phase so plugging is -5 0 5 10 15 20 25 30 35 40 45

avoided. AAs can achieve subcooling of greater Temperature, °C
than 22°C [40°F]. Due to the performance
Figure 6.26 Hydrate Prevention with LDHIs
characteristics of this inhibitor, it can perform
for longer periods of non-flowing conditions and may not require the addition of thermodynamic inhibitors
or pressure reduction after a shut-down or re-start. Figure 6.26 provides an example application of KHIs
and AAs for a pipeline.
Drawbacks of LDHIs include chemical cost, environmental issues (if discharged with produced
water) and possible emulsion formation in the liquid hydrocarbon stream. In addition, they do not inhibit
below the freezing point of water, 0°C [32°F]. The chemical compatibility of LDHIs with other production
chemicals, such as corrosion inhibitors, drilling fluid components, etc., can vary greatly. Both the effects
of the LDHIs on the performance of the production chemicals and the production chemicals on the perfor-
mance of the LDHIs must be studied to ensure expected performance in the field. Table 6.5 provides the
advantages and disadvantages of LDHIs.
Table 6.5
Comparison of KHIs and AAs Advantages and Disadvantages
Comparison KHIs AAs

Advantages 1. Injection of small volume of chemicals 1. Injection of small volume of chemicals
(0.1-1 wt %) (0.1-1 wt %)
2. Throw-away chemical (no regeneration 2. Throw-away chemical (no regeneration
required) required)
3. Can be used as a mixed inhibitor with 3. Greater degree of subcooling achievable
methanol or glycol to extend chemical over KHIs, up to 22°C [40°F]
inhibition applications
4. Can perform for longer periods in non-
flowing conditions
Disadvantages 1. Limited to 15.5°C [28°F] sub-cooling for sweet 1. High chemical costs
gas applications, 11°C [20°F] for sour gas 2. Environmental issues if discharged with
applications the produced water
2. High chemical costs 3. May induce chemical emulsions
3. May induce chemical emulsions 4. Requires a hydrocarbon liquid phase (re-
4. Sometimes incompatible with other oil-field quired to suspend hydrates in pipeline)
chemicals and salt 5. Sometimes incompatible with other
5. Do not inhibit below the freezing point of oil-field chemicals and salt
water, 0°C [32°F] 6. Do not inhibit below the freezing point
6. Only remain active for a limited transit time of water, 0°C [32°F]
after injection. High liquid residence times 7. May not be effective in systems with
in long tie-back subsea systems may preclude high water cuts
them from consideration as a result
CHAPTER 6 189
REFERENCES
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6.3 McCarthy, E. L., et al., Trans. AIME, Vol. 189 (1950), p. 241.
6.4 Olds, R.H. , Sage, B.H., and W.N. Lacy, “Composition of the Dew-point Gas of Methane - Water System,” Industrial and
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6.5 Maddox, R. N., Lilly, L. L., et al., Gas Conditioning Conference, Norman, OK. (Mar. 1988).
6.6 Robinson, J. N., et al., Trans. AIME, Vol. 263 (1977), p. 281.
6.7 Wichert, G. C. and E. Wichert, “Chart Estimates Water Content of Sour Natural Gas,” Oil & Gas J. (Mar. 29, 1993), p. 61.
6.8 GPSA Engineering Databook, 13th Ed. (2012).

6.9 Aoyagi, et.al.; RR-45, “I. The Water Content and Correlation of the Water Content of Methane in Equilibrium with Hydrates.
II. The Water Content of a High Carbon Dioxide Simulated Prudhoe Bay Gas in Equilibrium with Hydrates”, Gas
Processors Association (Dec. 1980).
6.10 Song, K. Y. and R. Kobayashi; RR-50, “Measurement and Interpretation of the Water Content of a Methane - 5.31 mole%
Propane Mixture in the Gaseous State in Equilibrium with Hydrate,” Gas Processors Association (Jan. 1982).
6.11 Song, K. Y. and R. Kobayashi; RR-80, “The Water Content of CO2 - Rich Fluids in Equilibrium with Liquid, Water, or
Hydrate,” Gas Processors Association (May 1984).
6.12 Ripmeester, J. A., et al., Nature, 135 325 (1987).
6.13 Tohidi, B., et al., “Effect of Heavy Hydrate Formers on the Hydrate Free Zone of Real Reservoir Fluids,” EPOC ’96, Stavan-
ger (Apr. 1996), SPE 35568.
6.14 Edmonds, B., Moorwood, R. A. S., and R. Szczcpanski, “Hydrate Update,” European Spring GPA Meeting, Darlington,
England (May 1998).
6.15 Cox, J.L., “Natural Gas Hydrates,” Butterworth Pub., Boston, MA (1983).
6.16 Deaton, W. M. and E. M. Frost, USBM Monograph 8 (1946).
6.17 Carson, D. B. and D. L. Katz, Trans. AIME, Vol. 146 (1942), p. 150.
6.18 Unruh, C. H. and D. L. Katz, Ibid., Vol. 186 (1949), p. 83.
6.19 Noaker, L. J. and D. L. Katz, Ibid., Vol. 201 (1954), p. 237.
6.20 Poettmann, F. H., “Here’s Butane Hydrates Equilibria,” Hydr. Proc., Vol. 63, No. 6 (June 1984), p. 111.
6.21 Robinson, D. B. and H. J. Ng, Hydr. Proc., (Dec. 1975), p. 95.
6.22 Sloan, E.D. et al.; “Vapor-Solid Equilibrium Ratios for Structure I & II Natural Gas Hydrates,” Proceedings 60th GPA An-
nual Convention, San Antonio, TX (1989).
6.23 Trekell, R. E. and J. M. Campbell, Proc. of Petr. Chem. Div. of Am. Ch. Soc. (Mar 1966), p. 61.
6.24 McLeod, H. O. and J. M. Campbell, J. Pet. Tech. (June 1961), p. 590.
6.25 Blanc, C. and J. Tournier-Lasserve, “Controlling Hydrates in High Pressure Flowlines,” World Oil, Vol. 211, No. 5 (1990),
p. 63.
6.26 Baillie, C. and E. Wichert, “Chart Gives Hydrate Formation Temperature for Natural Gas”; O&GJ, Vol. 85, No. 14, (Apr
6, 1987).
6.27 Nagata, I. and R. Kobayashi, Ind. Eng. Chem. Fund. (1966), p. 466.
6.28 Aoyagi, K., et al., Proc. GPA, Denver (1979), p. 25.
6.29 Parrish, W. R. and J. M. Prausnitz, Ind. Eng. Chem., Vol. II (1972), p. 26.
6.30 Robinson, D. B., et al., Proc. GPA, Dallas (1977), p. 11.
6.31 Holder, G. D. and J. H. Hand, AIChE J. (1982), p. 440.
6.32 Nasrifar, K.H., Moshfeghian, M., and R.N. Maddox, “Prediction of Equilibrium Conditions for Gas Hydrate Formation in
the Mixtures of Both Electrolytes and Alcohol”, Fluid Phase Equilibria, 146 (1998) p. 1-13.
6.33 Ballard, A.L., E. D. Sloan Jr., “The Next Generation of Hydrate Prediction I. Hydrate Standard States and Incorporation of
Spectroscopy”, Fluid Phase Equilibria, 194-197 (2002) p. 371-383.

6.34 Jager, M.D., Ballard, A.L., E.D. Sloan Jr., “The Next Generation of Hydrate Prediction II. Dedicated Aqueous Phase Fugac-
ity model for hydrate prediction”, Fluid Phase Equilibiria 211 (2003), p. 85-107.
6.35 Ballard, A.L., E. D. Sloan Jr., “The Next Generation of Hydrate Prediction Part III. Gibbs Energy Minimization Formal-
ism”, Fluid Phase Equilibria 218 (2004), p. 15-31.
6.36 Ballard, A.L., E.D. Sloan Jr., “The Next Generation of Hydrate Prediction: An Overview,” Journal of Supramolecular
Chemistry 2 (2002), p. 385-392.
6.37 Ballard, A.L., E. D. Sloan Jr., “The Next Generation of Hydrate Prediction IV. A Comparison of Available Hydrate Predic-
tion Programs,” Fluid Phase Equilibria 216 (2004), p. 257-270.
6.38 Hammerschmidt, E. G., Ind. Engr. Chem., Vol. 26 (1934), p. 851.
6.39 Ng, H. J., Chen, C. J., and D.B. Robinson, RR-92, “The Effect of Ethylene Glycol or Methanol or Hydrate Formation in
Systems Containing Ethane, Propane, Carbon Dioxide, Hydrogen Sulfide or a Typical Gas Condensate,” Gas Proces-
sors Association, (Sept 1985).

6.40 Ng. H. J., Chen C. J., and D.B. Robinson, RR-106, “The Influence of High Concentrations of Methanol or Hydrate Forma-
tion and The Distribution of Glycol in Liquid-Liquid Mixtures,” Gas Processors Association, April 1987.
6.41 Nielsen, R. B. and R. W. Bucklin, “Why not Use Methanol for Hydrate Control?,” Hyd. Proc., Vol. 62, No. 4 (Apr. 1983),
p. 71.
6.42 Raj Bishnol, P., et.al., “Hydrate Phase Equilibria in Inhibited and Brine Systems,” GPA Research Report RR-156, Tulsa,
Oklahoma, USA (Aug. 1996).
6.43 Ng, H. J., Chen, C. J., and D. B. Robinson, D.B.; RR-117, “The Solubility of Methanol or Glycol in Water-Hydrocarbon
Systems,” Gas Processors Association (Mar. 1988).
6.44 Ng, H. J., C. J. Chen, GPA RR-149, “Vapour-Liquid and Vapour-Liquid-Liquid Equilibria for H2S, CO2, Selected Light Hy-
drocarbons and a Gas Condensate in Aqueous Methanol or Ethylene Glycol Solutions,” GPA/GRI (Mar 1995).
6.45 R. B., Aicher, T. G., and R. M. Gray, “Methanol Hydrate Inhibition,” Laurence Reid Gas Conditioning Conference, Univer-
sity of Oklahoma (Feb. 2000).
6.46 R.H. Jacoby, Vapor-Liquid Equilibrium Data for the Use of Methanol in Preventing Gas Hydrates, Presented at the Gas
Hydrate Control Conference. May 5-6, 1953. Norman, OK.
6.47 Tohidi, B. and A. Chapoy, RR-211, “Hydrates in High Inhibitor Concentration Systems”, Gas Processors Association (Oct.
2011).
6.48 Argo, C. B., Blain, R. A., Osborne, C. G., and I. D. Priestley, “Commercial Deployment of Low Dosage Hydrate Inhibi-
tors in a Southern North Sea 69 Kilometer West-Gas Subsea Pipeline,” paper SPE 37255 presented at the SPE Oilfield
Chemistry Symposium, Houston, Texas USA (Feb. 18-21, 1997).
6.49 Corrigan, A., Duncum, S. N., Edwards, A. R., and C. G. Osborne, “Trials of Threshold Hydrate Inhibitors in the Ravens-
purn to Cleeton Line,” paper SPE 30696 presented at the SPE Annual Technical Conference, Dallas, Texas USA (Oct.
22-25, 1995).
6.50 Personal conversation with Ralph Hick & Graig Nazzer.
6.51 Song, et.al.; RR-187, “Low Temperature VLE Data for Water, CO2, and Light Hydrocarbon Systems”, Gas Processors As-
sociation (Jan. 2005).
6.52 Mehta, A. P., and E.D. Sloan, “Structure H Hydrates: The State-of-the-Art,” Proceedings 75th GPA Annual Convention,
Denver, CO. (1996).
6.53 Richon, et.al.; RR-198,“Water and Inhibitor Distribution in Gas Product Systems”, Gas Processors Association (Sept. 2008).
6.54 Chapoy, A., and B. Tohidi; RR-205, “Hydrates in High Inhibitor Concentration Systems”, Gas Processors Association
(Nov. 2010).
6.55 Moshfeghian, M., http://www.jmcampbell.com/tip-of-the-month/2011/08/a-simple-model-for-estimation-of-methanol-
loss-to-vapor-phase/, Aug. 2011.
6.56 Moshfeghian, M, “Hydrate Inhibition: A simple model for estimation of MeOH loss to the vapor phase”, GasTech Confer-
ence Newspaper, 8 Oct. 2012.
6.57 Mamroush, D. Trimeric, “GPA Project No. 975-7, Mehtanol in Natural Gas, An Update of Engineering Data Book Informa-
tion”, A summary of data presented in RR-149 and RR-198, (2011).
CHAPTER 6 191
APPENDIX 6A – TREKELL-CAMPBELL METHOD
This appendix provides the Trekell-Campbell correlation to predict hydrate formation temperature.
The Trekell-Campbell correlation takes into account the fact that molecules larger than methane
increase the ease of stable hydrate formation. This method(6.23) uses methane as the reference condition.
The additive effect of other molecules is then plotted in Figure 6A.1(a) thru Figure 6A.4 for a pressure
range 6.9-41.4 MPa [1000-6000 psia]. Each figure is for a specific pressure and the corresponding methane
hydrate forming temperature. The abscissa shows the displacement of this methane hydrate forming temper-
ature for the percentage of each component shown on the ordinate.
Notice in Figure 6A.1(a) & (b) that n-butane has a slightly positive effect on hydrate formation. In
Figure 6A.1(a) and Figure 6A.4 the temperature displacement is negative (n-butane becomes a nonhydrate
former). This change probably is due to distortion of the lattice with pressure which does not allow even the
largest cavities to hold a molecule as large as n-butane.
Figure 6A.4 is the negative correction (depression) for nonhydrate formers (pentanes plus). The
key parameter is:
yC
5+
1 y y (100) (6A.1)
C1 C
5+
or the ratio of the mol fraction of pentanes plus to the sum of the mol fractions ethane, propane and butanes.
Increasing this ratio is unfavorable to hydrate formation; there are too many large molecules present.
The following general procedure is recommended for this method:
1. Calculate the hydrocarbon dewpoint curve to locate line FEGC in Figure 6.7.
2. Using the Figure 6.7 MPa [970 psia] prediction chart, determine the hydrate formation tem-
perature by algebraically summing temperature displacements. Use the dry gas analysis for the
ordinate values and sum the ΔT values found on the abscissa to the temperature for methane
hydrate given on the figure. Correct this temperature for the effect of pentanes and heavier if
present.
3. Repeat the previous step at 13.8 MPa [2000 psia] and correct for pentanes and heavier.
4. Calculate the hydrate temperature at each remaining pressure for which there is a graph until
the hydrocarbon dewpoint pressure is reached.
5. Plot the calculated temperatures and fit the best curve through the points.
The procedure shows that pentane and heavier has a calculable effect on hydrate point, and the “K”
value is not infinity.
Limited data show that H2S and CO2 elevate the hydrate point less in natural gases containing
reasonable amounts of ethanes through propanes than would be expected from their binary data with
methane. In fact, the correction for CO2 is negligible for most gases tested. In the final analysis, one does
not need an exact hydrate forming prediction. A narrow range of 1-2°C [1.8-3.6°F] is suitable for design
and operation.

Figure 6A.1(a) Hydrate Prediction Correlations at 6.9 MPa [1000 psia]
CHAPTER 6 193
Figure 6A.1(b) Hydrate Prediction Correlations at 13.8 MPa [2000 psia]

CHAPTER 6 195

CHAPTER 6 197

CHAPTER 6
Figure 6A.4 Hydrate Prediction Correlations for Non-Hydrate Formers
199
Example 6A.1:
Temperature Displacement, ΔT, °C
0.01 + 100 = 9.5
Component Percent 6.9 MPa 13.8 MPa
1 – 0.8836 – 0.0101 C1 88.36 9.5 15.36
C2 6.82 2.9 2.2
yC C3 2.54 4.6 3.2
5 +
(100) iC4 0.38 1.3 0.8
1 – yC – yC
1 5+ nC4 0.89 0.2 0
C5+ 1.01 –1.2 –0.08
Totals 100.00 17.3°C 21.48°C
It is not recommended that you extrapolate the curves in Figure 6A.1(a)) thru Figure 6A.4. At some
composition the lines approach the vertical (infinite slope) and any increase in concentration produces no
further temperature deflection. But, you also must remember that the correlation is empirical and that any
extrapolation tends to increase the risk.

7
BASIC THERMODYNAMICS AND
APPLICATION OF ENERGY BALANCES

BASIC THERMODYNAMIC CONCEPTS
Thermodynamics is one of the foundations of all processing calculations, for it furnishes a means
by which one may quantitatively characterize a system in terms of measurable variables. This may be done
several ways, but the “macroscopic” approach is most convenient and will be used here.
In order to adequately describe the behavioral patterns of systems, man has had to invent concepts
such as pressure, temperature, volume, length, time force, mass, etc. This has been necessary because mere
use of our senses (smell, sight, touch, hearing) leads only to percepts such as cold and hot, small and large,
push and pull, etc., which involve a large amount of human judgment. Therefore, the effective communi-
cation of ideas, essential to engineering, breaks down because the percepts used mean different things to
different people.
Thermodynamics is based on rigid definitions of concepts so that quantitative conclusions are
possible. It is essentially a “language” wherein certain terms have certain meanings. Some of these terms
cannot be described simply by the senses. In order to be meaningful they must satisfy the following:
1. Be measurable directly or expressible as an exact mathematical function of other measurable
concepts or dimensions.
2. Be capable of being described in terms of dimensions and quantities available in our language.
3. Be capable of characterizing a system’s state and behavioral patterns so quantitative values of
the concepts fully describe the system.
4. Mutually vary; one with another, in a systematic way so they may be correlated and thus used
conveniently in engineering computations.
Although most of the concepts and dimensions used in thermodynamics are arbitrary (invented by
man for his convenience) and not a part of nature, the technique has proven so workable and exact that it
has led to the development of several absolute laws which all systems follow.
In order to make the arrangement work we must have carefully defined, measurable concepts and
dimensions. Three of the most important concepts are temperature, pressure and volume.
CHAPTER 7 201
BASIC THERMODYNAMICS AND APPLICATION OF ENERGY BALANCES
Mass Out System and Surroundings

SYSTEM The system is that portion of the
Energy In Energy Out
universe being studied; a single piece of
Accumulation, equipment or an entire plant. The surroundings
Reduction, or
Steady State are the portion of the universe surrounding the
system under study. The system boundary
Mass In is the interface between the system and
Boundary
surroundings.
Figure 7.1 Simple Schematic of a System, Surroundings and
Boundary
Basic Thermodynamic Accounting

Once the system has been defined the thermodynamic description of the system using all four
requirements stated previously can proceed as follows:
1. Develop a rigid definition of terms capable of accounting for all forms of energy and mass that
enter or leave any system.
2. Develop basic equations (called laws) that apply rigorously to all systems.
Mass Balance
A mass (or material) balance for the system may be written as:
mE - m B = / mi - / mo ! mc (7.1)
Where: mE = mass at end of time period

mB = mass at beginning of time period
mi = mass in mi mo
mo = mass out mE – mB
mc = mass changes due to atomic transformations
The summation sign (Σ) in front of mi and mo is used to show mc

that more than one stream may be entering or leaving a given system
being studied.
Figure 7.2 Mass Accounting
The term “mc” is zero unless atomic transformations are taking
place within the system; mass may only be created or destroyed by
conversion of an equivalent amount of energy.
If there is no accumulation of mass within the system under study, mE – mB = 0 which is referred
to as a “steady state” condition.
Equation (7.1) is an absolute equation in principle, but not in practice because:
1. We can never measure flow rates without some error.
2. In some systems, like a petroleum reservoir, it is impossible to measure all streams that enter
or leave the portion under study (or even be sure what streams enter or leave).
The material balance is reduced to a form where it contains only one unknown. The accuracy of this
number depends on how accurately all streams affecting the balance are identified and measured. The final
answer must reflect the algebraic sum of all errors.

Energy Balance
The energy balance is not so obvious even though the principle is the same as the mass balance.
Energy comes in many forms, many of which we cannot measure directly. But, it is not necessary to isolate
each for consideration so long as all forms are “accounted for.”
The intelligent thing is to divide the total energy into a convenient number of subdivisions. What is
needed is the least number of divisions whose energy level may be determined quantitatively.
In the classical thermodynamics approach energy may cross the boundary of any system in two
ways:
1. Associated with the mass entering or leaving

2. Independent of the mass
The subdivisions chosen must be compatible with these two mechanisms so that no energy is
divided between them.
The total energy change of the system is the algebraic sum of all energy crossing the boundary of
the system during the time period of concern, plus or minus any internal changes due to atomic transforma-
tions.
Before writing an energy balance it is necessary to have a means to define total energy entering
or leaving the system. This is not routine because many forms of energy can neither be seen nor measured
directly. The accepted approach is to define two forms of energy that may be calculated directly—potential
(PE) and kinetic (KE)—and then define other forms of energy that may be measured indirectly as mathe-
matical functions of pressure, volume and temperature.
Potential energy is defined generally as the energy possessed by a system as a result of its position
in a force field. In oil and gas processing, gravitational potential energy is the major consideration. For a
system whose height above the earth’s surface is negligible in relation to the earth’s radius, gravitational
potential energy (PE) may be found by the following equation:
mg
PE 2 - PE1 = DPE = g ^Z 2 - Z1h (7.2)
c
Where: PE2 – PE1 = change in gravitational potential energy of the system in time E – B and/or change as a
result of the different height of the inlet and outlet streams entering or leaving the system
Z2 – Z1 = change in height of system and/or streams in relation to a datum line (Z = 0)
For installations within several thousand feet of sea level “g” and “gc” are very nearly equal numer-
ically and may be canceled out with little loss of accuracy.
Kinetic energy is that energy possessed by a system by virtue of its motion. Velocity has the units
of length per unit time and is a means of specifying the relative motion of a body to that of the viewer. It is
customary in most process work of the type discussed herein to assume that the viewer has zero velocity,
i.e., is standing still. On the basis of these assumptions, KE may be found from Equation (7.3):
m(v 22 - v12)
KE 2 - KE1 =  KE = 2g c (7.3)
Where: KE2 – KE1 = change in kinetic energy of the system in time E – B

v = velocity relative to viewer
All other terms have been previously defined.
CHAPTER 7 203
The macroscopic velocity of any one stream is found by dividing the volume rate of flow by the
cross-sectional area of the channel or pipe. For pumps, compressors, blowers, and the like, changes of
kinetic energy are often ignored when calculating work and heat requirements.
Internal energy is a conceptual term defined as all of the energy possessed by a mass other than
potential or kinetic. The symbol “U” is used commonly to represent internal energy.
By this definition of “U,”
Total Energy = U + PE + KE (7.4)
For a closed system Equation (7.4) expresses the total energy possessed by a mass provided some
means for calculating internal energy is provided. In a closed system no mass crosses the system boundary
and the system boundary can move, i.e., the volume of the system can change.
In most process applications it is more convenient to treat the system as “open.” In an open system
mass can cross the system boundary and the system boundary is fixed. Also, in an open system the volume
of fluid entering at the inlet boundary (V1) can do so only by displacing an equal volume of fluid already
there at pressure P1. Thus, an additional energy, P1V1, is involved.
At the system exit the reverse is true and additional energy P2V2 is involved. To facilitate the
inclusion of these PV terms into the energy balance a new concept, enthalpy, is defined by the equation:
H = U + PV (7.5)
Since work (defined later) also may contain a PV term, sometimes there is confusion between work
and the PV term of Equation 7.5. In this equation the PV term is an energy change associated with the mass
involved. Work is non-mass associated.
As noted in later chapters enthalpy is the primary concept used in energy correlations. It is seldom
that one has a need to calculate “U” or “PV” separately in Equation (7.5).
The energy terms U, H, PE and KE are sufficient to describe the energy associated with the mass
contained in, flowing into or flowing out of, the system. The next step is to define energy terms independent
of mass.
There are two mechanisms by which energy may enter or leave a system without any mass being
involved. They are called work (W) and heat (Q).
The total amount of such non-mass associated
(U + PE + KE)E energy is the algebraic sum of Q and W.
(H + PE + KE)i (H + PE + KE)o
minus Heat (Q) is defined as all energy crossing
(U + PE + KE)B the boundary of the system in the prescribed time
period that is in no way associated with mass, solely
EC as a result of a temperature difference between the
Q W system and the surroundings. Heat gained by the
system is arbitrarily defined as plus (+). That lost is
Figure 7.3 Overall Energy Balance Example minus (–).
Work (W) is defined as all energy crossing
the boundary of the system in the prescribed time period that is in no way associated with mass, by any
mechanism other than a temperature differential, e.g., all non-mass associated energy crossing the boundary
other than that falling in the category of heat. Work done by the system (leaving it) is defined as plus (+).
That done on the system (entering it) is minus (–).

Thus a system can gain or lose energy in four ways: (1) energy associated with the mass entering,
(2) energy associated with the mass leaving, (3) work, and (4) heat.
If we put all this together you may write an overall energy balance.
(U + PE + KE) E - (U + PE + KE) B = / (H + PE + KE) i - / (H + PE + KE) o + Q - W ! EC (7.6)
Equation (7.6) is called The First Law of Thermodynamics.
Specific Applications
Equation (7.6) covers all systems. However, in most cases some terms are zero for a given system.
The first practical step is to eliminate from this general equation all terms whose numerical value is zero
(or so close to zero as to be negligible in the calculation being made). The following are useful guides in
eliminating terms from this First Law equation, to reduce it to the form in which it is applied.
1. (U + PE + KE) E - (U + PE + KE) B or (DU + DPE + DKE) E - B (7.7)

The left-hand side of the equation applies only to the system itself and not to energy associated
with mass entering or leaving. If the system is stationary during the time period of concern, KE
and PE are equal to zero. The left-hand side then reduces to ∆U.
If there is no accumulation of energy in the system (usually characterized by no accumulation of
mass), then U must also be zero. For the case where all three terms are zero the system is called
steady state. Since almost all systems discussed in this book are steady state systems, the working
equations developed for them are based on the left-hand side of Equation (7.6) being zero; i.e.,
∑(H + PE + KE)i –∑i(H + PE + KE)o + Q  W + Ec = 0
2. (H + PE + KE) i - (H + PE + KE) o or (DH + DPE + DKE) i - o (7.8)

All terms in this part of the equation apply only to the streams entering and leaving. Even though
in many systems there are elevation changes between inlet and outlet. DPE is normally small and
considered zero for design and analysis. Exceptions would include piping systems where there
are significant elevation changes, e.g., a wellbore. The change in kinetic energy, KE, is also
considered zero for most applications. In most systems velocity changes between inlet and outlet,
although measurable, are negligible. Exceptions include nozzles, ejectors or piping in relief and
flare systems where the outlet velocities can approach the speed of sound. It should be noted
that in some equipment, e.g., centrifugal compressors and pumps, there are significant internal
velocity changes but these are not relevant to overall energy balance for the equipment.
Equation 7.6 now reduces to: SHi  SHo + Q  W + Ec = 0
If in doubt, calculate PE and KE to be sure.
3. Q (Heat)
Heat is energy in transition across the boundary of the system; it is not a system property. It may
be assumed to be zero in the following circumstances:
a. There is no temperature difference between the system and its surroundings.
b. The system is properly insulated.
c. There is insufficient time for heat to be transferred.
CHAPTER 7 205
Condition (b) is used for insulated vessels. The heat loss or gain of about 5% or less ignored in the
balance is corrected when sizing the equipment. Condition (c) is normally used for steady state
flow when the system is a valve, pump or compressor, and the inlet temperature is near ambient
conditions.
When Q equals zero, the process is called adiabatic.
The plus sign in front of “Q” in the energy balance is based on the arbitrary sign convention that
heat entering the system is positive; that heat leaving is negative.
4. W (Work)
Work is also energy in transition across the system boundary. It is zero unless some mechanism
is provided for its transfer. The available mechanisms include the following, where energy is
transferred without associated mass being transferred:
a. Pumps, compressors, turbines and expanders connected to some driving, or driven,
device (rotating shaft).
b. Electrical wires crossing the system boundary.
c. Use of a magnetic field to transfer energy.
In the absence of a device meeting the definition of work, W = 0.
Work done on the system is negative. Work done by the system is positive. The general energy
balance equation is written to reflect this arbitrary definition.
5. Ec (Atomic Transformation)
None of the systems discussed in this book involve atomic transformation, i.e., destroying mass
to create energy, or vice versa. Therefore, Ec = 0.
Equation 7.6 can now be written as:
H out – H in = Q – W, or DH = Q –W (7.9)
This says the change in enthalpy of the streams crossing the system boundary is equal to the
amount of heat and work entering or leaving the system.
The Second Law of Thermodynamics – Entropy

Energy and material balances discussed above is not capable of describing the practical limits of a
process, or if it will work at all. It merely keeps track of the energy and mass quantities.
A third concept has been developed, known as entropy, to characterize how a process must proceed.
This concept is like all others; it cannot be perceived directly. It can, however, be expressed as a function of
pressure, volume and temperature. It likewise can be described statistically. As a practical matter, it should
be regarded as a concept that has proven useful in countless applications.
Entropy is a “yardstick” of the orderliness of a system; the higher the entropy the more disor-
derly it is. A gas possesses a higher entropy than a solid because its randomly moving molecules are more
“disorderly” than those in a solid. Thus, an entropy change as well as an enthalpy change occurs with every
change of phase.
This quantity called entropy may be calculated from pressure and temperature and fluid composi-
tion. Therefore, a value of “S” may be found for the system and the streams entering and leaving during
any given time interval.

Traditionally, in an attempt to give entropy some kind of physical meaning, thermal processes
have been used. In such processes only heat is transferred across the system boundary. Therefore, the
term (Q/Tb ) has been used to calculate the non-mass associated entropy crossing the boundary. Tb is the
temperature at the system boundary.
Using the definitions, the following equation is representative of an actual process:
S E – S B 2 / S i – / S o + / (Q/Tb) ! S c (7.10)
A convenient way to introduce an equal sign into the above equation is to add a quantity to the right-
hand side. This quantity is called the entropy production and represented by the symbol Sp. As the previous
equation would indicate, Sp is always a positive number when applied to an actual system.
S E - S B = / S i - / S o + / (Q/Tb) + S p ! S c (7.11)
Where: S E – SB = entropy change of the system in time period E – B

Si = entropy associated with all streams entering the system
So = entropy associated with all streams leaving the system
Tb = absolute temperature at boundary of the system
Sp = entropy production in the system
Sc = entropy changes accompanying any atomic transformations
Q = heat transferred to or from the system
Inasmuch as SP cannot be expressed as a function of measurable variables, except through applica-
tion of Equation (7.11), it must be regarded strictly as an empirical variable used to characterize the relative
efficiency of a system, the higher the value of SP the lower the efficiency. A numerical value may be found
only by determining values of the other terms in Equation (7.11) (or eliminating certain of them) and
solving for SP. Calculation of Sp for a process enables one to judge its approach to ideality (its efficiency).
For example, friction loss in fluid flow systems is a function of SP. If Sp = 0 there is no friction loss.
Equation (7.11) is known as the Second Law of Thermodynamics. The First and Second Laws
govern the behavior of all systems.
For rotating equipment like pumps, compressors and expanders it is inconvenient and impractical
to calculate SP. The standard approach is to assume a reversible process, i.e., SP = 0. It is also common to
assume that the system is adiabatic, Q = 0. If you further recognize that a compression or expansion device
is steady state, the left-hand side of the Second Law is zero. For all of these conditions, the Second Law
reduces to:
/ Si = / So or ∆S = 0 (7.12)
Systems where DS = 0 are referred to as isentropic. Although a true isentropic system is not thermo-
dynamically possible, the isentropic assumption simplifies the evaluation of many systems.
The First and Second Laws of thermodynamics may be combined to yield an equation of the form.
# VdP +  PE +  KE = -^T S h - W
b p
(7.13)
Where: Tb = absolute temperature of the flowing fluid
Equation (7.13) is applicable only for the isothermal flow of fluids. It serves as a basis for most
of the fluid flow equations used later. For the flow of incompressible liquids such as water, the ∫VdP term
becomes V(P2 – P1).
CHAPTER 7 207
Relationship Between Thermodynamic Properties

Macroscopic thermodynamics uses five conceptual property terms, three of which have already
been defined (U, H & S). Their defining equations are:
H = U + PV G = H - TS A = U - TS (7.14)
Where: G = derived property called “Gibbs free energy”
A = derived property called “Helmholtz free energy”
Each of the above equations include an “etc.” term which includes kinetic and potential energy as
well as surface energy, chemical energy, and all other forms of energy possessed by a system. These are not
included here to simplify the mathematics and because they are negligible or not relevant to most of the
systems we will consider in this book Gibbs free energy (G) and Helmholtz free energy (A) are important
derived properties of a system, but have little direct use in the processes covered in this manual.
In actual practice it is easier to write the basic equations in differential or finite difference forms.
As it turns out, we are always more interested in the change of U, H, S, G and A rather than their absolute
values. For example:
dH = dU + PdV + VdP
 H =  U +  (PV) =  U + (P2 V2 - P1 V1) (7.15)
dU = TdS - PdV + etc.
The above equations make it possible to relate H, U, and S to each other and to P, V, and T.
If we assume the “etc.” term is negligible, one equation in particular is very useful in the evaluation
of rotating equipment.
dH = TdS + VdP (7.16)
Finally, it is convenient to express enthalpy and entropy data in terms of a “base condition” at
which H and S equal zero. This base condition is often referred to as the datum point. Many tables of data
for water and steam, for example, arbitrarily assume H and S = 0 for saturated liquid water at 0°C [32°F].
The values read for any condition are therefore not the absolute value in relation to absolute zero but the
relative value above or below the datum point. This approach is convenient and accurate. When using data
from two sources for the same substance, it is necessary that they be based on the same datum point or their
values must be adjusted before they can be used in a calculation.
Many sources of data, whether a table or a graph, list only values of H, S, and V as functions of
temperature (T) and pressure (P). Corresponding values of U must be found from Equation (7.15).
The following equations show the relationship of H, S, and U as a function of P, V and T.
dh = C P dT + :V – T a dT k D dP
dV (7.17)
P
dU = C V dT + :a dT k T - PD dV
dP (7.18)
V
C P dT
T - a T kP dP
; E
V (7.19)
dS =
Where: Cp = heat capacity at constant pressure, i.e., (δH/δT)P

Cv = heat capacity at constant volume, i.e., (δU/δT)V
P, T = pressure and temperature expressed in absolute units
V = corresponding volume of system expressed as total volume or volume per unit mass

Equations (7.17)-(7.19) are valid for any process, or portion thereof, for which H, U, and S are
continuous functions of P, V, and T, and where no chemical reaction is involved. The relationship of V to P,
T and composition is provided by an Equation of State (EOS). Mathematical continuity is satisfied so long
as there is no change of phase of the system under study. A phase change represents a discontinuous process.
Equations (7.17)-(7.19) can be used only for those portions of a process where no phase change occurs.
H, U, and S are also point properties of a system, e.g., exact functions of P, V, and T. This means
that the ΔH, ΔS, and ΔU between any two points in a process are dependent only on the end conditions and
not on the path followed between these end conditions. It is this characteristic which makes H, U, and S so
valuable. One can devise any stepwise process between the end conditions to suit their calculation conve-
nience. The algebraic sum of the ΔH, ΔS, and ΔU changes for each step is equal to the total change between
the specified end conditions.
APPLICATIONS OF THERMODYNAMICS
The foregoing sections summarize the definition of terms and principles in thermodynamics. The
remainder of this chapter will look at their application to quantitatively define systems commonly found in
oil and gas processes. In addition, various methods of finding numerical values for quantities like H and S
will be discussed.
In most of the systems discussed herein, Equations (7.6) and (7.11) are simplified before their appli-
cation. As we have seen in the previous discussion, Equation (7.6) reduces to Equation (7.9) and Equation
(7.10) reduces to (7.11):
Systems where H = 0
If H = 0, Q and W are zero. Systems where this occurs include:
1. Adiabatic pipe segments where the line is either insulated or the heat transfer to or from the
surroundings is negligible.
2. Separators that do not contain heaters or coolers and are insulated or incur negligible heat transfer.
3. Valves and chokes.
Systems where H = –W
This equation is applied to virtually all rotating equipment, e.g., pumps, compressors, expanders.
Rotating equipment is generally assumed to be adiabatic, Q = 0. If we further assume that the system is
reversible (no internal friction) then SP = 0 and the system is isentropic. In order to facilitate calculations
it is sometimes convenient to assume that the system is not adiabatic. This is referred to as polytropic as
opposed to isentropic and will be discussed in more detail in Chapter 14.
Systems where H = Q
This equation is applied to heat transfer equipment. It is generally reasonable to assume that all of
the heat transferred is between fluids within the exchanger and that no heat is lost to the surroundings. For
fired heaters, the heat of combustion for the fuel is not included in the enthalpy term and must be considered
separately. This is an example of an etc. energy term discussed previously.
In the discussion above, the enthalpy change, H, represents the total stream enthalpy. It is often
more practical and convenient to use the specific enthalpy, Dh, where enthalpy is expressed per unit mass
or mol. Equation (7.20) can then be rewritten as follows:
Q - W = H = m h = m ^h 2 - h1h (7.20)
Where m is the mass or molar flow rate and h is the enthalpy per unit mass or per mol.
CHAPTER 7 209
For heat transfer systems, enthalpy correlations are not always available for the fluid passing
through the exchanger. In these cases the heat capacity, Cp, can be used in the energy balance if there is no
phase change and if the system operates at constant pressure. The latter assumption is valid for virtually all
heat transfer equipment. The assumption of no phase change is important and should be confirmed by VLE
calculations. When heat capacity is used, Equation (7.20) becomes:
Q = mC p DT = mC p ^T2 – T1h (7.21)
In the application of Equations (7.20) and (7.21), it is convenient to define the system so that either
Q and/or W is eliminated.
CHOICE OF SYSTEM
The first decision is the choice of system. It may be a single piece of equipment, several pieces, or
an entire module. The choice must be based on two primary considerations: (1) the unknown to be deter-
mined and (2) what data are available. As later correlations will show, if the fluid composition and flow rate
are known, you need only to define two thermodynamic properties to calculate the corresponding enthalpy
change.
Figure 7.4 is a system to pump and heat
crude oil. At the pump inlet, the P, T, oil composition
W (or specific gravity), and flow rate must be specified.
At the heater outlet, P and T must be specified. It is
C assumed that the flow rate at points A and C are the
A B
same. HA and HC can be determined from the stream
T, P and composition, but this leaves two unknowns
Q
in Equations (7.20) or (7.21): Q and W. The best way
to evaluate this system is to divide it into two parts:
Q=0 W=0
the pump and the heater. The pump will be calcu-
- W = H = HB- HA Q = H = HC- HB
lated first, assuming an adiabatic process (Q = 0). W
Figure 7.4 Crude Oil System Pump is calculated from the enthalpy change across the
pump (HB-HA). Since W = 0 in the fired heater, Q
A B C equals the enthalpy change from the pump outlet to
the heater outlet (HC-HB).
Figure 7.5 for a compressor and aftercooler
After-Cooler involves the same considerations. In preparing
W for a calculation, make a sketch of the equipment
involved. Write down known (or specified) condi-
tions. Is sufficient information known to make the
Compressor Q desired calculation, or are further specifications
(or assumptions) necessary? Do not make arbitrary
Q=0 W=0
- W = H = HB- HA assumptions. Use judgmental assumptions compat-
Q = H = HC - HB
ible with experience with such equipment and local
Figure 7.5 Compressor and After-Cooler System
considerations.
Units of Measurement
The basic energy units used are kilojoules (kJ), megajoules (MJ), and British Thermal Units (Btu).
Power, the time rate of transferring energy, usually is expressed as kilowatts (kW), megawatts (MW), horse-
power (hp) or Btu per hour (Btu/hr).

Specific enthalpy (h) is used most often as kJ/kg or Btu/lbm; specific entropy is kJ/(kg·°C) or
Btu/(lbm-°F). Both terms can also be expressed in molar units.
1 kJ = 1000 J = 0.001 MJ = 0.948 Btu, 1 Btu = 1.055 kJ
1 hp = 2685 kJ/h = 2545 Btu/hr = 0.746 kW = 550 ft-lbf/sec
1 Btu/lbm = 2.326 kJ/kg, 1 Btu/(lbm-°F) = 4.187 kJ/(kg·°C)
1 kW = 1.34 hp = 3600 kJ/h = 3 413 Btu/hr
Effect of Phase Condition

It is important to know what phase exists at the inlet and outlet of the system to accurately complete
the energy balance. Is the stream crossing the system boundary a subcooled liquid, saturated liquid,
two-phase, saturated vapor, superheated vapor, or dense phase? Mixture computations are less reliable than
those for single component systems. It is not convenient to use simple tables or figures. Mixture correlations
are based on some mixture physical properties and/or equations of state utilizing some form of combination
rule.
For a two-phase system, we must find h or s for the mixture. This in effect is the sum of the values
for vapor and liquid. As a practical matter, Equation (7.22) is typically used. Note that Equation (7.22) is
presented with enthalpies on a mass basis. The equation can also be applied with enthalpies on a molar basis.
h = (y)(h v) + (x)(h L) (7.22)

Where: h = enthalpy of two-phase stream per unit of mass
hv = enthalpy of saturated vapor per unit of mass
hL = enthalpy of saturated liquid per unit of mass
y = mass fraction of vapor in total stream = 1 – x
x = mass fraction of liquid in total stream = 1 – y
This equation can be also to find total specific volume (v) and total entropy (s) from saturated
values. It says that the total energy or specific volume is the sum of the two phases present. It may be
used for both single and multicomponent systems. The only difference is how one obtains values for the
saturated liquid and vapor. In most cases “y” and “x” will be found from a flash calculation when a mixture
is involved.
Enthalpy Calculation Alternatives

There are several methods you can use to calculate enthalpy changes between two points in a
system, such as:
1. Calculate “sensible heat” changes for a process step where no phase change occurs using
Equation (7.21).
2. For a phase change step, calculate “latent heat” from an appropriate correlation.
3. Calculate Δh directly from a correlation for a pure component or a mixture correlation based
on overall fluid properties.
4. Calculate Δh from an equation of state and basic thermodynamic equations.
Method 4 is the one used in computer simulations. Method 3 also is useful. It is not too often that
Method 2 will be used, but information is presented for those who choose this approach. Method 1 finds
application in high pressure gas (or liquid) heaters and coolers, which are essentially isobaric (constant
pressure) processes.
Heat Capacity of Natural Gas
The heat capacity of natural gas may be found from equations of state.(7.1) For most calculations
where the use of heat capacity is suitable, Figure 7.6 thru Figure 7.8 are appropriate. The heat capacity is
found at the average temperature and multiplied by gas mass flow rate and ΔT to obtain Q.
CHAPTER 7 211
Temperature, °F
0 100 200 300 400 500 600
3.8
0.9
3.6
3.4
Heat Capacity, Btu/lbm-°F

Heat Capacity, kJ/kg•°C
0.8
13 970 kPa [2000 psia]
3.2
3.0
6895 kPa [1000 psia] 0.7

2.8
2.6
3450 kPa [500 psia] 0.6
2.4
2070 kPa [300 psia]
2.2 690 kPa [100 psia]

Relative Density = 0.6 0.5
2.0
-50 0 50 100 150 200 250 300 350
Temperature, °C
Figure 7.6 Heat Capacity of 0.6 Relative Density Natural Gas
Temperature, °F
. 0 100 200 300 400 500 600
4.0
0.9
3.5
0.8 Heat Capacity, Btu/lbm-°F

13 970 kPa [2000 psia]

psia]
3.0
0.7
6895 kPa [1000 psia]
psia]
2.5 3450 kPa [500 psia]

psia] 0.6
2070 kPa [300 psia]

psia]
690 kPa [100 psia] Relative Density = 0.7 0.5
2.0
-50 0 50 100 150 200 250 300 350
Temperature, °C

Temperature, °F
0 100 200 300 400 500 600
4.4
1.0
4.0
Heat Capacity, Btu/lbm-°F

0.9
3.5 13 970 kPa [2000 psia]

0.8
3.0
6895 kPa [1000 psia] 0.7
2.5 3450 kPa [500 psia] 0.6

2070 kPa [300 psia]
690 kPa [100 psia] 0.5

2.0 Heat Capacity of Natural Gas
Relative Density = 0.8
1.8
-50 0 50 100 150 200 250 300 350
Temperature, °C
Example 7.1: 1 ´ 106 std m3/d [35.4 MM scfd] of a 0.7 relative density gas is heated from 50°C to
300°C [122-572°F] in a regeneration gas heater. The pressure is 5 MPa [725 psia].
Determine the heater duty in kW [Btu/hr].
50 + 300
SI Solution: Average temperature of gas = = 175 o C
2
From Figure 7.7, the average heat capacity of the gas = 2.7 kJ/kg °C
m=c 3 ma ka d k = 9.9
1 # 106 std m3 m (0.7)(29)kg kg
c
kmol
d 23.64 std m kmol 86 400 s s
Q = a9.9 s kc2.7 •o m^300 – 50 oCh = 6680 kW

kg kJ
kg C
122 + 572
FPS Solution: Average temperature of gas = = 347 o F
2
From Figure 7.7, the average heat capacity of the gas = 0.645 Btu/lbm–oF
35.4 MMscf ma l b - mol kc (0.7)(29)lbm ma l day k

m =c
lbm
=
day 379.5 scf l b - mol 24 hr 78900 hr
Q = a78 900 hr ka0.645 k 572 - 122hoF = 22.9 # 106 hr

lbm Btu ^ Btu
lbm o F
CHAPTER 7 213
Figure 7.6 thru Figure 7.8 were developed for hydrocarbon mixtures containing minimal amounts
of H2S, CO2 and N2. These curves were developed using the Peng-Robinson EOS. For those portions of
the graphs where the change in heat capacity with temperature is non-linear, an enthalpy correlation will
be more accurate.
A figure like Figure 7.7 is primarily used for approximate calculations. Normally, the enthalpy
change would be calculated directly from a correlation like that in Appendix 7A or a computer program.
Heat Capacity of Hydrocarbon Liquids

The heat capacity (CP) for hydrocarbon liquid may be estimated from the equation:
SI: C pa = 2.96 - 1.34c + T(0.006 20 - 0.002 34c) (7.23a)

FPS: C pa = 0.68 - 0.31c + T(0.000 82 - 0.000 31c) (7.23b)
SI FPS
Where: Cpa = average heat capacity kJ/kg·°C Btu/lbm-°F
γ = liquid sp. gr. (water = 1.0) — —
T = average temperature °C °F
Example 7.2: 133 m3/hr [20 000 bbl/d] of 35º API [g = 0.85] crude oil is heated from 21°C [70°F]
to 54°C [130°F] in a heater upstream of a crude oil dehydration unit. Determine the
duty of the heater.
SI Solution:
Step 1. Determine the mass flowrate of the crude oil.
c hr mc ma k = 31.4
133 m 850 kg 1 hr
3 kg
m3 3600 s s
Step 2. Estimate the heat capacity from Equation 7.23a, Tavg = 37.5
Cp = 2.96 – (1.34)(0.85) + (37.5)(0.006 20 – (0.002 34)(0.85))
Cp = 1.98 kJ/kg·°C
Step 3. Estimate heater duty from Equation 7.21
Q = mC p ^T2 – T1h = a s kc kg• %C m^54 – 21h C

31.4 kg 1.98 kJ º
Q = 2050 kW
FPS Solution:
Step 1. Determine the mass flowrate of the crude oil
a ka ka k^ h =
20 000 bbl 350 lbm 1d
d bbl 24 hr 0.85 248 000 lbm/hr
Step 2. Estimate the heat capacity of the oil from Equation 7.23b, Tavg = 100ºF
Cp = 0.68 – (0.31)(0.85) + (100)((0.000 82) – (0.000 31)(0.85))
Cp = 0.47 Btu/lbm-ºF
Step 3. Estimate heater duty from Equation 7.21
Q = (248 000)(0.47)(130 – 70)ºF = 7.0 MMBtu/hr

Latent Heat of Hydrocarbons

The latent heat is the amount of
enthalpy (energy) required to change phase
from liquid to vapor. Energy must be supplied
to vaporize; it is released on condensation.
For liquid hydrocarbons, the latent heat of
vaporization is roughly 15% that of water. It is
critical to know if phase changes occur in the
system due to the impact on the accuracy of
the energy balance. Latent heat is often signifi-
cantly higher than sensible heat in systems with

phase changes.
If heat capacity is used in a process
involving a phase change, the calculation must
be divided into two steps: (1) calculating the
Figure 7.9 Correlation for Estimating Latent Heat of
sensible heat due to change in P and T, and (2) Hydrocarbon Fluids
determining the latent heat change. Total Δh is
the sum of these two. If enthalpy correlations are used, the latent heat is included in the enthalpies.
Figure 7.9 is a correlation for latent heat based on fluid molecular weight, API gravity, and average
boiling point.
The latent heat shown is at atmospheric pressure; it will decrease with increasing pressure. The
following is a suitable pressure correction for use with this correlation:
Decrease latent heat 17 kJ/kg for each 1000 kPa increase above atmospheric pressure
[5 Btu/lbm per 100 psi increase].
As an alternative to Figure 7.9, the following equations may be used:
SI:  h L = ^4.19h^Tb /MWh^8.75 + 1.98 ln Tbh (7.24a)
FPS:  h L = ^Tb /MWh^7.58 + 2.03 ln Tbh (7.24b)
SI FPS
Where: Tb = average boiling point K °R
ΔhL = latent heat kJ/kg Btu/lbm
MW = molecular weight kg/mol lbm/lb-mol
Figure 7.9 can be used to estimate heat requirements in equipment where partial or complete vapor-
ization of a hydrocarbon liquid occurs. It can also be used for relief valve sizing in fire relief applications
(see Chapter 10) where knowledge of the heat of vaporization of the relieving fluid is required. Figure 7.9
is best applied to mixtures with a narrow boiling point range such as NGL or petroleum products and/or
in situations where the amount of vaporization is small relative to the total stream rate. It is less accurate
in applications where the boiling point range is large, such as unstabilized crude oil and condensate and
where a large portion of the stream is being vaporized. Example 7.3 shows the application of the “heat of
vaporization” approach.
CHAPTER 7 215
Example 7.3: An unstabilized light crude oil with an API gravity of 50 and a MW of 150 leaves a
separator at 60ºC [140ºF] and enters a feed preheater upstream of a crude oil stabiliz-
er. The system pressure is 2000 kPa [290 psia]. The oil leaves the exchanger at 250ºC
[482ºF] and is 10% vaporized on a mass fraction basis. Estimate the heat required per
kg [lbm] of feed.
From Fig 7.9 hvap at 1 atm = 270 kJ/kg [116 Btu/lbm]
Pressure Correction = –34 kJ/kg [–15 Btu/lbm]
Corrected hvap = 236 kJ/kg [101 Btu/lbm]
From Eq. 7.23 @ Tavg = 155ºC [311ºF] and rel. t = 0.78;
Cpa = 2.6 kJ/kg·ºC [0.62 Btu/lbm-ºF]

Q = (hvap)(vap. fr.) + (CPa)(T)
= (236)(0.1) + (2.6)(190) = 518 kJ/kg

= (101)(0.1) + (0.62)(342) = 222 Btu/lbm
Note that the sensible portion of the calculation is applied to the full stream, not just the liquid
fraction. This is because during the vaporization process, which occurs across a large temperature range,
sensible heat is being added to the liquid portion prior to vaporization and to the vapor portion after vaporiza-
tion. Technically, a vapor heat capacity should be applied to the vapor portion, but this increases the
complexity of the calculation and the difference in heat capacities is not that great.
Normally, Q would be calculated from enthal-
350 1050
pies using the equation: Q = mvhv + mLhL – mFhF.
Temperature, °C & MW of Vapor and Liquid
e
eratur
This would be the most accurate way to calculate 300 Temp 900
the required heat load because enthalpy is a point ge
Chan
Enthalpy Change, kJ/kg

function and does not depend on the temperature 250 alpy 750
Enth
path and change in fluid properties in the exchanger. d
MW of Liqui
200 600
For this example is the calculated “Q” from enthal-
pies is 510 kJ/kg [219 Btu/lbm] which is within 2% 150 450
of the values calculated using heat of vaporization. 100 MW of Vapor 300

The good agreement between the two methods is due
50 150
to the fact that the amount of vaporization is small
and the total heat required is primarily sensible heat. 0 0
If the amount of vaporization was increased, to say 0.0 0.1 0.2 0.3 0.4
Liquid Fraction on a Mass Basis
30%, the difference between the two calculation
methods is greater than 13%. Figure 7.10 shows the Figure 7.10 Crude Oil Vaporization Characteristics
vaporization characteristic for Example 7.3
Enthalpy Correlations for Pure Substances

Figure 7.11a and b are P-H diagrams for propane in SI and FPS units. All values shown are based
on a computer program(7.3) developed for use in modeling refrigeration systems. The datum point for these
figures is Enthalpy = 200 kJ/kg, Entropy = 1.0 kJ/kg·ºC for a saturated liquid at 0ºC. That is the point where
h and s for propane are arbitrarily assigned a value. Other sources of thermodynamic property information
for propane (table or graph) may be based on a different datum point and will have different absolute values
for h and s. In almost all engineering calculations we are interested in the change in enthalpy and entropy,
h and s. Enthalpy and entropy changes are independent of the datum point.

For any point inside the phase curve (saturated liquid to saturated vapor) the system will be two
phase. Note that in this region the temperature remains constant (temperature lines are horizontal) through-
out a constant pressure phase. For multicomponent systems this is not the case.
All conditions to the left of the saturated liquid curve represent a sub-cooled liquid. Conditions to
the right of the saturated vapor curve represent a superheated vapor. Conditions above the critical tempera-
ture and pressure represent a dense phase change.
In the single phase region, knowledge of the value of any two independent variables fixes the
value of the other three. In the two phase region, pressure and temperature are not independent so a second
property, v, h or s must be specified in addition to T or P to fix the other derived properties.
Figures like this for propane usually match experimental data to within a few percent. This error
is not significant because the uncertainty in input data to a calculation exceeds the error in the correlation.
Example 7.4: Saturated liquid propane at 1200 kPa [174 psia] is flashed across a valve to 200 kPa
[29 psia].
H=0
mFhF mLhL + mvhv
From Figure 7.11a and b determine the following:
1. Enthalpy and temperature of the liquid propane into the valve (hF, TF)
2. Temperature of the valve outlet (TL = TV)
3. Latent heat of propane at 200 kPa (hV – hL)
4. The vapor fraction of the valve outlet from Equation 7.22
Equation 7.22 hF = (y)(hv) + (x)(hL)
x = (l – y) substituting for x and solving for y:
h –h
y = hF – h L
v L
SI Solution:
1. From Figure 7.11a, the enthalpy and temperature of bubblepoint propane at

1200 kPa is:
hF = 280 kJ/kg, T = 31ºC
2. The temperature of propane at 200 kPa and 280 kJ/kg:
TL = Tv = –26ºC
3. Latent heat of propane at 200 kPa:
hL (bubblepoint fluid) = 139 kJ/kg

hv (dewpoint fluid) = 542 kJ/kg
Dhvap = hv – hL = 542 – 139 = 403 kJ/kg
4. The vapor fraction of the valve outlet:
280 – 139
y = 542 – 139 = 0.35
CHAPTER 7 217

FPS Solution:
1. From Figure 7.11b, the enthalpy and temperature of bubblepoint propane at
174 psia are:
hF = 123 Btu/lbm, TF = 90ºF
2. From Figure 7.11b, at 29 psia and h = 61 Btu/lbm
T = –14ºF
3. Latent heat of propane at 29 psia:
hL (bubblepoint fluid) = 61 Btu/lbm

hv (dewpoint fluid) = 235 Btu/lbm
Dh = hv – hL = 235 – 61 = 174 Btu/lbm
4. The vapor fraction of the valve outlet:
123 – 61
y = 235 – 61 = 0.35
Enthalpy Correlations for Mixtures

For mixtures, enthalpy and entropy may be calculated using one of three methods: 1) general
correlations based on one or more bulk fluid properties, 2) corresponding states correlations using mixing
rules and in some cases a third parameter, 3) equations of state. The first method is typically used in manual
calculations. The second and third methods typically require simulation although there are corresponding
states methods that can be solved manually, albeit tediously.
A number of useful correlations have been developed over the years based on overall fluid proper-
ties such as relative density or molecular weight. Appendix 7A provides a series of graphical correlations
for enthalpy as a function of T, P and MW. These figures are useful for planning, troubleshooting and
general manual calculations. Other correlations are available.(7.2-7.4)
When bulk properties are used as substitute for composition it is necessary to limit the range of
components in the mixture. As such, the graphical correlations presented in Appendix 7A are limited to
paraffin hydrocarbon mixtures containing no non-hydrocarbon components such as H2S, CO2 and N2.
For single phase streams, enthalpies can be read directly from the charts in Appendix 7A. For two-phase
streams the enthalpy of the mixture must be calculated from the enthalpy and mass fraction of each phase.

°C
100 °C
Specific Entropy = kJ/kg•K, Density = kg/m3, Temperature = °C
10 000
17
13 14 16 0°
12 C
/m³
11 0 15 0°
8000 0 0° 0° C
-90 °C
-80 °C
C C
-70 °C
°C 0°
100
°C C
CHAPTER 7
³
°C
600 k g
m³
³
³
6000 /m m³ ³
kg/
³
kg/
/m
kg kg/m
kg/m
0 150
/m
kg
25 200 g/m³
400
100 k
kg
5000
00
450
3
0
35
500 kg/m³
4000
90 °C
g-K
550 kg/m³
³
kJ/k
3000 80 °C 50 kg/m
5
³
2.4
1
40 kg/m
70 °C ³
40 kg/m
2000 60 °C
30 kg/m³
50 °C
40 °C
20 kg/m³
30 °C
1000
g-K
800 20 °C
K
Pressure (kPa)
kJ/k
kg-
g-K
10 kg/m³
kJ/
21.65
10 °C
5
8
600
.
kJ/k
21
5
g-K
1.2
2
kJ/kg-K
500 g-K
J/k
0.2 kJ/kg-K
kJ/kg-K
0 °C
0.4 kJ/kg-K
0.5
3k
g--K
0.6 kJ/kg-K
0.5
1 kJ/k
2
Propane Pressure Enthalpy Diagram - SI
400
-K
0.8 kJ/kg-K
-10 °C
.5 kJ/k
5 kg/m³
300 1.8
.5 kJ/kg
1.6
4 kg/m³
-20 °C
5 kJ/kg-K
200
1.4
3 kg/m³
20 °C
°C
-30 °C -30 °C
110 °C
100 °C
90 °C
60 °C
80 °C
0.5 kJ/kg-K
1.2
50 °C
40 °C
-50 °C
-80 °C
-70 °C
-80 °C
-70 °C
-50 °C
-60 °C
-60 °C
30 °C
10 °C
0 °C
1 kJ/kg-K
70 °C
130 °C
120 °C
-10 °C
-20 °C
-40 °C -40 °C
100
0 100
100. 200
200. 300
300. 400
400. 500
500. 600 700 800
800.
Lemmon, E.W., McLinden, M.O., Wagner, W.,"Thermodynamic Properties of Propane.
III. A Reference Equation of State for Temperatures from the Melting Line to 650 K Enthalpy (kJ/kg) Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
and Pressures up to 1000 MPa,", J. Chem. Eng. Data, 54:3141-3180, 2009. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
Reference State: Enthalpy = 200 kJ/kg, Entropy = 1 kJ/kg•K for the saturated liquid at 0°C Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (kJ/kg)
Figure 7.11a Pressure-Enthalpy Diagram for Propane (SI Units)
219
F
28
F
0°
240
F
60 °F
°F
26
1
Specific Entropy = Btu/lbm-°R, Density = lbm/ft3, Temperature = °F 0°
F
220
1000 ³ ³
/ f t³
/f t
t³
32
/ f t³
³ /f t
/ f t³
³
m
/ft³
lb ³ /f t lbm
0°
F
/f t
t³
lbm
bm
30
/ft lbm 12
m / f t³
m/f
lbm
m-°R
800 20 b
bm
24
lbm 14 0°
10 l f t³ F
26 l
8l
22
1 6 m/
34 lbm/ft³
32 lbm/f
30 lbm
tu/lb
28 lb
28
8 lb
0°
F
600 t³
0.6 B
200°F m/f
6 lb
0.15 Btu/lbm-°R
26
500
0°F
180°F ³
m/f t
0.1 Btu/lbm-°R
0.05 Btu/lbm-°R
4 lb
-°R
400
160°F 240
°F
lbm
220
tu/
°F
B
300 140°F
0 .65
36 lbm/ft³
2 lbm/ft³
120°F
38 lbm/ft³
200
100 °F
1 lbm/ft³
80°F
°R
m-
60 °F
/lb
tu
100
0 .7 B
80 40 °F
³
Pressure (psia)
0.5 lbm/ft
0.4 lbm/ft³
R
60
20 °F
°R-°
R °
50
mlb-m
t³
0.3 lbm/f
°R-°R
°R
Btut/ulb/
m-m
mR-°R
/lmb-°mR-
Propane Pressure Enthalpy Diagram - FPS
m-
40
5B
b-°
lb/lb
0 °F
/lb
/lb
tutu
tu
/lb/lm
0..555
tu
BBtut/u
5B
.455BB m/ft³
0..55
30
0.7
.4BBtu
0.4
0 0.2 lb
0.4
0
-°R
/lbm-°R
-20 °F
20
0.35 Btu
0.3 Btu/lbm
-40 °F
-°R
0.25 Btu/lbm-°R
³
0.1 lbm/ft
-80°F
-60°F
-120°F
-100°F
lbm
tu/
0.2 Btu/lbm-°R
B
0.8
10
0 50 100 150 200 250 300 350
III. A Reference Equation of State for Temperatures from the Melting Line to 650 K
Enthalpy (Btu/lbm) Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Reference State: Enthalpy = 200 kJ/kg, Entropy = 1 kJ/kg-K for the saturated liquid at 0°C
Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Figure 7.11b Pressure-Enthalpy Diagram for Propane (FPS Units)

Enthalpy Calculations for Mixtures

As discussed previously, enthalpy values for mixtures can be determined from three different
methods: 1) general correlations based on one or more bulk fluid properties, 2) corresponding states correla-
tions using mixing rules and in some cases a third parameter, and 3) equations of state. Once a correlation
has been selected, it must be used consistently.
General Correlations
Appendix 7A provides a series of graphical Vapor 1
correlations for enthalpy as a function of T, P, and MW.
These figures are useful for early planning, trouble-
shooting, and general manual calculations. An example

3 Feed
on how to apply the general correlations that are
provided in Appendix 7A follows.
Suppose you have a process in which vaporiza-
Liquid
tion or condensation is occurring as shown in Figure
2
7.12. To estimate the energy balance around the system, Q
determine the enthalpy on the streams leaving the
system boundary. The enthalpy of the gas is higher than Figure 7.12 Energy Balance Schematic
that of a liquid which accounts for the latent heat.
For these types of systems, a heat exchanger would be used to provide the cooling or heating for
the condensation or vaporization. Generally, there will be a small pressure drop as the fluids flow through
the exchanger.
The small pressure loss in most heat exchangers has little effect on the energy balance. At constant
temperature enthalpy increases with decreasing pressure but a very small change in pressure is not statisti-
cally significant with most enthalpy correlations.
In solving a vaporization or condensation problem (or any problem involving multiple streams),
remember that mass in equals mass out and energy in equals energy out, if there is no mass accumulation
in the system in question.
For our system above, the mass and energy balance follows:
m1 + m2 = m3 and m1h1 + m2h2 = m3h3 + Q
CHAPTER 7 221
Example 7.5: An LTS process is used to recover NGLs from a natural gas. A simplified flow dia-
gram is shown below:
T1 = 30°C [86°F]
P1 = 10 000 kPa [1450 psia]
MW1 = 19 1 2 3 Cold Separator
J-T Valve
Gas-Gas Exchanger
6 4
T6 = 25°C [77°F] T4 = -25°C [-13°F]

P6 = 6200 kPa [900 psia] P4 = 6200 kPa [900 psia]
MW6 = 18 MW4 = 35
The feed gas rate, q1 = 9.89 ´ 106 std m3/d [350 MMscfd]
The export (sales) gas rate, q6 = 9.38 ´ 106 std m3/d [332 MMscfd]
The liquid rate could not be adequately measured. The relative density of the cold
separator liquid is 0.48.
Calculate the mass and volumetric liquid rate leaving the cold separator, and determine
the duty of the gas-gas exchanger.
SI Solution:
Step 1: Define the system for the mass balance.

Step 2: Perform the mass balance on the system:
m1 = m6 + m 4, rearranging: m 4 = m1 – m6
ma ka k = 92.0 kg/s
9.89 # 106 std m3 /d 19 kg
m1 = c
1d

23.64 std m3 /kmol 86 400 s kmol
ma ka k = 82.7 kg/s
9.38 # 106 std m3 /d 18 kg
m6 = c
1d

23.64 std m3 /kmol 86 400 s kmol
m 4 = 92.0 – 82.7 = 9.3 kg/s, convert to a volumetric rate:
^9.3 kg/sh^3600 s/hh
q4 = = 70 m3 /h
^480 kg/m3h

T5 = -25°C
m5 = 82.7 kg/s
Step 3: Perform an energy balance around the gas-gas exchanger: P5 = 6200 kPa 5
Note that to solve the energy balance the sales gas 1 2 3

must be used since the feed gas temperature leaving the
exchanger is not known.
6 4
T5 = –25oC, from Figure 7A.11(a), h5 = 820 kJ/kg T6 = 25°C

P6 = 6200 kPa
Q = mv (h6- h5)
MW6 = 18

T6 = 25oC, from Figure 7A.11(a), h6 = 960 kJ/kg
Q = m5(h6 – h5) = 82.7 kg/s (960 – 820) kJ/kg = 11 600 kW
FPS Solution: 5
Step 1: Define the system for the mass balance. 1 2 3
Step 2: Perform the mass balance on the system:

6 4
m1 = m6 + m4, rearranging: m4 = m1 – m6
m1 = c a
350 # 106 scfd m 1 d
kc 19 lbm m = 730 000 lbm/hr

379.5 scf/lb - mol 24 hr lb - mol
m6 = c a
332 # 106 scfd m 1 d
kc 18 lbm m = 656 000 lbm/hr
m5 = 656 000
T5 = -13°F
379.5 scf/lb - mol 24 hr lb - mol

P5 = 900 psia 5
1 2 3
m4 = (730 000 – 656 000) = 74 000 lbm/hr
convert to a volumetric rate:
6 4
^74 000 lbm/hrh

T6 = 77°F Q = mv (h6- h5)
P6 = 900 psia
q4 = = 440 bbl/hr
^0.48h^350 lbm/bblh
MW6 = 18
Step 3: Perform an energy balance around the gas-gas exchanger:
T5 = –13oF, from Figure 7A.11(b), h5 = 355 Btu/lbm

T6 = 77oF, from Figure 7A.11(b), h6 = 414 Btu/lbm
Q = m1(h6 – h5) = 656 000 lbm/hr (414 – 355) Btu/lbm = 38.7 MMBtu/hr
REFERENCES
7.1 Abou-Kassem, J. H. and P. M. Dranchuk, SPE Paper No. 10980, Presented at Fall Meeting (1982).
7.2 Canjar, L. N. and V. J. Peterka, AIChE Jour., Vol. 2 (1956), p.343.
7.3 Lemmon, E. W., Huber, M. L., M. O. McLinden, NIST Standard Reference Database 23: Reference Fluid Thermodynamic
and Transport Properties-REFPROP, Version 9.0, National Institute of Standards and Technology, Standard Reference
Data Program, Gaithersburg, (2010).
7.4 Katinas, J. G. and R. P. Danner, Ibid. (Mar. 1977), p.157.
7.5 Maddox, R. N., private communication.
CHAPTER 7 223
APPENDIX 7A – ENTHALPY FOR HYDROCARBON FLUIDS
Appendix 7A is a series of figures for enthalpy as a function of T, P, and molecular weight. These
enthalpies are approximate but are useful for back of the envelope calculations. As illustrated by Figure 7A.1(a)
and Figure 7A.1(b), the enthalpy of a liquid at constant temperature is essentially independent of pressure.
Thus, only one figure is necessary for liquid. It is important to note that different correlations will use different
reference states. Thus, it is important to be consistent with the use of correlations for calculations and not to
“mix and match” different thermodynamic properties from the various correlations available. This will likely
result in gross errors in the energy balance.
These figures are based on the Mini-Sim version of the SRK equations of state.(7.5) Two sets of
figures are enclosed, one in metric and one in U.S. units. Where dashed lines are shown, the actual hydro-
carbon system may not be in the phase shown in the figure. That portion of the curve is, in effect, an
extrapolation of calculated data.
Values are shown for liquid molecular weights from 30-100. Above this range, other correlations
are advised. One alternative would be the use of Equations (7.23a)-(7.23b) and (7.24a)-(7.24b). Below this
range, you are looking at methane-ethane liquid for which this correlation is not suitable.
Values are shown for gas molecular weights from 16-30. This is considered the practical range for
this type of correlation. Pressures of 100 kPa−14.0 MPa [15-2000 psia] are plotted. To find a gas enthalpy
at a pressure between those shown, simply use arithmetic interpolation.
The figures in Appendix 7A are useful for early planning, troubleshooting, and general manual
calculations. They are simple to use, and the results generally are satisfactory. The figures are compatible
with the computer programs developed to go with this book for typical hydrocarbon streams composed
primarily of paraffin hydrocarbons.

CHAPTER 7
225
Figure 7A.1(a) Enthalpy, kJ/kg Hydrocarbon Liquid Figure 7A.1(b) Enthalpy, Btu/lbm Hydrocarbon Liquid
226

Figure 7A.2(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 100 kPa Figure 7A.2(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 15 psia
CHAPTER 7
227
Figure 7A.3(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 1.0 MPa Figure 7A.3(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 150 psia
228

CHAPTER 7
229
230

CHAPTER 7
231
Figure 7A.7(a) Enthalpy, kJ/kg Hydrcarbon Gas P = 3.5 MPa Figure 7A.7(b) Enthalpy, Btu/lbm Hydrocarbon Gas P = 500 psia
232

CHAPTER 7
233
234

CHAPTER 7
235
236

CHAPTER 7
237
238

8
FLUID FLOW
The flow of a fluid through a pipe segment with no external energy input or output may be described
by a combination of the first and second laws of thermodynamics. This results in Equation (8.1).
# VdP = - gg ∆ Z - ∆2gv
2
c c
- # TdS p (8.1)
Where: # VdP = the total energy change (per unit mass) of the fluid and is proportional to "head"
g
∆Z = the energy change (per unit mass) associated with a change in elevation (potential energy)
gc
∆ v2 = the energy change (per unit mass) associated with a change in velocity (kinetic energy)
2g c
# TdS p
= lost work due to irreversible effects, i.e., energy loss (per unit mass) due to friction
Equation (8.1) is as far as you can go using thermodynamics alone, for it provides no way of
solving for the term òTdSp, lost work.
The energy (per unit mass) required to overcome friction through a distance, L, can be represented
by the Darcy equation, Equation (8.2).
2fLv 2
friction head = g d (8.2)
c
The friction factor, f, is a proportionately constant and is a function of the relative roughness of the
pipe wall as well as fluid velocity, density, viscosity, and pipe diameter.
In Equation (8.2) the friction factor is referred to as a “Fanning” friction factor. Alternatively,
Equation (8.2) can be written in terms of a “Moody” friction factor.
When using the Moody friction factor the “2” is in the denominator rather than the numerator. The
Moody friction factor is 4 times greater than Fanning. In this book the Fanning equation will be used in all
correlations, unless noted otherwise.
CHAPTER 8 239
FLUID flow
Equation (8.1) can be written in terms of energy (head) or pressure per Equations (8.3a)-(8.3b).
These are often referred to as Bernouilli’s equations:
g ∆ v 2 2f Lv 2
∆ h = – g ∆ Z – 2g – g d
c c c (8.3a)
g t∆ v 2 t2fLv 2
∆ P = – g t∆ Z – 2g – g d (8.3b)
c c c
SI FPS
Where: ∆h = energy change of the fluid J/kg ft-lbf/lbm
∆P = pressure change in pipe segment Pa lbf/ft2

v = fluid velocity m/s ft/sec
g = gravitational force 9.81 m/s 32.2 ft/sec2
gc = mass, force constant lbm- f t
1.0 kg·m/N·s2 32.2
lbf - sec 2
L = length of pipe segment m ft
d = pipe diameter m ft
t = fluid density kg/m3 lbm/ft3
Z = elevation change of fluid m ft
f = Fanning friction factor — —
Evaluation of Friction Factor

The friction factor “f” must be evaluated empirically. A widely used correlation is the Moody plot
shown in Figure 8.1.(8.1)
Factor “f” depends on pipe roughness, diameter, fluid flowrate, and fluid properties. The dimen-
sionless Reynolds number on the abscissa of Figure 8.1 may be written in various forms.
dvt 4qt 4m
Re = n = rdn = rdn (8.4)
Any units that make Re dimensionless may be used. For fluid flow applications the following units
are most common.
SI FPS
Where: d = internal line diameter m ft
v = velocity m/s ft/sec
t = density kg/m3 lbm/ft3
n = viscosity kg/m•s lbm/ft-sec
m = mass flow rate kg/s lbm/sec
q = Volumetric flow rate m3/s ft3/sec
1 cp = 0.001 kg/m s ●
6.72  10-4 lbm/ft-sec

FLUID flow
2g
v2
hL
d
L
=6
Moody Friction Factor =
4/Re
dvρ
Re, Reynolds Number = μ
Figure 8.1 Friction Factors Using Moody Correlations(8.2)
Example 8.1: A 0.254 m [10 in] crude oil line handles 6400 m3 [40 260 bbl] per day of a 0.83 relative
density oil. The oil viscosity is 9.5 cp. The flow line is 10 km [6.15 mi] long and
discharges to a 100 kPa [14.5 psi] storage tank.
The storage tank is 100 m [328 ft] higher than the pump discharge. Determine the
necessary pump discharge pressure. The pipewall
roughness is assumed to be 38 µm [1500 µ in]. 100 kPa [14.5 psia]
No attempt is made here to calculate 2

in] s]
losses caused by pipe fittings. Such losses

[10 ile
m 5m
may be relevant and in real world situa-

54 6.1
tions should be evaluated. Normally 100m Storage

0.2 m [
[328 ft] Tank

they are added as an equivalent length
k
10
to the actual length of the pipeline.

Pump 1
For this example (10 km pipeline)
they will be negligible.
CHAPTER 8 241
FLUID flow

SI Solution:
d = 0.254 m
6400
v = = 1.46 m/s
(86 400)(0.785)(0.254) 2
n = (9.5)(0.001) = 0.0095 kg/m•s
t = (0.83)(1000) = 830 kg/m3

dvt (0.254)(1.46)(830)
n = = 3.2 # 10 4
0.0095
f 38 # 10 –6
d = 0.254 = 0.00015
From Figure 8.1, f = 0.023 (Moody) = 0.0058 (Fanning)
(2)(0.0058)(10 000)(1.46) 2 (830)

∆ Pf = = 8.08 # 105 N/m 2 = 808 000 Pa
(1.0)(0.254)
g
∆ Pelev = c g m (t) (∆ Z) = ^9.81/1.0h (830)(100) = 814 000 Pa
c
P2 – P1 = – ∆Pf – ∆ Pelev
(100 000 – P1) = –808 000 – 814 000
P1 = 1.72 ´ 106 Pa = 1.72 MPa

FPS Solution:
d = 10 in = 0.833 ft
(40 260)(5.61)
v = (86 400)(0.785)(0.833) 2 = 4.79 ft sec
n = (9.5)(6.72  10-4) = 0.000638 lbm/ft-sec
t = (0.83)(62.4) = 51.8 lbm/ft3
From Figure 8.1, f = 0.023 (Moody) = 0.0058 (Fanning)
^2h^0.0058h^6.15h^5280h^4.79h2 ^51.8h
∆ Pf = = 16 690 lbf/ft 2
^32.2h^0.833h
DPelev = (g/gc)(ρ)(ΔZ) = (32.2/32.2)(51.8)(328) = 16 990 lbf/ft2
P2 – P1 = ΔPf – DPelev
(2088 – P1) = –16 990 – 16 690
P1 = 35 768 lbf/ft3 = 248 psia

FLUID flow
In Example 8.1 ΔZ is positive since the liquid is going uphill. If the liquid had been flowing
downhill, ΔZ would have been a negative number. Also, in this example no effort was made to specify exact
pipe ID, the nominal diameter was used.
This type of correlation applies only to
Newtonian fluids. Gas and almost all liquids of
concern in this book are Newtonian in nature. p
gc
stic
Pla
Non-Newtonian Liquids gh
am
Bin
c
sti
One sometimes assumes (erroneously) that
Shear Stress, 
opla
ud
the liquids being used are Newtonian fluids. In fact, y Pse 

gc
many fluids do not truly fall within this category. on
ian
wt
There are several general classifications of liquids Ne
based on their rheological behavior: Newtonian, nt

ata
Dil
Bingham Plastic, Pseudoplastic and Dilatant.
The general curve for these are shown in
Figure 8.2.
Rate of Shear
Of these, the Bingham plastic and Newtonian
liquids are the most common models employed. For Figure 8.2 Shear Curves of Newtonian and
Non-Newtonian Fluids
a Newtonian liquid, the relationship is expressed by
the equation:
n dv
x = – g c drr m (8.5)
c
Where: µ = absolute viscosity

(dvr/dr) = shear rate for laminar flow in a circular pipe
As shown in Figure 8.2, this equation produces a straight line on cartesian coordinates starting at
the origin. The slope of the line is µ/gc.
A Bingham plastic, on the other hand, is a straight line that does not pass through the origin. It is
represented by the equation:
n p dv
x - x y = – g c drr m (8.6)
c
Where: xy = the intercept

np = plastic viscosity, a value found from the line slope
A Bingham plastic will not flow until the shear stress exceeds a value represented by xy, known
as the yield point. Drilling fluids consisting of colloidal clay particles suspended in liquid approximate
Bingham plastic behavior.
Pseudoplastic and dilatant fluids possess no yield point and exhibit nonlinear behavior. In addition,
there are fluids where behavior is time dependent. A thixotropic fluid will produce a double curve. When
increasing shear rates are imposed it will break down with time. If shear rate is then reduced no further
breakdown occurs. After exposure to high shear rates, this type of liquid will regain its original consistency
after a period of time. This property is useful in special applications.
CHAPTER 8 243
FLUID flow
A rheopectic liquid is one where at constant shear rate the shear stress increases with time, the
opposite of a thixotropic liquid.
It is common to characterize non-Newtonian liquids by an empirical power law formula:
dv n
x = –K c drr m (8.7)
Where: K = an overall measure of the liquid viscosity

= n/gc for Newtonian fluid
n = 1.0 for Newtonian fluid
= 0.0-1.0 for pseudoplastic fluids
= 1.0 for dilatant fluids

Equation (8.7) is a straight line on a log-log plot. The deviation of “n” from 1.0 (in either direction)
is a measure of the degree of non-Newtonian behavior.
The detailed calculation of the behavior of non-Newtonian liquids is beyond the scope of this book,
but more details are available in References 8.3 and 8.4, and in many references covering rheology of liquids.
Most oils may be treated as Newtonian liquids, particularly those with a relative density below
0.9. However, waxy crude oils and condensates as well as some emulsions of oil and water may exhibit
non-Newtonian characteristics, often pseudoplastic.
NEWTONIAN LIQUID FLOW

The Moody Chart (Figure 8.1) is based on the work of several researchers and is the most widely
accepted friction factor correlation. Its use requires knowledge of the pipe wall roughness which is seldom
known with certainty. The roughness is affected by several factors including manufacturing process (seamless
vs. ERW), number of butt joint welds and the extent of protrusion of the first weld pass into the pipe, corrosion,
and deposits such as scale, paraffins, asphaltenes, etc.
For carbon steel process piping the most common assumption is that the average roughness is 46 µm
[0.000 15 ft or 1800 nin]. This is often referred to as “commercial steel”. In actual fact, most carbon steel
piping in non-corrosive/non-scaling service, and certainly stainless steel alloys and plastic pipe are smoother
than this. It is not uncommon in long distance transmission pipelines that the pipe wall roughness ranges from
13-33 µm [500-1300 µin]. The effect of roughness on friction factor decreases with increasing pipe diameter.
Another issue with Figure 8.1 is that it is iterative when solving for diameter or flow. For this reason
several authors have developed friction factor correlations that are not iterative and/or where the friction
factor is implicit in the Darcy equation. Reference 8.5 provides an excellent comparison of several friction
factor correlations.
It is not possible to develop a simple algorithm to model the friction factor curves over a range of
Reynolds numbers and dimensionless pipe wall roughness.
However, if one assumes commercial steel pipe roughness and limits the range of Reynolds numbers
and pipe diameters to those most commonly encountered in process systems, it is possible to develop a
relatively simple correlation for “f”. One common form of this equation is:
A
f= (8.8)
Re n

FLUID flow
In actual fact, A and n vary with pipe diameter but it is not practical to develop a separate equation
for each pipe size. As a compromise we have developed two correlations: small pipe and large pipe.
0.0239
Small Pipe: 3" - 8" f= (8.9a)
Re0.134
0.0184
Large Pipe:10" - 20" f= (8.9b)
Re0.120
The small pipe correlation was developed for a range of Reynolds numbers from 20 000-1 000 000
and the large pipe correlation for a range from 70 000-3 000 000. The average error (relative to Figure 8.1)
in the small pipe correlation is 4.5% and 2.9% for large pipe.
Substitution of Equations (8.9a) & (8.9b) into the friction loss term in Equation (8.3a) & (8.3b)
results in the relationships in Table 8.1.
Table 8.1
Equation Substitutions for Small and Large Pipes
Small Pipe (3“-8” Nominal) Large Pipe (10“-20” Nominal)

Pressure Drop, ∆P
ALq1.866 c0.866 n0.134 BLq1.880 c0.880 n0.12
(8.10) (8.11)
d 4.866 d 4.880
Flow, q
a ∆P k a∆P k
0.536 0.532
AL d 2.608 BL d 2.596
(8.12) (8.13)
c0.464 n0.072 c 0.468 0.064
n
Diameter, d q0.385 c0.18 n0.025
q0.383 c0.178 n0.028
a∆P k
(8.14) (8.15)
a ∆P k
0.206 0.205
AL BL
SI FPS
Where: A = conversion constant 2.73 ´ 10–9 0.000 438
B = conversion constant 2.27 ´ 10–9 0.000 377
ΔP
= pressure drop kPa psi
q
= flow m3/h U.S. gpm
d
= diameter m in
L
= length m ft
c= rel. t
n = viscosity cp cp
Another liquid flow correlation often used for design of process piping is a graphical correlation
developed from calculations done on the M.W. Kellogg hydraulic slide rule and presented in the GPSA
Engineering Data Book & API 14E. This correlation is presented in Figure 8.3(a) & (b).
CHAPTER 8 245
246
FLUID flow
Figure 8.3a Pressure Drop for Hydrocarbon Liquids in Smooth Pipe — SI Units

CHAPTER 8
FLUID flow
Figure 8.3b Pressure Drop for Hydrocarbon Liquids in Smooth Pipe — FPS Units
247
FLUID flow
Notes for Figure 8.3a and Figure 8.3b:

1. Curves were developed using M. W. Kellogg hydraulic slide rule.
2. Chart assumes commercial steel pipe f = 46 nm [1800 nin].
3. Chart assumes relative density of liquid = 1.0. For other values, multiply pressure loss from
chart by the relative density at flowing conditions to the 0.82 power (c 0.82).
4. To adjust pressure loss for the effect of viscosity, multiply the value from the chart by n0.18,
where viscosity is in cp.
Example 8.2: Calculate the flow through a 6" schedule 40 pipe (0.154 m [6.065 in.]) of a C5+ NGL
product. The allowable pressure drop is 22.6 kPa/100 m [1.0 psi/100 ft]. At process
conditions, the relative density of the liquid is 0.64 and the viscosity is 0.27 cp.
SI Solution:
Use small pipe Equation (8.12) from Table 8.1
c m
0.536
^0.154h2.608
22.6
a ∆P k
0.536
d 2.608 –9
2.73 # 10 (100)
q = AL0.464 0.072 = = 180 m3 /h
c n ^0.64h0.464 ^0.27h0.072
Using Figure 8.3a. Correct ∆P/L to a fluid w/g = 1.0 and μ = 1.0 cp
22.6 a 0.64 k a 0.27 k = 41 kPa/100 m (equivalent ∆ P for water)

1 0.82 1 0.18
From Figure 8.3a, q = 180 m3/h

FPS Solution:
Use small pipe Equation 8.12 from Table 8.1
c m
0.536
^6.065h2.608
1
(0.000438)(100)
q = = 796 gpm
^0.64h0.464 ^0.27h0.072
Using Figure 8.3(b). Correct ∆P/L for rel. ρ = 1.0 & μ = 1.0
(1) a 0.64 k a 0.27 k = 1.83 psi/100 ft (equivalent DP for water)

1 0.82 1 0.18
From Figure 8.3b, q = 800 gpm
Equations (8.10 - 8.15), and Figure 8.3a & (b) were developed for a range of flows, diameters, and
fluid properties typical of liquids in process piping. Similar relationships can be developed for vapor
flow if one assumes the change in gas density is small (less than 10%) over a pipe segment. This is
typically the case for facility piping.
The Reynolds number for vapor flow in process piping is typically quite high ( >10 000 000). In
Figure 8.1 this region is referred to as “complete turbulence” and characterized by the fact that friction
factor is no longer a function of Re, only pipe diameter and roughness. If one assumes commercial steel
pipe, f depends only on diameter.
This diameter-based friction factor correlation can be inserted into equation 8.2 to develop a set of
relatively simple relationships for pressure drop, flow or diameter, where the friction factor is implicit in the
equation. These Equations are (8.16a)-(8.16c).

FLUID flow
∆ P100 = A a P kd 5.202 n
Tzc q2 (8.16a)
d
0.5
q = d ATz n d 2.601
∆ P100 P
(8.16b)
c
ATzc 0.192 0.384
d=d
P∆ P100 n
q (8.16c)
SI FPS
Where: ΔP100 = pressure drop per 100 units of pipe length 100 m 100 ft
T = gas temperature K °R
z = compressibility factor — —
c = gas rel. density — —
P = pressure kPa psia
qs = gas flowrate (std) 106 std m3/d MMscfd
d = pipe diameter m in
A = 0.0478 27.02
Example 8.3: 8.0 ´ 106 std m3/d [283 MMscf/d] of a 0.65 relative density natural gas flows to a
compressor at 2000 kPa [290 psia] and 40°C [104°F]. Engineering guidelines re-
quire the pressure drop not to exceed 11.3 kPa/100 m [0.5 psi/100 ft]. What diam-
eter pipe is required? Assume z = 0.91. Solve using Equation (8.16c).
SI Solution:
ATzc 0.192 0.384 (0.0478) ^313h^0.91h^0.65h 0.192
d=d =< F
P∆ P100 n
q ^8.0h 0.384 = 0.493 m
^2000h^11.3h
Therefore a nominal pipe size of DN 500 is required.

FPS Solution:
d=; E
(27.02)(564)(0.91)(0.65) 0.192
(290)(0.5) (283) 0.384 = 19.3 in
Therefore a nominal pipe size of 20" is required.
Valves and Fittings

Equations presented in Table 8.1, and equations (8.16a)-(8.16c) adequately describe flow of
Newtonian fluids (for liquids and gases) in straight runs of commercial steel pipe under conditions of fully
turbulent flow. The pressure drop through valves and fittings must be addressed separately. A common
method used to account for this additional pressure drop is the use of equivalent lengths (Le). Each fitting
(valve, tee, ell, etc.) is assigned an Le based on its size and geometry. These are documented extensively
in fluid flow literature. Reference 8.2 provides an excellent review of the theory of this approach and
Reference 8.6 tabulates Le values for the most common valves and fittings encountered in the hydrocarbon
industry. Figure 8.4 is a convenient nomograph for estimating Le for various types of fittings fabricated
from commercial steel pipe.
CHAPTER 8 249
FLUID flow
Once the Le of a fitting has been determined it is simply added to the length of the straight pipe
sections. The pressure drop calculation is then performed on the total pipe length including the Le additions.
In the planning mode it is often necessary to estimate the pressure drop through a pipe section
before the actual pipe layout has been determined. References 8.7 and 8.8 detail a method whereby pressure
drops can be estimated before detailed drawings have been completed. This is useful for predicting pumping
and compression requirements. The correlation accounts for a typical number of pipe fittings and valves
installed in a piping system.
Le /L = 1 + (0.347d1/2 + 0.216)Fc (8.17)

Where: Le/L = Total equivalent lengths per length of straight pipe

d = Nominal pipe diameter, in
Fc = Complexity factor (see table below)
Very complex piping manifolds 4

Manifold type piping 2
Normal piping 1
Long reasonably straight runs 0.5
Utility supply lines, outside battery limits 0.25
Example 8.4: Calculate the effective length of piping from point A to point B in the system shown
below. Pipe size is 0.254 m [10 in].
90° Std. Elbow (R/D = 1)

A 5m 15 m
2m
Fully Open 10 m
Gate Valve B
Std. Tee
From Figure 8.4:

10" fully open gate valve Le = 1.8 m [6 ft]
10” 90° std elbow Le = 8.2 m [27 ft]
10” tee (branch flow) Le = 18.0 m [60 ft]
For ΔP calculation, the effective length of the system
= 5 + 1.8 + 15 + 8.2 + 2 + 18.0 + 10 = 60.0 m [197 ft]

FLUID flow
m ft
Globe Valve, Open Gate Valve 1000 3000

3/4 Closed
1/2 Closed 600 2000
1/4 Closed in mm
Fully Open 400

1000
200 48
500 42 1000
Angle Valve, Open Standard Tee 36 900
100 800
300 30 700
60 200 24 600
Square Elbow 22
40 20 500
100 18
16 400
Equivalent Length of Straight Pipe

Swing Check Value, 20 14
Fully Open 50
Borda Entrance 12 300
10 30 10
d D 9
Nominal Diameter of Pipe

6 20 8 200
Close Return Bend Sudden Enlargement 7
d/D - 1/4 4
6
d/D - 1/2 10
d/D - 3/4 5
2 4½
Standard Tee 4 100
5
Through Side Outlet 90
3½
1 80
3 3
Ordinary Entrance 70
0.6 2 2½
Standard Elbow or Run of 60
D d
Tee Reduced 1/2 0.4 2 50
Sudden Contraction 1 40
1½
d/D - 1/4
0.2 0.7
d/D - 1/2 1¼ 30
d/D - 3/4 0.5
Medium Sweep Elbow or
Run of Tee Reduced 1/4 1
0.1 0.3
20
¾
0.06 0.2
45° Elbow
0.04 ½
Long Sweep Elbow or 0.1
Run of Standard Tee
Figure 8.4 Resistance of Valves and Fittings to Flow of Fluids
CHAPTER 8 251
FLUID flow
Economic Pipe Diameter

Equations within Table 8.1 and Equations
(8.16a)-(8.16b) provide the relationship between
flow rate, pressure drop and pipe size. They do not
provide line sizing criteria. For a given fluid flowrate,
the cost of the piping increases with increasing pipe
diameter, but pressure loss decreases, which reduces
pumping or compression costs.
The economic diameter will be the one Total Cost
Cost
which makes the sum of amortized capital cost

plus operating cost a minimum. This total cost can
be per unit time or per unit of production. You can
correlate this total cost versus diameter to determine
a minimum as illustrated in Figure 8.5. Capital
Cost
A number of economic pipe diameter
Operating
equations can be found in the literature. Each is Cost
based on cost data, both operating and capital.
Diameter
From a practical standpoint, the fact that Figure 8.5 Economic Pipe Diameter
pressure loss is a function of (1/d5) and commer-
cial piping is only available in discrete sizes makes determination of economic pipe diameter reasonably
straightforward. Engineering guidelines are typically developed in terms of velocity or (ΔP/L) which results
in pipe diameters near the optimum. Examples of such guidelines are shown in Table 8.2.
Table 8.2
Pipe Diameter Guideline Example
Typical Velocity
Liquid Lines m/s ft/sec
Noncorrosive liquid hydrocarbon flow 2-3 7-10
Water flow 1.5-2.0 5-7
Corrosive liquid flow (sour condensate, glycol, amine) 0.7-1.0 2-3
Centrifugal pump suction 0.7-1.0 2-3
Reciprocating (plunger) pump suction 0.3 1
Typical ΔP/L
Process Vapor Lines kPa/100 m psi/100 ft
Natural gas 0.33 to 0.66% of 0.1 to 0.2 % of
total pressure total pressure
Typical Velocities
Cross Country Oil Lines m/s ft/sec
Liquid Hydrocarbons / Crude Oil 1.5 – 2.5 5-8

FLUID flow
Average fluid velocity in a pipe can be calculated from the following equation, or from Figure 8.6:
q
v= A (8.18)
SI FPS
Where: v = average fluid velocity in pipe m/s ft/s
q = fluid actual volumetric flow rate m3/s ft3/s
A = cross-sectional area of the pipe m2 ft3
Figure 8.6 Velocity of Liquids in Standard Piping as a Function of Flow Rate
Excessive Velocity
Fluid velocity is subject to maximum limits for three reasons:
1. Noise generation
2. Erosion of pipe/valves/fitting walls
3. Accelerated corrosion resulting from failure to form a protective oxide layer (in carbon steel
piping)
The problems associated with excessive velocity are generally seen in piping where the flow is
disturbed, such as valves and fittings (elbows, tees, chokes, etc.). For high pressure liquids that are being
let down to a lower pressure, a maximum velocity of 6 m/s [20 ft/sec] is typically recommended to prevent
erosion in downstream piping.
CHAPTER 8 253
FLUID flow
If the liquid is corrosive, as is the case with rich amines or water in systems where the partial
pressure of CO2 exceeds about 100-150 kPa [15-22 psia], the maximum velocity to prevent erosion/
corrosion is typically below 1.5 m/s [5 ft/sec]. In cases where there are solids, such as sand present, then
excessive velocities should be avoided to prevent erosion. Care must be taken however, to maintain a suffi-
ciently high liquid velocity to prevent sand from settling out and plugging the pipe.
Pressure Surges
Pressure surges may occur in a liquid pipeline system when an event causes the fluid velocity to
suddenly change, such as:
1. Pump failure
2. Emergency Shutdown Down (ESD) activation

3. Rapid block valve closure
4. Slamming shut of a non-return valve (check valve)
When rapid velocity changes (i.e., flow rate) occur in a pipeline, pressure waves are generated
which travel upstream and downstream from the point of origin. The pressure in the pipeline behind these
propagating waves will increase or decrease rapidly. For example, if a pump fails, the flow into the pipeline
decreases rapidly, but the liquid downstream of the pump continues flowing forward due to its momentum.
The pump discharge non-return check valve closes shortly after the loss of the pump. The continued fluid
flow in the pipeline leaves behind a low pressure region. Eventually, the static head in the pipeline overcomes
the forward fluid momentum which reverses the liquid back towards the pump. A rapid pressure rise occurs
when the returning fluid impinges on the closed non-return valve.
Some of the energy is absorbed by the compressibility of the fluid and the expansibility of the pipe.
The more energy absorbed, the less the pressure rise. Thus, compressibility of the fluid is an important
factor. Since water and stabilized crude oils and condensates are essentially incompressible, they represent
the primary problem. Compressible liquids, such as NGLs pose less concern. Pressure surges are generally
not an issue in gas pipelines.
A thorough analysis requires a computer solution. Reference 8.34 provides an excellent summary
of the problem and some important references.
The maximum pressure surge is a function of two components:
a. The instantaneous pressure increase which occurs at the point of total blockage, and…
b. The subsequent pressure rise which occurs due to liquid “line pack”.
The instantaneous surge can be estimated from Joukowsky’s Equation(8.35).
∆ Ps = (A)( t) (c)(∆v) (8.19)

SI FPS
Where: ΔPs = surge pressure kPa psi
t = liquid density kg/m3 lbm/ft3
c = sonic velocity in liquid m/s ft/sec
Δv = velocity change m/s ft/sec
A = constant 0.001 0.000 216
“c” varies with the compressibility of the fluid, pipe diameter and pipewall thickness. For stabilized
crude oil and condensates “c” is approximately 1000-1200 m/s [3300-3900 ft/sec].

FLUID flow
In long pipelines, a long, slow pressure rise phenomenon known as “line pack” may occur when a
valve located a considerable distance from the pump closes. The frictional losses in long liquid transmis-
sion lines can be significant. For example the discharge pressure of a pump may range from 5000-10 000
kPa [725-1450 psia] with a minimum line pressure of 2000 kPa [290 psig] at the suction of the next pump
station. This hydraulic gradient allows for the pump to continue pumping fluid into the pipeline after the
valve has been closed. The additional pressure rise which occurs due to the “line pack” effect can be 1.5
to 3 times the instantaneous pressure surge(8.33) depending on the line segment length, sonic velocity and
normal steady state pressure gradient.
Surge pressures can be mitigated by slowing the valve closure time and/or installing a fast-response
pressure relief system near the point of surge origin. Rupture disks have also been used in this application.
Liquid Line Looping

The need often arises for increasing the flow rate per unit pressure drop in pipeline systems. This is
normally encountered where it is desired to increase the capacity of an existing system at a given pressure
drop which is common in expanding liquid or gas pipeline transmission systems. In older pipelines it may
be necessary to de-rate the pipeline operating pressure because of corrosion or other pipe damage. In order
to maintain the same flow capacity at lower pressure the capacity of the pipeline must be increased. This is
not commonly applied to in-plant piping.
The usual and most economical solution to
1 3 2 the problem is to place one or more lines parallel to
A C
the original, either partially or throughout the entire
length. Figure 8.7 shows a schematic view of a
simple loop system that may be used to illustrate the
LA L LA principles involved.
L The loop, and the line it parallels, are usually
equal in length throughout their common length.
Figure 8.7 Schematic of a Looped Piping System
Although conditions sometimes dictate a loop of
different length.
Loop Capacity
It is often desirable to calculate the capacity of an existing looped system. The most straight-forward
method of analyzing this problem is to convert the loop into a single line having the length of the looped
section with a diameter which gives the line the same capacity as the looped section. This is referred to as the
equivalent diameter, de. An alternative approach is to fix the diameter of the line and calculate the equivalent
length Le of the line so that the line capacity is equal to that of the loop.
This method can be derived from the small or large pipe flow equation, presented in Table 8.1. The
large pipe Equation (8.13) will be used as an example:
∆ P 0.532
c BL m d A2.596 (8.20)
A
qA = 0.468
c n0.064
A similar equation can be written for qB. Now envision a line with a diameter de and length Le
which has the same capacity as the looped section (qA+qB).
∆ P 0.532
c BL m de2.596 (8.21)
e
qA + qB = 0.468
c n0.064
CHAPTER 8 255
FLUID flow
Remember that (∆Pf)A = (∆Pf)B = (∆Pf)e. Substituting in the large pipe equation for flow into
Equation (8.21) for qA and qB and cancelling like terms gives:
de2.596 d A2.596 d B2.596

= + (8.22)
Le0.532 L A0.532 L B0.532
An identical approach can be used for small pipe. Equation (8.22) can be used to convert complex
looped systems into simple systems for capacity calculations.
Example 8.5: Calculate the capacity of the following system handling a 32° API gravity crude oil
with a viscosity of 3 cp. Allowable pressure drop is 1000 kPa [145 psi].
10”
10”
8” 14”
12”
6 km 10 km 25 km
Convert the first looped section into an equivalent length, Le, of 14 in. pipe:
14 2.596 10 2.596 12 2.596
= 0.532 + 0.532 , solve for Le Le = 5.1 km
L0.532
e 6 6
Similarly for the second looped section:
14 2.596 10 2.596 8 2.596
0.532 = 0.532 + , solve for Le Le = 22.4 km
Le 10 100.532
Total effective length of system = 5.1 + 22.4 + 25 = 52.5 km [32.6 mi]
Calculate q from Equation (8.13) in Table 8.1.
c m d2.596
∆P 0.532
–9
2.27 # 10 L
q =
c 0.468 n 0.064
µ = 3 cp
kPa 145 psi psi

L = 52 500 m = 0.019 m :172 128 ft = 8.42 # 10 -4 ft D
∆ P 1000 kPa
d = 0.356 m = 14 in
SI Units:
a
–9 k
0.532
0.019
(0.330) 2.596
2.27 # 10
q = = 330 m3 /hr
(0.865) 0.468 (3)0.064
FPS Units:
# –4 0.532
c 8.42 10 m
0.000 377 (14) 2.596
q = = 1456 gpm
(0.865) 0.468 (3)0.064

FLUID flow
Loop Length
Another common application of the loop calculation is to estimate the length of loop required to
increase the capacity of the system a given amount. This calculation can be made by establishing a pressure
balance for the system.
∆ Pf ∆P
c m ^L Ah + c f m ^L - L Ah = ^DPfhtotal (8.23)
L A L c
If we define X = LA/L (fraction of the system looped) we can write the equation:
∆Pf ∆P DP
c m ^ h + c f m ^1 - Xh = c f m
(8.24)
L A X L c L total
Equations (8.23) and (8.24) can be used to calculate (ΔPf/L)A and (ΔPf/L)C. The right hand term
(ΔPf/L)total is fixed by allowable pressure drop. Equation (8.24) can be solved for X.
Direct substitution of the equations provided in Table 8.1 for large and small pipes can be used to
calculate (ΔPf/L)A and (ΔPf/L)C.
Table 8.3
Equations for Lines in Parallel
Small Pipe (3" – 8" Nominal) Large Pipe (10" – 20" Nominal)
de2.608 d A2.608 d B2.608 de2.596 d A2.596 d B2.596

Equivalent Diameter = + (8.25) = + (8.26)
Le0.536 L A0.536 L B0.536 Le0.532 L A0.532 L B0.532
1 –c m
q 1.866
1 - cq m
q 1.880
1 q1
Looping Requirements X= 1.866 (8.27) X = (8.28)
d A2.608
1.880
= G 1 – = 2.596A G
d 2.596
1 - 2.608
dA + d B2.608 dA + d B2.596
q1 d 2.608 q1 d 2.596
Entire Line Looped = <1 + d B n F (8.29) = <1 + d B n F (8.30)
q dA q dA
q 1.866 q 1.880
Diameter of Original and X = 1.38 <1 - c q m F (8.31) X = 1.37 <1 - c q m F (8.32)
Parallel Lines the Same 1 1
SI FPS
Where: q = original flow m3/hr U.S. gpm
q1 = desired flow m3/hr U.S. gpm
X = fraction of line that is looped decimal decimal
CHAPTER 8 257
FLUID flow
Example 8.6: It is desired to increase the capacity of an existing pipeline system by 60%. The di-
ameter of the existing line is 12 inches [0.305 m]. Using Equation (8.27) and (8.28),
determine what percentage of the pipeline system must be looped if the diameter of the
loop is 14" [0.356 m].
1 – a1.6 k
SI Solution: 1.0 1.866
X= = 0.72 = 72%
^0.305h 2.608
1.866
1– = G

^0.305h 2.608 + ^0.356h 2.608
FPS Solution:
1 - a1.6 k
1.0 1.880
X= 1.880 = 0.72 = 72%
12 2.596
1 - ; 2.596 E
12 + 14 2.596
GAS FLOW
The fundamental thermodynamic equations used for liquid flow also may be used for gases.
Beginning with Equation (8.1), and using the Fanning friction factor to account for the frictional losses:
# VdP + gg ^∆ Zh + ∆2g^v h = – 2fgLdv

2 2
(8.33)
c c c
Assuming the following:

1. The flow is isothermal.
2. The changes in elevation are negligible, i.e., ΔZ = 0.
3. The flow is steady state.
4. Pressure loss due to kinetic energy changes are negligible.
These assumptions allow Equation (8.33) to be rewritten as:
2
- 32f Lm2
# VdP = - 2fg Ldv c
=
r 2 g c d5 t 2m (8.34)
To evaluate the integral term the following substitutions can be made.
mRTm z m 28.97cP
V= 29 c P and t m = RT z (8.35)
m m
where Tm and zm represent the mean temperature and compressibility factor over the pipe length
being evaluated.
Substitution of Equation (8.35) into Equation (8.34) and integration gives the “Basic Equation”
shown in Equation (8.36) where q is the gas flowrate at standard conditions, Tsc and Psc.
T _P12 - P 22i d5
0.5
q = K <PscF= fcLT z G (8.36)

sc m m

FLUID flow
All of the above assumptions are usually satisfactory on long distance transmission pipelines. The
assumption of isothermal flow often has little effect on calculation accuracy for most gas pipeline systems.
Heat transfer between the pipeline and surroundings will typically result in the gas cooling to ground or sea
temperature. For pipelines operating with high pressure drop, additional cooling may occur due to Joule
Thomson (J-T) expansion. The outlet temperature of high pressure drop pipelines may be below the under-
ground ambient temperature as a result of this J-T cooling.
The use of a mean compressibility factor zm is convenient. It may be determined at the average
pressure Pm, which in turn is estimated from Equation (8.37):
3 3
2 P - P2 P1 P2
Pm = 3 = 12 2 G = 3 <^P1 + P2h - d P + P nF
2
(8.37)
P1 - P 2
1 2
where P1 and P2 are the inlet and outlet absolute pressures, respectively. The mean temperature can be found
from Equation (8.38):
R T -T V
Tm = S 1 2 W+ T
S T1 - Tg W g
SS1n e T - T oWW
(8.38)
2 g
T X
Where: Tg = temperature of pipe surroundings
For long distance pipelines it is generally satisfactory to assume that Tm = Tg.
Standard Equations
Table 8.4 summarizes several standard equations derived from the basic flow equation based on
the average (mean) conditions. Equation (8.39) is the basic equation containing a friction factor “f.” The
Weymouth and Panhandle A and B equations are merely the basic Equation (8.39), where the friction factor
“f” is implicit in the equation using the friction factor correlations shown in the two right hand columns of
Table 8.4. The Weymouth equation assumes “f” depends only on pipe diameter; the Panhandle equations
use different correlations for “f” as a function of gas flow rate, relative density and pipe diameter. The
pipeline efficiency term “E” is to allow a means of “tuning” the equation to match actual pipeline perfor-
mance data. It is particularly useful for those equations where the friction factor is implicit in the equation.
CHAPTER 8 259
FLUID flow
Table 8.4
Summary of Gas Flow Equations
SI FPS
Basic (8.39) K = 5.746 ´ 105 K = 38.774
_P12 P 22i d5
0.5
T 1.000
= G
-
q = K <PsF Êh
s ^f h^ch^Lh^Tmh^z mh
Weymouth (8.40) K = 1.185 ´ 107 K = 433.49

T 1.000 _P12 - P 22i d5.333
0.5
q = K <PsF = G Êh 0.002 35 0.008

^ch^Lh^Tmh^z mh f=
d0.33
f=
d0.33
Panhandle A (8.41) K = 1.364 ´ 107 K = 435.87

T 1.0788 _P12 - P 22i d 4.854
0.5394
0.0192
q = K <PsF > 0.8541 H
0.0195
Êh f= f=
^qc/dh0.1461
s ^ch ^Lh^Tmh^z mh ^qc/dh0.1461
Panhandle B (8.42) K = 1.321 ´ 107 K = 737

_P12 - P 22i d 4.961
0.51
T 1.02 0.003 60 0.003 59
q = K <PsF > H (E) f=
^qc/dh
f=
^qc/dh 0.039 22
^ch ^Lh^Tmh^z mh
0.961 0.039 22
s
AGA (8.43) K = 38.774

K = 5.746 ´ 105
Ts 1.000 _P12 - P 22i d5

0.5 Partially Turbulent Fully Turbulent
q = K <P F = G ^Fth Ft = 4 log ^3.71 d/fh
s ^ch^Lh^Tmh^z mh Ft = Ff 1/fSPL
Re
= Ff ;4 log c m - 0.6E
1/f
SI FPS
Where: q = gas rate at Ts, Ps m3/d scf/day
P = absolute pressure kPa psia
Ps = pressure, standard conditions kPa psia
Tm = mean absolute temperature of line K °R
Ts = temperature, standard conditions K °R
Tg = ground temperature K °R
d = inside diameter of pipe m in
ε = absolute roughness m in
L = pipe length m mi
 = gas relative density — —
zm = mean compressibility factor — —
f = Fanning friction factor — —
E = pipeline efficiency — —
Re = Reynolds number — —
Ft = transmission factor ^ 1/f h — —
Ff = drag factor (see text below) — —

FLUID flow
The AGA equation estimates the friction factor under two conditions, “partially turbulent” and
“fully turbulent”. The “partially turbulent” correlation is the Colebrook-White equation for smooth pipe.
The smooth pipe assumption is corrected using a drag factor, Ff, which accounts for several pipeline charac-
teristics: pipe wall condition, welds, changes in direction, isolation valves, etc. It is comparable in principle
to the pipeline efficiencies in the Panhandle equation. The AGA(8.9) has developed a graphical correlation
for Ff as a function of the “bend index” in degrees/mile. For bare steel or pig-burnished pipe walls, the drag
factor varies from about 0.92 to 0.98 depending on the bend index.
In the “fully turbulent” region the friction factor is independent of Reynolds number and depends
only on the dimensionless roughness of the pipe.
In Figure 8.8 friction factors for 2 pipe sizes (254 & 762 mm [10 &30 in]) calculated from the
Colebrook-White equation compared to friction factors calculated from Weymouth, Panhandle A, and
Panhandle B. This figure shows the basic relationship of pipeline friction factors for the flow conditions
shown. For comparative purposes with Figure 8.1, the Moody friction factor has been used in this case. The
friction factor in the Weymouth equation is independent of Reynolds number. The Panhandle A equation is
parallel to the smooth pipe law (no roughness).
The Weymouth equation is frequently used for modeling gathering systems where there is little
knowledge of the condition of the pipe wall, or for systems that have small amounts of liquids present. It is
generally conservative for pipes smaller than 254 mm [10 inches] in diameter, and is overly conservative at
very high Reynolds numbers. Panhandle A is a model suitable for transmission systems with pipe sizes up
to about 610-762 mm [24-30 inches] in diameter. Panhandle B was developed for large diameter pipelines
greater than 914 mm [36 inches] in diameter.
0.02
0.019
0.018
0.017
0.016
Weymouth 254 mm [10 in std.]
0.015
0.014 254 mm [10 in std.],  = 46 m
0.013 254 mm [10 in std.],  = 30 m
Moody Friction Factor, f
0.012
762 mm [30 in XS],  = 46 m
0.011
762 mm [30 in XS],  = 30 m
Weymouth 762 mm [30 in XS]
0.01 Panhand 762 mm [3
0 in XS],  =
le B, E = 0.9 15 m
2
0.009
Pan
Panhand h and
le B le A
0.008 ,E=
0.9
2
Pan Sm
h and oot
0.007 le A hP
ipe
0.006
30 m = 1180 in
0.005
100 000
200 000
300 000
400 000
500 000
700 000
1000 000
2000 000
3000 000
4000 000
5000 000
7000 000
10 000 000
20 000 000
30 000 000
40 000 000
50 000 000
70 000 000
100 000 000
Reynolds Number, Re
Figure 8.8 Pipeline Friction Factor Correlation Comparisons
CHAPTER 8 261
FLUID flow
Figure 8.9 shows a comparison of the Colebrook-White equation versus AGA, again using the
Moody friction factor. Although Figure 8.9 shows a sharp change between partially turbulent and turbulent
flow, there is actually a transition zone. Equation (8.44) can be used to estimate the transition Reynolds
number for the AGA equation.
Re = 20.91 a f k :log a f kD
d 3.7d
(8.44)
If the actual Re is less than that calculated from Equation (8.44), the partially turbulent form should
be used. If greater, the fully turbulent flow equation is recommended. For gas transmission lines, the AGA
and basic equations are the most commonly applied to model existing pipelines, or for designing new
systems.
For most large diameter natural gas transmission lines operating in a dry non-corrosive environ-
ment, f = 13 – 33 nm [590 – 1300 nin] with 19 nm [750 nin] is a reasonable average. It should be
noted however that in corroded systems ɛ can be as high as 100 to 1000 nm [3940 to 39 400 nin]. Often,
internally coated pipe is used for gas transmission systems. For internally coated pipe, f = 2.5 – 5 nm
[100 – 200 nin] which will increases line capacity by reducing the frictional pressure losses of the line.
In Example 8.7 the range of answers obtained applies only to this example, but is indicative of
the range usually obtained. In the final analysis, the usefulness of a given equation will depend on experi-
ence. The Weymouth equation is often used on gas gathering systems since it maximizes the required pipe
diameter needs for a given flow and pressure drop.
0.02
0.019
0.018 AGA Partially Turbulent
0.017 AGA Partially Turbulent AGA Fully Turbulent
0.016 Drag Factor = 0.96
Moody Friction Factor
0.015
0.014
0.013
Moody Friction Factor, f
0.012 254 mm [10 in std],  = 30m

0.011
508 mm [20 in XS],  = 30m
0.01 762 mm [30 in XS],  = 30m
0.009
0.008
Sm
oot
0.007 hP
ipe
0.006
30 m = 1180 in
0.005
100 000
200 000
300 000
400 000
500 000
700 000
1000 000
2000 000
3000 000
4000 000
5000 000
7000 000
10 000 000
20 000 000
30 000 000
40 000 000
50 000 000
70 000 000
100 000 000
Reynolds Number, Re
Figure 8.9 Comparison of the Colebrook-White Equation to the AGA Equation Friction Factor

FLUID flow
Example 8.7: Determine flows using the Basic, Weymouth, Panhandle A and B, and AGA fully
turbulent equations (Table 8.4) from the following information.
SI FPS
Where: P1 = absolute pressure 3448 kPa 500 psia
P2 = absolute pressure 3103 kPa 450 psia
Ps = standard pressure 101.3 kPa 14.7 psia
Ts = standard temperature 288 K 520°R
d = inside diameter of pipe 0.3048 m 12 in
c = gas relative density 0.7 0.7
L = pipe length 16 100 m 10 mi
Tm = mean absolute temperature of line 300 K 541°R

zm = mean compressibility factor 0.96 0.96
n = viscosity 0.01 cp 0.01 cp
E = pipeline efficiency 0.92 0.92
 = roughness 19 µm 750 µ in
Solutions: q = gas rate at Ts, Ps 106 std m3/d MMscfd
Basic* 1.28 45.4
Weymouth 1.09 38.5
Panhandle A 1.38 48.9
Panhandle B 1.44 51.0
AGA (fully turbulent) 1.34 47.3
* friction factor obtained from Figure 8.1 is a Moody “f”. You must divide by 4 to obtain Fanning “f”.
Characteristics of Gas Transmission Systems

Table 8.5 provides some typical characteristics of gas transmission systems operating at approxi-
mately 6900 kPa [1000 psia]. For higher operating pressures >10 300 kPa [1500 psia], the values in the
table will be different.
Table 8.5
Characteristics of Gas Transmission Systems
Velocity 6.1-7.6 m/s [20-25 ft/s]

∆P/L 15-25 kPa/km [3.5-5.8 psi/mile]
Compressor Station Compression Ratios 1.3-1.6
Compressor Station Spacing 130-240 km [80-150 miles]
Maximum Velocity
The maximum allowable velocity in a gas line is governed by noise, pressure loss and erosion
considerations. Equation (8.45) is a guideline for establishing any maximum velocity limits for vapor lines.
Design velocity should be less than this maximum velocity.
A
v=
^th 0.5
(8.45)
SI FPS
Where: v = velocity m/s ft/sec
t = density kg/m3 lbm/ft3
A = constant 152 125
CHAPTER 8 263
FLUID flow
At a pressure of about 7.0 MPa [1000 psia] Equation (8.45) will show a maximum velocity of about
18-19 m/s [58-61 ft/sec]. At about 14.0 MPa the maximum velocity will be about two-thirds of this amount.
Corrections Due to Elevation Changes in Gas Pipelines

All equations like those shown in Table 8.3 are based on the assumption that the line is horizontal; i.e.,
there is no potential energy change affecting P1 and P2. In actual practice the line may have elevation changes.
For single phase gas flow a correction is sometimes made for the elevation differences between
Points (1) and (2). Before using the horizontal
equations some correction must be made to P1 or P2, 2
to convert the ΔP to what it would have been if the

line were horizontal, i.e., adjust ΔPtotal for ΔPelev due
to elevation change.
z
Since the gas is compressible and tempera-
ture varies, many models may be used. The simplest
equation uses a mean temperature and compressibil- 1
ity, ignores any kinetic energy changes and assumes
a constant friction factor. For these assumptions, one Figure 8.10 Pipeline Elevation Schematic
may derive the equation:
P
= d An
∆ Zc
ATm z m 1n PB (8.46)
SI FPS
Where: DZ = static head (pipeline elevation change) m ft
c= gas relative density — —
Tm = mean gas temperature K °R
zm = mean gas compressibility — —
PA= pressure at bottom of static column (horizontal) MPa psia
PB = pressure at top of static column (actual elevation) MPa psia
A= constant 29.28 53.34
Equation (8.46) also can be written in the form
PA = ^PBhêsh (8.47)
Where: e = 2.718
B
s = ∆Z c
A Tm z m
Subscripts A and B are used to show the pressure change due to head Z
only. Do not confuse these with measured (or specified) pressures P1 and P2. In
the uphill case, P2 used in the horizontal flow equations will be greater than the
actual P2. In Equation (8.47), actual P2 will be inserted as PB, and the calculated
value of PA will be the new P2 for use in the horizontal flow equations. For
A
downhill flow the horizontal P2 will be less than the actual P2 since DZ will be
a negative number. Figure 8.11 Head Change

FLUID flow
Example 8.8: A gas line runs uphill. The following data apply: B = 5 MPa
DZ = 500 m [1640 ft], Tm = 10°C [50°F],

zm = 0.80, γ = 0.70
Z = 500 m
P2 = 5.0 MPa [725 psia], P1 = 7.0 MPa [1015 psia]
A = 5.27 MPa
Determine P2 to use for the horizontal flow equation:
SI FPS
^500 mh^0.7h ^1640 fth^0.7h
s= = 0.0528 s= = 0.0528
^29.28h^283 Kh^0.8h ^53.34h^ 510%R h^0.8h
PA = 5 MPa e0.0528 = 5.27 MPa PA = 725 psia e0.0528 = 764 psia
(Which is equivalent P2 for horizontal flow) (Which is equivalent P2 for horizontal flow)
In Example 8.8, the total pressure drop of 2.0 MPa [290 psia] is allocated as follows: 1.73 MPa
[251 psi] is due to friction and 0.27 MPa [39 psi] is due to elevation change. If the line goes downhill (DZ
is negative), the equivalent horizontal P2 would be less than the actual P2. The effect at elevation change on
flow is approximately 6% (decrease for uphill, increase for downhill).
The alternative is to incorporate the pressure and length corrections directly into the flow equations.
The method shown is simpler and straight forward.
For most gas pipelines the correction for elevation changes is small relative to the total pressure
drop. If in doubt, include them in the calculation.
Gas Line Looping

The principles outlined for looping of liquid lines also apply to steady-state gas flow. Table 8.6
summarizes the resulting equations. The sketches below the table outline the nomenclature used. The
subscript (e) denotes a single line equivalent in length or diameter to another line in series or looped lines.
Example 8.9 and Example 8.10 illustrates the application of the gas flow equations in complex
systems. For simplicity, the Weymouth equation, uncorrected for gas compressibility, will be used as an
illustration of the principles involved.
CHAPTER 8 265
Table 8.6
266
Equations for Looped Gas Flow Systems
Basic Weymouth Panhandle

For Two Lines in Series
1 1 3
Equivalent Diameter, de 5 5 L 16 L 0.2060
L f (8.50)
B
(8.49) d B d LA n
LB
(8.48) d B d A n
B fB
d B d LA n d An
16
Equivalent Length, Le d 5 f (8.51) d 3 (8.52) d 4.854 (8.53)
B
L B d dA n
B A B
L B d d A n d fB n L B d dA n
For Two Lines in Parallel

Equivalent Diameter or Length – 8 8 8
Loops de or Le de2.5 d 2.5
A d 2.5
B
de 3 d A3 dB 3 de2.618 d 2.618
A d 2.618
B
= + (8.54) 1 = 1 + 1 (8.55) = + (8.56)
^fe Leh 0.5 ^fA L Ah 0.5 ^fB L Bh 0.5 Le 2 LA 2 LB 2 Le0.5394 L A0.5394 L B0.5394
Loops – Diameter and Flows Vary q 2 q 1.86

X = Fraction Looped q 0.5
1
1 - cq m
1
1 - cq m
0.5 5 1 X=
1 - cq m
1 8 2 X= 1
d 2 X= (8.57) (8.58) 86 (8.59)
dB 1 d A3 d 2.618
A
dA 2.618
dR = f 1 p d Bn ;1 - 1 + d 2E 1 -= G
dA d A + d 2.618B
1 -> 8 8 H
^ Rh d A3 + d B 3
FLUID flow
Entire Line Looped 8

q1 d 3 q1 d 2.618
(8.60) (8.61)
q 1 qA q
= +d Bn
qA
= 1 +d Bn
Diameters of Original and Parallel q 2 q 1.86

Lines are the Same 4 q 2 4
(8.63) (8.64)
1 3 1
X = 3 <1 - c q m F X = 3 <1 - c q m F
q1
(8.62) X = 4 <1 - c m F
X = Fraction Looped
LA LB Le 1 A 3 C 2
1 dA 3 dB 2 1 3 de 2 x
LA
x=LA’L
(a) (b) (c)

FLUID flow
Example 8.9: A portion of a gas-gathering system consists of a 154 mm [6.067 in] line 15 km
[9.32 mi] in length handling 228 000 std m3/d [8.07 MMscfd] with an average rel.
t of 0.64. The pressure of this section is 2590 kPa(g) [375 psig] and the average
outlet pressure is 2070 kPa(g) [300 psig]. The average temperature is 23°C [73°F].
zm = 0.9.
Due to a new well completion, it is desired to increase the capacity of this line 20% by
looping with additional 154 mm [6.067 in] line. What loop length is required? Let LA
represent the length of the loop section.
SI Solution:
Equation (8.63) in Table 8.6 can be used to estimate the loop length:
X = 3 81 – ` 1.2 j B = 0.407 LA = ^0.407h^15h = 6.1 km

4 1 2
FPS Solution:

Equation (8.63) in Table 8.6 can be used to estimate the loop length:
X = 3 81 – ` 1.2 j B = 0.407 LA = ^0.407h^9.32h = 3.79 mi

4 1 2
To complete the hydraulic analysis for large fields with many wells and tie-in points requires
calculation of the pressure at all of the nodal points using the technique outlined in Example 8.10. Due to
the system complexity this is almost always done with software.
Example 8.10: The system in the drawing below is to be designed for gas gathering. Well “A” is a gas
well that will deliver 84 700 std m3/d [3 MMscfd]. Production facilities at “B” handle
high gas-oil ratio oil wells. It is necessary to determine what compressor discharge
pressure is necessary to deliver 49 400 std m3/d [1.75 MMscfd] from point “B.” The
pressure at the transmission line (point “C”) is 2.07 MPa(g) [300 psig]. Average flow-
ing temperature is 29°C [85°F]. The relative t of the gas well gas is 0.63 and that of
the solution gas is 0.71. The line diameters shown have been arbitrarily fixed because
of pipe availability. z = 0.92, E = 0.92.
A D 152.1 mm [6.0 in] C
Once the pressure at point “D” is found, PB
16.1 km [10.0 miles]
may be determined. The average specific 0 in]
[4. s]
gravity in line CD is estimated. m ile
4m 0m
Estimate the relative density in line CD 10
2. [3.
m
B 8k
84.7 ^0.63h + 49.4 ^0.71h 4 .
= 0.66
134.1
Use the Weymouth equation (8.40) for the solution.
SI Solution:
Line CD
P D2 - ^2171h 2
0.5
288 = G
134 000 = 1.185 # 10 a101.3 k
7
^0.1521h 2.667 ^0.92h
^16 100h^0.66h^302h(0.92)

PD = 2447 kPa
CHAPTER 8 267
FLUID flow

Line BD
P B2 - ^2447h 2
0.5
49 400 = 1.185 # 107 a101.3 k = G ^0.1024h 2.667 (0.92)

288
^4830h^0.71h^302h(0.92)

PB = 2544 kPa
FPS Solution:
Line CD
520 = P B - ^314.7h
2 2 0.5
4.75 # 10 = 433.49 a14.7 k

6 G ^6h 2.667 (0.92)
^10h^0.66h^545h(0.92)
PD = 355 psia
Line BD
P D - ^355h
2 2 0.5
1.75 # 10 = 433.49 a14.7 k = G ^4h 2.667 (0.92)

6 520
^3.0h^0.71h^545h(0.92)

PB = 364 psia
Transient Flow in Gas Pipelines

All of the discussion to this point is based on steady state flow. Unsteady state flow is, however, an
important consideration. This cannot be adequately analyzed using manual calculations.
Any time the rate of withdrawal of gas from a line differs from the input, unsteady state flow is
occurring. During routine operations this occurs because the line is often used for storage to accommodate
diurnal variations in demand. During high demand periods, output exceeds input and pressure is declining
throughout the line. During low demand periods input exceeds output and the pressure is increasing. This
is referred to as “drafting” and “packing” of the pipeline, respectively.
To predict the behavior of the line, start with the basic continuity equations and then develop a
solvable model that will approximate the transient behavior of the pipeline system. Commercial simulation
software is available to model gas transmission line transient conditions. The software selected should be
reviewed carefully to ascertain it if fits the specific system situation.(8.10)
TEMPERATURE CHANGES IN PIPING

All of the gas flow equations presented in this chapter require the use of a single value of tempera-
ture. This will be some type of an average or mean temperature. In a numerical (computer) solution the
pipeline is divided into a series of sections. For each section, the average temperature of that section is
used; a manual solution may treat the entire pipeline as one section. The temperature used should be repre-
sentative of what actually occurs. The value used has a direct effect on the physical and thermodynamic
property values.
Prediction of the temperature distribution in the flowing system may be as important as the
pressure profile. It affects many design considerations. Crude oil pour points, gas hydrates, vapor-liquid
phase behavior and water content of gas are all temperature sensitive. A reliable temperature prediction is
an essential step in the calculation procedure.

FLUID flow
The temperature at any point is determined from the energy balance and heat transfer calculations.
If potential and kinetic energy changes are ignored, and work equals zero in the pipe section under consid-
eration, the energy balance for a steady state system reduces to ΔH = Q.
From heat transfer principles, Q = UAΔTlm. For a circular pipe this may be written as:
Q = (Uo)(πdoL)(ΔTlm) (8.65)
Where: Uo = overall heat transfer coefficient

π = 3.14
do = pipe diameter
L = pipe section length, m

ΔTlm = log mean ΔT = (ΔT1-ΔT2)/ln(ΔT1/ΔT2)
Q = heat lost in line section of length L, W (J/s), [Btu/hr]
ΔT1 = T1-Tg
ΔT2 = T2-Tg
Tg = normal ground or water temperature along the pipeline route (far enough away from
pipe to be undisturbed by it)
Typical pipeline temperature profiles are shown in

Figure 8.12. If the fluid temperature is greater than Tg, heat
leaves the system. If it is less than Tg, heat enters the system
and the pipeline temperature will approach Tg from below.
Line A is for the case where the effect of pressure
Tg TA2 on enthalpy is negligible. This is a simple heat transfer
T
TB2 process and the fluid temperature cannot drop below Tg.
Line B reflects the additional change in temperature due to
L0 L L
the effect of pressure on enthalpy. For most gas pipelines
Figure 8.12 Gas Pipeline Temperature Profile the outlet gas temperature will not be less than 2-3°C
[3.6-5.4°F] below the ground temperature.
If no phase changes occur in the pipeline section, the Equation (8.66) applies.
L2 P2
Urd∆ Tlm
∆T =- # mC p dL
+ # K JT dP (8.66)
L1 P1
Where: m = mass flowrate

Cp = mean heat capacity of fluid in the line segment
KJT = Joule-Thomson coefficient, (dT/dP)H
Solution of Equation (8.66) is iterative since ΔT and ΔTlm are dependent on each other. In addition,
the pressure drop per segment length must be known. This too is temperature dependent. The usual practice
is to divide the pipeline into segments based on length or pressure drop and solve each segment iteratively
over the entire length of the pipeline.
CHAPTER 8 269
FLUID flow
For liquids, the second term is typically small relative to the first term. Most liquids have a negative
J-T coefficient so there is actually a small temperature rise due to the pressure loss along the length of the
line.
In multiphase systems, the term (Cp )(DT) does not adequately account for the enthalpy in a line
segment. This term must be replaced with a Δh term which requires an EOS based thermodynamic property
routine in the iterative solution.
If the pressure drop in the line segment (dP) is small compared to the absolute pressure, the second
term of the equation (J-T effect) is often ignored. There are thus three basic solutions for the ΔT equation.
1. Use an enthalpy-PVT equation of state program and solve both terms.
2. Approximate the second term by assuming a series of Joule-Thomson expansions.

3. Ignore the second term completely and assume no phase change in pipeline.
Method (1) is a routine computer solution. Method (3) is a straightforward manual solution. Method
(2) is a carryover from pre-computer days as a manual method to calculate the effect of pressure on tempera-
ture. Both Methods (1) and (2) require iterative solutions.
Because of the J-T effect, it is possible for the gas temperature to be less than that of the ground.
This is only likely to occur with long lines operating with large pressure drops or at pressure let-down
stations. For lean, pipeline-quality natural gas the cooling due to J-T expansion is approximately 0.004 to
0.005°C/kPa [0.05-0.06°F/psi] at pipelines operating near 6900 kPa [1000 psia].
Assumptions underlying method (3) result in Equation (8.67):
T1 - Tg rd o U o L
ln e T - T o = mC (8.67)
2 g p
SI FPS
Where: Cp = heat capacity J/kg°C Btu/lb-°F
L= pipeline length m ft
T1= pipeline inlet gas temperature °C °F
T2= pipeline outlet gas temperature °C °F
Tg= ground or water temperature °C °F
do= outside pipe diameter m ft
Uo= overall heat transfer coefficient W/m2°C Btu/hr-ft2-°F
m = gas mass flow rate kg/s lbm/hr
= 3.14
Equation (8.67) is normally solved for T2 as shown in Equation (8.68). This equation provides a
method of estimating the temperature loss for a pipeline using simple calculations which can be useful in
certain situations.
T2 = Tg + ^T1 – Tgh ec
rd o U o L
mC p m (8.68)
Overall Heat Transfer Coefficient (Uo)

This is the single number that represents all of the resistances to heat transfer in series. As an
example, in a buried pipeline the following resistances to heat flow may occur as shown in Figure 8.13:

FLUID flow
1. Film coefficient between fluid and inside

pipe wall
Soil 2. Pipe wall
3. Pipe coating (if any)
4. Insulation (if any)
Pipe Wall 5. Concrete layer (if any)
6. Soil resistance (if buried)
Fluid Film
Coefficient 7. Water resistance (river bed crossings or sea-
bed)
Coating
Other coatings, such as a protective
outer jacket other than concrete may be present

Insulation and should be accounted for in the overall heat
Concrete transfer coefficient. For buried gas pipelines, the
Uo values in Table 8.7 can be used in Equation
(8.67) and Equation (8.68).
Figure 8.13 Buried Pipeline Diagram
Table 8.7
Typical Overall Heat Transfer Coefficient Values for Gas Pipelines
SI FPS
Overall Heat Transfer Coefficient, Uo W/m2oC BTU/hr-ft2-oF
Above ground pipeline, un-insulated(8.11) 4.0-8.5 0.7-1.5
Above ground pipeline, 50 mm [2" ] insulation(8.11) 0.6-1.1 0.1-0.2
Dry soil Wet Soil Dry soil Wet Soil
Buried, un-insulated pipe(8.11)
0.85 to 4.54 0.15 to 0.80
Dry soil Wet Soil Dry soil Wet Soil
Buried, insulated pipe(8.11)
0.28 to 1.14 0.05 to 0.20
Offshore buried line, un-insulated(8.11) 2.8-4.0 0.5-0.7
Offshore buried line, 50 mm [2"] insulation(8.11) 0.6-0.2 0.1-0.2
Offshore unburied line (laying on ocean floor exposed to water 45-68 8-12
currents), un-insulated(8.11)
Offshore unburied line (laying on ocean floor exposed to water
currents), 50 mm [2"] insulation(8.11) 0.6-1.1 0.1-0.2
Bundled flowlines with 54 mm [2-1/8 in] thickness polyurethane

insulation(8.12) 0.26 0.046
Bundled flowlines with 11 mm [7/16 in] thickness polyurethane

insulation(8.42) 10.6 1.87
As with a heat exchanger, the most reliable values of “Uo” are found by test. For buried pipelines,
the soil resistance is limiting. The lower end of the range provided in Table 8.7 applies to dry loosely-
packed soil and the higher end to tightly-packed soil with high moisture content.
A given line may cross several different heat loss environments. It should be recognized that a
calculation based on a single value of “Uo” cannot account for all conditions. A range of values, preferably
from test data, should be used.
CHAPTER 8 271
FLUID flow
Example 8.11: Determine the gas exit temperature for a 406 mm [16 in. pipe] diameter, 32 km [20 mi]
long un-insulated buried gas pipeline with the following conditions:
Gas flow rate: 2.82 ´ 106 std m3/d [100 MMscfd]
Gas relative density: 0.65
Gas heat capacity: 2.51 kJ/kg·ºC [0.60 Btu/lbm-°F]
Inlet Gas Temperature: 66°C [150°F]
Ground Temperature: 7°C [45°F]
Overall Heat Transfer Coefficient: 2.8 W/m2°C [0.5 Btu/hr-ft2-°F]
SI Solution:
1. Determine gas mass flow rate.
c 2.82 a
# 106 std m3 m 1 d
k a k = 26
18.8 kg kg
86 400 s c 23.64 std m3 m kmol
kmol
d s
2. Determine T2 from Equation (8.68).
- rd o U o L
T2 = Tg + ^T1 - Tgh e mC p
-^rh^0.406h^2.8h^32 000h
T2 = 7 + ^66 - 7h e ^26h^2510h
T2 = 17.2 %C
FPS Solution:
1. Determine gas mass flow rate.
a100 MMscf ka kc ma kc
1 day 1 # 106 scf lb- mol 18.8 lbm
m = 206 412
lbm
d 24 hr MMscf 379.5 scf lb- mol hr
2. Using Equation (8.68), determine T2.
- rd o U o L
T2 = Tg + ^T1 - Tgh e mC p
-^rh^1.33h^0.5h^105 600h
T2 = 45 + ^150 - 45h e ^206 412h^0.6h
T2 = 63 °F
Ground Temperature Tg
This is not a constant quantity but depends on air temperature to some degree. At a burial depth
below the “frost line” the soil temperature generally will vary from 2-16°C [35-60°F] seasonally. Maximum
ground temperature will lag air temperature by a month or two. About the same temperature range will be
encountered with burial in water over 30 m [100 ft] deep. In a body of water with no pronounced currents,
the fluctuation will be less. Some lakes will have a bottom water variation of no more than 3°C [5°F] year
round.
If there is a minimum allowed pipeline temperature then a temperature survey should be included in
the project planning. For preliminary considerations the minimum pipeline outlet temperature seldom will be
less than 0-1°C [32-34°F].

FLUID flow
Because of changes in Tg, the value of “Uo” will vary seasonally also. In a temperate climate with
discernible seasons, the “Uo” may be 50-60% higher in winter than in summer. In theory this should not
occur, “Uo” being independent of Tg, but it has been noted in tests.
Above Ground Lines

The previous equations do not apply for above ground lines. The maximum temperature of the fluid
in the line is the result of heat gain during the day by radiant heat transfer from the sun and the correspond-
ing loss by convection to the air. The relative rate of these would determine the rate of heating or cooling.
The temperature depends on:
1. Time of day
2. Wind velocity

3. Atmospheric conditions
4. Color and character of pipe surface
5. Air temperature (Ta)
6. Flow rate and properties of fluid in the pipe
There are no absolutely rigorous performance prediction methods, but actual data are available
from tests.
The maximum temperature for an above ground line may be estimated by Equation (8.69):(8.36)
R
T = ; rh E + Ta
^ ah (8.69)
SI FPS
Where: T = maximum temperature of fluid °C °F
R = solar radiation absorbed W/m2 Btu/hr/ft2
ha = air film coefficient for convection W/m2°C Btu/hr-ft2-°F
 = 3.1416
Ta = ambient air temperature °C °F
Values of R and ha may be estimated from Table 8.8.
Table 8.8
Values of R and ha
R Wind Velocity ha
Pipe Surface SI FPS m/s mph SI FPS
Highly oxidized steel 950 300 0 0 11.4 2.0
Oxidized 728 230 0.9 2 14.8 2.6
Normal 570 180 2.2 5 19.9 3.5
Bright 348 110 4.5 10 25.6 4.5
Aluminum Paint 285 90 6.7 15 28.4 5.0
White Paint 238 75 8.9 20 29.5 5.2
Equation (8.69) shows the maximum temperature possible with the sun directly overhead, a clear
sky and a line of sufficient length to achieve thermal equilibrium between radiation energy gain and convec-
tion loss. In a typical case, the rise in temperature above ambient will not exceed 10-16°C [18-30°F].
The actual temperature will likely be lower than the maximum unless the exposed line is very
long. Fluid properties, velocity, pipe length, season of the year (sun position) and geographical position
CHAPTER 8 273
FLUID flow
all influence the actual radiation effect. Since not all of these are constant with time, neither is the actual
conditions of the pipeline.
At night, even in a tropical climate, radiation losses to a clear, dark sky may be significant. So, rapid
temperature changes may occur.
Insulation. The purpose of insulation is to reduce the rate of energy gain or loss in a cost-effective
manner.
Subsea developments, particularly in deep water, have spurred new interest in insulated flowlines.
Deposition of hydrates and paraffins can be prevented by the use of inhibitors, or by maintaining the flowing
temperature above the hydrate and/or pour point. The second option required insulated lines.
Bundled flowlines are in widespread use in the Gulf of Mexico and North Sea. These lines use an
insulated conductor pipe which contains the production flowline, inhibitor line, heating medium, control
line, etc. The insulation is typically polyurethane. Typical overall heat transfer coefficients can be found for
these flowlines in Table 8.7.
MULTIPHASE FLOW
The use of multiphase flow systems is common practice in the oil and gas industry. Multiphase
flow is often encountered in the well tubing, flow lines and gathering systems. For transport of oil and gas
to downstream processing facilities the preference is a single pipeline in which both phases are transported
simultaneously for economic reasons. Even in gas pipelines where the gas enters the line as a single phase
fluid, condensation of liquids can occur due to pressure and temperature changes along the line.
Flow Regimes
As we have seen, the calculation of pressure drop in a single phase line is relatively straight-
forward. This is not true for multiphase systems. In a multiphase line the gas and liquid can behave in
a number of ways. The liquid may run along the bottom of the pipe (stratified or wavy flow) it may be
entrained as tiny droplets in the gas (mist flow) or it may form slugs (slug flow).
Figure 8.14 shows some of the common
flow regimes observed in horizontal multiphase
flow.
Bubble Slug
The behavior of these two-phase systems
depends on whether or not both the liquid and gas
phases are present as a continuous phase; i.e., a Plug Annular
continuous channel for flow exists for the phase.
In bubble flow the liquid is the continuous phase
and the gas is suspended in the liquid as bubbles. Stratified Spray
At the other end of the scale, spray or mist flow
occurs with small particles of liquid suspended in Flow
the gas. Gas is now the continuous phase, liquid the Wavy
discontinuous phase.
Figure 8.14 Various Two-Phase Horizontal Flow Regimes
In both cases the discontinuous phase may
be considered to be merely altering the flow behavior of the continuous phase. One very simple approach is
to modify the properties and/or friction factor of the continuous phase and then treat the system as single-
phase. In bubble flow, a single-phase liquid calculation would be made. In spray or mist flow a modified
gas correlation is used.

FLUID flow
In some of the flow regimes shown in Figure 8.14 both phases are continuous. This is a more
complicated system because of the interactions between discrete phases. In most systems, the gas moves
more rapidly than the liquid. There is a shear force at the phase boundary. The character of flow depends on
such variables as phase densities and viscosities, the velocity of each phase, gas-liquid ratio and properties
like surface tension.
In a given length of line several flow regimes might occur because of varying forces and gas-liquid
ratios. Changes in forces are typically due to the gravitational effects of elevation changes. Variations in
gas-liquid ratios are dictated by phase behavior as the temperature and pressure in the pipeline changes.
Consideration of variables like these is a necessary part of developing a correlation.
Figure 8.15 shows four basic regimes that occur in vertical flow. A fifth regime, not shown, may be
called froth flow. This occurs at high liquid throughputs when the gas bubbles in the liquid are dispersed in
an ever-increasing number of small bubbles.
In vertical flow the force of gravity opposes
the dynamic forces (instead of being at right angles
to it). This results in slippage. Consequently, vertical
flow exhibits some different characteristics than
horizontal flow and may be more complicated.
Direction of Flow
Consider friction loss for a moment. The

friction factor is a measure of irreversible energy
changes occurring in the pipe. In single-phase flow
the friction factor primarily is a representation of the
loss between the fluid and the pipe wall and is corre-
(a) Bubble (b) Plug (c) Slug (d) Mist
lated as a function of fluid properties, fluid velocity,
Figure 8.15 Vertical Two-Phase Regimes pipe diameter and pipe roughness.
In two-phase flow there are two phases, with different properties, interacting with the pipe wall as
well as with each other. A friction factor, therefore, depends on more, and complex, variables. The differ-
ence between correlations depends to a large extent on how these variables are treated in order to fit the
available data.
In addition to pressure drop due to friction, a second parameter important to design and operation
of multiphase systems is liquid holdup. The liquid holdup represents the fraction of the pipe cross-sectional
area which is occupied by liquid at any point along the line. Liquid holdup affects the area available for gas
flow and is important in estimating the size of liquid handling facilities (slug catchers) at the end of the line.
It also sets the fluid density in-situ which has a significant effect on pressure drop in the line, particularly in
vertical and inclined flow systems.
Each flow pattern (or regime) requires a different mathematical model to calculate pressure drop
and liquid holdup.
All models are based on the same thermodynamic principles and fluid flow principles discussed
previously. As with single-phase flow, a prediction of the “lost work” term (pressure drop due to friction)
is essentially empirical. Thus, any one method will be most reliable in the range of pipe sizes, fluid charac-
teristics, flow conditions and geometry, and gas-liquid ratios used to develop or validate the correlation.
There is no single best correlation for universal use. When using a given model, examine the kinds
of systems on which it is based. Verify if the model and its supporting data are physically compatible with
the system under consideration. Like all semi-empirical equations, extrapolation beyond the range of data
used to develop the correlation can lead to serious errors.
CHAPTER 8 275
FLUID flow
The primary areas of concern in multiphase systems are:

• Pressure drop/line sizing
• Liquid holdup
• Slugging and its effect on equipment sizing
Each of these will be discussed in the context of flowline/pipeline systems. Horizontal flow will
be emphasized. Vertical flow in well bores will not be covered. There are numerous references to this topic
in the petroleum engineering literature. Vertical flow in risers, particularly as it applies to slugging, will be
discussed.
Liquid Hold Up
Several equations and relationships are used in two-phase models.
mg m
qg = t qL = t L
g L
qg mg 4m g q mL 4m L
vsg = A = t A = vsL = AL = t A = (8.70)
g rt g d 2 L rt L d 2
qg vsg qL vsL
GVF = = LVF = =
q L + q g vsL + vsg q L + q g vsL + vsg
SI FPS
Where: qg = actual volumetric gas rate m3/s ft3/sec

qL = actual volumetric liquid rate m3/s ft3/sec
vsg = superficial gas velocity m/s ft/sec
vsL = superficial liquid velocity m/s ft/sec
mg = gas mass flow kg/s lbm/sec
mL = liquid mass flow kg/s lbm/sec
A = inside cross-sectional area of pipe m2 ft2
tg = gas density (at flowing conditions) kg/m3 lbm/ft3
tL = liquid density (at flowing conditions) kg/m3 lbm/ft3
d = inside pipe diameter m ft
LVF = liquid volume fraction dimensionless
GVF = gas volume fraction dimensionless
The liquid volume fraction (LVF) must not be confused with the liquid holdup fraction. LVF
assumes that the velocity of the liquid and gas phases are the same. The liquid volume fraction is equivalent
to the ratio of the liquid volumetric flowrate to the total volumetric flowrate (at the inlet, or at the outlet if
liquids condense in the line). It can be determined from VLE calculations at the temperature and pressure
along every point in the line.

FLUID flow
The liquid holdup fraction represents the fraction of the pipe cross-sectional area that is occupied
by liquid at any point along the line. The liquid holdup is the volume of liquid present in the line for any
given operating condition. This is a key parameter in estimating pressure drop in multiphase pipelines with
inclined or vertical flow. It is also an important parameter for sizing downstream equipment which must be
able to operate properly when the liquid holdup in the line changes as a result of pigging or flowrate changes.
A
m L = AL (8.71)
Where: λL = liquid holdup fraction

AL = cross-sectional area occupied by liquid
A = cross-sectional area of the pipe
It follows that the gas holdup fraction, λg, is

equal to Ag/A or 1–λL.
In multiphase systems where the gas
Liquid Holdup
production rate is low, the system is said to be

“gravity dominated” with high liquid holdup in
uphill sections, λL > LVF, and low liquid holdup in
36 in
downhill sections, λL < LVF.
30 in
24 in As the gas production rate increases,
the system becomes more “friction-dominated”.
Gas Production The liquid holdup fraction decreases as the liquid
velocity approaches the gas velocity. This is referred
36 in to as “no slip”. At very high gas production rates,
λL = LVF. Slip refers to the condition where the two
phases flow through the pipeline at different veloci-
Liquid Holdup Fraction
30 in
ties. Under most conditions the liquid phase, which

24 in Superficial Gas Velocity ≈ 3 m/s [9.8 ft/s] is more dense and viscous, has a lower velocity than
the gas, thus λL > LVF.
Figure 8.16 illustrates the general relation-

λL = LVF (No Slip)
ship for liquid holdup fraction and total liquid holdup
vs. gas production rate in a typical horizontal multi-
phase gas pipeline. As the gas velocity increases the
Gas Production liquid holdup decreases in the line.
Figure 8.16 Example Relationship for Liquid Holdup
Fraction and Total Liquid Holdup in Pipe –
lines as a Function of Gas Production Rate
Dimensionless Groups
In addition to Reynolds number, several dimensionless groups are also used to characterize fluid
behavior.
CHAPTER 8 277
FLUID flow
Froude Number
This dimensionless group represents the ratio of inertial force to gravity force. It can be used to
characterize flow whenever gravity force influences fluid flow.
v v2
Fr = 0.5 or Fr = gd
^gdh
(8.72)
The form at left is the basic equation. The right-hand expression is oftentimes more convenient to
use and is often referred to as a Froude No. even though it is actually (Fr)2 .
Weber Number
The dimensionless group is defined as the ratio of inertial force to surface force. It is equal to twice
the ratio of kinetic energy to surface energy of a given volume of fluid. It may be written as:
v v 2 td
We = or We =
`v j
0.5 v (8.73)
td
Once again the right-hand form often is used because of its convenience. This dimensionless group
is a logical correlation parameter where one phase is discontinuous because interfacial tension (σ) affects
droplet size.
Euler Number
This dimensionless group is the ratio of applied pressure force to inertial force. It is a suitable corre-
lating function in a flow system where pressure force is a controlling force, particularly if one of the fluids
is compressible. It is written as
v v2 t
Eu = 0.5 or Eu =
c 2∆ P m
2∆ P (8.74)
t
In the above three dimensionless groups the nomenclature is as follows:
Where: v = effective fluid velocity
t = fluid density
g = acceleration of gravity
v = interfacial (surface tension)
d = diameter of pipe
P = pressure
MULTIPHASE FLOW CORRELATIONS

All multiphase correlations are some form of a momentum balance and continuity equation contain-
ing terms for the head, friction and acceleration effects.
dP = f tp t tp v tp + gt tp sinU + t tp v tp d dv tp n
2
a l d n
dL 2g c d gc gc dL
S S S 1 44 4 2 444 3
(8.75)
total friction elevation acceleration
Equation (8.75) includes several assumptions: 1) steady state, 2) no pumps or compressors in the
system, and 3) adiabatic. With these limitations, this provides the basis of most fluid flow calculations.

FLUID flow
The early approach to multiphase modeling was to develop empirical relationships to describe the
two-phase friction factor, ftp and liquid holdup (which determines phase velocities and densities). In many
cases these empirical relationships were applicable to only one flow regime, so several different relation-
ships (often by different researchers) were used in the modeling of pipelines as the flow regime changed.
Today, the approach is to use one model (often termed a mechanistic model) to describe the system
over a wide range of flow conditions and validate the model using empirical data from actual flow systems.
Table 8.9 provides a summary of common two-phase correlations.
Table 8.9
Summary of Two-Phase Flow Correlations
Correlation Comments
Vertical Flow
Duns & Ros Good in mist and bubble flow regions. Estimates liquid holdup and provides a flow regime
map.
Hagedorn & Provides better pressure drop predictions for vertical upward flow. Most accurate for angles
Brown of inclination greater than 70 degrees. Estimates liquid holdup but does not provide a flow
regime map.
Beggs & Brill Good for all angles of inclination. Predicts the most consistent results for a wide range of
conditions. Methods in process simulators typically programmed to account for both static
head losses, and hydrostatic recovery.
Aziz, Govier & Tends to slightly over predict pressure drop; other correlations tend to under-predict. This
Fogarasi method can be used to bracket the solution when doing hand calculations. Most accurate
for angles of inclination greater than 70 degrees. Accounts for liquid hold up and provides
a flow regime map.
OLGAS State-of-the art mechanistic model, and the most accurate predictions for vertical two-phase
flow. Good for all angles of inclination. Accounts for static head losses, and hydrostatic
recovery.
Horizontal Flow
Lockhart- Applicable for annular and annular mist flow regimes if a flow pattern is known in advance.
Marinelli Not applicable for large pipe diameters. Generally over-predicts pressure drop.
Eaton Should not be used for very high or very low liquid holdups. Works well for 0.1 to 0.35 liquid
holdup ranges.
Taitel-Dukler Tends to under-predict pressure drop and liquid holdup.
Beggs & Brill Tends to under-predict liquid holdup.
Modified Was developed as a means of estimating pressure drop of hilly terrain for wet-gas pipelines.
Flanigan The liquid holdup in the pipeline is not directly estimated. Good model for pressure drop
estimation for systems where the gas is the continuous phase, i.e., high gas-oil ratios.
OLGAS This mechanistic model provides a more accurate prediction than the other horizontal flow
correlation-based models.
Correlation-based models, such as Beggs & Brill, or the Eaton equation do not provide adequate
liquid holdup predictions for all pipeline scenarios. These predictions do not trend properly with respect to
gas velocity and pipeline angle of inclination dependencies on liquid holdup. These methods over-estimate
liquid holdup at high gas rates, and grossly underestimate it at low rates, with errors that can be greater
than 100% for certain systems(8.13). A representative elevation profile of the pipeline is essential to provide
accurate liquid holdup predictions.
In general the mechanistic models provide more accurate predictions of pressure drop and liquid
holdup than the correlation-based models. The mechanistic models may give errors in the range of 40% for
certain ranges of gas / liquid flow rates.
CHAPTER 8 279
FLUID flow
Horizontal Two-Phase Flow Superficial Gas Velocity, vSG, ft/sec
0.1 1.0 10 100 500

Flow Regime Maps 5.0 Dispersed Flow
20
10
Flow regime can affect model
Superficial Liquid Velocity, vSL, ft/sec

selection in evaluating multiphase flow
Superficial Liquid Velocity, vSL, m/s

1.0 Bubble, Slug
systems. Elongated
Bubble Flow
Flow
Figure 8.17 is a simple flow regime 1.0

Annular,
map for two-phase flow in horizontal pipes. Annular Mist
Flow
It was generated using air and water at 0.1
low pressure in small diameter lines but it

is useful for visualizing how flow regimes

Stratified Wave 0.1
Flow Flow
change depending on gas and liquid flow

0.01
rates.
Figure 8.18(8.14) shows another 0.01
0.1 1.0 10 100
widely used flow regime map for horizontal
Superficial Gas Velocity, vSG, m/s
or near-horizontal pipes. Relatively small
deviations from horizontal flow can signifi- Figure 8.17 Flow-Pattern Map of Mandhane et. al. (8.37)
cantly change the flow regime boundaries for Horizontal Two-Phase Flow in Pipes
on a flow regime map. As little as a 5% inclination can increase the slug flow region dramatically.
101
Annular Dispersed Liquid (AD)

F vs X Dispersed Bubble (DB)
100
T vs X
F vs X
T or F
10-1
Stratified Wavy (SW) Intermittent (I)
10-2 101
K vs X Region of Operation
for Gathering Lines
K
Region of Operation
StratifiedSmooth
Stratified Smooth (SS)
(SS) for Flowlines
10-3 100
10-3 10-2 10-1 100 101 102 103 104
X
R V 0.5 R V 0.5
Sc DPf m W DP
c fm
0.5
F== G vsg
S W tg
S L sLW
X=S S
T=S
L sL W ^t L – t gh d g cos i
DP W ^t L – t gh g cos iW
Sc L f m W T X
T
sg
X K = ^Fh^Reh sL
0.5
Figure 8.18 Flow Regime Map for Horizontal Two-Phase Flow — Taitel-Duckler Correlation(8.14)

FLUID flow
The following nomenclature is to be used with the equations in Figure 8.18.
SI FPS
Where: (ΔPf/L) = pressure drop per unit length Pa/m psi/ft
t = fluid density kg/m3 lbm/ft3
g = gravitational acceleration 9.81 m/s2 32.17 ft/sec2
d = inside pipe diameter m ft
i = angle of inclination (horizontal = 0°) degrees degrees
subscripts g and L = refer to gas and liquid phase, respectively
Horizontal multiphase pipelines with low liquid loading and operating at velocities of 3-5 m/s
[10-16.4 ft/sec] are in the stratified wavy regime.
Example 8.12: Estimate the flow regime of a horizontal gas pipeline operating at 6900 kPa [1000
psia] and 15°C [59°F]. The gas density is 73 kg/m3 [4.6 lbm/ft3], the liquid den-
sity is 700 kg/m3 [43.7 lbm/ft3], and the liquid viscosity is 0.5 cp. The gas rate is
5  106 std m3/d [177 MMscf ]. The gas MW is 18 and the gas viscosity is 0.015 cp. The
inside pipe diameter is 0.432 m [17 in]. The condensate loading is 56 m3/106 std m3
[10 bbl/MMscf]. For the flowing conditions in the pipe, the following conditions
apply:
SI Solution:
vsL = 0.022 m/s (Re)sL = 13 300 (ΔP/L)L = 0.01 Pa/m
vsg = 4.1 m/s (Re)sg = 8.6  106 (ΔP/L)g = 15.8 Pa/m
R V 0.5
Sc ∆ Pf m W
S L sLW = a 0.01 k 0.5 =
X=S 15.8 0.025
∆P W
Sc L f m W
sg
T X 0.5
F== G vsg = ;
tg
E ^4.1h = 0.68
73 0.5
^t L - t gh d g cosi ^700 - 73h^0.432h^9.81h^1.0h
From Figure 8.18, the flow regime is stratified wavy.

FPS Solution:
vsL = 0.073 ft/sec (Re)sL = 13 300 (ΔP/L)L = 4.4  10-5 psi/100 ft
vsg = 13.4 ft/sec (Re)sg = 8.6  106 (ΔP/L)g = 0.07 psi/100 ft
R V 0.5
Sc ∆ Pf m W 0.5
S L sLW = c 4.4 # 10 -5 m =
X=S 0.07 0.025
∆P W
Sc L f m W
sg
T X 0.5
F== G vsg = ;
tg
E ^13.4h = 0.68
4.6 0.5
^t L - t gh d g cos i ^43.7 - 4.6h^1.417h^32.17h^1.0h

From Figure 8.18, the flow regime is stratified wavy.
CHAPTER 8 281
FLUID flow
Pressure Drop
No line buried in the ground or under water is truly horizontal. The word “horizontal” simply
means that the length is a much larger number than any elevation change. In such lines two-phase flow
occurs uphill and downhill as well as horizontally. Some aspects of vertical flow are occurring simultane-
ously with said horizontal flow.
Figure 8.19 is a view of a near-horizontal line where the magnitude of the uphill and downhill
portions has been obtained by survey. The vertical axis is exaggerated relative to the horizontal axis to
better show the elevation changes. Unlike single-phase flow, each change in elevation between points (1)
and (2) affects pressure drop.
If the velocity of the liquid entering a low spot is insufficient to carry it over the next “hill,” liquid
will collect in the low spot as shown in Figure 8.20.
As this liquid builds up, the cross-sectional
area available for gas flow decreases. At some point 2
there is sufficient pressure force to start the liquid
Zd Zu
moving. A portion is “gas-lifted” over the hill and
the remainder slips back. The liquid flowing onwards Zu
contributes to liquid buildup in the next low spot. Zd
Then, in time, it surges. This process is repeated
Zu
successively as liquid moves down the line.
1
This represents an inefficient use of pressure
energy. It takes energy to overcome liquid inertia Figure 8.19 Near-Horizontal Line
and produce the momentum required. This contrib-
utes to higher pressure loss. For this reason, it is
desirable to maintain sufficient flow rates to minimize
liquid holdup.
Pressure drop must be balanced (higher ΔP
requires more compression power) against liquid
holdup (higher liquid holdup requires larger liquid
handling facilities, i.e., slug-catchers) for facility Figure 8.20 Liquid Collecting in a Low Spot
design considerations. The relationship is illustrated
in Figure 8.21 by superimposing a typical pressure
loss curve over the liquid holdup curve.
Liquid Holdup
Liquid Holdup
For a typical gas pipeline delivering gas Pressure Loss
and associated liquids from an offshore platform or
for an onshore gas gathering system the initial and
“end-of-life” production rates are often substantially
less than the “peak” or “plateau” production rates.
Pressure Loss
This means that early and late in life of the system,

the pressure drop will be low but liquid holdup will Minimum
P
be high. More importantly, small changes in the
production rate can give rise to large changes in
liquid holdup which can result in slugging. On the Gas Flow Rate
other hand, at high throughputs slugging is less
important, but pressure drop is high (ΔP µ q2). Figure 8.21 Pipeline Pressure Loss and Liquid Holdup
vs. Gas Flow Rate

FLUID flow
It is important that the project team responsible for the pipeline design evaluate the operating
envelopes over the field life. This is a critical interface between the subsurface team (reservoir and produc-
tion engineers) who provide production forecasts and the “surface” people (pipeline and facility engineers)
who must design the system.
Rigorous computer models are generally employed to evaluate the pipeline system over the life of
the project. However, the Modified Flanigan correlation has proved useful for preliminary determination of
pressure loss in the pipeline as a function of flow parameters.
Modified Flanigan Correlation(8.15)

This work was done on field systems and even though it is relatively simple has proven useful for
estimating pressure drop on multiphase gas pipelines with low-liquid loading. The relationship between gas
flow rate, diameter and pressure drop is represented by the Panhandle A equation (Table 8.4). Two correc-
tions are made for two-phase flow.
1. The value of outlet pressure (P2) is adjusted for the pressure loss (DP2) due to uphill and down-
hill flow of two phases, including the effect of liquid holdup.
2. The efficiency term (E) is correlated to reflect measured system performance based on gas
velocity and liquid-gas ratio.
As modified the Panhandle A equation becomes:
Ts 1.0788 ; P1 – ^P2 + DP2h E

q = K` j c1 m
2 2 0.5394
(8.76)
0.4606 2.6182
cd m E tp
Ps Tm Lz m c
SI FPS
Where: q = gas rate at standard conditions std m3/d scf/day
P = absolute pressure kPa psia
Ps = pressure, standard conditions kPa psia
Tm = mean absolute temperature of line K °R
Ts = temperature, standard conditions K °R
d = inside diameter of pipe m in
L = pipe length m mi
g = gas relative density — —
zm = mean compressibility factor — —
Etp = two-phase efficiency Fraction Fraction
K = constant 1.364  107 435.87
ΔP2 = correction to P2 for elevation changes including liquid
kPa psi
head
CHAPTER 8 283
FLUID flow
The pressure correction (ΔP2) for inclined flow is calculated from Equation (8.77):
∆ P2 = A _t L E h / Z u – t g / Z di (8.77)
SI FPS
Where: A = constant 0.009 81 0.0069
tL = liquid density kg/m3 lb/ft3
tg = gas density kg/m3 lb/ft3
Z = fluid static head m ft
Eh = liquid head factor (Figure 8.22) — —

Zu = uphill heads m ft
Zd = downhill heads m ft
The head terms are found from the line profile as shown previously.
Figure 8.22 is a correlation to find the liquid head factor in Equation (8.77). At low velocity the
head loss is high. Liquid collects in the low spots and is lifted periodically. As velocity decreases to 2-4 m/s
[6-13 ft/sec] this head loss increases rapidly. Above about 8 m/s [26.2 ft/sec] there is little effect of velocity
on head pressure loss, and in fact the flow regime will likely be entering the mist or annular mist region.
Superficial Gas Velocity, vsg, ft/s

0 5 10 15 20 25 30 35 40 45 50
1.0
Equation of line between 1–10 m/s [3–30 ft/s]

Eh = 1/[1 + 0.33 (A vsg)0.92]
0.8
Where: A = 3.94 (Metric)
A = 1.2 (U.S.)
Liquid Head Factor, Eh
0.6
0.4
0.2
0
0 2 4 6 8 10 12 14 16
Superficial Gas Velocity, vsg, m/s
Figure 8.22 Flanigan's Liquid Head Factor(8.15)

FLUID flow
Superficial gas velocity may be calculated from the relationships provided in Equation (8.70) or it
may be calculated from Equation (8.78), below:
q z m Tm
vsg = Âh (8.78)
d 2 Pm
SI FPS
Where: q = gas flow rate at standard conditions 106 std m3/d MMscfd
d = internal pipe diameter m in
Pm = mean pressure in section kPa psi
Tm = mean temperature in section K °R

A = constant for conversion 5.19 60.0
zm = compressibility at Tm and Pm
The two-phase “efficiency” (Etp) in Equation (8.76) is found from Figure 8.23. The vsg on the
abscissa is the same one used for Figure 8.22. The “R” is the liquid-gas ratio in the pipeline segment.
At the upper right end of this curve the line contains a relatively small amount of liquid. The
efficiency approaches that of a dry gas line. One of the advantages of the Flanigan correlation is that as
the liquid loading approaches zero, Etp approaches 0.92. This boundary condition is consistent with actual
pipeline performance.
In many lines, the liquid/gas ratio, R, varies throughout the length. As the gas cools, R increases.
This cooling follows normal temperature reduction patterns. On a long line, the value of R quickly stabi-
lizes. If one knows R only at the inlet and outlet of such a line, using R at the outlet is the better of the two
values since it probably exists for most of the line length. Alternatively, one can use a liquid holdup correla-
tion such as Eaton (see next section) to estimate R.
1.00
Panhandle Flow Efficiency Fraction, Etp
0.80
0.60
0.50
0.40
0.30
0.25
0.20
0.15
0.10
Figure 8.23 Flanigan's Efficiency Correlation
CHAPTER 8 285
FLUID flow
Because of the variation of R, P and T with length, a long line is sometimes divided into segments
for calculation purposes. An average or mean P and T is estimated for each section. R is determined from
an equilibrium calculation at these values. The ΔP of the segment is found after determining its regime and
appropriate equation. If numerous segments in series are used, the calculation quickly becomes too time-
consuming to be done manually.
Three different calculations are possible using the Flanigan method.
1. Flow rate and diameter known, solve for pressure drop. This is a straight-forward solution.
Solve Equation (8.76) for (P2 + ΔP2). P2 is the desired outlet pressure or if P2 is fixed, solve
equation for inlet pressure P1.
2. Flow rate and pressure drop known, solve for diameter. Assume a diameter to start a trial-and-
error process. For this assumed value calculate ΔP2 and Etp and solve Equation (8.76) for “d.”
When the value calculated checks the assumed value (within standard pipe sizes), the correct
diameter is known.
Use Equation (8.78) for an assumed superficial velocity of 8 m/s [26 ft/sec] to estimate an initial
value for d. This same assumption is also used in Figure 8.23 and Figure 8.24 for the first trial.
3. Pressure drop and diameter known, solve for flow rate. This also is trial-and-error. Assume a
flow rate. This fixes a velocity for the first trial. When the assumed value agrees with the value
calculated in Equation (8.76) a solution has been reached.
One can use the same velocity estimate as in (2) above and Equation (8.78) to estimate an
initial value for “q”.
This modified Flanigan approach has proven useful for lines where Etp exceeds 50%. Below this
value, the combination of gas velocity and liquid holdup is such that a more complex system exists.
Liquid Holdup Correlation

As stated earlier, liquid holdup is that
1.0
fraction of a pipe segment which is occupied by
Water Gas Data
liquid. A correlation to estimate liquid holdup is 0.9
2” Pipe 5-2500 bpd
important to analyzing two-phase flow systems
Liquid Holdup Fraction, L
0.8 4” Pipe 50-5500 bpd

because the liquid holdup fraction not only deter- 0.7
0-0.28 x 106 std m3/d
[0-10 MMscf/day]
mines the cross sectional area available for gas flow,
0.6
but also determines the liquid inventory in the line.
This is important for pigging operations and estima- 0.5
tion of slug size. It is also important for establishing 0.4
the two-phase density for vertical or inclined flow. 0.3
One method of estimating liquid holdup 0.2
is to simply assume that the liquid holdup fraction 0.1
is equal to the liquid volume fraction. The liquid 0.0
volume fraction can be estimated from the inlet 0.001 0.01 0.1 1 10
liquid content or by a VLE calculation at the T & P X
of the pipeline. This method relies on the assump-
tion that the gas and liquid travel through the pipe at Figure 8.24 Eaton Liquid Holdup Correlation
the same velocity, i.e., “no slip.” This assumption is
only valid at high gas velocities when the liquid is entrained in the pipe as a mist or spray.
For other flow regimes, such as stratified (smooth or wavy), the vapor typically travels at a higher
velocity than the liquid. In these systems the liquid accumulates in the line until it reaches an equilibrium liquid
holdup. At this equilibrium condition, the liquid rate in is equal to the liquid rate out, but the actual holdup can
be significantly greater than the inlet liquid content.

FLUID flow
Where:
N0.575 N 0.1
d Ln
P 0.05 1
c m
Lv
X =
N gv Pb 0.0277 N Lb (8.79)
Nd
vsL c gvL m
t 0.25
NLv = liquid velocity number (8.80)
vsg c gvL m
t 0.25
Ngv = gas velocity number (8.81)
da v L k
gt 0.5
Nd = diameter (8.82)
g 0.25
NL = liquid viscosity number nL c m (8.83)
t L v3
SI FPS
and
P = line pressure kPa psia
Pb = base pressure 101.325 kPa 14.7 psia
vsL = superficial liquid velocity m/s ft/sec
tL = liquid density kg/m3 ft/sec
v = liquid surface tension N/m lbm/ft3
d = pipe inside diameter m ft
nL = liquid viscosity kg/m•s lbm/ft-sec
NLb = the base water viscosity number 0.002 26
Convenient Conversions: 1 cp = 0.001 kg/m·s = 6.72 ´ 10–4 lbm/ft-sec = 1 MPa·s

1 dyne/cm = 0.001 N/m = 2.20 ´ 10–3 poundal/ft
The Eaton liquid holdup correlation(8.16)provided in Figure 8.24, is one of the few hand calcula-
tion models available to estimate liquid holdup. The Eaton correlation should be used for horizontal or
near-horizontal pipelines. It tends to be somewhat high relative to actual data for large diameter pipelines
with relatively low liquid loadings. References 8.31 and 8.38 provide a summary of various liquid holdup
correlations compared to actual data. The Eaton liquid holdup factor, X, is calculated from Equation (8.79)
for use with Figure 8.24.
Example 8.13: A 0.254 m [10 in] diameter pipeline handles 2.12  106 std m3/d [75 MMscf/d] of
natural gas. The mean pipeline pressure and temperature are 6900 kPa and 15°C
[1000 psia and 59°F] respectively. The gas MW and compressibility factor are 18.5
and 0.8. The LGR is 56 m3/106 std m3 [10 bbl/MMscf]. At pipeline conditions, the
liquid properties are:
t = 680 kg/m3 [42.5 lb/ft3]
v = 0.015 N/m [0.033 poundal/ft]
nL = 0.000 3 kg/ms [0.000 20 lbm/ft-sec]
Determine the liquid hold up fraction from Figure 8.24.
CHAPTER 8 287
FLUID flow

SI Units:
q ^4h
vsL = AL = ^0.001 37 m3/s h< F = 0.027 m/s
^3.141h^0.254h 2
qg ^4h
vsg = A = c 86 400 ma 6900 ka 288 k^0.8h< F = 5.67m/s
2.12 # 106 101 288
^3.1416h^0.254h2
N Lv = 0.027 ; E
0.25
680
= 0.22
^9.81h^0.015h
N gv = 5.67 ; E
0.25
680
= 47
^9.81h^0.015h
^9.81h^680h 0.50
N d = 0.254 < F = 169
^0.015h
9.81
N L = 0.0003 ; 3E
0.25
= 0.0024
^680h^0.015h
N 0.575 N L 0.1
- axis Parameter, Figure 8.24 = = Lv Gc P m < 0.0277 F N n
1
d
0.05
X N P
gv b Nd Lb
^0.223h
=; Ea 6900 k 0.0277 Ea 0.002 26 k
0.575
1 0.0024 0.1
;
0.05
46.8 101 ^169h

= 0.01
Figure 8.24, Liquid Holdup Fraction ≈ 2-3%.
FPS Units:
q ^4h
vsL = AL = 0.049 ft3 /s < F = 0.089 ft/s
^3.14h^0.833h2
qg ^4h
vsg = A = c 86 400 ma1000 ka 519 k^0.8h < F = 18.7 ft/s
75 # 106 14.7 519
^3.1416h^0.833h2
N Lv = 0.089 ; E
0.25
42.5
= 0.22
^32.2h^0.033h
0.25
42.5
N gv 18.7 47
32.2 0.033
32.2 42.5 0.5
N d 0.833 < F 170
^0.033h
32.17
N L = 0.000 20 ; 3E
0.25
= 0.0024
^42.5h^0.033h

N 0.575
N L 0.1
X - axis Parameter, Figure 8.24 = = NLv Gc P m < N 0.0277Fd N n
0.05
1
gv Pb d Lb
^0.224h
=; Ea1000 k 0.0277 Ea 0.00226 k
0.575
1 0.0024 0.1
;
0.05
47.1 14.7 ^170h

= 0.01
Figure 8.24, Liquid Holdup Fraction ≈ 2-3%.

FLUID flow
Liquid holdup depends on several parameters

including liquid density, surface tension, viscosity,
pipe diameter, gas density, gas velocity, and line incli-
VL , Liquid Hold Up
nation. Gas velocity is probably the most important
parameter. As noted earlier, liquid holdup can increase VL1
dramatically when the gas velocity falls below 2-4
m/s [6-13 ft/sec]. It should also be recognized that VL2
the liquid holdup varies along the length of the line. A
rigorous analysis of liquid holdup involves breaking
the pipeline into segments and analyzing each line Q1 Q2 Gas Flow
segment separately. Figure 8.25 demonstrates what Figure 8.25 Pipeline Liquid Holdup
happens to the liquid holdup in a pipeline as the gas

flow changes. At Q1, the gas flow is low and the corresponding liquid holdup, VL (liquid inventory) in the line
is relatively high (VL1). As the gas flow is increased to Q2, the increased gas velocity sweeps additional liquids
out of the line, resulting in a new pipeline liquid inventory, VL2. The difference in liquid volumes between VL2
and VL1 is the volume of liquid that will be displaced from the pipeline and must be handled in the facilities at
the end of the line. The Cunliffe model, which follows, is one method available for predicting the slug volume
due to an increase in gas flows.
Vertical Two-Phase Flow

The principles of vertical flow are the same as for horizontal or inclined flow except that gravita-
tional forces are acting in an opposite direction to flow. The segregation patterns are different. Figure 8.26
illustrates the effect of the variables on vertical flow behavior.
100
50
20
10
Liquid Velocity Number, NLV
Froth Flow Froth Flow
Region l Region ll Region lll
1
on
Bubble Flow
si t i
n
Tra
0.5
Heading
0.2
Plug Flow Slug Flow Mist Flow
0.1
0.1 0.2 0.5 1 2 5 10 20 50 100 200 500 1000
Gas Velocity Number, Ngv
Figure 8.26 Duns and Ros Vertical Flow Regimes(8.17)
CHAPTER 8 289
FLUID flow
The liquid and gas velocity numbers are identical to those presented in the Eaton correlation
presented in Equation (8.79).
In region I the flow is gravity dominated. The pipe is almost completely filled with liquid and the
vapor phase is present in small bubbles. The bubbles move at a different velocity than the liquid but except
for their effect on density have almost no influence on the pressure drop.
In region II the vapor phase is more pronounced than in region I. For liquid velocity numbers less
than 0.5, increased gas flow causes the bubbles to combine and form plugs or slugs which almost fill the
pipe cross-section. The vapor plug velocity is higher than the liquid velocity. Both phases have a significant
effect on pressure drop.
As the vapor velocity number increases to 15-20 the slug flow regime transitions to mist flow. At
this point the gas becomes the dominant phase and the flow begins to change from gravity dominated to
friction dominated. In region III, the vapor phase is continuous and the liquid is entrained as droplets. The
pipe wall is coated with liquid and its presence affects the friction factor. The pressure drop is controlled
almost exclusively by the gas phase.
Froth flow occurs at the boundary of regions I and II at liquid velocity numbers greater than about
2. At these rates no plug or slug flow is observed and no discernible flow pattern exists.
Regardless of the specific correlations used for calculation of a particular vertical system, Figure
8.26 and the implications of it provide a real insight into what is going on in the vertical pipe.
The primary factors are liquid and gas velocities, pipe diameter, fluid viscosity, liquid surface
tension and fluid density. Gas-oil ratio is a factor but may be represented (indirectly) by the superficial
velocities and diameter. Stated simply, the type of flow is governed by fluid physical properties, their
relative quantities and the degree of turbulence and other forces affecting fluid distribution in the pipe.
SLUGGING
Slug flow is a flow regime which can occur across a wide range of multiphase flow conditions
and pipe geometries. Slug flow is intermittent, i.e., the flow can change from near 100% liquid to 100%
vapor. This creates serious design and operation problems for process equipment. High liquid rates may
fill separators causing process trips due to high level. High vapor rates can lead to flaring or temporar-
ily overload compressors causing trips due to compressor instability and/or high pressure. Because of its
complex nature, the prediction of slug length, slug frequency, and pressure drop by theoretical correlations
is difficult.
There are three basis mechanisms for slug formation.
1. Hydrodynamic. This is the normal slugging pattern encountered in pipelines and flowlines and
is the result of the instability of the stratified gas/liquid interface at certain flow conditions. For
horizontal pipe the occurrence of this type of slugging can be estimated from a flow regime
map similar to Figure 8.18.
2. Terrain Induced. This type of slugging is caused by significant elevation changes along the
pipeline such as geographical features or vertical risers. This type of slugging is system spe-
cific and more difficult to model than hydrodynamic slugging.
3. Operational. Transient slugging can occur due to changing flowrates and pressures along the
pipeline, pigging operations, or start-up and commissioning activities.

FLUID flow
Slugging is a complex phenomenon. Its

occurrence is due to an instability at the gas-liquid
Gas Liquid
interface causing liquid blockages to reach the top
4
1
of the pipe, see Figure 8.27. Four zones exist in the 3 2
slug: (1) mixing zone, (2) slug body, (3) film or tail Mixing
and (4) bubble. The size of the slug depends on a Zone L
m
complicated balance of gas and liquid transfer from

Film and Bubble Zone L f Slug Zone Ls
the mixing zone to the tail. Hydrodynamic slugs
depend on gas and liquid flowrates, pipe inclination, Slug Unit Lu
surface tension and fluid densities. As a slug grows,

the leading edge of the slug scoops up the slower Figure 8.27 Idealized Slug Unit(8.39)
moving liquid film and accelerates it to the velocity

of the slug in the mixing zone. Liquid is shed from the tail to a trailing film which moves at a lower velocity
than the slug body.
Estimating the frequency and length of slugs is the key consideration when sizing and operating
inlet separation facilities (i.e., slug catchers and the associated piping and controls). Many of the early
empirical slug flow studies were performed on small diameter < 50 mm [2 in] pipe. One of the first studies
done on large diameter flow lines was that of Brill, et. al.(8.18) From this data set, a correlation for slug length
was developed. This correlation predicts slug lengths of an order of magnitude longer than those suggested
from earlier small diameter pipe based correlations. The correlation predicts slug length as a function of
pipe diameter only.
8 0.1B
Ls = e a + b(ln d) (8.84)
SI FPS
Where: Ls = slug length m ft
a = – 65.8 –25.4
b = 59.1 28.5
d = inside pipe diameter mm in
This correlation was based on essentially horizontal flowlines 300-600 mm [12-24 in] in diameter
and 4600 m [15 000 ft] in length. Because it was developed over a limited range of flow conditions it is
suggested that use of the correlation be limited to the following conditions:
Diameter > 150 mm > 6 in

vsg 1.5-15 m/s 5-50 ft/sec
vsL 0.3 to 1.5 m/s 1-5 ft/sec
A flow regime map should be consulted to see if slug flow will exist at the conditions of interest.
Slug length is also a function of line length. Slug formation is a dynamic process and slugs can
swallow up adjacent slugs in a long pipeline. It should then be expected that for shorter lines the mean slug
length will be less and for longer lines, greater.
The dimensionless mean slug length, Ls/d, predicted from the Brill data is 300 to 350 for large
diameter lines. This is significantly higher than the range of 12-30 from experimental data on small diameter
lines.
Finally, Equation (8.84) predicts the mean slug length. The Prudhoe Bay data suggests that slug
lengths are log-normally distributed.(8.18) This is a reasonable assumption although other researchers have
suggested different probability distributions.(8.19)
CHAPTER 8 291
FLUID flow
For separator design, the assumption that the slug is 100% liquid is conservative. The liquid holdup
fraction in the slugs measured by Brill at Prudhoe Bay ranged from about 0.4 to 0.83, liquid holdup fraction
in the gas bubble was about 0.2.
Severe Slugging
Severe slugging is usually terrain or transient induced. It is often seen in riser flow on offshore
platforms. The mechanism for slug flow in a riser is illustrated in Figure 8.28.
Liquid blocks the gas flow at the base of the riser. A slug forms in the riser and flowline as gas
pressure increases behind the slug in the flowline. Eventually the gas pressure is sufficient to push the slug
up the riser and into the separator. A gas bubble is then produced into the separator following the slug as
some liquid falls back down the riser and contributes to the formation of the next slug.
The velocity of the slug can be significantly greater than the average velocity as the gas expansion
accelerates the slug up the riser. This can not only create level control problems at the separator but can
exert excessive forces at the pipe bends, particularly in low pressure piping with thinner pipe wall.
For severe slugging in riser flow, the flowline must be completely blocked to gas flow. This can
occur due to a declining flowline into the riser which creates an acute angle at the riser base or terrain-
induced undulations in the flowline. Secondly, the hydrostatic pressure build-up in the riser due to the slug
formation must exceed the rate of gas pressure build-up in the flowline. When these conditions exist, the
riser fills with liquid before the gas can force the liquid slug out of the line.
a) Initial Slug Formation P = Psep b) Slug Forms in Line and Riser P = Psep
To Separator To Separator
Ga Ga
s s
Oi Oi
l l
P ≈ Psep
P > Psep
c) Maximum Slug Length P = Psep d) Slug Moves into Separator P > Psep
To Separator To Separator
Ga Ga
s s
Oi Oi
l l
P = Pmax P < Pmax
Figure 8.28 Slug Formation Steps(8.26)

FLUID flow
Pots, et al.(8.20) suggested the following equation, which expresses the ratio between these pressure
build-up rates, to predict the existence of severe slugging in risers.
^ zRT/MW h m g
Pss = (A) d n (8.85)
^ gL F y gF h m L
SI FPS
Where: Πss = pressure buildup ratio — —
z = gas compressibility factor — —
R = ideal gas law constant 8314 J/K·kmol 1545 lbf/°R-lb-mol
T = temperature K °R
MW = gas molecular weight kg/kmol lbm/lb-mol

LF = flowline length m ft
y gF = average flowline gas holdup dimensionless
mg = gas mass flowrate kg/s lbm/sec
mL = liquid mass flowrate kg/s lbm/sec
A = conversion constant 1.0 32.2
Pots suggests that if Πss is less than 1.0, severe slugging may occur. Further, the approximate length
of slugs can be estimated from the riser height divided by Πss. Limited empirical evidence suggests actual
slug lengths are somewhat less than predicted by Equation (8.85).
Example 8.14: Check to see if the flowline depicted below will be expected to operate in the severe
slugging regime.
LF = 6000 m [19 700 ft] mg = 1.8 kg/s [4.0 lbm/sec]
T = 54°C [129°F] mL = 9.5 kg/s [20.9 lbm/sec]
Z = 0.95 MW = 22 ȳgF = 0.7
6^0.95h^8314h^327h /22@ 1.8
Pss = a k = 0.54
^9.81h^6000h^0.7h
SI Units: 9.5
6^0.95h^1545h^589h /22@ 4.0

Pss = ^32.2h a k = 0.54
^32.2h^19 700h^0.7h
FPS Units: 20.9
The pressure build up ratio is less than 1, thus severe slugging is expected.
The riser height for this system was 47 m, so the estimated slug length is
0.54 = 87 m 6286 ft@

47
Actual data(8.21) for the system in Example 8.14 indicated a mean slug length of 97 m [318 ft] and
median slug length of 74 m [243 ft] when measured by densitometer (compared to the 87 m [286 ft] calcu-
lated above). The empirical data in this system showed the slug distribution was skewed to the right and the
99 percentile slug was 345 m [1134 ft] in length.
Other conditions frequently present where severe slugging in risers has occurred are:
1. The flow line slopes downward immediately upstream of the riser, i.e., there is a low point in
the sea bed line upstream of the riser.
2. The flow regime in the flowline is stratified upstream of the riser.
CHAPTER 8 293
FLUID flow
Severe slugging typically occurs late in the field life at low flow conditions where the pressure drop
is gravity dominated rather than friction dominated.
Production Ramp-Up Slugging

Slugging may also occur due to transient conditions, primarily due to flow rate changes and pigging
operations. When the flow rate through a two-phase pipeline is increased, the difference in equilibrium
liquid holdup between the initial and final holdup will be displaced from the pipeline as a slug or surge. This
can be observed in Figure 8.28 and Figure 8.29. Cunliffe(8.22) developed a simple approach for estimating
the production of this liquid based on data from the Marlin pipeline.
This approach is valid for horizontal and gently sloping pipelines. A modified version of this corre-
lation has been developed by Shell and is presented below.

Figure 8.29 shows an example of liquid production into a slug catcher at the outlet of a pipeline
after an increase in flow rate.
Liquid flow will increase following a time delay of “A” after the inlet flow rate change has been
initiated. The period of liquid surge will have a duration “B” when the increased liquid flow rate will be
at a level “C”. Following the surge period, the liquid production will decline to the final steady flow rate.
The Cunliffe(8.22) method requires steady state liquid holdup values at various flowrates similar to
Figure 8.29. These can be generated from a simulation of the pipeline.
Liquid Entering Slugcatcher
tA tB
qC
Flowrate into
line increases
Time Following Increase in Flow Rate
Where: tA = delay time = mean gas residence time/2

tB = period of surge = mixture residence time + period of change
qC = maximum liquid flow rate = new liquid flow rate + (holdup difference/tB)
gas residence time = L[(1 – λL)/vsg]
mixture residence time = L/(vsg + vsL)
holdup difference = initial – final holdup volume
period of change = period in which upstream gas flow rate is increased
λL = average liquid holdup fraction in the pipe
L = pipeline length
vsg = superficial gas velocity
vsL = superficial liquid velocity
Figure 8.29 Example Liquid Production Exiting a Pipeline Following an Increase in Flow Rate

FLUID flow
Example 8.15: A near horizontal 0.305 m [12 in] diameter pipeline carries production from an offshore
platform to an onshore processing facility. The mean pipeline pressure is 10 300 kPa
[1500 psia] and the mean temperature is 20°C [68°F]. The gas MW = 18.9 and the
mean compressibility factor is 0.75. The condensate-gas ratio (CGR) is:
280 m3 : 50 bbl D

106 std m3 MMscf
The mean condensate properties are:
t = 690 kg/m3 [43.1 lb/ft3]
v = 20 dynes/cm [0.044 poundal/ft]
n = 0.3 cp [0.000 20 lbm/ft-sec]

The pipeline length is 128.8 km [80 mi] and it is desired to estimate the size and duration
of the liquid surge created by ramping up the flow from 1.0 ´ 106 std m3/d [35 MMscfd]
to 6.0 ´ 106 std m3/d [212 MMscfd] over a two (2) hour period.
For convenience the following values have been calculated using the Eaton Method.
Low Rate High Rate

vsɡ 1.17 m/s [3.83 ft/s] 7.00 m/s [23.0 ft/sec]
vsL 0.044 m/s [0.15 ft/s] 0.27 m/s [0.88 ft/sec]
Liquid hold up fraction 0.23 0.10
Liquid hold up volume 2160 m3 [13 600 bbl] 940 m3 [5900 bbl]
Using the equations presented in Figure 8.29, determine the following:

• Delay time
• Period of surge
• Maximum liquid flow rate
SI Units:
Step 1: Determine Mean Gas Residence Time (High Rate)
gas residence time = L 7^1 - m Lh /vsgA
mean gas residence time = 128 800 m a 7.0 m/s k = 16 560 s = 4.60 h
1 – 0.1
Step 2: Determine Delay Time

mean gas residence time
t A = 2
t = 4.60 = 2.3 h
A 2
Step 3: Determine Mixed Residence Time (High Rate)
L
mixture residence time = v + v
^ sg sLh

128 800 m
mixture residence time = = 17 720 s , 5.0 h
^7.0 + 0.27h m/s
CHAPTER 8 295
FLUID flow

Step 4: Determine Period of Surge
t B = mixture residence time + period of change
t B = 5.0 + 2.0 = 7 h
Step 5: Determine New Liquid Flow Rate
new liquid rate = c a

280 m3 c 6 # 106 std m3 m 1d
3m k = 70 m
3
6
10 std m d 24 h h
Step 6: Determine Maximum Liquid Flow Rate
hold up difference
q c = new liquid flow rate + tB
70 m 3 62160 - 940@ m 3
m3
q c = h + 7h
= 244
h
If the receiving terminal is unable to handle the maximum liquid rate, a longer ramp up
time should be used. A different liquid hold up correlation will give different results.
FPS Units
Step 1: Determine Mean Gas Residence Time (High Rate)
5280 ft ^1 - 0.1h
mean gas residence time = ^80 miha mi kc 23 ft/s m = 16 530 s = 4.6 hr
Step 2: Determine Delay Time
mean gas residence time 4.6 hr
t A = 2
=
2
= 2.3 hr
Step 3: Determine Mixed Residence Time (High Rate)
^80 miha k
5280 ft
L mi
mixture residence time = = = 17 690 s , 5.0 hr
vsg + vsg ^23 + 0.88h ft/s
Step 4: Determine Period of Surge

t B = mixture residence time + period of change = 5.0 + 2.0 = 7.0 hr
Step 5: Determine New Liquid Flow Rate
new liquid rate = a MMscf ka ka k=

50 bbl 212 MMscf 1 d bbl
day 24 hr 442 hr
Step 6: Determine Maximum Liquid Flow Rate
hold up difference
q c = new liquid flow rate + tB
442 bbl ^13 600 - 5900 bblh bbl bbl
q c = hr
+
7 hr
= 1542
hr , 37 000 day
If the receiving terminal is unable to handle the maximum liquid rate, a longer ramp up
time should be used. A different liquid hold up correlation will give different results.

FLUID flow
Erosional Velocity
Experience has shown that on pipelines, production manifolds and other lines transporting
two-phase flows that a loss of wall thickness occurs by erosion and corrosion. The velocity of the two-phase
flow should be maintained below the erosional velocity for that particular system, and can be estimated by:
^K hÂh (8.86)
v max =
t 0.5
SI FPS
Where: v = velocity m/s ft/sec
t = two-phase density at flowing temperature and pressure kg/m3 lbm/ft3
A conversion constant 1.23 1.0
=
K = empirical constant 100-200 100-200
Equation (11.22) in Chapter 11, Volume 2 provides the equation to calculate the two-phase density.
API 14E previously recommended three values of K; 100 for normal design calculation, 125 for
intermittent service, 150 for the “never exceed” value. Industry experience has found that these guidelines
are conservative, if the two-phase stream meets one of the following conditions:
1. Solids-free fluids that are not anticipated to be corrosive.
2. Solids-free fluids when corrosion is controlled with an inhibitor.
3. Solids-free fluids and corrosion resistant alloy piping materials.
In these cases, K values between 150 to 200 may be used for continuous service. Values up to 250
have been used successfully in intermittent service.
These values are, in general, based on erosion/corrosion limitations in bends, elbows, and fittings.
Metal loss is accelerated by high fluid velocities, presence of sand and corrosive components in the fluid.
For flow lines where solids and/or corrosive contaminants are present, or where K values of greater than
100 are used, periodic surveys to assess the pipe wall thickness are recommended.
While Equation (8.86) possesses the advantage of computational simplicity, it does not account
for factors such as flow geometry, type of metal, sand size, Reynolds number, and acceptable corrosion
rate. Reference 8.23 puts forward several alternative methods of estimating erosional velocities incorpo-
rating sand particle size and fluid properties. In high sand production environments the erosional velocity
for methane can be significantly less than for liquids.
Slug Mitigation
Some method of slug mitigation is necessary to ensure stable operation of separation of the produc-
tion/processing facility. The most common methods are:
1. Liquid Storage: Slug catchers are separators with extra-large liquid capacity. This method is
simple and robust, but can be quite expensive due to the vessel cost. The liquid may be stored
in the primary separator or it may be stored downstream in lower pressure (and less expensive)
vessels.
2. Choking: For riser flow in particular, this method has proven effective for severe slug mitiga-
tion. First proposed by Yocum(8.24) and Cady.(8.25) Schmidt(8.26) confirmed the effectiveness of
choking. Choking changed the flow regime from severe slugging to bubble flow.
3. Gas Injection: Gas injection at the bottom of the riser (it has also been used in near-horizontal
pipelines) increases the velocity of the fluids, decreases liquid holdup and changes the flow
regime to normal slugging or annular mist flow. It can be effective in reducing slug length, but
the required gas injection rates at the base of the riser are often quite high (2-3 times the normal
rate), increasing compression cost.
CHAPTER 8 297
FLUID flow
4. Control Schemes: This method is similar to choking in that a separator control scheme is
employed which controls the flow regime in the riser and flowline. Two methods have been
employed. The first uses control logic whereby the separator level is controlled by a valve on
the gas outlet and the separator pressure is controlled by the valve on the liquid outlet. A sec-
ond, more sophisticated method, controls the gas rate to maintain a constant mixture flowrate.
Liquid rate is on level control.
In both of these methods, the following precautions should be considered. First, additional
separation, including oil dehydration, often takes place downstream of the primary separator. It
is important that the capacity of these vessels be adequate to handle transient liquid rates.
Second, the primary separator pressure can vary. It may be necessary to operate the separator
further away from the design pressure to provide the necessary operating margin to avoid
unnecessary trips.
5. Pigging: This is a method of controlling the slug size and slug arrival frequency. In addi-
tion, frequent pigging of the line reduces liquid holdup and accordingly the pressure drop. If
pigging is infrequent, the liquid removed from the line during a pig run will approximate the
equilibrium liquid holdup in the line. Pig-induced slugs can be quite large if the equilibrium
liquid holdup is high. Shell(8.27) has developed a by-pass pig which allows a portion of the liquid
(8-15%) to “leak” through the pig. This has resulted in smaller pig-induced slugs.
Pipeline pigs come in many forms for
Cups different applications: (1) removal of
liquids collecting in lines during opera-
Fill Hole tions or used for hydrostatic testing, (2) to
Squeegee Pig Sphere Foam Pig
scrape wax, scale and other solids from the
Brushes pipe walls, (3) to isolate different liquids in
Brushes
product pipelines, and (4) to apply internal
pipe coatings for corrosion protection (5)
smart pigs (in-line inspection tools) that
travel through the pipe and measure and
Brush Pig Foam Brush Pig
record irregularities that may represent
Figure 8.30 Pipeline Pigs / Scrapers corrosion, cracks, laminations, deforma-
tions and other defects.
Guidelines for selecting and using pigs are readily available.(8.29, 8.40-8.41) There are three general
classifications: scraper or brush type, foam type and spheres. The choice depends on service
and the need to pass through valves and turn corners.
The design and operation of launchers and receivers is summarized in Reference 8.27.
6. Other: A few methods proposed include small subsea separators to remove the bulk of the gas
from the liquid, this gas is then routed to the platform through a separate riser. This method
will cause the flow regime in the main riser to revert to bubble flow. A second method is to
decrease the riser size or use multiple, smaller risers. This increases velocity in the riser and
improves flow stability. Both of these methods preclude the use of pigging.
Dense Phase Pipelines

For the transportation of natural gas from remote locations to the central processing facility, there
are three options:
1. Operate the pipeline from the production location to the processing facility in the two-phase
regime where all gas and liquids travel in a single line.

FLUID flow
2. Separation of the liquids and conditioning of the gas at a remote location. Gas and liquids
transported in separate single phase lines.
3. Operate a dense phase pipeline to the processing facility.
The decision as to which option to use is driven largely by economics and the local conditions at
the site.
There are a number of systems worldwide using wet gas dense phase pipelines. When the fluid is
transported in the dense phase, the pressure is maintained above the cricondenbar pressure. The system
is designed such that no liquids will condense in the pipeline. The operating difficulties associated with
two-phase flow and slugging are eliminated. The need for liquids handling equipment (slug catchers for
example) at the receiving terminal is eliminated with the exception of separators installed to handle liquids
generated during blowdown or depressuring activities. A more detailed discussion of natural gas phase
behavior, including dense phase, can be found in Chapter 4. In addition, the required pipeline diameter for
dense phase operation is often smaller than for two-phase systems.
Pipeline pigging requirements are either reduced or eliminated (depending upon the system design).
However, dense phase pipelines require more compression power as compared to a two-phase pipeline due
to higher operating pressure. The phase envelope of the gas flowing into the pipeline must also be managed
to ensure no liquids condense in the pipeline. This is done by controlling the pressure and temperature of the
separation stages at the remote operating facility. The design pressure of the dense phase pipeline is higher
than that required of the two-phase pipeline, but the reduced diameter often results in less steel required
to build the pipeline. This can translate into significant capital cost savings. A comparison of the listed
transport options are provided in Table 8.10.
Table 8.10
Pros and Cons of Produced Natural Gas Transportation Options
Option Pros Cons

Two-phase
1. Single pipeline required (larger diam- 1. Requires liquid holdup management of
Pipeline
eter than dense phase option). pipeline (pigging operations, other slug
2. Minimal remote equipment required. mitigation techniques). May require
3. Allows transportation of all produced liq- significant liquid handling capacity at
uids. terminal facility (slug catchers generally
have high capital cost).
2. May result in difficult operations dur-
ing production turndown periods.
Remote Separation
1. Pipeline operational reliability (assuming 1. Two to three pipelines are required
and Conditioning
facility is operating as intended). (depending upon the level of condition-
2. Hydrate prevention may not be required. ing, and the disposition of the water
3. Allows transportation of all produced phase).
liquid. 2. The cost and complexity of the remote
conditions facility increases.
Dense Phase 1. Single, smaller diameter pipeline re- 1. More complex facilities and compres-
Pipeline quired sometimes resulting in reduced sion required at remote location.
pipeline costs. 2. Operational difficulties occur if two-
2. Pigging and liquid handling facilities at phase conditions are present in the
terminal location not required. system (no equipment provided to deal
3. Operational problems associated with with liquids).
two-phase pipelines are eliminated. 3. Frequently requires hydrocarbon liquid
disposition at the remote facility.
CHAPTER 8 299
FLUID flow
APPLICATION OF THE TECHNOLOGY

The design of multiphase pipelines is a specialist endeavor. Numerous correlations are available;
the majority employ sophisticated simulation programs. The methods presented in this chapter are useful
for planning and reality check calculations. Reference 8.31 provides a comparison of some of the more
popular horizontal correlations with empirical data.
In general, pressure drop is adequately handled (within normal engineering uncertainty) by most of
the currently used correlations. Liquid holdup predictions are less accurate when compared to experimental
data. These models are based on steady-state flow. Transient models have proven useful in evaluating and
recognizing potential problems.
The process/facility engineer will not typically be expected to provide a detailed analysis of
multiphase systems. It is nonetheless important to be cognizant of the major issues and ramifications of
multiphase systems. To assist in this process the following checklist has been provided:
1. Have flowrates over the full life of the pipeline been considered, e.g., gas-liquid ratio, pressure,
water, inhibitors, etc.?
2. Have the thermodynamic and physical properties of the fluids been accurately determined?
3. Is the flow regime sensitive to temperature? Have heat transfer calculations been properly
performed?
4. Is water present? If so, have hydrate formation and corrosion been adequately addressed?
5. If corrosion is possible, is the flow regime consistent with adequate distribution of corrosion
inhibitors on the pipewall?
6. For items 4 and 5 above, have all flow conditions, including stoppage, been considered?
7. What is the maximum equilibrium holdup in the line? Has it been considered at all flowrates?
8. Is pigging necessary to control liquid holdup?
9. Is a slug catcher required? What size is it? Can the size be reduced by implementing a pigging
program or by changing pigging frequency?
10. Where will liquid accumulate during a flow stoppage? What is the size of a transient induced slug?
11. Is severe slugging anticipated? Can it be reduced by choking, control modifications, gas lift, etc.?
12. If slugging is anticipated, have forces at elbows, tees, and other fittings been evaluated?
There is no way one can designate which calculation methodology to use. The problem is very
much like that in well logging or PVT behavior. The choice is dictated by what is known about the system
under study.
The more recent, mechanistic models tend to be more general and may be applied on a broader
basis than the older methods. However, it is recommended that one of the older methods be included as a
reality check. For horizontal flow, where the liquid loading is within the correlation limits and gas is the
primary phase, the modified Flanigan approach presented earlier may be suitable. If mist flow is indicated,
Duns and Ros is a candidate for both horizontal and vertical flow. If liquid is the continuous phase (bubble
flow), a regular liquid flow equation with correction of physical properties for gas bubbles may be used.
The calculation results should be regarded as a range of expected performance. The total system
should operate within the pressure drops and liquid handling ranges calculated.

FLUID flow
Physical Properties Correlations

Fluid properties affect two-phase flow calculations more than often recognized. The accuracy of the
hydraulic simulation depends on the accuracy of the fluid property correlations. These correlations can be
divided into two categories: compositional and non-compositional models.
Compositional models typically employ EOS and/or corresponding states correlations as discussed
in Chapter 3. Non-compositional models predict bulk fluid properties from measurable properties such as
the relative densities of the gas and liquid, GOR, and water cut.
One commonly used non-compositional model is the “Black Oil Model”. In-situ properties such as
density, viscosity and surface tension are calculated from empirical correlations using the bulk properties as
input. Drawbacks of non-compositional models include approximation of the true VLE in the pipeline and
the lack of correlations for thermodynamic properties such as J-T coefficient.
MULTIPHASE FLOW SPLITTING

The flow in a line may be split between two or more lines at some point. This occurs in distribution
systems, at surface facilities, river crossings and the like. In a two-phase system the liquid split will not
necessarily be the same as that of the gas.
There are three forces involved in deter-
B mining the amount of liquid entering each branch
of the tee shown Figure 8.31: inertial, gravitational
and centripetal. If the flow is A to B the inertial
forces tend to keep the liquid flowing in a straight
line. The gravitational forces tend to pull the liquid
C to the bottom. Thus, the angle of the side connec-
tion should make a difference. Everything else being
A
equal, a tee in a vertically upward position should
get less liquid than one in the downward position.
Where the side branch is horizontal, gravity should
Figure 8.31 Multiphase Flow Splitting – Branch of the Tee have little effect on the split.
As the gas enters a side branch, C, a circular motion is imparted to it. When a mass traverses a
circular path with constant speed, the velocity changes in direction but not in magnitude. An unbalanced set
of forces occur which cause acceleration toward the center of the circle. It takes energy to produce accelera-
tion so that a localized pressure change (drop) occurs.
Fluid always flows in a direction toward the lowest pressure available. In a horizontal tee, liquid
will only enter the side tee if the centripetal forces produce a driving force in that direction that overcomes
the inertial forces for straight-ahead flow.
Newton’s First Law of Motion says that a mass in motion will move in a straight line unless acted
on by unbalanced forces causing it to deviate. In this case, the forces are gravitational and centripetal, the
equations for which are:
F mg/g c F mv 2 /r
1 44 2 44 3 1 44 2 44 3 (8.87)
Gravitational Centripetal
Where: r = radius of circular motion
CHAPTER 8 301
FLUID flow
100 5
Upstream Gas Velocity, m/s [ft/s] Upstream Gas Velocity, m/s [ft/s]
3 [10] P=3.0 MPa [435 psia] 3 [10] P=3.0 MPa [435 psia]
80 4 7 [23] d=7.5 cm [3 in]
Branch Gas Velocity, m/s

5 [16] d=7.5 cm [3 in]
Note: 3 and 5 m/s [10 and 16 ft/s]
Gas Flow to Branch, %
7 [23]
curves overlie one another
60 3
40 2
20 1
0 0
0 20 40 60 80 100 0 20 40 60 80 100
a) Liquid Flow to Branch, % b) Liquid Flow to Branch, %
Figure 8.32 Behavior of Two-Phase Grid System
Centripetal force, a major consideration in flow-splitting, depends on velocity, the radius of the
pipe and the mass involved. Velocity, in turn, depends on total flow rate. Theory suggests that the amount
of liquid entering a sidebranch would depend on the amount of gas entering that branch. This has been
confirmed experimentally.(8.23, 8.28, 8.32) Figure 8.32 shows the result of a test on a gas system in the Nether-
lands by Oranje and co-workers.
Notice the effect of upstream velocity on behavior. At 3-5 m/s [10-16 ft/sec] velocity the curves are
linear; at 7 m/s [23 ft/sec] a break occurs at about 85% of the liquid flowing to the branch. This shows the
effect of velocity on behavior.
Hong(8.28) expanded this type of study. Although the work was done at low pressures in 9.5 mm
[3/8 in] transparent pipe, the results check reasonably well with Oranje’s work in 76 mm [3 in] pipe at
higher pressure.
When the gas/liquid flows into “C” and out “A” and “B” the liquid split is proportional to the gas
split when 15-85% of the gas enters “A” or “B.”
MECHANICAL DESIGN OF PIPING

In addition to sizing the pipe to accommodate the flowing fluid at a reasonable pressure drop it is
also important to mechanically design the piping to withstand the forces which act upon it. For piping inside
a processing facility the code used almost universally around the world is ANSI B31.3 “Process Piping,
ASME Code for Pressure Piping”. This code sets out the procedures for the design, installation and testing
of process piping.
Several forces can act upon the piping once it is installed in a facility. These include the hoop stress
applied by the pressure of the fluid in the pipe as well as external forces applied laterally or longitudinally.
Except for small pipe sizes the hoop stress is typically the limiting stress and consequently sets the wall
thickness of the pipe. Under B31.3 the relationship between the maximum allowable internal working
pressure, pipe diameter, wall thickness and material strength is given by the equation:

FLUID flow
Pd o
t= (8.88)
2 ^SEW + PYh
SI FPS
Where: t = wall thickness mm in
Y = coefficient for ferritic steel below 482°C [900°F] 0.4 0.4
P = internal design pressure MPa psi
do = pipe outside diameter mm in
W = weld joint strength reduction factor for ferritic steel below
1 1
482°C [900°F]
S = allowable stress value MPa psi
E = joint efficiency
Equation (8.88) may also be written in terms of pressure.

2tSEW
P = d - 2tY (8.89)
o
The wall thickness “t” can vary by ± 12.5% due to the mill tolerance. When applying Equation (8.88)
you must divide “t” by 0.875 to determine the nominal wall thickness. Similarly, in Equation (8.89) you
should multiply “t” by 0.875 before calculating P.
In addition it is common practice to include a corrosion allowance in the design. Typical values
range from 1.6 mm [1/16 in] for non-corrosive systems to 3.2 mm [1/8 in] in systems where some corrosion
is anticipated.
The Appendix tables show maximum allowable internal pressures for several pipe sizes as a
function of pipe diameter and wall thickness calculated using Equation (8.89). These were determined for
commonly used carbon steel piping (A-53 Gr. B, A-106 Gr. B, A-333 Gr. 6 and API 5L Gr. B). For other
piping materials the maximum allowable pressure must be calculated using Equation (8.64) and the stress
value for that material.
For pipelines the approach is similar but the codes are different.
Liquid: ANSI B31.4 “Liquid Transportation Systems for Hydrocarbons, LPG, Anhydrous
Ammonia and Alcohols.”
Gas: ANSI B31.8 “Gas Transmission and Distribution Piping”
The relationship between design pressure and wall thickness is given by Equation (8.90).
2 ^SMYSh t
P= ^FhÊh^Th (8.90)
do
SI FPS
Where: P = design pressure MPa(g) psig
SMYS = specified minimum yield strength of pipeline material MPa psi
t = wall thickness mm in
do = outside pipe diameter mm in
F = design factor (see below) — —
E = joint efficiency — —
T = temperature derating factor 1.0 for temperatures below
121°C [250°F]
CHAPTER 8 303
FLUID flow
The design factor, F, depends on the population density and amount of infrastructure along the
pipeline route. For gas pipelines it varies from 0.4 to 0.8. For liquid lines F = 0.72.
The joint efficiency, E, is a function of the pipe construction. For seamless pipe and for longitudi-
nally welded pipe which has been 100% radiographed, in accordance with the code, E = 1.0. For other
longitudinally welded pipe, E < 1.0.
Flanges
RF = Raised Face
For nominal pipe sizes larger than 1-1/2
to 2 inches [DN 40 to 50], the most popular
method of pipe connection is flanges.

Flanges are available in several designs:
screwed, slip-on, socket weld and welding
neck. Of these, welding neck flanges are most
Heat Code commonly used in the oil and gas industry.
Material Designation
Wall Thickness
Manufacturer Nominal Size Pressure Matching Pipe Flanges are typically forged or cast and
Rating Face Designation
are manufactured from the same materials as
the piping. The strength of the flange depends
Figure 8.33 Pipe Flange on its thickness, number of bolts and bolting
material.
Flanges are available in discrete pressure ratings specified by ASME/ANSI B16.5 “Pipe Flanges and
Flange Fittings.” For carbon steel flanges (Material group 1.1) Figure 8.34 shows the maximum allowable
operating pressure as a function of temperature for flange classes ANSI 150, 300, 600, 900, 1500, and 2500.
The maximum pressure ratings for flange classes are provided at 38oC [100oF], and are derated at higher
operating temperatures. The maximum allowable
Temperature, °F
operating pressure for flanges manufactured from 0 100 200 300 400 500 600 700
45 000
a different material will differ from those shown in Class 2500
Figure 8.33. 40 000

6000
In developing a set of piping specifications 35 000 5000

for process piping, most companies establish pipe
30 000
classes tied to the flange rating. For example, one 4000
Pressure, kPa
Class 1500
pipe class will be developed for all piping using 25 000 Pressure, psia
ANSI 150 flanges and a separate class for 300, 600, 3000
20 000
900 flanges and so on. This means that the piping and
all piping components are designed to the maximum 15 000
Class 900
2000
pressure of the flange. Class 600
10 000
As an example, for the ANSI 300 pipe class 5000

Class 300 1000
the design pressure (assuming carbon steel materials Class 150
at ambient temperature) would be 51.1 barg [740 0

-50 0 50 100 150 200 250 300 350 400
0
psig]. All piping components used in this class Temperature, °C

would have a minimum design pressure of 51.1 barg
Figure 8.34 Maximum Pressure Rating vs. Temperature
[740 psig]. In other words, the flange is the weakest for Carbon Steel Flanges
point in the system. (Materials Group 1.1) – B16.5

FLUID flow
REFERENCES
8.1 Moody, L. F., Trans., ASME (1944), p. 671.
8.2 Tech. Paper No. 410, “Flow of Fluids Through Valves Fittings and Pipe,” Crane Co. (2009).
8.3 Craft, B. C. et al., Well Design, Drilling and Production, Prentice-Hall, Englewood Cliffs, New Jersey (1962).
8.4 Sulton, A. A., “Sizing Pipe for Non-Newtonian Flow,” Chem. Engr. (Dec. 19, 1988), p. 140.
8.5 Gregory, G. A. and M. Fogarasi, “Alternate to Standard Friction Factor Equation,” Oil and Gas J. (Apr. 1, 1985), p. 120.
8.6 GPSA Engr. Data Book, GPSA, Tulsa, Oklahoma (1987).
8.7 Hooper, W. B., Chem Eng. (May 17, 1982), p. 127.
8.8 Brown, G. S., Chem. Eng. (Mar. 16, 1987), p. 85.
8.9 “Steady Flow in Gas Pipelines,” AGA (1965).

8.10 Zhou, J. and M. A. Adewumi, “Simulation of Transients in Natural Gas Pipelines,” SPE Jour. (Nov. 1996), p. 202.
8.11 Manning, Francis S., and Richard E. Thompson. Oilfield Processing, Vol. 2: Crude Oil. Tulsa: PennWell, 1995. Print.
8.12 Pallersen, T. R., et al., “Danish Line Insulated Against Hydrate Formation,” Oil and Gas J. (Apr. 21, 1986), p. 50
8.13 Shea, R.H., Rasmussen, J., Hedne, P., Malnes, D., Oil and Gas J. (May 19, 1997).
8.14 Taitel, Y. and A. E. Dukler, “A Model for Predicting Flow Transitions in Horizontal and Near-Horizontal Gas-LiquidFlow”,
AlChE Jour., 22 (1979), p. 47-55.
8.15 Flanigan, O., Oil and Gas J. (Mar. 10, 1958), p. 132.
8.16 Eaton, B. A., et al., “The Prediction of Flow Patterns, Liquid Holdup, and Pressure Losses Occurring During Continuous
Two-Phase Flow in Horizontal Pipelines,” Jour. Pet. Tech., Trans., AIME 240 (June 1967), p 815-828.
8.17 Duns, H., Jr , and N.C.J. Ros: “Vertical Flow of Gas and Liquid Mixtures in Wells,” Proc. Sixth World Pet. Congress, Frank-
furt (June 19-26, 1963). Section II, Paper 22, p. 6.
8.18 Brill, J. P., et al., “Analysis of Two-Phase Tests in Large-Diameter Flow Lines in Prudhoe Bay Field,” SPE Jour. (June 1981),
p. 363-78.
8.19 Bernicott, M. F. and J. M. Drouffle, “A Slug Length Distribution Law for Multiphase Transportation Systems,” SPE Jour.
(May 1991), p. 166.
8.20 Pots, B. F. M., Bromilow, I. G. and J. J. W. F. Konijn, “Severe Slug Flow in Offshore Flowline/Riser Systems,” SPE Jour.
(Nov. 1987), p. 319.
8.21 Burke, N. E. and S. F. Kashou, “Slug-Sizing/Slug-Volume Prediction: State of the Art Review and Simulation,” SPE Jour.
(Aug. 1996), p. 166.
8.22 Cunliffe, R. S., “Prediction of Condensate Flowrates in Large-Diameter High Pressure Wet Gas Pipelines,” Australian
Petroleum Exploration Association Conference, APEA Jour. (1978), p. 171.
8.23 Oranje, L., Oil and Gas J. (July 2, 1973), p. 39.
8.24 Yocum, B. T., “Offshore Riser Slug Flow Avoidance: Mathematical Models for Design and Optimization,” SPE4312, Pre-
sented at SPE European Meeting, London, England (Apr. 1973).
8.25 Cady, P. D., “How to Stop Slug Flow in Condenser Outlet Piping,” Hydr. Proc. & Petr. Ref. (Sept. 1963), p. 42, 192.
8.26 Schmidt, Z., et al., “Choking Can Eliminate Severe Pipeline Slugging,” Oil and Gas J. (Nov. 12, 1979), p. 230.
8.27 Wu, H. L., et al., “By-pass Pigs for Two-Phase Flow Pipelines,” 13th Annual Continental GPA Meeting (Sept. 1996), Flor-
ence, Italy.
8.28 Hong, K. C., Jour. Pet. Tech. (Feb. 1978), p. 290.
8.29 Webb, B. C., Oil and Gas J. (Nov. 13, 1978), p. 196.
8.30 Webb, B. C., Oil and Gas J. (Nov. 27, 1978), p. 74.
8.31 Baker, A., Nielsen, K., and A. Gabb, “New Correlations – 3 part series,” Oil and Gas J. (14 Mar., 21 Mar, and 28 Mar., 1988).
8.32 Bergman, D. F. et al., AGA Project PR 26-69, Univ. of Michigan (1969).
8.33 Pressure Surge Theory, Part XIV, Pipeline News (Oct. 1955).
8.34 Stewart, T. L., Oil and Gas J. (Nov. 22, 1971), p. 55.
CHAPTER 8 305
FLUID flow
8.35 Joukowsky, N. and O. Simin, “Water Hammer,” AWWA Proceedings Vol XXIV (1904), p. 44-58.
8.36 Elstout, R., Oil and Gas J. (Oct. 25, 1965), p. 141.
8.37 Mandhane, J. M., Gregory, G. A., and K. Aziz, “A Flow-Pattern Map for Gas-Liquid Flow in Horizontal Pipes,” Int. J.
Multiphase Flow (1974) 1, p. 537-553.
8.38 Shea, R. H., et al., “Holdup Predictions for Wet Gas Pipelines Compared,” Oil and Gas J. (May 19, 1997), p. 73.
8.39 Scott, S. L., Shoham, O., and J. P. Brill, “Prediction of Slug Length in Horizontal, Large-Diameter Pipes,” SPE Jour. (Aug.
1989), p. 335.
8.40 Hara, A., Oil and Gas J. (May 1, 1978), p. 56.
8.41 Diab, S. Y., Oil and Gas J. (Mar. 7, 1983), p. 112.
8.42 Brown, T. S., et al., “Application of a Transient Heat Transfer Model for Bundled, Multiphase Pipelines,” SPE 36610 (Oct.
1996), Denver, Colorado.

APPENDIX
APPENDIX 8A
FLUID flow
APPENDIX 8A – ALLOWABLE WORKING PRESSURES FOR CARBON STEEL PIPING
Table 8A.1
Allowable Working Pressures for Carbon Steel Piping – SI (CA = 1 mm)
(A-53 Gr. B, A-106 Gr. B, A-333 Gr. 6, API 5L Gr. B)
ANSI B31.3 – Corrosion Allowance = 1 mm
(Use for training and illustrative purposes only)
MAWP, kPa
Flow Area, -28 to
DN Sched. O. D. mm W. T. mm I. D. mm m2 204°C 260°C 316°C 371°C
15 40 21.34 2.77 15.80 0.000 196 19 424 18 355 16 801 16 025

80 3.73 13.87 0.000 151 32 027 30 265 27 703 26 422
160 4.78 11.79 0.000 109 46 641 44 076 40 345 38 479
XXS 7.47 6.40 0.000 032 90 265 85 301 78 079 74 469
20 40 26.67 2.87 20.93 0.000 344 16 372 15 471 14 161 13 507
80 3.91 18.85 0.000 279 27 015 25 530 23 368 22 288
160 5.56 15.55 0.000 190 45 239 42 751 39 132 37 322
XXS 7.82 11.02 0.000 095 73 297 69 266 63 402 60 470
25 40 33.40 3.38 26.65 0.000 558 16 944 16 012 14 656 13 979
80 4.55 24.31 0.000 464 26 480 25 024 22 906 21 846
160 6.35 20.70 0.000 337 42 229 39 917 36 528 34 839
XXS 9.09 15.22 0.000 182 68 924 65 133 59 619 56 862
40 40 48.26 3.68 40.89 0.001 313 13 187 12 462 11 407 10 880
80 5.08 38.10 0.001 140 20 879 19 731 18 061 17 226
160 7.14 33.99 0.000 907 32 829 31 024 28 397 27 084
XXS 10.16 27.94 0.000 613 51 873 49 020 44 871 42 796
50 40 60.33 3.91 52.50 0.002 165 11 443 10 814 9899 9441
80 5.54 49.25 0.001 905 18 523 17 504 16 022 15 282
160 8.71 42.90 0.001 445 33 195 31 369 28 714 27 386
XXS 11.07 38.18 0.001 145 44 904 42 434 38 842 37 046
80 40 88.90 5.49 77.93 0.004 769 12 208 11 537 10 560 10 072
80 7.62 73.66 0.004 261 18 527 17 508 16 026 15 285
160 11.13 66.65 0.003 489 29 408 27 791 25 438 24 262
XXS 15.24 58.42 0.002 680 43 044 40 677 37 233 35 512
100 40 114.30 6.02 102.26 0.008 213 10 613 10 030 9181 8756
80 8.56 97.18 0.007 417 16 404 15 502 14 190 13 533
160 13.49 87.33 0.005 989 28 194 26 643 24 388 23 260
XXS 17.12 80.06 0.005 034 37 389 35 333 32 342 30 846
150 40 168.28 7.11 154.05 0.018 639 8778 8295 7593 7242
80 10.97 146.33 0.016 817 14 698 13 889 12 714 12 126
160 18.26 131.75 0.013 633 26 433 24 979 22 865 21 807
XXS 21.95 124.38 0.012 151 32 659 30 862 28 250 26 943
200 40 219.08 8.18 202.72 0.032 275 7929 7492 6858 6541
80 12.70 193.68 0.029 460 13 219 12 492 11 434 10 905
XXS 22.23 174.63 0.023 950 24 900 23 530 21 538 20 542
160 23.01 173.05 0.023 520 25 900 24 475 22 403 21 367
250 40 273.05 9.27 254.51 0.050 874 7336 6933 6346 6053
XS 12.70 247.65 0.048 169 10 526 9947 9105 8684
80 15.09 242.88 0.046 329 12 781 12 078 11 056 10 544
160 28.58 215.90 0.036 610 26 078 24 644 22 557 21 514
CHAPTER 8 307
FLUID flow
Table 8A.1 (Cont'd)

MAWP, kPa
Flow Area, -28 to
300 S 323.85 9.53 304.80 0.072 966 6361 6011 5502 5248
40 10.31 303.23 0.072 214 6971 6587 6030 5751
XS 12.70 298.45 0.069 957 8832 8347 7640 7287
80 17.48 288.90 0.065 552 12 615 11 922 10 912 10 408

160 33.33 257.20 0.051 956 25 773 24 356 22 294 21 263
350 20 355.60 7.93 339.75 0.090 659 4665 4408 4035 3848
S 9.53 336.55 0.088 959 5784 5466 5003 4772
40 11.13 333.35 0.087 275 6910 6530 5977 5701
XS 12.70 330.20 0.085 634 8025 7584 6942 6621
80 19.05 317.50 0.079 173 12 596 11 903 10 896 10 392
160 35.71 284.18 0.063 425 25 173 23 788 21 774 20 767
400 20 406.40 7.93 390.55 0.119 797 4075 3851 3525 3362
S 9.53 387.35 0.117 841 5050 4772 4368 4166
40 12.70 381.00 0.114 009 7002 6617 6057 5777
80 21.44 363.53 0.103 791 12 487 11 801 10 802 10 302
160 40.49 325.43 0.083 175 25 061 23 683 21 678 20 675
450 20 457.20 7.93 441.35 0.152 988 3617 3418 3129 2984
S 9.53 438.15 0.150 777 4482 4235 3877 3697
XS 12.70 431.80 0.146 439 6210 5868 5372 5123
40 14.28 428.65 0.144 310 7073 6684 6119 5836
80 23.83 409.55 0.131 736 12 403 11 721 10 728 10 232
160 45.24 417.53 0.136 917 24 959 23 586 21 589 20 591
500 20 508.00 9.53 488.95 0.187 767 4028 3807 3484 3323
XS 12.70 482.60 0.182 922 5579 5272 4826 4603
40 15.09 477.83 0.179 320 6754 6383 5842 5572
80 26.19 455.63 0.163 045 12 322 11 644 10 659 10 166
120 38.10 431.80 0.146 439 18 498 17 480 16 001 15 261
160 50.01 407.98 0.130 725 24 891 23 522 21 531 20 535
600 S 609.60 9.53 590.55 0.273 908 3350 3166 2898 2764
40 12.70 584.20 0.268 049 4637 4382 4011 3825
80 30.96 547.68 0.235 579 12 223 11 551 10 573 10 084
120 46.03 517.55 0.210 376 18 732 17 702 16 204 15 454
160 59.54 490.53 0.188 979 24 778 23 415 21 433 20442

FLUID flow
Table 8A.2
MAWP, kPa
Flow Area, -28 to
15 40 21.34 2.77 15.80 0.000 196
80 3.73 13.87 0.000 151 3487 3295 3016 2877
160 4.78 11.79 0.000 109 15 935 15 058 13 784 13 146
XXS 7.47 6.40 0.000 032 52 661 49 765 45 552 43 445

20 40 26.67 2.87 20.93 0.000 344
80 3.91 18.85 0.000 279 4427 4183 3829 3652
160 5.56 15.55 0.000 190 20 455 19 330 17 693 16 875
XXS 7.82 11.024 0.000 095 44 948 42 476 38 880 37 082
25 40 33.40 3.38 26.64 0.000 558
80 4.55 24.31 0.000 464 8271 7816 7155 6824
160 6.35 20.70 0.000 337 22 483 21 247 19 448 18 549
XXS 9.09 15.21 0.000 182 46 439 43 885 40 170 38 312
40 40 48.26 3.68 40.89 0.001 313 1277 1207 1105 1053
80 5.08 38.10 0.001 140 8460 7995 7318 6980
160 7.14 33.99 0.000 907 19 600 18 522 16 954 16 170
XXS 1016 27.94 0.000 182 46 439 35 250 32 266 30 774
50 40 60.33 3.91 52.50 0.002 165 1943 1836 1681 1603
80 5.54 49.25 0.001 905 8647 8171 7479 7133
160 8.71 42.90 0.001 445 22 516 21 278 19 477 18 576
XXS 11.07 38.18 0.001 145 33 563 31 717 29 032 27 690
80 40 88.9 5.49 77.93 0.004 769 5678 5366 4911 4684
80 7.62 73.66 0.004 261 11 766 11 119 10 177 9707
160 11.13 66.65 0.003 489 22 240 21 017 19 238 18 348
XXS 15.24 58.42 0.002 680 35 349 33 405 30 577 29 163
100 40 114.3 6.02 102.26 0.008 213 5559 5253 4809 4586
80 8.56 97.18 0.007 417 11 185 10 570 9675 9227
160 13.49 87.33 0.005 989 22 631 21 386 19 576 18 670
XXS 17.12 80.06 0.005 034 31 551 29 815 27 291 26 029
150 40 168.28 7.11 154.05 0.018 639 5364 5069 4640 4426
80 10.97 146.33 0.016 817 11 169 10 555 9662 9215
160 18.26 131.75 0.013 633 22 672 21 425 19 611 18 704
XXS 21.95 124.38 0.012 151 28 771 27 188 24 887 23 736
200 40 219.08 8.18 202.72 0.032 275 5313 5021 4596 4383
80 12.70 193.68 0.029 460 10 524 9946 9104 8683
XXS 22.23 174.62 0.023 950 22 028 20 816 19 054 18 173
160 23.01 173.05 0.023 520 23 012 21 746 19 905 18 985
250 40 273.05 9.27 254.51 0.050 874 5242 4954 4534 4325
XS 12.70 247.65 0.048 169 8393 7932 7260 6925
80 15.09 242.87 0.046 329 10 622 10 037 9188 8763
160 28.58 215.90 0.036 610 23 755 22 449 20 548 19 598
CHAPTER 8 309
FLUID flow
Table 8A.2 (Cont'd)

MAWP, kPa
Flow Area, -28 to
300 S 323.85 9.53 304.80 0.072 966 4603 4350 3982 3798
40 10.31 303.23 0.072 214 5207 4921 4506 4296
XS 12.70 298.45 0.069 957 7050 6662 6098 5816
80 17.48 288.90 0.065 552 10 795 10 201 9337 8906
160 33.32 257.20 0.051 956 23 816 22 506 20 601 19 648

350 20 355.6 7.92 339.75 0.090 659 3078 2909 2663 2540
S 9.53 336.55 0.088 959 4187 3957 3622 3455
40 11.13 333.35 0.087 275 5303 5012 4587 4375
XS 12.70 330.20 0.085 634 6409 6056 5544 5287
80 19.05 317.50 0.079 173 10 937 10 336 9461 9023
160 35.71 284.18 0.063 425 23 395 22 108 20 237 19 301
400 20 406.4 7.92 390.55 0.119 797 2691 2543 2327 2220
S 9.53 387.35 0.117 841 3658 3457 3165 3018
40 12.70 381.00 0.114 009 5595 5287 4839 4616
80 21.44 363.52 0.103 791 11 036 10 429 9546 9105
160 40.49 325.42 0.083 175 23 506 22 213 20 332 19 392
450 20 457.2 7.92 441.35 0.152 988 2390 2258 2067 1971
S 9.52 438.15 0.150 777 3248 3069 2810 2680
XS 12.70 431.80 0.146 439 4964 4691 4294 4095
40 14.27 428.65 0.144 310 5821 5501 5036 4803
80 23.83 409.55 0.131 736 11 113 10 501 9612 9168
160 45.24 417.53 0.136 917 23 576 22 280 20 394 19 451
500 20 508 9.53 488.95 0.187 767 2921 2760 2526 2409
XS 12.70 482.60 0.182 922 4461 4216 3859 3681
40 15.09 477.82 0.179 320 5629 5319 4869 4644
80 26.19 455.63 0.163 045 11 161 10 547 9654 9208
120 38.10 431.80 0.146 439 17 296 16 345 14 961 14 270
160 50.01 407.97 0.130 725 23 647 22 346 20 455 19 509
600 S 609.6 9.53 590.55 0.273 908 2430 2297 2102 2005
40 12.70 584.20 0.268 049 3710 3506 3209 3060
80 30.96 547.67 0.235 579 11 256 10 636 9736 9286
120 46.02 517.55 0.210 376 17 729 16 754 15 336 14 627
160 59.54 490.52 0.188 979 23 741 22 435 20 536 19 586

FLUID flow
Table 8A.3
Allowable Working Pressures for Carbon Steel Piping – FPS (CA = 1/16 inch)
ANSI B31.3 – Corrosion Allowance = 1/16 inch
Nominal MAWP, psia

Pipe Flow Area, -20 to
Size, in Sched. O. D. in W. T. in I. D. in ft2 400°F 500°F 600°F 700°F
1/2 40 0.840 0.109 0.622 0.0021 1616 1527 1398 1333
80 0.147 0.546 0.0016 3360 3176 2907 2772
160 0.188 0.464 0.0012 5380 5084 4653 4438
XXS 0.294 0.252 0.0003 11 386 10 759 9849 9393
3/4 40 1.050 0.113 0.824 0.0037 1425 1347 1233 1176
80 0.154 0.742 0.0030 2913 2753 2520 2403

160 0.219 0.612 0.0020 5456 5156 4719 4501
XXS 0.308 0.434 0.0010 9362 8847 8098 7724
1 40 1.315 0.133 1.049 0.0060 1694 1601 1466 1398
80 0.179 0.957 0.0050 3037 2870 2627 2506
160 0.250 0.815 0.0036 5252 4963 4543 4333
XXS 0.358 0.599 0.0020 9000 8505 7785 7425
1-1/2 40 1.900 0.145 1.610 0.0141 1393 1316 1205 1149
80 0.200 1.500 0.0123 2486 2349 2151 2051
160 0.281 1.338 0.0098 4184 3953 3619 3451
XXS 0.400 1.100 0.0066 6886 6507 5957 5681
2 40 2.375 0.154 2.067 0.0233 1247 1179 1079 1029
80 0.218 1.939 0.0205 2258 2133 1953 1862
160 0.343 1.689 0.0156 4350 4111 3763 3589
XXS 0.436 1.503 0.0123 6019 5688 5207 4966
3 40 3.500 0.216 3.068 0.0513 1489 1407 1288 1228
80 0.300 2.900 0.0459 2395 2263 2072 1976
160 0.438 2.624 0.0376 3956 3738 3422 3263
XXS 0.600 2.300 0.0289 5911 5585 5113 4876
4 40 4.500 0.237 4.026 0.0884 1322 1249 1143 1091
80 0.337 3.826 0.0798 2155 2036 1864 1778
160 0.531 3.438 0.0645 3850 3638 3330 3176
XXS 0.674 3.152 0.0542 5171 4887 4473 4266
6 40 6.625 0.280 6.065 0.2006 1127 1065 975 930
80 0.432 5.761 0.1810 1980 1871 1713 1634
160 0.719 5.187 0.1467 3672 3470 3177 3030
XXS 0.864 4.897 0.1308 4570 4319 3953 3770
8 40 8.625 0.322 7.981 0.3474 1038 981 898 856
80 0.500 7.625 0.3171 1802 1703 1559 1486
XXS 0.875 6.875 0.2578 3488 3297 3017 2878
160 0.906 6.813 0.2532 3633 3433 3142 2997
CHAPTER 8 311
FLUID flow
Table 8A.3 (Cont'd)

Nominal MAWP, psia

Pipe Flow Area, -20 to
Size, in Sched. O. D. in W. T. in I. D. in ft2 400°F 500°F 600°F 700°F
10 40 10.750 0.365 10.020 0.5476 974 921 843 804
XS 0.500 9.750 0.5185 1435 1356 1242 1184
80 0.594 9.562 0.4987 1761 1664 1524 1453
160 1.125 8.500 0.3941 3683 3480 3186 3038
12 S 12.750 0.375 12.000 0.7854 847 801 733
699
40 0.406 11.940 0.7773 936 884 809 772
XS 0.500 11.750 0.7530 1205 1139 1042 994
80 0.688 11.370 0.7056 1752 1655 1515 1445
160 1.312 10.130 0.5592 3654 3453 3161 3015
14 20 14.000 0.312 13.380 0.9758 609 575 527 502
S 0.375 13.250 0.9575 771 728 667 636
40 0.438 13.120 0.9394 934 882 808 770
XS 0.500 13.000 0.9218 1095 1035 947 903
80 0.750 12.500 0.8522 1756 1659 1519 1449
160 1.406 11.190 0.6827 3575 3378 3092 2949
16 20 16.000 0.312 15.380 1.2895 532 503 460 439
S 0.375 15.250 1.2684 673 636 582 555
40 0.500 15.000 1.2272 955 903 826 788
80 0.844 14.310 1.1172 1749 1653 1513 1443
160 1.594 12.810 0.8953 3568 3372 3087 2944
18 20 18.000 0.312 17.380 1.6468 472 446 408 390
S 0.375 17.250 1.6230 597 564 517 493
XS 0.500 17.000 1.5763 847 801 733 699
40 0.562 16.880 1.5533 972 919 841 802
80 0.938 16.120 1.4180 1744 1648 1508 1439
160 1.781 16.440 1.4738 3561 3365 3080 2938
20 20 20.000 0.375 19.250 2.0211 537 507 464 443
XS 0.500 19.000 1.9690 761 720 659 628
40 0.594 18.810 1.9302 932 880 806 769
80 1.031 17.940 1.7550 1738 1642 1503 1434
120 1.500 17.000 1.5763 2632 2487 2276 2171
160 1.969 16.060 1.4071 3557 3361 3077 2935
24 S 24.000 0.375 23.250 2.9483 447 422 386 368
40 0.500 23.000 2.8853 633 598 547 522
80 1.219 21.560 2.5358 1731 1636 1498 1428
120 1.812 20.380 2.2645 2674 2527 2313 2206
160 2.344 19.310 2.0341 3549 3354 3070 2928

FLUID flow
Table 8A.4
Nominal MAWP, psia

Pipe Size, Flow Area, -20 to
in Sched. O. D. in W. T. in I. D. in ft2 400°F 500°F 600°F 700°F
1/2 40 0.840 0.109 0.622 0.00211
80 0.147 0.546 0.00163 173 164 150 143
160 0.188 0.464 0.00117 1954 1847 1691 1612
XXS 0.294 0.252 0.00035 7205 6809 6232 5944
3/4 40 1.050 0.113 0.824 0.00370
80 0.154 0.742 0.00300 374 354 324 309

160 0.219 0.612 0.00204 2674 2527 2313 2206
XXS 0.308 0.434 0.00103 6186 5846 5351 5103
1 40 1.315 0.133 1.049 0.00600
80 0.179 0.957 0.00500 981 927 848 809
160 0.250 0.815 0.00362 3024 2858 2616 2495
XXS 0.358 0.599 0.00196 6467 6111 5594 5335
1-1/2 40 1.900 0.145 1.610 0.0141 40 37 34 33
80 0.200 1.500 0.0123 1075 1016 930 887
160 0.281 1.338 0.00976 2681 2534 2319 2212
XXS 0.400 1.100 0.00660 5233 4945 4526 4317
2 40 2.375 0.154 2.067 0.0233 165 156 143 136
80 0.218 1.939 0.0205 1132 1070 980 934
160 0.343 1.689 0.0156 3134 2962 2711 2586
XXS 0.436 1.503 0.0123 4729 4468 4090 3901
3 40 3.500 0.216 3.068 0.0513 742 701 642 612
80 0.300 2.900 0.0459 1622 1533 1403 1338
160 0.438 2.624 0.0376 3137 2964 2713 2588
XXS 0.600 2.300 0.0289 5031 4755 4352 4151
4 40 4.500 0.237 4.026 0.0884 743 702 643 613
80 0.337 3.826 0.0798 1557 1471 1347 1285
160 0.531 3.438 0.0645 3213 3036 2779 2651
XXS 0.674 3.152 0.0542 4503 4255 3894 3715
6 40 6.625 0.280 6.065 0.2006 735 695 636 607
80 0.432 5.761 0.1810 1576 1489 1363 1300
160 0.719 5.187 0.1467 3241 3063 2804 2674
XXS 0.864 4.897 0.1308 4124 3897 3567 3402
8 40 8.625 0.323 7.982 0.3474 738 697 638 609
80 0.500 7.636 0.3171 1493 1410 1291 1231
XXS 0.875 6.875 0.2578 3159 2985 2732 2606
160 0.906 6.813 0.2532 3301 3120 2856 2724
10 40 10.750 0.365 10.020 0.5476 734 694 635 605
XS 0.500 9.750 0.5185 1190 1125 1030 982
80 0.594 9.562 0.4987 1513 1430 1309 1248
160 1.125 8.500 0.3941 3416 3228 2955 2818
CHAPTER 8 313
FLUID flow
Table 8A.4 (Cont'd)

Nominala MAWP, psia

Pipe Size, Flow Area, -20 to
in Sched. O. D. in W. T. in I. D. in ft2 400°F 500°F 600°F 700°F
12 S 12.750 0.375 12.000 0.7854 645 610 558 533
40 0.406 11.938 0.7773 733 693 634 605
XS 0.500 11.750 0.7530 1000 945 865 825
80 0.688 11.374 0.7056 1543 1458 1334 1273
160 1.312 10.126 0.5592 3430 3241 2967 2829

14 20 14.000 0.312 13.376 0.9758 426 403 369 352
S 0.375 13.250 0.9575 587 555 508 484
40 0.438 13.124 0.9394 749 708 648 618
XS 0.500 13.000 0.9218 909 859 786 750
80 0.750 12.500 0.8522 1565 1479 1354 1291
160 1.406 11.188 0.6827 3371 3185 2916 2781
16 20 16.000 0.312 15.376 1.289 373 352 322 308
S 0.375 15.250 1.268 513 485 444 423
40 0.500 15.000 1.227 794 750 687 655
80 0.844 14.312 1.117 1582 1495 1369 1305
160 1.594 12.812 0.8953 3390 3203 2932 2796
18 20 18.000 0.312 17.376 1.647 331 313 286 273
S 0.375 17.250 1.623 456 430 394 376
XS 0.500 17.000 1.576 704 665 609 581
40 0.562 16.876 1.553 829 783 717 684
80 0.938 16.124 1.418 1595 1508 1380 1316
160 1.781 16.438 1.474 3402 3215 2943 2807
20 20 20.000 0.375 19.250 2.021 410 387 354 338
XS 0.500 19.000 1.969 633 598 547 522
40 0.594 18.812 1.930 802 758 694 662
80 1.031 17.938 1.755 1604 1516 1388 1323
120 1.500 17.000 1.576 2493 2356 2157 2057
160 1.969 16.062 1.407 3414 3226 2953 2817
24 S 24.000 0.375 23.250 2.948 341 322 295 281
40 0.500 23.000 2.885 526 497 455 434
80 1.219 21.562 2.536 1620 1531 1401 1337
120 1.812 20.376 2.264 2559 2418 2213 2111

9
PROCESS CONTROL AND
INSTRUMENTATION
This chapter is an overview of control and instrumentation fundamentals. Specific control system
applications are covered in the appropriate chapter dealing with the system design, for example; compressor
control in Chapter 14 and fractionator control in Chapter 16. These specific control system applications will
supplement the basic instrumentation and control principles presented in this chapter. Poor process control
is the logical result when communication between the facilities engineer and the instrumentation engineer is
lacking; the process and control responses are not compatible with each other. The process and instrumenta-
tion specialists must perform as a team to properly integrate their capabilities.
The detailed specification of process control is always important; for proper controls are essential
if the process is to perform as desired. Even though the control specialists are primarily responsible, the
operator must necessarily be conversant with the problem, that is, understand the numerous principles
involved and properly maintain the equipment.
The operator must recognize that the controllers, transmitters and control valves, were specified on
the basis of an assumed set of operating conditions. As facility operation parameters vary, some adjustment
in the control system may be necessary. If the characteristics of the controls plus their related valves are
understood, this is not a difficult problem. In many cases re-adjustment of controls or change of control
valve trim size is all that is required.
Many problems occur from over- and under-control of the process. The problem with under-control
is that an unstable process results. This usually occurs when the installed cost of the facility is critical and/
or the vendor minimizes controls for competitive reasons. The only way to guard against this is to visualize
the normal process changes that will occur and make a judgment decision jointly with the vendor about the
minimum controls needed.
Over-control is a more subtle problem than under-control, even though the extra cost is an obvious
disadvantage. It is often the assumption that the more controls you hang on a piece of equipment, the better
the control system. To a point this is correct. Beyond that point, you have controls “fighting” each other.
Frequently the superfluous instruments are disconnected at a later date and not used in the control system.
This is particularly true when too many alarms are added to the system.
Quality and characteristics of the controls can be just as important as their number. For example,
a modified inverted bucket steam trap is available as a liquid level controller for small glycol absorbers. It
will work and is a bit cheaper than a regular liquid level controller. It is, however, less reliable and more
subject to plugging. Which to use is a judgment decision. Does the increased reliability of the unit justify
CHAPTER 9 315
process control and instrumentation
the higher capital cost? Another important facet is choosing a type of control suitable for the circumstance.
A control that might work quite well in a plant using dry instrument air, having good maintenance, and
protected from the elements may be totally unsatisfactory in a typical oil field production situation. Some
compromise is necessary in the latter situation.
The following discussions illustrate some of the basic aspects of control.
CONTROL OBJECTIVES AND CONCEPTS

The objective of a control system is to prevent deviation of a process variable from a desired
set-point.
Processes are defined in terms of the process variable under consideration. There are five such
variables:
1. Pressure
2. Temperature
3. Flow
4. Level
5. Composition
Several factors affect the ultimate control system selected to accomplish the control objective.
These include:
1. The control requirements of the equipment item or process system.
2. Rate of change (min, normal, & max) of the controlled variable for a given change of the ma-
nipulated variable.
3. Interactions with other control loops.
4. Control stability considerations.
5. Importance of maintaining controlled variable at a constant value.
6. System cost and complexity.
7. Penalties (costs) incurred due to poor control.
Feedback Control Systems

Controller
(may be locally mounted or remotely
The most common type of control system is
mounted in the control room)
LIC
a closed loop or feedback control. The simple level
Level
controller shown in Figure 9.1 is an example of a
Controller feedback control system.
Output
Control Loop
Measuring Device
(Displacer Element)
In this example, level is the controlled

variable, and effluent flow rate is the manipu-
Control Valve
Flow
lated variable. The control signal is generated by
comparing the value of the controlled variable (level)
Figure 9.1 Simple Level Control System to a desired value called set point. The difference
between the two values is termed the error signal. In
a feedback control loop the controller output is a function of the error signal. The controller output typically
is electronic (4-20 mA) or pneumatic (20-100 kPa(g) [3-15 psig]).
The controller output signal is sent to the control valve resulting in a particular valve position or
valve opening. Control valves are specified such that a well-defined relationship exists between the flow

through the valve and the valve position; hence any change in the control signal results in a predictable
change in the flow rate of fluid leaving the equipment. The changing rate of the liquid leaving the vessel
causes a corresponding change of the level in the vessel. The dynamics of this change; that is, (Δlevel/
Δflow), are a function of flow rates, vessel size and geometry. The controller output is a function of the
difference between the measured variable and the set-point, or, the error.
The level control system in Figure 9.1 may also be shown in terms of the flow of information. This
is called a control system block diagram and is shown in Figure 9.2.
Process Changes and Upsets

Process control systems respond to changes or upsets to the process. These are referred to as load
changes. Load changes may directly affect the controlled variable (level) or the manipulated variable (flow).
An example of a load change to the controlled variable is an increased inlet flow to the vessel. An example
of a load change to the manipulated variable is downstream pressure from the control valve. Either of these
load changes requires a response from the control system. Increased inlet flow rate requires the controller
to open the control valve so that Out = In. A decreased downstream pressure increases the flowrate through
the valve which requires the controller to close the control valve since flow is a function of valve differential
pressure. When the primary feedback loop cannot adequately respond to load changes, then more complex
control systems may be required. This will be discussed in a later section.
Comparison in Controller (Level Control)
Set Point Error

Control
Signal
Loads { Process
Controlled
Variable
+ Level Controller Valve
_ (4-20 mA) Manipulated (Level)
20-100 kPa Variable
(Liquid Flow from Vessel)
(Level Transmitter)
(Feedback)
Measurement Transmitter Signal
Measurement
Figure 9.2 Process Control Block Diagram for Level Control System
Deadtime and Capacitance

The flow of information in the feedback control loop is not instantaneous. The existence of delay,
or lags, in the process has an important effect on the performance of the control system. A lag is defined as
the period of time it takes for the controlled process variable to begin changing once the output from the
controller has changed the manipulated variable. Lags may be considered in two categories: deadtime and
capacitance.
Deadtime is defined as the time delay between change in the control signal and the beginning of its
effect on the measured value of the controlled variable. For example, if the flow into pipeline is increased,
a period of time elapses before a change in the outlet flow is detected. This elapsed time is a function of the
line length and fluid velocity. Because deadtime is caused by the time to move material from one point to
another, it is frequently referred to as transportation lag.
Deadtime interferes with good control inasmuch as it represents an interval during which the
controller has no information about the effect of a load change or control action already taken. When
designing a control system every attempt should be made to minimize this delay by properly locating instru-
ments and sampling points, ensuring sufficient mixing, and minimizing transmission lags.
CHAPTER 9 317
Capacitance refers to that portion of the process where energy and/or mass can accumulate.
Examples include mass stored in a separator or energy stored in a heat exchanger. The larger the vessel is in
relation to the flows, the larger the capacitance and hence the more slowly the controlled variable changes
for a given change in the manipulated variable. The capacitance of the process tends to reduce disturbances
and hence makes control less difficult.
The capacitance of the process is measured by its time constant. The time constant may be calculated
from the differential equation used to model the process, but as an approximation is roughly equal to the
process residence time.
System Gain
Another parameter to be considered in the control loop is the system gain. The system gain is
defined as:
∆ output
gain = (9.1)
∆ input
Each box in Figure 9.2 has a characteristic gain.
Valve Gain
For example, the valve gain, Kv, is the change in flowrate through the valve divided by the change
in controller output (the input signal to the valve). An oversized control valve will exhibit a large gain since
small valve movements result in large flowrate changes.
Process Gain
The process gain, Kp, is related to the capacitance of the process. For the level control system in
Figure 9.2, the process gain is the change in level divided by the change in outlet flowrate. A large vessel,
such as a tank will exhibit a small process gain since a change in flowrate will have little effect on level.
Conversely, a small scrubber will exhibit a larger gain since liquid capacity is small and even a small
flowrate change can have a significant and immediate effect on level. Processes which have a large gain are
generally characterized as “fast” and processes with small gains, “slow.”
Many processes are linear; that is, Kp is constant for any process load condition. Examples include
level control in vertical separators, flow control and pressure control on separators. Some processes are
non-linear. This means that Kp changes with the process load.
Non-linear processes may require a more complex control system. Several control valve charac-
teristics are non-linear. These are often used to cancel out or “linearize” the non-linear process gain.
Alternatively, in programmable logic controllers (PLCs) and distributed control systems (DCSs), the
controller gain can be adjusted to compensate for the non-linear process. Controller gain will be discussed
in more detail in the next section.
Loop Gain
The loop gain is the product of the individual gains in the loop.
K L = Kc K v K p K t (9.2)
Where: Kc = controller gain

Kv = valve gain
Kp = process gain
Kt = transmitter (measuring device) gain

To avoid instability, the loop gain should be less than one (1.0) under dynamic feedback conditions.
The mathematical analysis of the loop gain under dynamic conditions is complex and beyond the scope of
this text, but a general understanding of loop stability can be acquired by considering steady state gains.
In general, a large gain in one loop element must be compensated for by a small gain somewhere
else. For example, if the process exhibits a large gain, in other words fast, such as flow controller, the
controller gain will often be low. Conversely, for a slow process, such as level control in a large vessel, the
controller gain might be large.
Response Characteristics of Process Systems
Understanding the response characteristics of various processes allows the control engineer to
design an effective control system. Summarized below are typical response characteristics of the four
major control loops. The knowledge of these is useful when discussing controller modes and control valve
selection.
Fluid Flow:
1. Small capacity
2. Negligible deadtimes
3. Fast-responding process and is therefore subject to “noise” and resultant instability
Pressure:
1. Generally large capacity
2. Small dead time
3. Fast-responding process but is somewhat self-regulating. Large capacity and gas compressibility
helps dampen process oscillations making this a stable process (low noise)
Liquid Level:
1. Generally large capacity (dependent upon vessel design)
2. Small dead time
3. Precise control can be sacrificed for stability. For example, the liquid level can be allowed to
oscillate for the sake of maintaining constant flows
Temperature:
1. Large capacity
2. Large dead time
3. Large time constant
4. Slow to respond to load changes
Stability of Automatic Control Systems
All control modes when configured properly can return a process variable to a steady value
following a disturbance. This characteristic is called “stability.” Stability is the ability of a control loop to
return a controlled variable to a steady, non-cyclic value, following a disturbance.
Control loops can be either stable or unstable. Instability is caused by a combination of process
time lags discussed earlier (i.e., capacitance, resistance, and transport time) and inherent time lags within
a control system. This results in slow response to changes in the controlled variable. Consequently, the
controlled variable will continuously cycle around the set-point value.
Oscillations describe this cyclic characteristic. There are three types of oscillations that can occur in
a control loop. They are decreasing amplitude, constant amplitude and increasing amplitude. Each is shown
in Figure 9.3.
CHAPTER 9 319
(a)
Decreasing amplitude (Figure 9.3(a)). These
oscillations decrease in amplitude and eventually stop
with a control system that opposes the change in the
Response
controlled variable. This is the condition desired in an

Decreasing Amplitude
automatic control system. It is desirable for the variable
to “line out” (98%) within 4 cycles or less.
(b)
Constant amplitude (Figure 9.3(b)). Action of the
controller sustains oscillations of the controlled variable.
Response
The controlled variable will never reach a stable condition;

therefore, this condition is not desired.
Constant Amplitude
Increasing amplitude (Figure 9.3(c)). The control

(c) system not only sustains oscillations but also increases
them. The control element has reached its full travel limits
Response
and causes the process to go out of control.
Increasing Amplitude
Time
Figure 9.3 Control Loop Stability
CONTROL MODES
The manner in which the feedback signal from the transmitter is conveyed via the controller to the
control valve is very important. The manner in which this valve moves as the controlled variable leaves
its set point is critical for good control. The control valve and its internal’s and the controller must be a
“matched pair” whose response characteristics are compatible with those of the process.
Controllers
A controller is a device that generates an output signal based on the difference between the measured
variable and the desired value. The desired value is also known as the set point.
This input error signal represents the amount of deviation between where the process system is
actually operating and where the process system is desired to be operating. The controller provides an
output signal to the valve, which adjusts the flow of a process stream to reduce this deviation. The charac-
teristic of this output signal is dependent on the type, or mode, of the controller.
The controller characteristics are determined by the control modes. The actual controller mode
ultimately chosen depends on the process dynamics, control objective and controller cost. The four basic
control modes are:
1. On/Off (Snap-Acting)
2. Proportional (Throttling)
3. Integral (Reset)
4. Derivative (Rate)
On/Off
On-off control is the simplest of all control modes and consequently the least expensive in terms
of initial cost and maintenance. A room thermostat is an example of on/off control. In field facilities, on/off

control is referred to as snap-acting. Level controls on low pressure separators and temperature controls on
indirect fired heaters are sometimes snap-acting. In these cases the dump valve or fuel valve is either open
or closed depending on the signal from the controller. No attempt is made to “throttle” the valve based on
the error signal. Snap-acting controllers have the advantage of simplicity, ruggedness and ease of mainte-
nance, and are particularly well suited for remote field locations using wet instrument gas.
In many cases the irregular value of the controlled or manipulated variable resulting from
an off/on control will cause the value of the controlled variable to oscillate. This may create serious
operating and control problems downstream of the process. In these cases proportional or throttling
control is used.
Proportional Control
Proportional control is the basic action employed in all controllers not using snap-action. It is
defined as control action in which a continuous linear relation exists between the value of the controller
output and the error signal. The ratio of change of controller output (air pressure or electric current) to a unit
change of the error is the controller gain (Kc):
Output = K c (error) + B (9.3)

Where: Output = controller output usually expressed as a percent
Kc = controller gain, the characteristic sensitivity constant of the controller relating output to input
Error = difference between value of measured (controlled) variable and set point
B = manual bias
The bias, B, is the controller output necessary to maintain operation when the error is zero. Zero
error means the process is operating at its set-point. Again, the actual controller output is either a varying
air pressure or electrical signal.
Table 9.1
Proportional Control
20 40 60 80 100 kPa
3 5 9 12 15 psi
4 8 12 16 20 mA
1 2 3 4 5 VDC
0% 25% 50% 75% 100% percent full range; direct acting
100% 75% 50% 25% 0% percent full range; reverse acting
In the proportional control mode, the final control element is throttled to various positions that
are dependent on the process system conditions. For example, a proportional controller provides a linear
stepless output that can position a valve at intermediate positions, as well as “full open” or “full closed.”
The controller operates within a band that is between the 0% output point and the 100% output point and
where the output of the controller is proportional to the error.
Proportional Control and Gain

Another way of expressing controller sensitivity is proportional band. The proportional band
expressed as a percentage, relates to the percentage of the full range of the measuring device that the
controlled variable has to traverse for the controller to fully stroke the valve. It is numerically equal to
(100/Kc ).
CHAPTER 9 321
A good illustration is a typical level-control application shown in Figure 9.4 using a displacement-
type instrument; that is, one which does not float on top of the liquid but depends on the varying buoyancy
force as the liquid level changes.
Note that the narrower the proportional band, the more sensitive the control. A proportional band
setting of zero is equivalent to snap-acting control: when the sensitivity of a controller is adjusted the scale
is almost always in terms of proportional band. Figure 9.4 shows the output of a level controller with 50%
and 100% proportional bands.
Proportional Band Width and Gain

100 100
P.B.% = K = Gain (9.4)
P.B. 10% 25% 50% 100% 200%

Gain 10 4 2 1 0.5
Assume that the displacer element in Figure 9.4 is 750 mm [30 in] in length. If the PB was 100% it
would take a 750 mm [30 in] change in level to cause the controller output to go from 0 to 100% or vice
versa. If the proportional band was 10%, a 75 mm [3 in] change in level would accomplish a 0-100%
(100-0%) change in controller output.
4 mA 12 mA 20 mA
20 kPa 60kPa 100 kPa
[3 psi] [9 psi] [15 psi]
Controller Controller Controller

Output Output Output
Controller Output with 100% Proportional Band, Gain = 1.0

Controller output changes from 0 to 100% of control range with level change of 100% of float length.
4 mA 12 mA 20 mA
20 kPa 60 kPa 100 kPa
[3 psi] [9 psi] [15 psi]
Controller Controller Controller
Output Output Output
Controller Output with 50% Proportional Band, Gain = 2.0

Controller output changes from 0 to 100% of control range with level change of 50% of float length.
Figure 9.4 Output of a Level Controller
The width of the proportional band used depends on the capacitance of the process system, the
speed of the corrective action needed, and the limits of control desired. A narrow proportional band usually
is desirable when capacitance is high and fast corrective action is desired. Hence, slow process reaction
rate is advantageous to proportional control. Large lag or dead time limits the application of this control

by itself. Proper valve sizing for the flow rate is a critical factor. The optimum proportional band setting is
the least that may be used without “cycling”, as presented in the stability of automated controls discussion.
Offset
In many control loops proportional-only action is adequate to meet the control objective. However,
with proportional action alone, the controller output (the valve position) can change only if the measured
value of the controlled variable changes. In other words, in the following separator example (Figure 9.5 and
Figure 9.6), the only way the control valve position (% open) can be varied is if the level in the separator
changes. This results in offset. Offset is the difference between the measured value of the controlled variable
and the set point. In other words, it is the error signal required by the controller to bring the process back to
steady state (inflow = outflow). Figure 9.4 and Figure 9.5 illustrate offset.
^PBhÔutput – Bh Output – B
Offset = 100
=
KC (9.5)
In Figure 9.5, the level controller is operating at steady state conditions. The level is at 50% and for
the sake of simplicity we will assume that this is also the set point and the control valve has linear character-
istics. The controller output is at 50% and the control valve is 50% open. The capacity of the control valve
at this opening is 100 m3/d. In equation form:
Output = PB êrrorh + B = a100 k^0%h + 50% = 50%

100 100
Gas Gas
A higher level is required
5
to make the controller
output increase.
1 4 For valve to open more,

controller output must increase.
Inlet flow
Level is at Controller increases Level is at
50% float PB = 100% 75% float
Inlet 50%
LIC
LIC Controller
PB = 100%
NLL
NLL For flow through control valve
3 to increase, the valve must be
open. More air pressure is required
on the diaphragm.
Outlet flow should

2 increase 50%
100 m3/d
[630 bpd]
6 Offset is 25%
of float range 150 m3/d
[950 bpd]
Controller Output = 62 kPa Controller Output = 83 kPa
[9 psi] = 50% [12 psi] = 75%
12 mA 16 mA
Figure 9.5 Level in Separator at Normal Flow Figure 9.6 Level in Separator when Liquid Flow Increases 50%
— No Offset — Offset Present
In Figure 9.6, the liquid flow rate into the separator increases by 50%, the flowrate through the
control valve must increase by 50% if the outlet flow is to equal the inlet flow. The new control valve
position must be 75% open to stabilize the level in the separator. This, in turn, requires a controller output
of 75%. For a proportional-only controller this requires an error signal (offset) of 25% as illustrated in the
Equation:
Output = PB êrrorh + B = a100 k^25%h + 50% = 75%
100 100
CHAPTER 9 323
If we assume that the displacer element in the above example is 750 mm [30 in] in length, the offset
would be 750 ´ 0.25 or 188 mm [7.5 in].
In many systems offset is not a problem. In the preceding separator example (Figure 9.6), offset
would probably not be a serious problem because the objective of the control system is to keep the outlet
oil rate equal to the inlet rate. The actual level in this separator is not important as long as it is between the
high and low level alarms.
However, if the vessel is a chiller filled with refrigerant it could be important that the refrigerant
level be kept above the process tube bundle. In this case offset would be intolerable. Offset can be minimized
by increasing controller sensitivity (narrowing the proportional band) but a controller which is too sensitive
may be unstable and oscillate at the smallest upset.
In the preceding example if we assume that the proportional band is 20%, the offset would be:
PB Ôutput - Bh 20 ^75 - 50h
Offset = 100
=
100
= 5%
Integral (Reset)
Integral action (or reset) is added to the
controller to minimize or eliminate offset. In propor- Setpoint
Controlled
tional action, the amount of valve movement is Variable
proportional to the error. By contrast, the amount
Step Change
of correction applied with integral action depends Integral Action
on both the magnitude and duration of the error. Controller Proportional Action
Output
Therefore the prime purpose of reset is to prevent
offset and maintain the controlled variable on the
set-point even as the process load changes.
The equation of a controller with propor- Controlled Set Point
tional plus integral (P + I) action is: Variable
Output = K 8error + ^l/I th # êrrorh dtB (9.6) Gradual Change Integral Action
Controller Proportional Action
Output
Where: It = integral time, min
Figure 9.7 is a simple illustration of the Open Loop Proportional + Reset Control
response of a P + I controller placed in manual
mode (open loop control). Open loop is defined in Figure 9.7 Open Loop Response Characteristics of a
P+I Controller
Appendix 9B, Definition of Terms.
P+I Control
In actual practice with this type of controller (P + I) the two corrections occur simultaneously. The
proportional will act when the measured or controlled variable is changing. As soon as it starts changing,
an error is generated and the integral action starts adding to the output as well. When a change in process
load takes place, the controlled variable is returned to the set point with a minimum of cycling. The initial
movement of the valve corresponding to a change in the measured variable is due to proportional action,
but the ultimate movement of the valve to its new position is due entirely to integral. As a result, it is often
said that integral lags proportional action. The proportional action provides the initial response to correct
for the upset, while the integral provides the gradual correction to bring the controlled variable back to the
set point as shown in Figure 9.7.

Figure 9.8 is an example of the response of a control loop that has the setpoint changed from 50
to 70% when in automatic (closed loop) mode. Closed loop is defined in Appendix 9B, Definition of
Terms. Note that the lag time is defined by the time between the peaks for the output and the peaks for the
measurement. The deadtime is defined by the time from when the change is made to when the process
starts to change.
Setpoint Controller Output Controlled Variable

100 100
Lag Time
80 80
Setpoint
Change System Response
Controller Output, %
60 60
Level, %
40 40
20 20
Deadtime
0 0
59:30 00:00 00:30 01:30 01:30 02:00 02:30 03:00 03:30 04:00 04:30 05:00
Time
Figure 9.8 Closed Loop Response Characteristics of a P+I Controller
Derivative (Rate)
Proportional plus integral control may not provide correction that is rapid enough for certain
processes. Derivative or rate response may therefore be added to “anticipate” a change in process load
and transmit a corrective signal to minimize the lag. This action usually corrects on the basis of the rate
of change of the measured variable. The equation for a controller with proportional plus integral plus
derivative action (P + I + D) is:
Output = K :error + _1 I ti # êrrorh dt + D ^dy t dthD (9.7)
Where: Dt = derivative time, min
(dy/dt) = derivative of controlled variable with time
Figure 9.9 shows the simple response of a

proportional plus derivative controller (P + D). When Gradual
Change
the controlled (measured) variable starts increasing, Controlled Set Point
the derivative response is added based on the rate of (measured)
Variable
change. When the controlled variable stops changing,
the derivative portion of the controller output signal
drops out. Since the controlled variable stabilized at a Proportional Derivative Response
new higher value, the output has to stabilize at a new Response Removed
higher value also. Derivative Proportional Only

Controller Response Response
Output
Derivative action is seldom needed. Propor-
tional plus integral will handle most process
Time
conditions. Because derivative control is propor-
tional to the rate of change of the measured variable, Figure 9.9 Open Loop Response Characteristics of a
it causes the control valve to reach a required new P+D Controller
position more quickly.
CHAPTER 9 325
Processes having large lags often need this action wherein the valve is moved farther and faster to “get
ahead” of the process load change so that proportional or proportional plus integral can take over. If this early
rapid movement is compatible with the lag, it will counteract the lag, for this reason it is said that rate action
leads proportional.
Derivative action is normally specified only for some temperature control systems which are charac-
terized by large process and measurement lags.
Controller Action Applications

The general applications of the various combinations of control action is summarized in Table 9.2.
Table 9.2
Control Modes vs. Application
Process
Control Mode Reaction Rate Load Changes Applications
Size Speed
On-Off: Two-position with Slow Any Any Large-capacity temperature and lev-
differential gap (space (tens of seconds el installations. Storage tanks, hot-
between the two levels) to hours) water supply tanks, room heating,
compressor suction scrubber level.
Floating (uses integral only), Fast Any Slow Processes with small deadtime but
single-speed with adjustable (seconds to larger lag times. Industrial furnaces
dead band (rate output is a minutes) and air conditioning.
function of error magnitude)
Proportional Slow to moderate Small Moderate Pressure, temperature, and level
(many seconds to where off-set is not objectionable.
tens of minutes) Separator level control, pressure-
reducing stations.
Proportional-plus-integral Any Large Slow to Most applications, including flow.
(reset) (seconds to moderate Not suitable for batch operations un-
many minutes) less over-peaking (over-shoot) is al-
lowed.
Proportional-plus-derivative Moderate Small Any Where increased stability with mini-
(rate) (minutes to mum overshoot and lack of reset
tens of minutes) wind-up is required. Compressor
discharge pressure. There is offset.
Propor tional-plus-integral- Any Large Fast Batch control; processes with sudden
plus-derivative upset; temperature control and com-
pressor anti-surge control.
CONTROL LOOP CONFIGURATIONS

Direct Acting/Reverse Acting
As discussed, the controller receives a process input signal from the temperature, level, pressure, or
flow transmitter. It compares this input condition with the set point. If the two are not the same, the controller
changes the output signal to the control valve so that it will open or close in order to bring the process condition
back to the set point, or to steady state. In most applications, an increase in the process input signal will result
in an increase in the controller output.
In Figure 9.1, a simple level control system was presented. As the level rises in the vessel, the process
input signal to the controller increases. The controller increases the output signal to the control valve so that it
will open to bring the level in the vessel back to the set point. This is an example of a direct acting mode, i.e.,
increasing process signal causes an increase in controller output.

However, there are situations in which an

increase in the process input must be followed by a
decrease in the controller output. For a hot oil heater,
if the process temperature increases above the set point,
the controller will need to close the hot oil control valve
to reduce the flow of hot oil to the heater. In this case, an Direct Acting
Wet Inlet Gas
increase in the process input to the controller needs to be
followed by a reduction in the controller output. This is
a reverse acting mode.
TEG To Flash Tank
Both of the examples assume that increasing FC
pressure on the valve actuator opens the valve. When
this is the case, the valve is referred to as a Fail Closed Reverse Acting
(FC) valve since a loss of air pressure would cause the
valve to close. This is the most common control valve Return to
configuration but in some cases the desired fail position Stabilizer
upon loss of air pressure is open. This is referred to as
a Fail Open (FO) valve. The choice of the valve fail
position (FC or FO) is typically set by the process safety Stabilizer Bottoms
Fuel Gas
philosophy. FC
In most cases the decision as to the type of valve Figure 9.10 Examples of Controller – Control Valve
(FC or FO) is made initially then the controller (direct or Combinations
reverse acting) is selected. It is important to recognize
that the controller and control valve must be selected in combination rather than individually.
Table 9.3 shows the four most common combinations used.
Table 9.3
Effect of Increase in Process Input to Controller and Control Valve Movement
Control Valve Movement

Loss of Air
Controller Type Control Process Signal Pressure to the
Mode Mode Increases Actuator Typical Application
Direct Fail Open Closes Opens
Direct Fail Closed Opens Closes Level Control Valve, Flow Control Valve
Reverse Fail Open Opens Opens Pressure Control Valve on a Separator
Reverse Fail Closed Closes Closes Fired Heater Fuel Control Valve
Split-Range Control
FC
Split range control is an example of a control
20–60 kPa system where the number of manipulated variables
[3–9 psi]
exceeds the number of controlled variables. Typically with
split range control a single controller is used to operate
60–100 kPa multiple valves over differing portions of the controller’s
[9–15 psi]
output range. An example of this is provided in Figure 9.11
FC
for control of the inlet pressure to an expander in a gas
processing plant.
Figure 9.11 J-T Bypass Control on an Expander
CHAPTER 9 327
A common control philosophy for an expander process is that the inlet pressure to the expander is
controlled by adjusting the flow rate through the expander which is normally accomplished by changing the
inlet guide vane position. However, once the expander reaches its maximum capacity any additional flow
through the facility must bypass the expander. The additional flow is handled through an expander bypass
valve (often referred to as the J-T valve). Thus, one controller (PC) must manipulate two devices: inlet
guide vanes and J-T valve. For purposes of this example we will assume that both devices fail closed so the
pressure controller will be direct acting: increasing process signal increases controller output.
In this example of split range control, the controller manipulates the guide vanes from 0-50% output
(3-9 psi, 20-60 kPa, 4-12 mA) and manipulates the J-T valve from 50-100% output (9-15 psi, 60-100 kPa,
12-20 mA). In this way, when the expander capacity is reached the PC signal seamlessly opens the J-T valve.
Cascade and Feed Forward Control

TC Vapor Out In many cases the simple feedback
control system similar to that shown in
Figure 9.1 is adequate to meet the control
Cooler Oil Out objectives. In some instances, however, a
Hot Oil In more complex system may be required
due to the nature or severity of the load
changes on the system. This is especially
Basic Process Liquid In Process Liquid Out true for sluggish systems such as tempera-
ture control.
Temperature Hot Oil Load Load Load
Controller Flow Rate A common reboiler configura-
SP + Gain Manipulated Process
Variable
(Reboiler)
tion on a fractionation column is shown
-PID-
Set Point
±
(MV)
Controlled in Figure 9.12. This is a kettle type
(Temperature)
Error Feedback
Variable (CV)
Outlet Vapor
reboiler (see Chapter 12) using hot oil as
Temperature the heating medium. The function of the
Basic Control Loop reboiler is to provide heat input to the
fractionator by vaporizing a portion of the
Figure 9.12 Simple Temperature Control bottoms stream from the column. In its
simplest form, the flow rate of hot oil is
manipulated by a temperature controller
on the vapor stream leaving the reboiler.
Vapor Out
RSP (In some cases the temperature measure-
Remote Set Point
ment is on the tower itself.)
This control system may be
adequate as long as there are not signifi-
cant load changes to the system. One
Process Process common load change is the flow rate of
Cascade Liquid In Liquid Out hot oil. If the hot oil flow rate decreases
due to an upset in another part of the
Temperature Hot Oil Rate Hot Oil Load Load Load
processing facility, there will be less heat
Controller Controller Flow Rate
SP + Gain Gain Manipulated Process input to the reboiler. Eventually, this will
Variable
Set Point
-PID- -PID-
(MV) (Reboiler)
Controlled cause the vapor temperature to decrease,
(Temperature) ± Error
Variable (CV)
Error Feedback (Flow)
Outlet Vapor
but the time lag between the load change
Remote Set Point
(RSP) Feedback (Temperature)
Temperature and the change in temperature may be
significant. Eventually, the hot oil rate will
Cascade Control Loop
be increased by the temperature controller
Figure 9.13 Cascade Control System but the recovery time can be significant (5
to 10 times the lag time).

For this process a cascade control system is typically used. In a cascade system, the hot oil valve is
manipulated by a flow controller. The set point on the flow controller is adjusted by the temperature control-
ler. The temperature control loop is often referred to as the master or primary loop and the flow control
loop is referred to as the slave or secondary loop. For cascade control to be effective the slave loop should
have a much faster response time than the master loop. The response time of the slave loop is typically four
times faster.
In the cascade control config-
Vapor Out
uration, load changes to the hot oil RSP
flow (manipulated variable) would Remote Set Point
be immediately handled by the flow Cooler Oil Out

controller with minimal upset to the

temperature control loop. If the load Hot Oil In
change was on the actual process
itself and more or less heat input was
Cascade with Feed Forward Process Liquid In Process Liquid Out
required, the temperature controller Function
Process
would adjust the set point on the flow Block
controller. In a cascade system, the Hot Oil

Temperature Hot Oil Rate Load Load Load
master controller has a fixed set point Controller Controller
Flow Rate
Manipulated
SP + +
and the slave controller has a floating Set Point
Gain
-PID-
Gain
-PID-
Variable
(MV)
Process
(Reboiler)
± ± Controlled
set point. (Temperature) Error Error Feedback (Flow) Variable (CV)
Outlet Vapor
In most cases, the controller Temperature
Remote Set Point
Feedback (Temperature)
(RSP)
in the slave (secondary) loop is a flow Cascade Control Loop with Feedback
controller. The controlled variable in
the master (primary loop) is typically Figure 9.14 Feed-Forward Control System
temperature, pressure or level. There
are two reasons for this. First, flow controllers will control flow without regard for any other variable in
the system. For example, a flow controller on the outlet of a tank may drain the tank dry or allow it to run
over unless the flow rate setpoint is adjusted by the master level controller. Secondly, in any cascade control
system, the valve control valve is manipulating the flow rate of a fluid.
Figure 9.12 and Figure 9.13 illustrate feedback control. These control loops are reactionary, they
react after the disturbance occurs.
Feed forward control describes the practice of measuring, upstream of the actual equipment, one
or more process variables that change frequently and where the changes cause upsets in the process. The
affected control loop will often have response times that are much greater than the period of the distur-
bances. This is especially true in fractionation systems.
In Figure 9.14, the flow rate of the process fluid entering the reboiler is measured. Many times it
may be the flow rate of the feed to the fractionator. A feed-forward control system senses the change in
the process fluid flow and sends a signal to the hot oil valve to either increase or decrease the hot oil rate
based upon the change in the process fluid rates. Feed temperature could also be measured and the heat duty
calculated. In this case the feed forward signal would then be a required heat duty.
Measuring the change of the inlet flow allows the cascade control loop to predict the hot oil flowrate
required to keep the vapor outlet temperature nearly constant. The FY element in Figure 9.14 indicates an
algorithm is used to combine the measured vapor temperature and inlet process flowrate to calculate a
required reboiler duty. This calculated value sets the feed forward signal to the hot oil flow control valve
reducing the impact of process rate changes.
Feed-forward control anticipates changes in the controlled variable and adjusts the manipulated
variable accordingly. Feed-forward control by itself is open-loop control in that it does not rely on feedback
CHAPTER 9 329
of the measured value of controlled variable. It is almost always used in conjunction with a feedback control
loop, often called “feedback trim.” This feed-forward action allows the hot oil valve to start moving to a
new position as the load change (process flow) is occurring. Feed-forward control finds wide application in
fractionation and distillation systems.
Ratio Control
Ratio control is another application of feed-forward control. It is used to control the relationship
(ratio) between two process variables. Figure 9.15 illustrates a common ratio control scheme used for Sulfur
Recovery Units (SRUs). The conversion of H2S to sulfur in the reactors decreases if the H2S:SO2 ratio
leaving the reactor furnace deviates from 2:1. Control of the H2S:SO2 ratio is achieved by manipulating the
air rate to the reaction furnace at the inlet of the SRU.

The air flow is adjusted based upon the composition and flow rate of the acid gas. The acid gas
rate and composition varies with upstream process operations. The acid gas rate and composition is not
controlled and varies with upstream process generators.
The H2S/SO2 concentration ratio in the tail gas provides a feed-back signal to the air flow control-
ler. This signal is usually applied to a separate small trim-air control valve. This controller suffers from an
unavoidable long delay of 2-4 minutes in detecting, and responding to, off-ratio conditions. This delay is
the time for the reacting gases to make their way through the Claus plant.
Reflux PT Manual Bias

Drum
Calculations
TT
%H2S Calculated
Air Requirement
FT AT
Acid Gas
H 2O
S.P. N2
Claus Plant
FIC CO2
Air Tail Gas
AIC
Trim Air S
Control H2S/ SO2
Valve Optional
Figure 9.15 Air Control for a Claus Plant
CONTROL VALVES
The control valve not only must be matched to the controller but it must be compatible with the
pressure, temperature, flowrate and nature of the fluids being handled. Metallurgy, cost, deliverability, parts
availability, and service are important considerations.
All valves control by varying the area available for flow. Thus any valve that can be moved manually
can also be moved by a controller. Figure 9.16 shows some of the valve types commonly used. The choice
depends on many factors.
The two most common types of control valves used in production/processing facilities are sliding
stem and rotary valves. The most popular type of sliding stem valves is the globe valve, as shown in Figure
9.17. Sliding stem valves are widely used because of their versatility. They can handle a wide range of flow

conditions, pressure drops, and temperatures. They also tend to result in the most stable control because
they typically require a higher pressure drop than other types of control valves which provides for tighter
flow control from the valve.
Figure 9.16 Schematics of Different Types of Control Valves(9.1)
CHAPTER 9 331
Rotary valves include butterfly valves and characterized ball valves. These valves have a higher
capacity at a given pressure drop than sliding stem valves because of a larger flow area. This is an advantage
for viscous fluids or applications where the available pressure drop is limited. Rotary valves are much less
expensive than sliding stem valves per unit of flow.
A butterfly valve is shown in Figure 9.18. It consists of a disk mounted on a rotating shaft. It has
a very high capacity and is widely used in low pressure applications in gas flow. Characterized ball valves
are constructed similar to standard ball valves, but the ball is notched with a crescent shape that produces a
predictable flow characteristic as the valve opens. The flow characteristic is equal percentages for high flow
applications and linear for low flow. Like butterfly valves, characterized ball valves are less expensive than
sliding stem valves per unit of flow, but are more robust than butterfly valves and are more suitable in high
turndown applications. A cutaway of a characterized ball valve is shown in Figure 9.16.
The globe valve in Figure 9.17 shows the major features of this common type of control valve.
There are three basic parts: 1) the topworks (actuator) that drives the 2) trim and the 3) body. In
given models the three are interchangeable to meet both control and process needs.
Figure 9.18 Butterfly Valve
Air
Diaphragm Spring
Force Force
P1 P2
Unbalance
Force
Figure 9.17 Globe Valve Figure 9.19 Control Valve Forces
The plug moves up and down when the unbalance force acting on it is greater or less than the sum
of the other two forces involved; the diaphragm force and the spring force. These forces are illustrated in
Figure 9.19. The unbalanced force is created by the differential pressure across the valve acting upon the
plug area. When the upward and downward forces are balanced the plug is stationary.

The valve shown in Figure 9.17 would be fail open because in the event of air (gas) pressure failure,
the spring would force it wide open. The valve could be converted to fail closed by placing the plug under
the seat or by changing the spring in the actuator. As discussed earlier, the fail position of the valve is an
important choice required to allow the system to fail safe.
Control valves can be balanced or unbalanced. Balancing is a general term to indicate that the force
exerted on the plug due to differential pressure has been balanced. Balancing can be accomplished by either
reducing the pressure drop across the plug or by reducing the effective area upon which the pressure drop
acts. The valve shown in Figure 9.17 is an example of an unbalanced valve. The cage-guided valve shown
in Figure 9.20 is an example of a balanced valve. A hole is drilled through the plug effectively equalizing
the pressures above and below the plug. Double ported valves, although not widely used today, are another
example of a balanced plug valve.
The primary advantage of a balanced valve is the force required to actuate the valve is reduced
resulting in a smaller, cheaper actuator. The primary disadvantage is that a secondary leak path in the valve
is created. Balanced valves will generally not shut off as tightly as unbalanced valves.
The diaphragm area, seat
opening, plug shape, and spring tension
must be matched to provide satis-
factory control in the service range
anticipated. They are not indepen-
dent factors. The specification process
begins with the selection of the plug
and seat size and shape. Figure 9.21(a)
illustrates the effect of stem movement
on the variable orifice behavior. With a
flat plug the flow area increases rapidly
with stem movement. Close control of
flow rate is difficult with this quick-
opening type of plug. The linear plug,
on the other hand, does not increase
area so rapidly with stem movement.
Figure 9.21(b) shows different
types of plugs used in different
services. Some have an extension of Figure 9.20 Cage-guided Control Valve (Courtesy of Fisher Controls)
the stem below the seating portion so
that the full area of the seat is never available for flow. These are called throttle plugs. Cage-guided valves
(Figure 9.20) are widely used. The valve characteristic is determined by the shape of the ports in the cage.
Cage-guided valves have the advantages of high capacity, flexibility, and can employ a balanced plug which
minimizes actuator size.
Valve Selection
Figure 9.21(c) shows the effect of valve trim on performance. When the valve travel is 0 the valve
is fully closed and the flow rate is zero. At a valve travel of 100% the valve is fully open and the flow rate
is at its maximum. The ΔP across the valve will depend on valve position.
CHAPTER 9 333
Flow
Area
Seat
Quick Opening Plug Linear Plug
a)
Single & Double Port Valve Plugs Cage Guided Valve Trim
b)
100
Valve Characteristics
Equal percentage: Produces an
equivalent percentage change in flow g
for equal increments of valve travel 80
g Plu
in
Percentage of Maximum Flow
(see Table 9.1). Valves having this en

characteristic exhibit a low gain at low Op
ick
travel and a high grain at high travel.

Qu
60
Linear: Denotes equal change of flow ugg
rr PPllu
for equal change in travel at all points. eeaa
LLiinn
g
lu
Quick opening: Denotes a very rapid

eP
lug
change in flow, (in some cases as much 40 ttl

ro
eP
Th
ag
as 80%) in the first 10% travel.

nt
ce
Other valve characteristics can be Pe
ual
produced by varying the shapes and Eq
20
relationships of valve plugs and seats,
or by cam or linkage arrangements in
valve positioners.
0
0 20 40 60 80 100
Closed Open
Percentage of Valve Travel
c)
Figure 9.21 Performance of Valve Trim

The relationship between valve capacity and travel can be adjusted by changing the valve trim.
Several different types of flow characteristics are available. The most common are listed in the bottom of
Figure 9.21. For a linear characteristic valve, the valve capacity is linear with valve travel.
If pressure drop available at the valve is relatively constant over the control range, the desired
characteristic is linear. Linear trim is often used in liquid level control, antisurge valves, fuel gas control
valves, etc.
With equal percentage characteristic valves, equal increments of valve travel produce equal percent-
age increases in valve capacity. This is illustrated in Table 9.4 and Figure 9.21(c).
When pressure drop varies over the control range, as is the case in pump control, equal percentage
trim may be specified because it linearizes the flow vs. travel relationship. Due to its high range ability (ratio
of valve capacity at maximum and minimum controllable flows through the valve), equal percentage trim is
also used in systems where the valve needs to control at low flow rates but also have a high capacity, e.g.,
bypass valves. Equal percentage valves are also specified in most temperature control applications.
The normal sizing procedure is to select a valve (or trim) size such that over the range of anticipated
flows the valve will operate between 25-75% open. The valve should not be sized to “operate on the seat”
(less than 10% open) or to operate wide open (greater than 90% open) as this may create stability problems
and limit the flexibility of the process.
Table 9.4
Equal-Percentage Valve Characteristics
(For the equal-percentage valve characteristics in figure 9.19(c))
% Maximum Capacity 0 6 12 24 48 100

% Lift or Travel 0 20 40 60 80 100
From Table 9.4, the percentage increase in flow is approximately 100% for each 20% change in
valve travel.
Table 9.5 provides some typical control valve selection criteria that should be taken into consider-
ation when selecting control valves for specific applications.
Table 9.5
Control Valve Selection Criteria
Capacity and range of fluid flow rates Flow characteristic, linear, etc.
Pressure drop – minimum, normal, maximum Cost
Erosion Rate of closure
Corrosion – materials (sour service) Failure position
Noise Local environment
Cavitation / Flashing Reliability / Maintenance acceptance
Shutoff (allowable leakage) Existing Valves in Service
Actuators
A key step in valve specification is selecting the valve actuator. A vital part of every automatic
control loop, it provides the muscle, or motive force, required to position the valve. And, since stability and
operability of the loop hinge on satisfactory actuator performance, the actuator must be able to adapt to the
many varying static and dynamic forces created by the valve.
CHAPTER 9 335
For the many available valve styles, there are four basic actuator types suitable for throttling control:
1) spring-and-diaphragm: 2) pneumatic piston: 3) electric motor; and 4) hydraulic or electro-hydraulic.
The pneumatic spring and diaphragm actuator similar to that pictured in Figure 9.22 is very common,
and offers a simple design, low cost and high reliability.
Diaphragm actuators normally operate
with air supply ranges of 20-100 kPa(g) [3-15 psig]
or 40-200 kPa(g) [6-30 psig]. The most important
advantage of the spring and diaphragm actuator is
the ever-present capability for fail-safe actions.
Valves may be selected to fail open or closed on loss
of instrument air signal. One of the critical aspects

of specifying a control valve is designation of the
fail position.
The primary disadvantage of the spring
and diaphragm actuator is its limited capability.
Much of the diaphragm thrust is used to overcome
spring tension and does not result in usable output
at the valve. When the thrust requirements exceed
9 kN [2000 lbf] the spring and diaphragm actuator
may not be cost effective. In these cases piston or
hydraulic actuators are normally specified.
The relative advantages/disadvantages of Figure 9.22 Pneumatic Spring and Diaphragm Actuator
four types of actuators are summarized in Table 9.6.
Table 9.6
Actuator Advantages/Disadvantages
SPRING-AND-DIAPHRAGM PNEUMATIC PISTON

PRO CON PRO CON
• Low cost, simple and • Limited torque availability • High torque capability • Fail-safe operation often
robust • Limited temperature range • Compactness and light requires accessories
• Stiffer than piston type • Inflexibility to changing weight • Positioner normally
• Inherent fail-safe action service conditions • Available in longer travel required
• Low supply-pressure • Larger and heavier than lengths • Higher cost
requirement piston type • Adaptable to high ambient • High supply-pressure
• Adjustability • Limited travel temperatures requirement
• Maintainability • Usually not suitable for • Adaptable to varying • Requires sealing (O-ring)
larger valves valve-torque requirements between piston and
• Ability to throttle without cylinder
positioner • Fast stroking-speed
possible
• Fast stroking speeds
possible
ELECTRIC MOTOR ELECTRO-HYDRAULIC/HYDRAULIC
PRO CON PRO CON
• Compact • High cost/torque ratio • High torque • High cost
• Suitable for remote • Lack of fail-safe action • Very high actuator • Complexity
applications • Limited throttling ability stiffness • Large size and weight
• Doesn’t need air supply • Slow stroking-speed • Excellent throttling accessories
• Less maintenance stiffness
• Lack of adjustability
requirements • Fast stroking-speed
• Best suited for larger
valves

Valve Positioners
The valve positioner is basically a relay that senses both instrument signal and valve stem position.
The positioner applies the necessary pressure to the diaphragm to achieve a valve position which corresponds
to the instrument signal. If the positioner receives a 50% signal, it will apply enough pressure to cause the
actuator to stroke 50% of its travel. The positioner will apply the full available supply pressure to accomplish
this, if necessary.
Table 9.7 provides conditions that favor the Use of valve positioners.
Table 9.7
Conditions That Favor the use of Valve Positioner
When a split range is required

When a maximum loading pressure greater than the instrument signal is required
When the best possible control is desired for certain systems, i.e., minimum overshoot
and the fastest recovery from disturbances
When it is desirable to linearize the flow through the valve by use of characterized cams
Increase control system resolution: i.e., fine control
Minimize packing friction effects: i.e., high-temperature packing
Negate flow-induced reactions to higher pressure drops
Increase speed of response to a change in process*
Overcome seating friction in rotary valves
Allow longer distance between controller and control valve*
Allow wide range variation: i.e., operate at less than 10% travel under normal conditions
Allow increased usage of 4-20 mA electronic signal
Increase fast venting (unloading) capability*
Permit use of piston actuators
*May be achievable with a volume booster.

Valve positioners should not be used as a signal booster. In these cases, one-to-one or two-to-one
pneumatic volume boosters can be purchased at substantially lower cost. When the controller signal is electronic
a valve positioner also serves as an I/P transducer to convert the electronic control signal to a pneumatic signal.
Valve positioners with digital communications have unequalled “on-board” data gathering capabili-
ties, alarms and diagnostics as well as standard positioner functionality. In addition, when used with Foundation
Fieldbus, the PID control blocks can reside in the positioner. They have advanced diagnostics integration and
automated valve data analysis available with leading asset management software. The software may be used
either as a standalone program or integrated with major host systems.
INSTRUMENTATION
Level Measurement
Measurement and control of liquid level is an integral part of both plant and field processing. A
number of mechanisms are used. Those prevalent in oil and gas production and processing are:
1. Mechanical or pneumatic operated valve directly actuated by a float
2. Control valve actuated by a displacement “float"
3. Control valve actuated by a DP cell
The displacement “float” is the most common used level measurement option in production opera-
tions. The displacement float is not a true float since total movement usually is less than 6 mm [0.25 in]. It
CHAPTER 9 337
operates on the Archimedes Principle which states that a body will be buoyed by a force equal to the weight
of the liquid displaced. The displacement element is typically 76 mm [3 in] in diameter. For ordinary level
service it is 360-380 mm [14-15 in] long but longer units are available. The specified mass of the float varies
depending on the fluid density.
The differential pressure (DP) cell measures the hydrostatic head of liquid in a vessel. It uses a
differential pressure transmitter with one measurement at the bottom and the other at the top of the vessel.
The high pressure side of the transmitter is connected at, or below the lower range to be measured. The low
pressure side of the transmitter is connected to the vapor space of the vessel above the upper level range to
be measured through a reference line. This reference line (sensing the vapor pressure of the vessel) must
be maintained free of liquids or condensed liquids to ensure there is no liquid head on the low side of the
transmitter. The high pressure side is exposed to the hydrostatic head of the liquid plus the vapor pressure
exerted on the liquid’s surface. The vapor pressure is equally applied to the low and high pressure sides of
the cell, thus the output of the DP transmitter is directly proportional to the hydrostatic head, i.e., the level
in the vessel.
Guided wave radar consists of a transmitter, an antenna, and a receiver with a signal processor. The
transmitter is mounted on the top of the vessel. An electromagnetic wave is aimed downward at the surface of
the fluid. The signal is radiated by a parabolic dish or horn-type antenna towards the surface of the liquid. A
portion of this signal is reflected back to the antenna where it is collected and routed to the receiver. A micro-
processor calculates the “time of flight” and calculates the level of liquid in the vessel. The “time of flight” is
the period between the transmission of the radar pulse and the reception of the return echo. The speed of the
reflected wave is a function of the dielectric constant of the fluid, thereby allowing the instrument to measure
the interface level between two different liquids.
Table 9.8
Level Measurement Technologies
Level Maximum Typical

Measurement Type Applications Temperature Inaccuracy Comments
Capacitance Clean fluids — prone to fouling 1094oC 1-2% FS Interface between conductive
which can lead to erroneous [2000oF] layers and detection of foam is
indication a problem.
Differential Pressure Where the density of the fluid 650oC 0.1% AS Only extended diaphragm
is relatively constant [1200oF] seals or repeaters can elimi-
nate plugging. Purging and
sealing legs are also used.
Displacement Float Where the density of the fluid 430 oC 0.5% FS Not recommended for Sludge
is relatively constant [800oF] or Slurry.
Level Gauges Used where local level indica- 370 oC 6.4 mm Contains glass which may not
tion is required at the vessel [700 oF] [0.25 in] be allowed in some processes.
Guided Wave Radar Requires applications where 230 oC 3.0 mm Interference from coating,
there is a sufficient difference [450 oF] agitator blades, spray or
between the vapor and liquid excessive turbulence.
densities
Ultrasonic Good for difficult fluids — 150 oC 1% FS Presence of dust, foam, dew
corrosive, fouling, viscous [300 oF] in vapor space, sloping or
and dirty liquids. Ultrasonic fluffy process material inter-
sensors are non-contact, and feres with performance.
therefore impervious to these
characteristics
FS = in percent Full Scale, AS = % of Actual Span
A capacitance instrument consists of a metal rod covered with Teflon insulation if the liquid conducts
electricity. If the liquid is dielectric it consists of a metal rod inside a metal tube. The capacitance of the system
varies linearly with level changes. The corresponding signal change can be used to control level.

A sonic and ultrasonic instrument uses waves above 20 kHz transmitted by a transducer/sensor head
that are bounced off the liquid surface. This can be used to measure liquid-foam interfaces, solids, slurries, etc.
Table 9.8 provides a listing of the most common level instruments, including measurement range,
typical applications, and pros and cons.
Pressure Measurement
Many instruments have been invented to measure pressure. Pressure range, sensitivity, dynamic
response and cost, all vary by several orders of magnitude, from one instrument to the next.
Because most control systems operate with electrical signals, pressure or force must be converted
to current or voltage before further processing or analysis. Capacitive and piezoresistive signal transducers
are the most commonly used sensor for this purpose.

Capacitive sensors detect pressure as a capacitance associated with the distance between two or
more) diaphragms which changes in response to a change in pressure. In piezoresistive pressure sensors,
pressure changes the resistance by mechanically deforming the sensor by enabling the resistors in a bridge
circuit. For example to detect pressure as a proportional differential voltage across the bridge.
Conventional resistive pressure measurement devices include film resistors, strain gauges, metal
alloys, and polycrystalline semiconductors.
Table 9.9 provides example pressure measurement technologies in oil and gas facilities.
Table 9.9
Pressure Measurement Technologies
Pressure Typical
Measurement Operating Typical
Type Applications Pressures Inaccuracy Comments
Dead Weight Bench testing or 100-70 MPa Certificate of Dead weight testers are precision built primary
Tester field calibration with [15-10 000 psig] NIST traceability pressure standards, used for testing, setting, cali-
portable units brating or repairing pressure measuring devices
within the test points.
Manometer Heating & Ventila- Determined by 1/2 of minor scale Normally used for in. of water or mm of mercury
tions; Control Room size, graduation for on low pressure or vacuum.
or Pressurized areas 0-187 mmHg liquid type; 1%
monitoring [0-100" WC] for digital type
Bourdon Tube Pressure gages; 0-10.3 MPa 2% FS depending Typical of sensors used in pressure gages. Special
pneumatic control- [0-1500 psig] on size and type gages can read .5% of scale.
lers
Bellows Pneumatic systems; 1725 kPa 0.5% FS Used in older types of pressure controllers and re-
differential pressure [0-250 psig] corders and in indicating switches and gages.
transmitters
Capacitance All processing 0.09 mm Hg to 69 0.025% AS Most popular due to low manufacturing costs,
systems MPa simple construction, high reliability. Linear-
[0.05" WC to ization is done w/software so a broad span of
10 000 psig] pressure ranges can be handled by a single trans-
ducer.
Strain Gage All processing 0-200 MPa 0.25% AS Many used in oil & gas facilities, but not as popu-
systems, extreme [0-30 000 psig] lar as capacitance types.
high pressures
Piezoelectric Small compact 0-69 MPa 0.5% FS When pressure, force or acceleration is applied to
transmitters used for [0-10 000 psig] a quartz crystal, a charge is developed across the
dynamic measure- crystal that is proportional to the force applied.
ment for equipment High sensitivity, good linearity, small size, and
monitoring high speed. Must be temperature compensated.
Inductive Pressure, valve posi- 0-90 MPa 0.5% FS Motion created by pressure or movement is con-
(LVDT) tion, motion control [0-13 000 psig] verted to changes in frequency. Higher cost, less
depending on type reliable. Not generally used for process unless to
of device sense position.
AS = in percent of Actual Span FS = in percent of Full Scale WC = water column
CHAPTER 9 339
Temperature Measurement
Temperature can be the most difficult of all process variables to control. Temperature control systems
are characterized by large process and measurement lags. Temperature controllers (other than snap-acting)
may employ derivative (rate) action to counteract the system lag and speed up controller response.
Table 9.10
Temperature Measurement Technologies
Typical Operating Typical Inac-

Device Type Applications Temperatures curacy Comments
Glass Laboratories & Ther- –200°C to 260°C 1/2°C to 2°C Glass thermometers must be handled with
Thermometer mowells in process [-330°F to 500°F] [1°F to 5°F] care. Generally an electronic probe is used in
piping Depending on Depending on the field or a temperature gage installed. Low
model model cost.
Change-of- Confirmation that the –30°C to 260°C 2% of reading Change-of-state temperature sensors consist of
State temperature of a piece [–22°F to 500°F] labels, pellets, crayons, lacquers or liquid crys-
of equipment or a ma- tals whose appearance changes once a certain
terial has not exceeded temperature is reached. Low cost.
a certain level
Filled Systems Controllers with capil- Gas Pressure from Determined by Consists of a temperature sensor, or bulb,
lary tubes for remote –273°C to 760°C final connected by a small bore tube, or capillary,
location from sensor, [–460°F to 1400°F] indicating to a bourdon, bellows, or diaphragm motion
temperature gages, Liquid Expansion device. element.
temperature switches from Typically 1-3%
–184°C to 315°C
[–300°F to 600°F]
Bimetallic General process –70°C to 500°C 1% FS Consists of a strip of two different metals
Thermometers indications and process [–94°F to 930°F] welded together. The metals have a large dif-
switches ference in thermal expansion coefficients.
Least accurate. Low cost.
Thermocouple J & K are most com- See Table 9.3 Depends on Most often used and least understood. Must
monly used tem- type, tempera- be installed properly using proper terminals,
perature sensors for ture and range. wire, and other materials. Cold Junction
process measurements Can be from Compensation (CJC) is critical to accurate
and control 1-4°C [2-7°F] readings. Less expensive per point than RTD.
of reading Response times slower than RTD.
Resistance Generally used where –250°C to 850°C 0.5% AS More stable and accurate than thermocouples.
Temperature tight temperature [–418°F to 1562°F] Temperature range is not as broad. Higher in-
Devices (RTD) control or reference is stalled cost per point than thermocouples. Most
needed accurate and faster response.
Thermistors Reference temperatures –40°C to 150°C 0.5% AS with Resistance-temperature relationship of a
for control room equip- [–40°F and 302°F] compensation thermistor is negative and highly nonlinear
ment; overload sensors but repeatable. Electronic compensation is
in equipment used. Not generally used for process control
due to maximum temperature limitation.
Lower cost.
Infrared (Ther- Anywhere you need –50°C to 3000°C ±2°C [±4°F] or Measures the amount of radiation emitted by
mal Imaging non-contact tem- [–58°F to 5432°F] ±2% of reading a surface. Higher cost. Good for measuring
Cameras) perature measurement, Depending on higher temperatures and larger surface areas.
such as equipment model An infrared device is like a camera, and thus
temperature profiles, covers a certain field of view. Proper use re-
flares, exhausts, energy quired to get accurate readings. Many types
audits, condition moni- available and cost has come down also.
toring, etc.
AS = in percent of Actual Span FS = in percent of Full Scale

The most common temperature measurement devices are:

1. Thermometers
a. Liquid filled
b. Bimetal
2. Filled Systems
3. Thermocouples
4. Electric resistance devices
5. Radiation pyrometers
Selection of the best sensor for a given application is a function of temperature range, accuracy,
speed of response, initial cost, and maintenance requirements.
Table 9.10 provides a listing of common temperature measurement instruments along with the
typical range, applications, and pros and cons.
Flow Measurement
For fluids encountered in hydrocarbon systems flow control loops are characterized by very rapid
responses. When the flowmeter is located reasonably near the control valve, the flow process will respond
faster than the instruments in the control loop. Because of the negligible lags in the flow system and the
noisy signal received from the flowmeter, the proportional band setting on a flow controller is typically wide
(200%). Integral action is rapid (approx. 0.05 min/repeat).(9.3) Derivative action should not be specified on
a flow controller because it responds to the noise in the system and amplifies it, leading to unstable control.
Flow is the most difficult of the process variables to measure. It cannot be measured directly as
can pressure and level, rather it is measured by inference, e.g., differential pressure, turbine rotation, etc.
In addition, flow measurement must be made in the fluid itself, not in parallel to the fluid. For such reasons
many flow measurement techniques have been developed. This text will concentrate on those used in the
oil and gas industry.
The choice of a meter is determined by its mechanical and measurement reliability and its range.
The reliability is a matter of experience and testing. The range needed must be established by preliminary
design calculations. Rangeability is the ratio of the maximum to minimum flow of a meter while maintain-
ing accuracy.
Measurement of flow rate traditionally has been purely mechanical or has used some type of
differential pressure measurement. In fiscal measurement applications the orifice meter has been the most
common type, although turbine, Coriolis, and ultrasonic meters are also widely used.
The following section reviews several flow measurement options.
Coriolis Meters
Coriolis meters measure mass flow directly. This can be a significant advantage in applications
where the flowrate for fiscal purposes is required on a mass or standard volume basis. Turbine, sonic and
orifice meters require on-line density measurement (or computation) to determine mass flow rate. Coriolis
meters can be used to measure fluid density at flowing conditions.
The sensor operates by application of Newton’s Second Law of Motion:
Force = (mass)(acceleration) (9.8)
The flowmeter uses this law to determine the precise amount of mass flowing through the sensor
tubes. These meters are selected when direct mass flow measurement is desired.
CHAPTER 9 341
Figure 9.23 provides a schematic of a Coriolis meter, shown in horizontal view. The meters are
installed in the vertical position. The fluid momentum in the measuring tube bends causes the tubes to twist.
Due to Newton’s Second Law of Motion, the amount of sensor tube twist is directly proportional to the
mass flow rate of the fluid. Sensor tube twist is proportional to mass flow and is determined by measuring
the time difference exhibited by the velocity detector signals. The velocity of the fluid in each tube is
measured with detectors. The velocity signals are sent to a transmitter where they are processed and
converted to an output signal that is proportional to the mass flow rate.
A Coriolis meter can be used to calculate net
oil production from a test separator.(9.8) Water cut can
be determined by comparing the emulsion density to
the reference densities of oil and free water. Coriolis

meters are also widely used for fiscal metering of
NGLs.
They are compact, have a high rangeability
(20:1) and are accurate (±0.2%). Drawbacks include
initial cost and potential failure of the flow tube if
the material of construction is not compatible with Figure 9.23 Coriolis Meter (Courtesy Micromotion)
the fluid being measured. Currently, the maximum
diameter of these meters is 35 mm [14 in] diameter.
Ultrasonic Meters
Two common types of sonic meters are: 1) the Doppler (time of flight) and 2) contra-propagating or
“transit time”. Doppler meters require particulates or bubbles in the flow, and are not commonly used in the
oil and gas industry.
Contra-propagating, or transit time,
L
flow meters feature the most advanced
Transducer Upstream
non-invasive flow measurement technol-
ogy available. The transit time flow meter
utilizes two transducers which function as
45°
both ultrasonic transmitters and receivers Flow
as shown in Figure 9.24. The flow meter Velocity
D
Ultrasonic
operates by alternately transmitting and Path
receiving a frequency modulated burst of
sound energy between the two transducers. Transducer Downstream
The burst is first transmitted in the direction
Figure 9.24 Sonic Flow Meter
of fluid flow and then against the direction
of fluid flow. Since sound energy in a moving liquid is carried faster when it travels in the direction of fluid
flow than it does when it travels against fluid flow, the times of flight will be different. This difference is
accurately measured in both directions and can be converted into a flowrate.
Transit time flow meters are applicable to natural gas metering.(9.4) This type of meter has been
increasingly used for large gas lines because it non-intrusive, and causes no pressure loss. It can measure
flow in either direction and indicate the flow direction as well. The range ability is about 100:1.
In tests on large pipelines the single path sonic meter agreed with orifice measurements within
about ±0.5% for an accuracy of ±2.0%. Multipath sonic meters, with additional transducers and additional
paths, have accuracies within ±0.5% and are popular for offshore fiscal measurement because deck space
requirements are less than that required for orifice meters.

The following standards are generally applied when using sonic meters for custody transfer:
API MPMS 5.8 — Manual of Petroleum Measurement Standards Chapter 5 – Metering – Section 8 –
Measurement of Liquid Hydrocarbons by Ultrasonic Flow Meters Using Transit Time Technology
AGA REPORT NO. 9 — Measurement of Gas by Multi path Ultrasonic Meters
ISO 17089-1:2010 — Measurement of fluid flow in closed conduits – Ultrasonic meters for gas – Part 1:
Meters for custody transfer and allocation measurement
Turbine Meters
Rotor Assembly
Bearing
The turbine meter has a wide range of appli-
U/S
Spring Clip
Assembly Cone cability except for fluids with a viscosity greater than
Thrust
Washer 10-15 cP. Range ability is about 20:1 for liquids and
up to 100:1 for gases in some instances.
D/S Cone
Thrust Washer
Turbine meters come in various configura-
Journal
Coil tions, but they all transmit a signal based on rotational
Coil Bosses
Nut Washer speed which in turn is a function of flow rate and fluid
Flow properties. The choice should be based on experience.
Bearings can be troublesome. Ball bearings
may be susceptible to damage by abrasive solids;
Housing sleeve bearings tend to be more trouble-free but range
ability may be reduced.
Figure 9.25 Turbine Meter
A screen upstream of the meter is often
desirable. If used, it should be robust enough to
withstand the differential pressure due to plugging. In a liquid meter, flashing, cavitation or too much vapor
should be avoided since vapor can over-speed the turbine causing inaccurate measurement and possibly
bearing failure. If the line is to be heat traced it is best not to mount the signal preamplifier on the meter
body to prevent overheating.
When properly selected, turbine meters can be used for custody transfer. Their acceptance has been
slow in some areas due to lack of proven experience compared to the orifice meter. The acceptance rate
in liquid service has been higher than for gas service because they can be proved more readily; however,
turbine meters are widely used for fiscal measurement of natural gas in Europe.
Repeatability is often ±0.5% on test and accuracy is within ±1%. Like all meters these values are a
function of meter condition.
The axial flow turbine meter has proven useful for high gas flow rates. Its range ability is up to
100:1 and it has a linear response to flow rate. A summary of performance of these meters is found in Refer-
ences 9.10-9.12.
Orifice Meters
A common flow measurement option is to
measure the pressure drop across a known flow
restriction. This signal can be converted into a
flowrate. The orifice meter is the most widely used of
these meters. The orifice meter shown in Figure 9.26
is composed of a flow element (orifice plate), a flow
element holder, a differential pressure device, a static
pressure device, a temperature device and a flow Figure 9.26 Schematic of an Orifice Plate
CHAPTER 9 343
computer. Field measurement may not always use a temperature device; instead, an assumed process temper-
ature is used for process control. Orifice meters are the most commonly used flow measurement device in oil
and gas facilities. Traditionally, they have also been used for custody meter transfer, but are being replaced
by newer technology, such as ultrasonic. Orifice meters are easy to install, have low cost and are easy to
replace. These meters require inlet flow conditioning to ensure even distribution of the flow. Orifice meters
result in high head loss, and their accuracy is affected by wear and installation conditions.
Venturi Meters
Venturi meters, like orifice meters, use
differential pressure across a known restriction to
measure flow. A schematic of a venturi meter is
shown in Figure 9.27. The analysis is equivalent to Steep Shallow

that of the orifice meter. The venturi meter offers Inlet
Section
Throat Downstream
Section
lower pressure loss for measurement of all kinds of
fluids. It has a rangeability of about 3.5:1. It is
sometimes used to measure the suction flow to
P1 P2
centrifugal compressors because its pressure drop is
lower than an orifice meter. Compared to orifice
meters, venturi meters have reduced flow condition-
ing requirements and higher flow capacity for the
same differential pressure. Their accuracy is less
High Pressure Tap Low Pressure Tap
affected by wear and installation conditions, but they
have a higher initial cost. Figure 9.27 Schematic of a Venturi Meter
Positive Displacement Meters

Positive displacement flow meters operate by isolating and counting known volumes of a fluid (gas
or liquid) as it flows through the meter. By counting the number of passed isolated volumes, a flow measure-
ment is obtained. Each positive displacement design uses a different means of isolating and counting these
volumes. Summing the number of volumes passed in a given time provides the flow rate. Sliding vane
meters are used for custody transfer of low pressure
gases as well as liquids. They are one of the highest
performance positive displacement meters. As
shown in Figure 9.28 a sliding vane meter contains a
rotor assembly fitted with four spring-loaded sliding
vanes so that they make constant contact with the
cylinder wall. The rotor is mounted on a shaft that is
eccentric to the center of the meter chamber.
Multiphase Flow Measurement

Multiphase flow measurement in the oil and
gas industry implies the measurement of a fluid that
contains oil, water, and gas, but does not measure
solids in the flow. The most common multiphase
measurement method is a test separator where all Figure 9.28 Sliding Vane Meter
three phases are separated and measured individu-
ally. When using gravity separation, time is required to separate the gas from liquid (1 to 3 minutes) and oil
from water (10 to 30 minutes). This results in the instantaneous measurement of oil rates, water rates and
gas rates that are not coincident in time with the incoming flow stream. You must average instantaneous
readings over some period of time, typically 12 to 24 hours.

Definitions:
• Gas volume fraction – GVF is the ratio of actual gas volume to the sum of actual gas volume
plus the actual liquid volume
• Water cut – WC or water liquid ratio (WLR) is the ratio of water volume to the sum of water
volume plus the oil volume
• Flowing density – The instantaneous density of the combined flowing phases
• Slip – the relative velocity between different density material flowing in a common pipe or
enclosure
Multiphase flow meters calculate the instantaneous oil, water, and gas rates which are coincident
with process flow rates at that point in time. This allows much shorter test durations, possibly on the
order of 1 to 3 hours. This capability stems from high-speed computers and proprietary software coupled
with process end devices. The end devices include pressure, temperature, differential pressure, water cut,
conduction and gamma radiation densitometers. The main difficulty with modern multiphase meters is the
empirical models do not represent all potential measurement conditions. As a result the meters need to be
calibrated on-site.
The process conditions in the pipe create a challenging environment for multiphase measurement.
These include fluid viscosity, fluid bubble size, bubble-point, liquid and gas densities, water cut, vertical
or horizontal flow, and flow regimes. Flow regime describes the flow conditions in the pipe e.g., laminar,
wavy, slug, mist, etc., as discussed in Chapter 8. Stratified or wavy flow is substantially different from
annular mist flow. These differences in flow conditions pose problems for the empirically derived software
used in multiphase meters. Multiphase flow meters may require recalibration as the flow regime changes,
or the actual gas volume fraction changes over the life of the field.
Slip or hold-up is another significant problem in multiphase measurement because the instanta-
neous measurement of each phase is not coincident. A three-phase gravity separator is an example of an
extremely high slip condition in order to accomplish phase separation.
Most multiphase flow meters must be calibrated in the field under actual operating conditions and
fluid composition and require a reference measurement for comparison.
Figure 9.29 shows typical GVFs for various production scenarios.
Multiphase meters tend to fall into two general categories. The first category is mostly liquid with
some gas such that gas volume fraction is less than approximately 90%. There is a gap from approximately
80% gas volume fraction to 95% gas volume fraction where fluid slugging or annular mist flow begins to
occur. Multiphase meter performance tends to degrade as gas volume fraction increases and as water cut
either goes below 5% or above 90 to 95%. Multiphase meter vendors may use GVF maps, as shown in
Figure 9.29 to describe the operating area for their meters.
Listed in Table 9.11 and Table 9.12 are examples of various instrument technologies used in multi-
phase meters. Reference 9.9 - 9.12 discuss multiphase flow measurement.
CHAPTER 9 345
Actual Gas Flow (ft3/d)

3.5 35 350 3500 10 500
1000 6300
5% GVF
30% GVF
80% GVF
Land-based
95% GVF Mature Production
99% GVF 0%
Actual Liquid Flow Rate (bbl/d)

-9
Actual Liquid Flow Rate (m3/d)
0
100 F5 630
GV
ate
r R WC ng
e
w r R wi ion
Lo ighe r GO Flo duct
H we Pro ift
Lo sL
Ga 0%
F >9
GV
10 63
s
Meter Operating Range
t Ga
We 95
%
>
G VF
1 6.3
0.1 1 10 100 300
Actual Gas Flow (m3/d)
Figure 9.29 Multiphase Flow Meter Operational Ranges
Table 9.11
Instrument Technologies Used in Multiphase Meters — No Fluid Separation
Water cut
GVF Oil Water Process
WC Flow density continuous continuous Rate Instruments
GVF < 95% Gamma Permittivity Conductivity Mass-Venturi P, T, ΔP
WC < 100% densitometer
GVF < 80% Full range
Dual venturi 0-100% microwave watercut P, T, ΔP
WC < 100% PD meter
GVF < 100% Gamma Infrared Venturi-sonar P, T, ΔP
WC < 100% densitometer
GVF < 85% Dual velocity
— Permittivity Conductivity P, T, ΔP
WC < 70% Flow profile
Table 9.12
Instrument Technologies Used in Multiphase Separation
Water cut
GVF Water Process
WC Flow density Oil continuous continuous Mass rate Instruments
GVF < 60-80%
Compact Coriolis Coriolis Conductivity Coriolis P, T, ΔP
hydrocyclone
Solution from
GVF < 95% Dual venturi 0-100% microwave watercut P, T, ΔP
dual venturi
GVF 95-99.5% Dual venturi 0-100% microwave watercut Coriolis P, T, ΔP

REFERENCES
9.1 Chalfin, S., Chem. Eng. (Oct. 4, 1974).
9.2 Tuss, B., Perry D., and G. Shoup, “Field Tests of the High Gas Volume Fraction Multiphase Meter,” SPE 36594, Denver,
Colorado (Oct. 1996).
9.3 “Basic Instrumentation,” Petr. Ent. Serv., Texas Univ., Austin, Texas (1964).
9.4 Munk, W. D., Ibid. (Sept. 6, 1982), p. 113.
9.5 Corcoran, W. S. and J. Honeywell, Chem. Eng. (July 7, 1975).
9.6 November, M. H., Oil and Gas J. (Apr. 3, 1972), p. 69.
9.7 Evans, H. J., Ibid. (Aug. 20, 1973), p. 67.
9.8 Liu, K. T. and G. E. Kouba, “Coriolis-based Net Oil Computers Gain Acceptance at the Wellhead,” Oil and Gas J. (June
27, 1994), p. 42.
9.9 Al-Taweel, A.B., et al., “Development and Testing of Multiphase Metering Unit Using Coriolis Meters,” SPE 38785, San
Antonio, Texas (Oct. 1997).
9.10 “Multiphase Meter to Undergo North Sea Tests,” Oil and Gas J. (Apr 17, 1995), p. 69.
9.11 Letton, W., et al., “Topside and Subsea Experience with the Multiphase Flow Meter,” SPE 38783, San Antonio, Texas (Oct.
1997).
9.12 Gaisford, S., Amdal, J., and H. Berentsen, “Offshore Multiphase Meter Nears Acceptable Accuracy Level,” Oil and Gas J.
(May 17, 1993), p. 54.
CHAPTER 9 347
APPENDIX 9A – DEFINITION OF TERMSAPPENDIX 9A
Table 9A.1
Example Instrumentation Symbols & Identification Legend
Controllers Readout Devices

“Indicating”
or Self-
First “Measured Actuated
Letter Variable” Recording Indicating Blind Control Valves Recording Indicating
A Analysis ARC AIC AC AR AI
B Burner/ BRC BIC BC BR BI

Combustion
E Voltage ERC EIC EC ER EI
F Flow Rate FRC FIC FC FCV FR FI
L Level LRC LIC LC LCV LR LI
P Pressure PRC PIC PC PCV PR PI
PD Differential PDRC PDIC PDC PDCV PDR PDI
Pressure
S Speed/ SRC SIC SC SCV SR SI
Frequency
T Temperature TRC TIC TC TCV TR TI
Z Position ZRC ZIC ZC ZCV ZR ZI
First “Indicating” Alarms Transmitters
Letter or
“Measured High Shut Low Shut Solenoids, Relays,
Variable” Down High Low Down Recording Indicating Blind Computing Devices
A Analysis ASDH AAH AAL ASDL ART AIT AT AY
B Burner/ BSDH BAH BAL BSDL BRT BIT BT BY
Combustion
E Voltage ESDH EAH EAL ESDL ERT EIT ET EY
F Flow Rate FSDH FAH FAL FSDL FRT FIT FT FY
L Level LSDH LAH LAL LSDL LRT LIT LT LY
P Pressure PSDH PAH PAL PSDL PRT PIT PT PY
PD Differential PDSDH PDAH PDAL PDSDL PDRT PDIT PDT PDY
Pressure
S Speed/ SSDH SAH SAL SSDL SRT SIT ST SY
Frequency
T Temperature TSDH TAH TAL TSDL TRT TIT TT TY
Z Position ZSDH ZAH ZAL ZSDL ZRT ZIT ZT ZY

DEFINITION OF TERMS
See ANSI/ISA-S51.1 for a complete listing of “Process Instrumentation Technology” terms.
Commonly used control terms include:
Accuracy – Degree of conformity of a measured value to an accepted standard value or closeness of a
reading or indication of a sensor to the actual value of the quantity being measured.
Air to open (ATO) – This is a valve that needs air to create enough actuator force to open the valve to flow
and is generally referred to as “Direct acting.”
Air to close (ATC) – This is a valve that needs air to create enough actuator force to close the valve to flow
and is generally referred to as “In-direct” acting.

Capacity – In process control, capacity refers to the ability of a piece of equipment to accumulate and store
fluids.
Capacitance – is the capacity of the component per some unit quantity. For example the tank capacity
(volume) vs. tank level.
Cascade control – a control system in which there are at least two control loops. The main slow outer
primary loop’s output dynamically changes the set point of the faster, inner secondary control loop. Cascade
control is used to reduce the effects of measured variable changes.
Control loop – A group of instruments within a process that includes measuring (controlled process variable),
comparing (measured or controlled to setpoint), Function block and final control element (manipulated
process variable) whose function is to maintain a process variable at a setpoint.
Closed Loop – a system that monitors its output and makes corrections to reduce error. By monitoring the
output the system can correct for disturbances.
Control valve – A type of final element whose function is to vary the manipulated process variable in order
to maintain the controlled process variable at set point.
Controlled variable – The controlled process variable is sometimes referred to as the “measured variable”
and is the pressure, liquid level, temperature, flow rate or composition that is to be controlled.
Controller – a device in a control loop whose function is to provide a control signal to the manipulated
variable in order to maintain the controlled variable at set point. Often the controller compares setpoint to
controlled variable, develops an error and applies gain and function at the controller output.
Dead band – Valve-actuator assemblies or other equipment may have spots in their control range where
a reversing control signal does not change the device output. Dead band is typically expressed as a % of
control range, should be less than 2%, and acts as a delay.
Delay (dead time) – is the time between when a process changes and the time when the measured (controlled)
variable senses the delayed process change. Digital instruments have small time delays due to their small
sampling interval.
Derivative response – a controller response that provides an immediate corrective action based on the time
rate of change of a variable. The derivative action may be on the error or the controlled variable.
Diaphragm motor valve – a term applied to a control valve actuator that uses air or gas pressure to open
and close it.
Direct acting – a term describing the result of actuator action on a valve. When the valve’s actuation force
increases the valve opens (ATO). Also a controller, control valve, actuator, or other device in which the
value of the output signal increases as the value of the input increases
CHAPTER 9 349
Distributed Control System (DCS) – is a system of computers and controllers where the process is remotely
controlled by control loops local to the process and these remote controllers communicate via networks
with the central controller. Typically the networks and central controller are redundant and the remote
controllers may or may not be redundant.
Disturbance – Refer to Load also. Disturbances can also come from non-process control loop related items
other than the load. For instance, loss of hot oil temperature or sudden rain fall on a heat exchanger for the
load.
Drift – is the change of equipment calibration with supply pressure, time, voltage, temperature, and vibration
and is expressed as % / % parameter change.
Dynamic conditions – where the process is continually changing.
Equal percentage – is the valve inherent characteristic that changes the flow capacity the same percentage
of initial flow for equal percentage changes of stem travel.
Error – In an active control loop it is the result of the controlled variable being different from the current
set point.
Fail closed valve (FC) – a valve that fails to the closed (zero flow) position upon loss of actuator force.
Generally a spring causes this action but not always. Refer to Air to open.
Fail open valve (FO) – a valve that fails to the open position upon loss of actuator force. Generally a spring
causes this action but not always. Refer to Air to close.
Fail-safe – A term used to describe valve action on loss of actuator force. Whether the valve should be open
or closed on failure is determined as part of process safety evaluation.
Fast opening trim (quick open) – is the valve inherent characteristic trim that may be more than 40-60%
flow capacity when the stem or plug is only 20 to 40% open.
Feedback control – is the maintaining of a desired process operating point by comparing the controlled
variable to a reference (set-point) and correcting based on the magnitude of error.
Feed forward – a portion of the process is fed forward to a control loop for the purpose of anticipating
and aiding a process control loop to maintain setpoint. Feed forward in itself is not a feedback mechanism.
There is no error correction in the feed forward path.
Final element – A device (often a valve but not always) in a control loop that is driven by the control
function block to maintain the controlled process variable at set point.
Gain – is the incremental change of output divided by the incremental change of input. For example, the
gain of a valve is the change of flow capacity for a given change of trim movement.
High Select – Designed to select the higher of two signals to provide a continuous output to a control
device.
I/P – Current to pressure transducer.
Indirect action – is a term describing the result of actuator action on a valve. When the valve’s actuation
force increases the valve closes (ATC).
Inner valve assembly (trim) – Refer to Valve trim.
Inherent flow characteristics – A valve is built to provide a certain flow capacity at a given trim or stem
position at constant pressure drop. These flow capacities may be linear, fast opening, or equal percentage.
However, once installed the inherent characteristic changes shape and becomes the installed characteristic.
Integral response – a controller response that provides an integrated error signal over time. Integral action
is usually used in conjunction with proportional action (PI). Integral action slows the control loop response
and may create process variable overshoot.

Linear trim – a valve’s inherent characteristic trim that changes valve capacity linearly with trim (stem)
travel.
Load (disturbance) – An undesired change that takes place in a process that tends to adversely affect the
value of a controlled variable. A change from normal process conditions. It may be the result of a pump
turning off or on, pump recycle, a well on or off production or utilities on or off (steam).
Lower range value (LRV) – The lowest value of the measured variable that a device is adjusted to measure.
Low Select – Designed to select the lower of two signals to provide a continuous output to a control device.
Manipulated variable – The process variable that is changed after a process load change in order to maintain
the controlled process variable at set point.
Measured variable – A quantity, property, or condition which is measured. It can also be called the controlled
variable when it is the variable to be controlled and is the process variable (flow, level, pressure, tempera-
ture or composition) which is measured and fed back to the controller.
Minutes per repeat – Expresses the degree of integral action in how much time the integral output takes to
develop a magnitude equal to the proportional response and is expressed as minutes per repeat (MPR). The
bigger the number the slower the response.
Normal conditions – The process conditions of temperature, pressure, level, flow and composition that
occur when the process is performing “normally.” This “normal” state may change with seasons, i.e., more
steam in the winter. Control loop set points are “normally” set for “normal” operations.
Normally closed valve – A valve that is normally closed and not used for normal process operation or
control.
Normally open valve – A valve that is normally open but not used for process control.
Offset – The difference between the control point and the desired condition. The steady-state deviation
when the set point is fixed.
Open Loop – a system that does not monitor its output. Open-loop systems cannot correct for disturbances.
Pneumatic controls – Controls that use vapor in the form of air or natural gas for operation.
Programmable Logic Control (PLC) – A computer that has been hardened for operation in extreme facility
environments of temperature, humidity and vibration. They contain many types of preprogrammed Function
blocks (preconfigured programming) one of which is PID. These devices may also contain function blocks
for ratio control, bias, linearization, valve characterization, etc. They may be programmed by an operator
with a computer.
Proportional control – the control mode that causes the controlled (measured) variable to change in propor-
tion to the error or difference between set point (SP) and measured or controlled variable.
Repeatability – The closeness of agreement among a number of consecutive measurements of the output
for the same value of the input under the same operating conditions, approaching from the same direction,
for full range traverses.
Repeats per minute (RPM) – the degree of integral action measured in how many times the integrator
output would equal the proportional response magnitude and is expressed in repeats per minute (RPM).
The bigger the number the faster the response.
Ratio control – Maintains the relationship between two variables to control a third variable. Ratio control
systems actually are the most elementary form of feed forward control.
Reset (integral) – Expressed in repeats per minute (RPM) or minutes per repeat (MPR). Reset is the time it
takes the control error signal to equal the magnitude of proportional response. See Integral response.
Reverse Acting – A controller, control valve, actuator, or other device in which the value of the output signal
decreases as the value of the input increases.
CHAPTER 9 351
Self-operated controller – an actuator-valve unit assembly which is actuated directly by the controlled
variable.
Sensitivity – The ratio of the correct output change for the smallest input change after the process has
reached steady state. For example, an actuator-valve assembly that responds properly to a small (1%)
actuator input change is sensitive.
Servomechanism – is a feedback control system in which the controlled variable is a position.
Setpoint – is the value of a process variable that is the desired normal control point such as level, pressure,
temperature, flow or composition.
Snap-action (on-off) – The rapid opening or closing of a valve in response to the process variable reaching
a predetermined setpoint. On-off is the simplest, least expensive control mode but normally requires large
“capacitance” or storage. For example the on-off control of temperature for a building.
Span – The algebraic difference between the upper and lower range-values.
Split Range – Control in which the output of a controller is split to two or more control valves, each capable
of operation over a different range of the output signal. For example, one valve opens from 4-12ma and the
other opens from 10 to 20 ma.
Stability – the ability of the system to settle into a steady-state response.
Static conditions – is the point of unchanging process conditions. See Normal conditions.
Supply air (or gas) – that supply of clean, dry vapor necessary to operate a pneumatic controller or valve.
Natural gas is sometimes used instead of air in remote locations.
Suppressed zero – The range in which the zero value of the measured variable is less than the lower range
value. The terms: elevation, elevated range, and elevated span are frequently used to express the condition
in which the zero of the measured variable is less than the lower range value.
Topworks (motor) – It is that portion of the control valve assembly which opens and closes the valve, also
referred to as the actuator.
Upper range value (URV) – The highest value of the measured variable that a device is adjusted to measure.
(This value corresponds to the top of the span.)
Valve trim – Valve trim consists of a moving part (stem and plug) and a stationary part (seat) that is
firmly supported within the valve structure. The moving part varies the valve’s effective flow orifice which
changes the valve’s flow capacity. Refer to Inherent flow characteristics.

APPENDIX 9B – STANDARD CONTROL SYMBOLS

Figure 9B.1 Some Standard Control Symbols (See also ANSI/ISA-S5.1 to S5.5)
CHAPTER 9 353
354
10
RELIEF AND FLARE SYSTEMS
The relief and flare system is one component of the process safety system. A process safety system
is required to reduce the risks associated with the malfunction of plant equipment due to mechanical failure,
process excursion outside of the normal operating envelope, and in the event of a fire.
Excursions outside of the normal operating envelope can lead to equipment failure and/or loss of
containment, personnel injuries or fatalities. The process safety system should prevent these excursions and
reduce the fire and explosion escalation risks. There are many independent protection layers associated with
a production or processing facility as shown in Figure 10.1. The process safety system represents two of the
independent layers of protection provided for production and processing facilities.
The primary protection of the process safety system is the instrumented shutdown system (safety
instrumented system (SIS) or emergency shutdown systems (ESD)). The secondary protection is the relief
and flare system. The intent is for the safety instrumented system to mitigate the overpressure scenario
before the relief and flare system is required to. The process safety system may or may not be completely
independent from the process control system, depending upon the safety philosophy of the company. On
occasion, low integrity safeguards in the instrumented shutdown system may be implemented within the
process control system provided the components of the system meet required performance specifications.
Another option is to maintain the safety instrumented system completely independent from the process
control system.
y Emergency Response
Communit
Plant Emergency Response
otection (Relief Devices and Di
hy s ical Pr kes)
P a tic Action SIS or ESD
Au to m
Operator Inte
larms and rven
r itica A
l tion
C rm s an d O perato r S
la up erv
ss A isio
oce Plant Design n
Pr
Figure 10.1 Independent Protection Layers for a Facility
CHAPTER 10 355
Overpressure Protection
The process safety system must be able to provide protection at the maximum pressure (and other
operating parameters) that can be generated by the worst credible scenario. There are three options to
protect the facility against overpressure:
1. Fully rated equipment
2. Relief devices (valves, rupture discs, etc.)
3. Instrumented protective function only (HIPS)
For fully rated equipment, the design pressure is greater than the maximum overpressure source.
For flowlines, this is the Shut-In Tubing Head Pressure (SITHP) or higher. This option has been successfully
employed in simple wellhead separation facilities, but is seldom economical in more complex facilities.
The pressure relief device is the final overpressure protection for process equipment and is the
minimum legal protection requirement (prior to HIPS being accepted by regulatory agencies) for vessels and
piping. What constitutes a pressure relief device varies by the code which covers the protected equipment.
Instrumented protective functions (IPF) are part of the safety instrumented system. When they are
the sole source of protection for the equipment they are a high integrity pressure protection system (HIPS),
which is discussed in more detail later in this chapter. IPF’s are designed to keep the process within the design
envelope and to prevent the escalation of abnormal conditions into major hazardous events. They typically
isolate the unit to remove the source of energy which can result in overpressure. Two examples are:
1. Blocking the inlet and opening the outlet of a vessel
2. Removing the heat from a distillation tower to remove the energy required for overpressure
The selection of the overpressure protection method is a function of legal requirements, engineer-
ing judgment, acceptable risk level, and life-cycle costs.
Causes of Overpressure
A simplistic view of how overpressure occurs is:
Input > Output (10.1)
Pressure increases when the mass entering a vessel is greater than the mass leaving. The same is
true for heat input (this includes process heaters, fires, and chemical reactions).
There are many potential causes of overpressure in a system. Identifying sources of overpressure
should be based on the unique characteristics of the mechanical and process design of each facility and/or
system evaluated. Some common causes of overpressure are summarized in Table 10.1 along with simple
evaluation guidelines. An evaluation of the mass balance and energy balance around the system for each
relieving scenario will result in the relieving rate required for that scenario. Each relieving device is designed
based on a relieving scenario and corresponding relief rate (and required pressure relief device area). Note
that the pressure relief device may be sized based on one scenario and the combined relief header sized on
a different scenario.

Table 10.1
Relief Scenarios
Relieving Case Comments

Closed outlet on vessels This can be either a vapor outlet or liquid outlet scenario.
(blocked outlet)
Overfilling of surge or Grading of the storage vessel area is important to drain any potential leaks to
storage vessel a safe location. It should also be designed to minimize the spread of fire via
spilled flammable and combustible materials. Berms are often used to provide
containment around the vessels to contain the vessel contents in the case of
vessel failure.
Failure of automatic controls In addition to a general utility failure each control loop should be evaluated for
the potential of failure and malfunction where individual control valves can
either close or open inadvertently.
An example is a liquid level control valve from a high pressure separator to a
lower pressure separator. Normally this valve will fail closed to prevent over
pressuring the downstream equipment. In a malfunction the valve could open
fully. The downstream relieving requirement would be designed for the full
flow of high pressure vapor through the malfunctioning valve.
Plant wide utility failure Instrument air – all instruments go to the failure position
Power failure – all electrical equipment (non-UPS) stops—this might include
pumps, compressors, air cooled exchangers
Fuel gas failure
Cooling water failure
Heat medium failure (steam, hot oil, etc.)
Inert gas failure
Partial equipment failure The failure of one pump, one compressor, or one air cooled exchanger, etc.
Heat exchanger tube rupture Complete opening of a heat exchanger tube. If the exchanger design meets
(severed tube) certain pressure rating ratios relief of the low pressure side is not required.
Thermal expansion Liquid filled equipment blocked in and subject to heat input (piping, vessels,
heat exchangers are particularly susceptible).
Entrance of highly volatile These systems cannot be calculated due to the number of variables. Administra-
material tive and engineering controls are required to mitigate these circumstances.
Water into hot oil
Light hydrocarbon into hot oil
Pool fire The maximum volume of a potential pool of liquid should be evaluated to
determine maximum heat output from the fire.
Jet fire A jet fire gives a high velocity flame that can impinge on equipment causing a
localized hot spot. This can cause overheating and vessel rupture or structural
support failure. This evaluation is often done to determine fireproofing insulation
requirements.
Off spec product flowing These systems cannot be calculated due to the number of variables. Adminis-
into LPG or Crude Oil tanks trative and engineering controls are required to mitigate these circumstances.
The scenarios developed for the relieving cases must be evaluated and documented. The operator
response time and the response of the basic process control system should be included in the evaluations.
In developing scenarios, the potential for one failure to cause another failure should be evaluated.
However, two unrelated failures are typically not considered as a failure case.
For relief systems, it is important to consider the risk of valve blockage. Wax and hydrates in
particular can block relief valves. Heat tracing can be implemented to mitigate blockage risk, however, the
tracing system then becomes safety critical and must have a high level of reliability. Relief devices are the
most common method to protect systems from over pressure.
CHAPTER 10 357
Relief and Flare Systems

The components of an example relief and flare system are shown in Figure 10.2, and may include
some or all of the following components:
1. Pressure blowdown valves/relief control valves
2. Pressure relief device(s)
3. Relief device discharge piping or tailpipe
4. Flare system sub-header
5. Flare system main header
6. Flare knock out drum
7. Flare knock out drum liquid transfer pumps

8. Flare stack
9. Purge gas system
10. Pilot gas
11. Flame front generator (ignites the pilot on the flare tip)
12. Flare tip
BDV-100 Purge Gas
PSV-100 PSV-200
PSV-101 PSV-201 Flare Tip
Velocity
PSV-102 PSV-202 Seal
Purge Gas Pilot Gas

Sub-Headers
Main Header Flame Front Ignition
PSV-300 Purge Gas
PSV-301
PSV-302
Flare KO
PSV Lateral or Tailpipe Drum
PSV = Pressure Safety Valve
BDV = Blowdown Valve
Liquids to Closed Drain
Figure 10.2 Example Relief and Flare System
The pressure relief device installed on the equipment provides the physical protection for the
equipment and connected piping. The relief devices are designed to prevent the overpressure from exceeding
the mechanical strength of the equipment. They protect personnel from the consequences of equipment
failure, and prevent loss of containment if the discharge is routed to a flare. The device automatically opens
to discharge fluids to a flare header, or to the atmosphere, at a pre-determined set pressure.
The flare system sub-headers and headers collect all discharged fluids from blowdown valves (if
provided at the facility) and pressure relief devices, and routes them to the flare knock-out (KO) drum. This

drum is located at the low point in the system and is designed to separate any liquids that may be present in
the flare system. This prevents excessive liquids carry-over to the flare tip. Any liquids that build up in the
flare KO drum are pumped to a closed drain, or other liquids disposal system. The gas from the flare KO
drum flows up the flare stack, and to the flare tip. The flare tip is designed to combust all gas releases. A
purge gas system is provided for the flare sub-header, main headers, and flare tip to prevent air ingress into
the flare piping and equipment. This is important to prevent the equipment from being filled with a poten-
tially combustible atmosphere if there are any hydrocarbons present in the flare header system.
PRESSURE RELIEF DEVICE

There are five common types of pressure relief devices:
1. Conventional Pressure Relief Valve

2. Balanced Bellows Pressure Relief Valve
3. Pilot Operated Relief Valve
4. Rupture Disc
5. Rupture Pin (also known as buckling pin)
Often times, it is common to refer to pressure relief valves (all types) as pressure safety valves.
Conventional Pressure Relief Valve

Conventional pressure relief valves open
based on the differential pressure between the inlet
Cap
of the relief valve and the outlet. Figure 10.3 shows Stern (Spindle)
a conventional relief valve. Notice that the top of Adjusting Screw
the valve seat is exposed to the back pressure of the
discharge line. If a conventional pressure relief valve
is set to open at 100 psig with zero back pressure, it
will open at 120 psig if it has 20 psig of back pressure.
Vent
If the relief valve setting is adjusted to account for Spring (Plugged)
Bonnet
back pressure, it will open early if no back pressure
exists. For instance if it is expected to have up to 20
psig back pressure and the set pressure is 100 psig, it
will open at 80 psig with no back pressure. This may Seating Surface
be below the normal process pressure and would
Disk
result in an unnecessary relief. If the back pressure
is known to be constant then it can be accounted for
in the set pressure. If the back pressure is variable, Adjusting Ring
such as the case in flare headers, it is impractical to Body
Nozzle
use conventional pressure relief valves. Conven-
tional relief valves are typically vented directly to Figure 10.3 Conventional Safety Relief Valve
the atmosphere.
Once a conventional relief valve opens excessive inlet and/or outlet pressure losses can cause the
relief valve to close. When the relief valve closes the differential pressure will build up again, and the relief
valve will open. This can occur at a very rapid cyclic rate, known as chattering. Chattering reduces the valve
capacity and can cause mechanical damage to the valve, resulting in valve failure.
CHAPTER 10 359
Balanced Bellows Relief Valve

Balanced bellows relief valves use a bellows to reduce the effect of back pressure on the set pressure
of the valve. Figure 10.4 shows a balanced bellows type relief valve. The area covered by the bellows is
equal to the seat area of the valve opening, so back pressure does not affect the pressure at which the valve
opens to the same degree as a conventional relief valve. Back pressures in excess of 30 to 45% (depending
on valve manufacturer) can affect the relieving capacity. These bellows relief valves are commonly vented
to closed relief headers. These valves are more complex than conventional valves and corrosion, fatigue or
overpressure can cause failure of the bellows. If the bellows develop a leak, they operate like a conventional
relief valve. To mitigate the effect of a leak the bellows are vented to the atmosphere through a threaded
hole in the bonnet. This hole must remain open on a balanced bellows valve. On a conventional relief valve
a plug is threaded in the hole.

Bellows are subject to a maximum allowable pressure. Exceeding this pressure can cause failure of
the bellows. The maximum pressure for the bellows can be found in API 526 Flanged Steel Pressure Relief
Valves, and in the valve manufacturer catalog. The
catalog will likely refer to pressure and temperature
Cap
limits are based on API 526. API 526 is a purchasing
Stern (Spindle)
Adjusting Screw specification for flanged steel relief valves. It defines
flange to flange dimensions, orifice sizes (D through
T), pressure and temperature limits. Manufacturer's
specifications may allow for higher back pressure for
the mechanical integrity of the bellows than API 526.
Spring Vent
(Unplugged)
Some of the perceived problems of excessive back
Bonnet
pressure on bellows can be resolved by contacting
Bellows shield the manufacturer for more detailed information.
the PSV rod
Some company standards require the valve to be in
Bellows
compliance with API 526, which will result in the
Seating Surface manufacturer quoting the API 526 bellows pressure
Disk limit.
The other issue with back pressure is the
Adjusting Ring effect on the flow performance of the relief valve.
Body
The reduction in performance of balanced bellows
Nozzle
valves is greater than “and occurs sooner than”
Figure 10.4 Balanced Bellows Safety Relief Valve for pilot operated relief valves. The bellows in the
balanced bellows valves gets stiffer as a result of the
1.00 increased back pressure and prevents full lift. This
0.90 results in reduced capacity prior to subsonic flowing
0.80 occurring.
Kb = Back Pressure Correction Factor
0.70
API 520 Part 1 Sizing, Selection, and Instal-
Generic, 10% Accumulation
0.60
lation of Pressure-relieving Devices in Refineries,
Manufacturer A, 10% Accumulation
Manufacturer B,
A, 16% Accumulation
0.50
Part 1 – Sizing and Selection, provides a generic
0.40
graph (plotted on Figure 10.5) showing the effect
0.30
of back pressure on relief valve performance. A
0.20
review of three manufacturers showed two with
Pbackpressure = kPa(g) [psig]
0.10
no correction or de-rating required with up to 45%
Pset = kPa(g) [psig]
0
0 5 back pressure and one with correction starting at
10 15 20 25 30 35 40 45 50 55 60 65 70
100* P /P
30% back pressure. It is important to use the back
backpressure set
Figure 10.5 Balanced Bellows Back Pressure Correction pressure correction from the specific relief valve
Factor manufacturer.

Pilot Operated Relief Valve

In Pilot Operated Relief Valves (PORV) the seating force is supplied by the vessel pressure, which
is routed through a pneumatic pilot to the top of a piston. Figure 10.6 shows a schematic of a PORV. Since
the area on the top of the piston is greater than the seat area, the seating force is at a maximum just below
the set pressure.
When the set pressure is reached, the pilot
vents the pressure on the piston to the atmosphere Pilot Pilot
or to the discharge line and the relief valve opens. Exhaust
PORVs are not affected by back pressure until it
Backflow
becomes subsonic and even then the effect is not Preventer

large. Up to 80% back pressure can be tolerated (optional)
with only a 20% reduction in flow. PORVs have
blowdown as low as 2%, which allows the process
vessel to be operated much closer to the set pressure.
Blowdown is the difference between the set pressure
and the closing point pressure of the valve, and is
Outlet
usually expressed as a percentage of set pressure.
The pressure sensor for the pilot is normally Pressure Piston
Sensing
connected to the inlet side of the PORV, but if Line
required can be located remotely from the PORV, Seat
such as on the protected vessel. This is particularly
useful for relief valves that have excessive inlet Main
Valve
losses. Relocating the pilot to the vessel provides Inlet
for a stable operation and reduces the probability of Figure 10.6 Pilot Operated Relief Valve
chatter.
PORV’s have several options which can be added. Among those options are pilot filter, backflow
preventer, modulating pilot and non-flowing pilot. All of the available options should be reviewed prior
to purchase. A standard PORV will open when the downstream (relief header) pressure is greater than the
upstream pressure. This can be prevented by the use of a backflow preventer on the pilot.
Modulating pilots change the operation of the PORV into more of a pressure control valve. The pilot
controls the PORV so that it will partially open if the flow is low. This prevents the PORV from cycling.
Most times a modulating non flowing pilot is desirable. A pop acting PORV is preferred for relief
valves that vent directly to the atmosphere. This maintains a high relief valve tailpipe velocity and good air
mixing (resulting in a very short flammable mixture range) when the valve is open. A filter in the pilot line
will help maintain a clean pilot when fouling may occur. Using a non-flowing pilot is also desirable in this
case.
Buckling Pin Valves

Buckling pin valves appear similar in appearance to a PORV. It has a piston that is held down by a
thin pin. Gas pressure exerts upward force on the piston. When the gas pressure gets to the set point the pin
buckles and allows the piston to rise. It is a non-reclosing device, but unlike the rupture disc the pin can be
replaced externally in a matter of minutes.
CHAPTER 10 361
Rupture Discs
Rupture discs may be used in lieu of relief valves. There are several types available.(10.1) They are
simple, inexpensive, robust and have a higher capacity than a relief valve with the same inlet nozzle size
(with the possible exception of the full port PORV). The drawbacks are fairly obvious. They relieve the
entire system contents, requiring shut-down of the system to be replaced. They cannot be tested and they
suffer from fatigue when operated for prolonged periods near their burst pressure. Still they find many
applications in oil and gas processing. A common application is on shell and tube heat exchangers to protect
the shell side of the exchanger from overpressure if a tube failure occurs in high pressure service. They
are sometimes installed below a relief valve to prevent leakage, particularly when the fluid is toxic (e.g.,
H2S) or expensive, but this may result in a reduction in the relief valve capacity. In addition they are used
in fouling service to protect the relief valve from fouling deposits. When rupture disks are used below the
relief valve, the non-fragmenting type should be used.(10.5) The reduction in relief valve capacity must be
evaluated to ensure the equipment is protected for the required rates. Installing the rupture disc upstream of
the relief valve also makes the relief valve more likely to fail the 3% inlet loss requirement.
Vapor Relief Valve Sizing

Approximately 90% of the relief valves in gas processing facilities are in vapor relieving service. To
provide an example of the equations used in sizing relief valves, only the vapor equation will be presented.
Refer to API 520 Standard Part 1 for the other sizing equations if required.
For vapor relief, the relief valve flow rate is calculated based on the area of the orifice multiplied
by the sonic velocity of the gas multiplied by the density of the gas at sonic conditions. Equation (10.2) is
used for the relief valve sizing:
w Tz
A = CK P K K MW (10.2)
d l b c
SI FPS
Where: A = PRV orifice area mm2 in2

See Table 10.3 See Table 10.3
C = PRV Coefficient – function of the gas specific heat See Table 10.2 See Table 10.2
ratio
Kd = effective discharge coefficient obtain from valve manufacturer
P1 = inlet pressure, Equation (10.3) kPa psia
Kb = back pressure correction factor obtain from valve manufacturer
Kc = combination factor (only used with installations 1.0 or 0.9 note 1 1.0 or 0.9 note 1
with a rupture disk upstream of PRV)
T = inlet gas temperature at relieving conditions K oR
z = inlet gas compressibility factor at relieving condi- — —
tions
MW = inlet gas molecular weight kg/kmol lbm/lb-mol
w = vapor mass flowrate kg/hr lbm/hr
Note 1: If there is no rupture disk upstream of the relief valve, Kc = 1.0. If there is a rupture disc
upstream of the relief valve and the combination factor is not known then 0.9 is used.
The relief header back pressure must be known to provide a basis for the back pressure correction
factors (Kb) to properly size the relief valves.
C is the PRV coefficient. It is a function of k, which is the ratio of ideal gas heat capacities
(Cp/Cv) at relieving temperature. It is important to use the ideal gas value. Cp is the ideal constant
pressure heat capacity in kJ/kg•K [Btu/lbm-oR], and Cv is the ideal constant volume heat capacity kJ/kg•K
[Btu/lbm-oR]. A value of 0.0239 [315] can be used if you do not have a value for k.

The set pressure, Pset, is the inlet pressure in Table 10.2

kPa [psia] at which the relief valve is set to open. C PRV Coefficient
This is generally the design pressure of the vessel. C
The design pressure is the maximum pressure (with k SI FPS
coincident design temperature) that is expected in the
1.00 0.02390 315
vessel. The Maximum Allowable Working Pressure
(MAWP) is the maximum gauge pressure (with 1.10 0.02480 327
coincident design temperature) an ASME Section 1.15 0.02521 332
VIII Code Stamped vessel may be operated. The 1.20 0.02560 337
MAWP will be equal to or greater than the vessel 1.25 0.02600 342
design pressure. 1.30 0.02630
347
The steel plate used in fabricating vessels 1.35 0.02670 352
comes in discrete sizes, which may result in thicker 1.40 0.02700 356
walls than are necessary to meet the design pressure.
This may or may not be reflected in the MAWP. The MAWP is defined at the top of a vessel. Normal liquid
static head must be allowed for in the design. The vessel is hydrostatically tested with the pressure gauge on
the top of the vessel. P1 is the inlet pressure to the relief valve, in kPa [psia], of the gas at relieving condi-
tions.
The equation for P1 is:
P1 = ^Psethâccumulation factorh +Patm (10.3)
SI FPS
Where: P1 = relieving pressure kPa psia
Pset = pressure relief valve opening set pressure kPa(g) psig
Patm = atmospheric pressure kPa psia
Maximum allowed accumulated pressure = Pset (accumulation factor)
Relief Design Accumulation Factor

One relief valve 1.10
Multiple relief valves 1.16
Fire sizing 1.21
There may be instances that the PRV set pressure is not at the MAWP. In those cases use Pset in
place of MAWP.
It should be noted that relief valve orifices may be specified as API (American Petroleum Institute)
or Effective Orifice Area A, mm2 [in2], which are provided in Table 10.3. The Effective Orifice Area is
simply another term used for the API area. This effective orifice area is used in combination with the API
discharge coefficient, Kd, which is not the actual discharge coefficient of the nozzle. Kd generally has a
value of 0.975. Note that this is the area used in Equation (10.2).
Another area used in the industry is the ASME Orifice Area, AASME. The ASME orifice area calcu-
lation uses, KdASME, which is the actual measured discharge coefficient of the valve multiplied by 0.9. It
should be noted that (A)(Kd ) » (AASME )(KdASME ).
Table 10.3 provides the API orifice sizes and associated valve sizes. Also shown is the ratio of the
orifice area to the inlet pipe area. As this ratio increases the allowable pipe length and fittings upstream of
the relief valve (required to meet the 3% pressure inlet loss) decreases.
CHAPTER 10 363
Table 10.3
API Orifice Area/Inlet Pipe Area
Pipe Inches 1 1.5 1.5 2 3 4 6 6 8
ID, Inches 1.049 1.61 1.61 2.067 3.068 4.026 6.065 6.065 7.981
Pipe, in 2 0.864 2.036 2.036 3.355 7.393 12.730 28.890 28.890 50.030
Orifice, Orifice,
Orifice mm 2 in 2
D 71 0.11 0.127 0.054 0.054
E 126 0.196 0.227 0.096 0.096
F 198 0.307 0.355 0.151 0.151
G 325 0.503 0.247 0.150
H 506 0.785 0.386 0.234
J 830 1.287 0.384 0.174

K 1186 1.838 0.249
L 1841 2.853 0.386 0.224
M 2323 3.6 0.283
N 2800 4.34 0.341
P 4116 6.38 0.501
Q 7129 11.05 0.382
R 10 323 16 0.554 0.554
T 16 774 26 0.520
12 1.5  2 1.5  3 23 34 46 68 6  10 8  10
Value Body Size (Inlet Diameter  Outlet Diameter), in.
Figure 10.7 illustrates several relief valve terms, and illustrates the pressure relationships for
pressure relief valves.
Relief Valve Installation

Relief valve performance is sensitive to inlet and outlet piping configurations.(10.2, 10.3, 10.4)
Important factors to consider are the size and orientation of both the inlet and the discharge piping.
The inlet pipe size should never be less than the relief valve inlet flange and is often one size larger. The
pressure loss in the inlet piping should not exceed 3% of the set pressure of the relief valve. The discharge
pipe size should never be less than the relief valve outlet pipe size and in many cases is at least one pipe
size larger. Back pressure induced by discharge piping should not create a back pressure on the valve that
will restrict the required capacity of the valve.
If the relief valve is to be blocked in for maintenance and testing, a full opening (full bore) block
valve must be used and when in service, the block valve must have administrative controls to ensure it is
open (chain locked, car sealed open, etc.).
When a relief valve opens, a blowout thrust is imposed on the centerline of the outlet pipe which
induces a bending moment on the vessel or piping. It is often necessary to reinforce the piping or vessel
wall or to support the relief valve to account for this effect. This may also require 300 ANSI flanges on the
relief valve outlet, particularly when the back pressure on the system is high.
Finally, a relief valve testing and maintenance program is absolutely necessary to ensure proper
operation and response of the valve when it is required. API RP 520 Part 2 Sizing Selection and Installation
of Pressure-Relieving Devices in Refineries, Part II – Installation, provides guidelines for pre-installation
handling and inspection. Local, state, and national authorities may have specific inspection intervals that
must be adhered to as a minimum. Company specific guidelines may be more stringent. API RP 576 Inspec-
tion of Pressure – Relieving Devices, provides information on testing requirements.

Vessel Typical Characteristics of

Pressure Vessel Requirements
Pressure Pressure Relieve Valves
Maximum allowable Maximum relieving

accumulated pressure 121 pressure for
(fire exposure only) fire sizing
120
Maximum allowable Multiple valves maximum

accumulated pressure for relieving pressure for
116
multiple-valve installation
process sizing
(other than fire exposure) 115

Single valves maximum
relieving pressure for
process sizing
Maximum allowable Maximum allowable

accumulated pressure for 110 set pressure for supplemental
single-valve installation valves (fire exposure)
Percent of maximum allowable working pressure (gauge)
(other than fire exposure)
Overpressure (Maximum)
105 Maximum allowable set pressure

for additional valves (process)
Maximum allowable Maximum allowable set pressure

working pressure or 100 for single valves
design pressure Simmer
(typical)
Start to open
Blowdown (typical)
(see Note 6)
95
Closing pressure
for a single valve
Maximum expected
operating pressure 90 Leak test pressure (typical)
(see Notes 5 and 6)
85
Notes:
1. This figure conforms with the requirements of Section VIII of the ASME Boiler and Pressure Vessel Code.
2. The pressure conditions shown are for pressure relief valves installed on a pressure vessel.
3. Allowable set-pressure tolerances will be in accordance with the applicable codes.
4. The maximum allowable working pressure is equal to or greater than the design pressure for a coincident design temperature.
5. The operating pressure may be higher or lower than 90.
6. Section VIII, Division 1, Appendix M, of the ASME Code should be referred to for guidance on blowdown and pressure differentials.
Figure 10.7 Pressure Relationship for Pressure Relief Valves
CHAPTER 10 365
Example 10.1: The first stage separator of a production facility is shown below:
PSV
Shutdown
Logic
LO To Flare Header
LO FO
PSDH
Production Header FC
PC PC
FC To Compressor
LC
FC To 2nd Stage Separator
The controlling scenario for the PRV is the blocked in case. For this scenario and
PRV, the following conditions apply:
SI FPS
Normal operating gas rate = 0.92 ´ 106 std m3/d 32.5 MMscfd
Normal operating pressure = 3100 kPa(g) 450 psig
Required relieving gas rate = 35 270 kg/h 77 757 lbm/hr
MAWP (Pset) = 3450 kPa(g) 500 psig
Back pressure of relief header = 2070 kPa(g) 300 psig
Temperature = 49 oC 120 oF
Gas relative density (in-situ) = 0.75 0.75
z = 0.88 0.88
k = 1.24 1.24
C = 0.0259 341
Kd = 0.975 0.975
Kc = (there is no rupture disc installed
1.0 1.0
upstream of the relief valve) =
The accumulated pressure for a single valve installation is 110%.

Part A: Assume a single pilot operated relief valve, Kb = 1.0.
Part B: Assume a single balanced bellows relief valve, Kb = 0.5. (from Figure 10.5)
SI Solution:
Determine P1 from Equation 10.3
P1 = ^PsethÂccumulationh + Patm = ^3450h^1.1h + 101 = 3896 kPa
T = 49 o C + 273 = 322 K


Part A: Determine the required PRV orifice area for a pilot operated relief valve from Equation
(10.2):
w Tz ^35 270h ^322h^0.88h

A = CK P K K = = 1290 mm 2
d 1 b c MW ^0.0259h^0.975h^3896h^1.0h^1.0h ^0.75h^29h
From Table 10.3 the relief valve size is a 3L4.

Part B: Determine the required PRV orifice area for a balanced bellows relief valve from
Equation (10.2):
w Tz ^35 270h ^322h^0.88h

A = CK P K K = = 2590 mm 2
d 1 b c MW ^0.0259h^0.975h^3896h^0.5h^1.0h (0.75)(29)
The required area is double the area the PORV required. From Table 10.3, the relief
valve size is 4N6.
FPS Solution:
Determine P1 from Equation (10.3):
P1 = ^PsethÂccumulationh + Patm = ^500h^1.1h + 14.7 = 565 psia
T = 120 o F + 460 = 580 o R
Part A: Determine the required PRV orifice area for a pilot operated relief valve from Equation
(10.2):
w Tz ^77 757h ^580h^0.88h

A = CK P K K = = 2.0 in 2

d 1 b c Mw ^341h^0.975h^565h^1.0h^1.0h ^0.75h^29h
From Table 10.3 the relief valve size is a 3L4.
Part B: Determine the required PRV orifice area for a balanced bellows relief valve from
Equation (10.2):
w Tz (77 757) (580)(0.88)

A CKdP1KbKb MW (341)(0.975)(565)(0.5)(1.0) (0.75)(29) 4.0 in2
The required area is double the area the PORV required. From Table 10.3, the relief
valve size is 4N6.
CHAPTER 10 367
FLARE HEADER SYSTEMS

Figure 10.8 highlights the flare header system. The sizing of the flare header system is typically
done using computer programs. The relief headers are sized to accommodate all coincident relieving cases
while ensuring that the back pressure on the relief valves is below the pressure that will affect the valve's
capacity. Pressure drop in the flare system is calculated from the flare tip back to the relief valve(s). The
flare header calculations should be done for common utility failures, as these tend to generate the maximum
back pressure in the header. The flare header calculations can be either steady or dynamic. Calculations
that are done on a steady state basis are performed with the peak rate from each relief valve added to the
relief header on a continual basis. Calculations done on a dynamic basis can have loads entered at different
times and have the loads vary with time. The dynamic calculations should result in lower calculated back
pressures and higher allowable relief header loads; however, this requires a more complicated simulation.
An obvious dynamic load is a depressurization load, which is discussed later in this Chapter.
BDV-100 Purge Gas
PSV-100 PSV-200
Sub Header
Sub Header
PSV-101 PSV-201 Flare Tip
Velocity
PSV-102 PSV-202 Seal
Flare Header
Sub Header System
Purge Gas Pilot Gas
Flame Front Ignition

Main Header
PSV-300
Main Header Purge Gas
PSV-301
PSV-302
Flare KO
Drum PSV = Pressure Safety Valve
Figure 10.8 Flare Header System
Pressure drop through the flare tip is generally provided by the flare tip vendor. Piping pressure
drop is calculated using the isothermal compressible flow method outlined in API 521 Pressure-reliev-
ing and Depressuring systems, on a segment by segment basis. Flare tip size is generally based on flame
retention. Flame retention is another term for flame stability, thus the flame will not lift-off, or blow-out for
a properly sized flare tip. The main header is sized on the maximum required flow rate for the worst case
scenario. Each sub-header (discharge of two or more relief valves) is sized based on the maximum flow rate
required from the valves in that sub-header. The sizing flow for the PRV tail pipe or “lead” is a function of
the relief valve type. For conventional and pop action pilot operated valves the flow through the tail pipe is
the full capacity of the valve at relieving conditions. For modulating pilot operated valves, rupture disks,
or any other non-reclosing device the flow through the tail pipe is the required relieving flow. The tail
pipes handle the relief valve rated flow while the headers are designed for the required relieving rate. The
required relieving rate is determined from the various relief scenarios defined for the facility which may
occur simultaneously.
For screening purposes the velocity can be estimated at a Mach number of 0.5 with a maximum of
0.7.

There can be several flare headers in one facility, depending upon the resulting discharge conditions
from the relief valves:
1. High Pressure — This flare header will have relief valves with a relieving pressure above
2000 kPa (300 psig) and can discharge to a specialty high pressure drop (sonic) flare tip. High
pressure systems will have smaller diameter piping than a low pressure system for the same
mass flow rate. Sonic flare tips are better able to provide smokeless flaring without additional
equipment.
2. Low Pressure — These systems have sources with less than 2000 kPa (300 psig) relieving
pressures. They are designed for low back pressures and may have a pipe type flare tip for low
pressure drop.
3. Wet — This is a flare system with vapor or liquid water. Typically this system is constructed
of carbon steel and operates in the 16 to 316°C [60 to 600°F] range.

4. Dry — This flare system has no water and can operate down to –46°C [–50°F].
Material of construction might be low temperature carbon steel.
5. Cold — Flare header temperatures may be below –46 °C [–50 °F] and the material of con-
struction will be stainless steel.
Intermediate temperature ranges should be investigated regarding the expected temperature in the
flare header and the possible presence of water. Ambient conditions can also have an impact on header
design and metallurgy.
Flare header piping should slope from the relief valve outlet to the knockout drum. Various site
constraints may preclude sloping all valves to a single drum. In this case multiple knockout drums may be
necessary. (The outlet from one drum is elevated and slopes to the next drum.)
Flare Header Purge Gas Requirements

Flare systems require purge gas flow up the flare
stack to prevent air from ingressing back into the flare during Atmospheric Air
normal plant operation (that is, the flare pilots are burning
but there is not a relieving event). If air is allowed to migrate
down the stack and into the flare system an explosive mixture
could result. Some facilities use a water seal at the base of
the flare stock to prevent air infiltration. These are primarily
used where there is the potential for a high temperature relief
that might cause a vacuum in the flare header system after the
relieved material has cooled. This is a common application in
refineries. In addition to the water seal, a higher contraction
purge rate may be required.
Buoyancy seals and velocity seals shown in Figure
10.9 are two technologies for reducing the required purge Liquid drain
to closed drain
gas rates. The buoyancy seal forms a gravity seal to reduce Molecular Seal Velocity Seal
the required purge rate to 0.003 m/sec [0.01 ft/sec]. Disad-

(Buoyancy Seal)
vantages of the buoyancy seal are the complex flow path and Figure 10.9 Purge Gas Reduction Equipment
the possibility of liquid collection in the seal annulus. If the
liquid is water it can freeze, reducing the purge gas rate which in turn can damage the flare tip due to
burnback.
The velocity seal is a truncated cone installed pointing upward which results in a higher velocity
exciting the cone and directing the infiltrating air back out the tip. The required purge rates are expected to
be around 0.006 to 0.012 m/sec [0.02 to 0.04 ft/sec].
CHAPTER 10 369
Flare Knockout Drum (KO)

The flare KO drum is sized to prevent liquids in the relieving stream from reaching the flare stack
and tip. This prevents “burning rain”, combustion instability, and smoke formation. Both horizontal and
vertical vessels are used. Mist extractors are not normally used except offshore where space is at a minimum.
If used these should be robust (not wire mesh) and a relieving device should be installed to allow the KO
drum to be bypassed. The diameter of the drum can be calculated using the method in API 521 based on a
droplet size with a diameter between 300 and 600 nm (when no mist eliminator is used). The liquid capacity
of the drum is a variable that must be determined on a case by case basis. Some examples are maximum
liquid relief load for 90 seconds or one well for 15 minutes (offshore).
In some cases pumps are used to remove the liquid from the knockout drum during a relieving
scenario. For design purposes these pumps can be sized to pump out the drum from high liquid level in 15
minutes. Many times two pumps are installed and if the level rises when the primary pump is operating the
secondary pump starts. The size of the pumps should not be a factor in the sizing of the knock out drum
since they cannot be assured of starting during an emergency situation.
Flare Tips and Stack

In most cases the flare tip is supported on a vertical flare stack. The stack height or distance from
personnel or equipment is determined by the calculation of the radiation from the flare tip at maximum
relieving rate. In some cases the flare tips are located at ground level surrounded by a structure that
minimizes the effects of radiation on the surrounding facilities. The advantage of a vertical flare stack is a
reduced plot area requirement relative to a ground flare. A ground flare requires a staging instrumentation
system so that as the relieving rate increases additional valves are opened to maintain the mass flowrate
through the tips reasonably constant. This assists with mixing and smoke minimization. Smokeless flaring
in vertical flares is achieved with air addition, steam addition, or high pressure drop which enhances mixing
with atmospheric air.
Flare tips can be divided into two groups: subsonic and sonic. The subsonic tips are used in applica-
tions requiring low relief header back pressures. The subsonic tips require the addition of steam or air to
produce smokeless flaring. The sonic tips can achieve smokeless flaring as the result of the high gas veloc-
ities entraining air. Some sonic tips are designed with openings that can be varied to allow for a greater
smokeless range. Flare tips require inspection and/or replacement every 2 to 5 years. The heat flux at the
flare tip frequently results in distortion or damage to the tip.
To Individual Pilots
Ignitor
PI
Fuel Gas
View Port
PI
Air
Pressure Pressure Needle

Regulator Gauge Valve
Figure 10.10 Flame Front Generator

Flare ignition and pilot systems are necessary to ignite the relieving gas. Each flare tip will have
up to 3 pilots. Multiple pilots are necessary to ensure ignition regardless of wind direction. Wind can blow
the combustible gas away from a single pilot and prevent ignition. Pilots are designed to remain lit continu-
ously. If the pilot goes out it must be relit. There are four primary methods for pilot ignition: flame front
ignition, electronic spark ignition, ballistic ignition and use of a flare gun.
The most common type of pilot igniter is the flame front generator (FFG) (see Figure 10.10). A FFG
mixes fuel and air at grade (up to 1.6 km [1 mile] from the flare) and ignites it. The resulting flame front
travels along a pipe to the flare tip and ignites the pilot. The advantage of the FFG is it can undergo mainte-
nance while the flare is in operation. FFG can have problems with corrosion in the piping downstream of
the ignition point.
Electronic spark ignition provides a spark either inside the pilot piping or just outside of it. The
main problem with the electronic spark ignition system is it cannot be serviced while the flare is in operation.
The ballistic ignition system consists of a guide tube and an ignition pellet. The guide tube origi-
nates a safe distance from the flare and terminates at the flare tip. The ignition pellet is inserted in the guide
tube and propelled up the tube to the flare tip using compressed air. The ignition pellet hits the flare tip and
provides a shower of sparks, igniting the flare gas. No pilots are required. This system is highly reliable
although damage to the guide tube can prevent the ignition pellet from getting to the flare tip.
The final method of flare ignition is the flare gun. This method relies on a person firing a flare gun
at the flare tip. This requires the operator to have some skill at hitting a target from a safe distance. Most
sites will have this as a backup system.
Most operators will incorporate a minimum of two methods for pilot/flare ignition in their design
to ensure their flare can be ignited safely and reliably.
In addition to a reliable ignition system, flame monitoring is also often performed. Primary methods
of flame monitoring are thermocouples, flame ionization and optical monitoring. The first two methods
cannot undergo maintenance during operation. Optical monitoring uses a camera aimed at the flare and is
displayed in the control room. This is a simple, reliable system but may fail during adverse weather condi-
tions.
Flare Radiation
The radiation from a flare can harm personnel and objects close to the flare (see Table 10.4). There
are several methods for calculating the radiation from an elevated flare. The point source model, presented
here, is the simplest method and can be used for screening. More accurate methods involve calculating
the radiation from the flame envelope as described in API 521 and typically require specialized computer
programs. Flare radiation is a function of gas composition, flame emissivity, type of flare tip, relative
humidity and wind.
Whether solar radiation is included in calculating the thermal radiation is company specific. The
effect of maximum solar radiation at the same time as the maximum flare radiation is dependent on the
timing of the flaring event, wind exposure, and the alignment of the sun with the flare flame.
CHAPTER 10 371
Table 10.4 (10.6)

Effect of Thermal Radiation
Thermal Radiation Level

Recommendations / Comments
kW/m2 Btu/hr-ft2
9.46 3000 Limit personnel access (a few seconds)
6.31 2000 Personnel access up to 1 minute – Typical location for fence line
4.73 1500 Personnel access up to several minutes with appropriate clothing Note 1
1.58 500 Continuous exposure – Typical location for fence line for public
0.8-1.0 250-330 Solar radiation
Note 1: Appropriate clothing would be comparable to the standard PPE required in oil and gas facilities (at a
minimum 100% cotton clothing, long sleeves, long pants, work boots, hard hat, work gloves, etc.).
The radiation from an elevated flare can be estimated from Equation (10.4):
xFQ
K= (10.4)
4r D 2
SI FPS
Where: D = distance from mid-point of flame to point of interest m ft
τ = fraction of heat transmitted through the air (typically = 0.91) — —
F = fraction of heat radiated by the flame (typically 0.1 to 0.4) — —
Q = total flare heat release kW BTU/hr
K = radiation intensity kW/m2 BTU/hr-ft2
The fraction of heat transmitted through the air is a function of the ambient air temperature, relative
humidity, and the distance between the source and the receiver.
The heat release from a flare is calculated from Equation (10.5).
Q = Âh^qh^LHVh (10.5)
SI FPS
1/2 L Where: A = unit conversion factor 1000 0.0417
L
Q = total flare heat release kW Btu/hr

q = standard volumetric flow std m3/d MMscfd
LHV = lower heating value MJ/std m3 Btu/scf
H’
D
H
Flare Stack
Detailed calculations for determining τ and data for the

fraction of heat radiated by a flame (F) are provided in API 521.
Grade Figure 10.11 provides the dimensional references for a flare stack.
These references are used to determine the flare stack height required
R
for a given set of flaring conditions, or for the determination of
Figure 10.11 Dimensional radiation intensity at various locations for a given flare stack height
References for a under a defined flaring event.
Flare Stack

Example 10.2: Determine the heat release and required flare stack height for the following set of
conditions:
Maximum Gas Flowrate 5.66 ´ 106 std m3/d [200 MMscfd]
Gas Relative Density 0.75 0.75
Gas Temperature 37.8oC [100oF]
Gas Lower Heating Value (LHV) 46.5 MJ/std m3 [1250 BTU/scf]
k, ratio of specific heats 1.24 1.24
Pressure at flare tip—from vendor 115 kPa [16.7 psia]
F, fraction of heat radiated 0.15 (Engineering Decision)
t, fraction of heat transmitted through air 0.91 (Engineering Decision)

K, allowable radiation at a distance of 45.7 4.725 kW/m2 [1500 BTU/hr-ft2]
m [150 ft] from the base of the flare stack
L, flare flame length 113 m [374 ft]
Vertical Flare Stack
No Wind
SI Solution:
1. Determine the heat release of the flare:
Q = (A)(q)(LHV)
Q = ^1000hc a
5.66 # 106 std m3 m 1 d
k 46.5 MJ =
86 400 s c std m3 m 3.05 10 kW
# 6
d
2. Determine distance from the mid-point of the flame to the point of interest (45.7 m)
from the base of the flare stack.
xFQ
D = 4r K
^0.91h^0.15h^3.05 # 106h
D = = 84 m
^4h r ^4.73h
3. Knowing R = 45.7 m, and D = 84 m, solve for H¢, the height to the center of the flame
(see Figure 10.11)
Hl = ^D 2 – R 2h = ^84 2 – 45.7 2h = 70 m
4. Solve for the flare stack height, H, knowing H¢ and L

1 113
H = Hl – 2 L = 70 – 2 = 14 m
FPS Solution:
Q = (A)(q)(LHV)
Q = ^0.0417h a 200
MMscf k a1250 Btu k = 10 400 MMBtu/hr
d scf
CHAPTER 10 373

1. Determine distance from the mid-point of the flame to the point of interest (R =150
ft) from the base of the flare stack.
xFQ
D = 4r K
^0.91h^0.15h^10.5 # 109h
D = = 275.ft
^4h^rh^1500h
2. Knowing R = 150 ft, and D = 275 ft, solve for H¢, the height to the center of the flame
(see Figure 10.11)
Hl = ^D 2 – R 2h = ^275 2 – 150 2h = 230 ft

3. Solve for the flare stack height, H, knowing H¢ and L
1 374
H = Hl – 2 L = 230 – 2 = 43 ft
SAFETY INSTRUMENTED SYSTEM

A Safety Instrumented System (SIS), is an instrumented protection system which is independent of
the process control system. A SIS may also be referred to as an emergency shutdown system (ESD), or a
safety interlock system. A SIS can include any combination of high pressure sensors, level sensors and
temperature sensors which send signals to a logic solver which actuates shutdown valves to block in the
sources of overpressure. The SIS brings the process to a safe state when the process deviation is not corrected
by the process control system, or operator intervention. Its only role is safety; there are no process control
functions in the SIS.
The SIS is designed to provide Table 10.5
any number of Safety Instrumented Safety Integrity Levels
Functions (SIFs). These are the protec-
tive functions programmed within the SIL PFD Range Safety(1-PFD) Availability Risk Reduction
Factor (1/PFD)
SIS, each with a Safety Integrity Level
1 10 -1 ® 10 -2 90-99 % 10-100
(SIL) necessary to achieve the desired
risk reduction for a specified hazard 2 10 -2 ® 10 -3 99-99.9 % 100-1000
scenario. The SIL is a discrete level (one 99.9-99.99 % 1000-10 000
3 10 -3 ® 10 -4
out of four categories) used to specify
the probability that a SIF will perform its 4 10 -4 ® 10 -5 > 99.99 % 10 000-100 000
required function under all operational
states within a specified time period. A few examples of a SIF are:
1. High pressure in a vessel closes a SDV (shutdown valve) in the inlet line to the vessel.
2. Low liquid level in a vessel closes a SDV in the liquid outline line.
3. High temperature shutdown on a furnace will close a SDV in the main fuel gas supply.
The SIL categories are defined in Table 10.5, and are based upon the probability of failure on demand
(PFD) of a particular Safety Instrumented Function (SIF).
It should be noted that a SIL applies only to a specific safety instrumented function, not the entire
safety instrumented system, nor a single component of the SIF (e.g., sensor, final element).

A SIL of 3 qualifies as a high integrity protection system (HIPS, also referred to as high integrity
pressure protection system—HIPPS) and is about 10 times less likely to fail to operate than a mechanical
pressure relief device. A HIPS can be used in lieu of a pressure relief valve to protect ASME Section VIII
equipment, although this is not typical. More typical is to size the pressure relief device based on the HIPS not
working and size the relief header based on the HIPS working. Depending on the number of HIPS in a process
facility, a number of them may be assumed to fail when calculating the relief header load. A common applica-
tion is installing a HIPS in an existing facility to debottleneck (reduce predicted back pressure) a relief header.
There are times when required relieving rate to prevent overpressure is not well known. An example
is a flow line for a producing well. Well production is not always predictable. Using instrumentation to shut
in the well to protect downstream equipment is a desirable overpressure protection method. Other examples
are fluid blow-by (both single and two-phase) to a distillation system. The increased gas will vaporize liquid
in the distillation column and increase the required relieving rate. The gas rate can be sufficiently high to
cause massive entrainment in the distillation column and make sizing the downstream pressure relief device
more difficult. In addition, the high gas rate may damage the distillation column internals and cause operating
problems later due to the mechanical damage. Using instrumentation to isolate the source of the overpressure
can be effective.
LO
Logic Solver
2oo3 Voting
To Flare
LO FO
PT PT PT
From Gas Well FC FC
FC To Compressor
LC
FC To 2nd Stage Separator
Figure 10.12 High Integrity Protection System
Figure 10.12 depicts a HIPS used to protect a separator from excessive pressure. There are three
pressure transmitters which send their signals to a logic solver. The logic solver monitors the output from
all three pressure transmitters and if two out of three pressure transmitters exceed the shutdown setpoint,
the inlet valves are closed. Note there are two inlet isolation valves in series. The normal process control
maintains pressure on the vessel. If the pressure rises above the set point on this pressure controller excess
gas (not handled by the compressor) is routed to flare. The HIPS can be set up to actuate prior to the control
valve opening to the flare, but is typically set at a higher pressure than the control valve to flare. The
pressure relief valve is the final protection for this vessel.
CHAPTER 10 375
DEPRESSURIZATION/ BLOWDOWN
Depressurization or blowdown is simply any means to reduce the pressure in a system by allowing
the gas to vent to a safe location. Many facilities have installed blowdown or depressuring systems that vent
equipment to the relief or vent header.
Emergency Depressurization:
1. Reduce the consequences of a fire
2. Reduce the consequences of a hydrocarbon leak event
Emergency depressurization is typically done using blowdown valves that are not modulating.
These may or may not have a restriction orifice downstream to limit the flow required to achieve the desired
depressurization time. The blowdown systems can be initiated either manually or automatically, depending
upon the system design.
Fires
Fire on a vessel results in heat input to the vessel. The portion of the vessel wall which is wetted
by liquid will be cooled by vaporization of the liquid when exposed to the fire. This can moderate the wall
temperature due to the ability of the boiling liquid to remove heat from the wall. The vaporized liquid leaves
the vessel either through the normal process outlet or via a pressure relief valve. The un-wetted portion of
the vessel (gas section) does not have a high internal heat transfer coefficient and much of the heat results
in increasing the temperature of the vessel wall. The tensile strength of metal decreases as the temperature
increases. This can lead to vessel failure. One solution is to depressurize the vessel. The required time for
depressurization can be determined based on metal wall thickness, whether the vessel is insulated, etc.
The default time is to depressurize the vessel from the operating pressure to 50% of the design pressure
or MAWP in 15 minutes. This criteria is based upon the vessel wall temperature versus stress to rupture
and generally applies to carbon steel vessels with wall thickness of 25.4 mm [1 in] or greater. Vessels with
thinner walls may require a somewhat faster depressuring rate.
Calculating Depressurization Rates

The change in mols (mass) of fluid in the system with time is represented by dn = –CPdt. The
constant C is easily calculated by using sonic conditions for the depressuring valve (refer to ANSI/ISA
S.75.01 Flow Equations for Sizing Control Valves, or IEC 60534-2-1) or by defining the required depressur-
ization rate and calculating as below. The following equation is valid as long as the flow conditions are sonic:
P1 = P0 e
zRTCt
V
(10.6)
SI FPS
Where: C = initial flowrate through valve divided by kmol/min.kPa lb-mol/min-psia
the initial upstream pressure
P1 = pressure at time t kPa psia
P0 = initial pressure kPa psia
R = universal gas constant 8.314 kPa•m3/kmol•K 10.73 psia-ft3/lb-mol-oR
T = initial temperature K oR
t = time minutes minutes

z = initial gas compressibility factor — —
V = volume to depressure m3 ft3

The depressurization process largely occurs under sonic conditions. Once the vessel pressure
decline drops below 200-300 kPa [30-45 psia], the flow becomes sub-sonic. At this point Equation (10.6)
no longer applies. When a vessel is depressurized, the physical properties of the gas in the vessel (pressure,
temperature, and compressibility factor) are changing over time. For simplified hand calculations, assuming
the initial temperature and compressibility factor is a reasonable assumption.
Determining the required depressurization rate for a fire condition for equipment handling both
vapors and liquids (separators, reboilers, fractionation columns, etc.) is more complex. The vapor generated
from heat input to the liquid during the depressur- 6000
ization period, and the effects of reduced pressure

850
5500 800
on the system (vaporization of liquid and vapor 5000

750
700
expansion) should be included in the blowdown 4500 650

600
rate. This typically requires a computer simulation.

4000
550
Pressure, psia
Pressure, kPa
3500 500
450
Figure 10.13 is an example of a depres-

3000
400
2500
surization curve. The vessel is depressured to 50%

350
2000 300
of the design pressure in 15 minutes and 95% in 1500

250
200
60 minutes. This substantially mitigates the risk of 1000 150

100
vessel failure for a vessel exposed to a pool fire. It 500

50
should be noted that the vessel may or may not be

0 0
0 5 10 15 20 25 30 35 40 45 50 55 60
Time, Minutes
operating at the design pressure of the vessel when
depressuring is initiated. Figure 10.13 Vessel Depressuring
A plant depressurization system is typically operated so that not all systems are blowdown at the
same time. Depressurization can be staged by the use of instrumentation to reduce the peak relief rate. The
flow to the relief system will decay over time and additional blowdown valves can be opened to maintain
the flow rate and minimize depressurization time. Computer simulation programs for the depressurization
flow as well as flare header flow and pressure are available.
Atmospheric Venting
Historically, many pressure relief valves have been vented directly to the atmosphere. This is less
common in new installations today as a result of environmental restrictions and safety concerns. In specific
cases gas can be safely vented to the atmosphere. Venting each relief valve individually results in high
velocity venting, and a short flammability zone. Any relief valves vented directly to atmosphere must have
a dispersion analysis performed to ensure flammable or toxicity hazards are not created. Another hazard
with venting is the potential for liquid relief with subsequent fallout to the ground. Venting can eliminate
the need for or substantially reduce the size of a flare collection system. The effect of back pressure on relief
valve flow is eliminated. This is an important advantage given the complexity of evaluating simultaneous
relief from multiple relief valves and their impact on relief system back pressure.
LPG storage is an example of a facility using atmospheric venting. The relief case in these facilities
is fire relief which is a rare event. Another example of atmospheric venting of relief devices is in compressor
stations. The discharge vapor is predominantly methane and is lighter than air which will easily disperse.
The decision to use atmospheric venting versus a flare depends upon the local permitting requirements, the
fluids being discharged and the results of the dispersion analysis.
An important drawback to atmospheric venting is that most hydrocarbons, particularly methane,
have a substantially higher greenhouse effect than CO2.
CHAPTER 10 377
Environmental
Flares can impact the environment with light, smoke, noise, and emissions of combustion products
and by-products. Combustion is dependent upon many factors, and can be up to 98% efficient in flare tips.
The combustion products will contain CO2, CO, SO2, SO3, and oxides of nitrogen. As a result, flaring is
limited in many jurisdictions to emergency conditions. Routine venting to the flare for maintenance and
minor process upsets can often be captured in a flare gas recovery system. A flare gas recovery system,
similar to the one shown in Figure 10.14 will minimize emissions and allow recovery of valuable hydro-
carbons. A flare gas recovery system does not recover gas from a relieving event but allows recovery of gas
leakage and minor flaring that occurs under normal operating conditions. Back pressure is held on the flare
system by a water seal or a quick acting control valve. This back pressure allows a positive suction pressure
at the flare gas recovery compressor, or educator in some facilities. The compressor discharge is returned
to a low pressure system or to a fuel gas system where the recovered gas can be utilized. During a relieving
event the water seal is blown or the quick opening valve opens. In the case where a back pressure control
valve is used, a rupture disk or other quick opening relieving device is installed in parallel with the valve to
protect the system if the valve fails to open during a relieving event.
Purge Gas
PSV-200
Recycle
To Process
PSV-201 Flare Tip
Velocity
PSV-202 Seal
Rupture Disc
From Areas Sub Header LC
100 & 300 Pilot Gas
Main Header Flare Gas Recovery Flame Front

Ignition
FO Purge Gas
Flare KO
Drum
PSV = Pressure Safety Valve
Figure 10.14 Flare Gas Recovery System
REFERENCES
10.1 Nazario, F. N., “Rupture Discs – A Primer,” Chem. Engr. (June 20, 1988), p. 86.
10.2 Van Boskirk, B. A., Chem. Engr. (Aug. 23, 1982), p. 77.
10.3 Papa, D. M., Hydr. Proc. (May 1983), p. 79.
10.4 Westman, M. A., “Rapidly Design Safety Relief Valve Inlet Piping Systems,” CEP (Mar 1997), p. 80.
10.5 The Report of the BP U.S. Refineries Independent Safety Panel Review, (Jan. 2007).
10.6 ANSI/API Stnadard 521, Sixth Edition, (Jan. 2014).

APPENDIX A – TYPICAL SYMBOLS

APPENDIX A – TYPICAL PFD SYMBOLS
TYPICAL SYMBOLS
VALVES
Check Manual Control Emergency Pressure

Valve Valve Valve Shutdown Valve Relief Valve
SEPARATORS
Vertical Horizontal 3 Phase Vertical Filter Horizontal Filter

Separator Separator Separator Coalescer Coalescer
COLUMNS FIXED BEDS
Trayed Packed Demethanizer Mole Sieve Bed Charcoal Filter

Column Column
CARTRIDGE TYPE FILTERS
Dust Filter Cartridge Filter
APPENDIX A 379
TYPICAL SYMBOLS
HEAT EXCHANGERS
Generic Shell & Tube Shell & Tube Shell & Tube Shell & Tube
Shell & Tube Shell & Tube Brazed Aluminum (BAHE) Plate & Frame (PFE)
(Reboiler) (Chiller)
AIR COOLERS FIRED HEATERS
Generic With Actuated Louvers

Fuel TC
PUMPS
Centrifugal Centrifugal Reciprocating Reciprocating Reciprocating
COMPRESSORS
Centrifugal Reciprocating Reciprocating Screw Expander / Expander

Compressor

APPENDIX B – GENERAL CONVERSION FACTORS
GENERAL CONVERSION FACTORS

Base SI Metric Units SI prefixes and multiplication factors
Quantity Name Symbol Prefix SI Symbol Factor

Length.................................................... meter m tera.......................................... T 1012
Mass....................................................... kilogram kg giga......................................... G 109
Time....................................................... second s
mega....................................... M 106
Electric current..................................... ampere A
kilo......................................... k 103
Thermodynamic temperature............. kelvin K
hecto....................................... h 102
Luminous intensity............................. candela cd
Amount of substance........................... mole mol
deka........................................ da 101
deci......................................... da 10-1
Important derived and supplementary SI units centi........................................ c 10-2
Quantity Name Symbol Formula milli........................................ m 10-3
Electric capacitance....... farad F A-s/V micro...................................... µ 10-6
Electric charge................ coulomb C A-s nano........................................ n 10-9
Electric conductance..... siemens S A/V
pico......................................... p 10-12
Electric inductance........ henry H Wb/A
femto...................................... f 10-15
Electric potential............ volt V W/A
atto.......................................... a 10-18
Electric quantity............. coulomb C A-s
Electric resistance.......... ohm Ω V/A
Electromotive force........ volt V W/A
Energy.............................. joule J N-m
Energy flux...................... watt W J/s
Force................................. newton N kg-m/s2
Frequency........................ hertz Hz 1/s
Luminous flux................. lumen 1m cd-sr
Magnetic flux.................. Wb V-s
Magnetic flux density... tesla T Wb/m 2
Power................................ watt W J/s
Pressure............................ pascal Pa N/m 2
Quantity of heat.............. joule J N-m
Solid Angle...................... steradian sr
Work................................. joule J N-m
GENERAL CONVERSION FACTORS
APPENDIX B 381
general conversion factors
To convert from to Multiply by To convert from to Multiply by

acre...................................... hectare 0.40469 Btu/pound mol-°F.............. joules/mol-kelvin 4.18680
acre...................................... meter2 4046.9 bushel................................... decimeter3 35.23910
acre-feet.............................. meter3 1233.5 bushel................................... meter3 0.03524
ampere-hour....................... coulomb 3600.0 calorie.................................. joule 4.18400
angstrom.............................. nanometer 0.10000 calorie/pound...................... joule/kilogram 9.22414
astronomical unit.............. gigameter 149.598 centipoise............................ newton-second/meter2 0.00100
atmosphere......................... bar 1.01325 centipoise............................ pascal-second 0.00100
atmosphere(normal)......... kilopascal 101.325 centistoke........................... millimeter2/second 1.00000
atmosphere (normal).......... pascal 101 325 chain..................................... meter 20.1168
atmosphere (1 kgf/cm3)..... pascal 98067 cycle/second........................ hertz 1.00000

bar........................................ kilpascal 100.000 darcy..................................... micrometer2 0.98692
bar........................................ pascal 100 000 degree (angle)..................... radian 0.01745
barrel (42 U.S. gal)............. meter3 0.15899 °F/100 foot........................... millikelvin/meter 18.2269
barrel/acre-foot................... decimeter3/meter3 0.12889 °F-foot2-hour/Btu............... kelvin-meter2/watt 0.17611
barrel/day............................ decimeter3/second 0.00184 dyne..................................... millinewton 0.01000
barrel/day............................ meter3/day 0.15899 erg........................................ microjoule 0.10000
barrel/day (1 kg/dm3)......... tonne/annum 58.0304 erg........................................ millijoule 0.00010
barrel/foot........................... meter3/meter 0.52161 fathom.................................. meter 1.82880
barrel/hour.......................... decimeter3/second 0.04416 foot....................................... centimeter 30.4800
barrel/hour.......................... meter3/hour 0.15899 foot....................................... meter 0.30480
barrel/U.S. ton.................... meter3/tonne 0.17525 foot/day................................ meter/day 0.30480
board-foot............................ meter3 0.00236 foot/°F.................................. meter/kelvin 0.54864
British thermal unit........... joule 1055.1 foot/hour.............................. meter/hour 0.30480
British thermal unit........... kilojoule 1.05506 foot/hour.............................. millimeter/second 0.08467
British thermal unit........... watt-hour 0.29288 foot/minute.......................... centimeter/second 0.50800
Btu/bhp-hour...................... watt/kilowatt 0.39301 foot/minute.......................... meter/minute 0.30480
Btu/foot3.............................. kilojoule/meter3 37.259 foot/minute.......................... meter/second 0.00508
Btu/foot3.............................. kilowatt-hour/meter3 0.01035 foot/second.......................... meter/second 0.30480
Btu/U.S. gallon................... kilojoule/meter3 278.716 foot/second 2........................ meter/second 2 0.30480
Btu/U.S. gallon................... kilowatt-hour/meter3 0.07742 foot2..................................... centimeter2 929.030
Btu/hour.............................. watt 0.29307 foot2..................................... meter2 0.09290
Btu/minute.......................... watt 17.5843 foot2/hour............................ millimeter2/second 25.8064
Btu/second.......................... kilowatt 1.05506 foot2/second........................ millimeter2/second 92.9030
Btu/hour-foot2.................... watt/meter2 3.15459 foot3..................................... decimeter3 28.3169
Btu/hour-foot3.................... watt/meter3 10.3497 foot3..................................... meter3 0.02832
Btu/hr-foot2-°F................... watt/meter2-kelvin 5.67826 foot3/day.............................. decimeter3/second 0.00033
Btu/second-foot3-°F........... kilowatt/meter2-kelvin 20.4418 foot3/day.............................. meter3/day 0.02832
Btu/hour-foot3-°F............... watt/meter3-kelvin 18.62950 foot3/day.............................. meter3/hour 0.00118
Btu/second-foot3-°F........... kilowatt/meter3-kelvin 67.0661 foot3/foot............................. meter3/meter 0.09290
Btu/hour-foot2-°F/foot...... watt/meter-kelvin 1.73074 foot3/hour............................ decimeter3/second 0.00787
Btu/hour-foot2-°F/inch..... watt/meter-kelvin 0.14428 foot3/hour............................ meter3/hour 0.02832
Btu/second-foot2- °F/inch watt/meter-kelvin 519.220 foot3/minute........................ decimeter3/second 0.47195
Btu/pound mass.................. joules/gram 2.32600 foot3/minute........................ meter3/minute 0.02832
Btu/pound mass.................. watt-hour/kilogram 0.64611 foot3/pound......................... meter3/kilogram 0.06243
Btu/pound mol.................... joules/mol 2.32600 foot3/pound mol.................. meter3/kilomol 0.06243
Btu/pound-°F...................... joules/gram-kelvin 4.18680 foot3/second........................ meter3/second 0.02832

General Conversion Factors

footcandle........................... lux 10.0764 kilometer/hour.................... mile/hour statute 0.62137
footcandle-second............. lux-second 10.0764 kilowatt-hour...................... kilojoule 3600.0
foot-pound force................ joule 1.35582 kilowatt-hour...................... megajoule 3.60000
foot-pound/U.S. gallon..... kilojoule/meter3 0.35817 knot...................................... kilometer/hour 1.85200
foot-pound/minute............. milliwatt 22.5970 lambert................................. candela/meter2 3183.1
foot-pound/minute............. watt 0.0226 link....................................... meter 0.20117
foot-pound/second............. watt 1.35582 meter.................................... foot 3.28084
gallon U.S. liquid............... meter3 0.00379 meter2................................... foot2 10.7639
gallon U.S./foot.................. meter3/meter 0.01242 meter3................................... barrel (42 U.S. gal) 6.28981
gallon U.S./horsepower-hr decimeter3/megajoule 1.41009 meter3................................... foot3 35.3147

gallon U.S./horsepower-hr millimeter3/joule 1.41009 meter/minute....................... foot/minute 3.28084
gallon U.S./1000 barrel..... centimeter3/meter3 23.8095 meter3/minute..................... gallon U.S./minute 264.172
gallon U.S./foot3................. decimeter3/meter3 133.681 micron.................................. micrometer 1.00000
gallon U.S./hour................. decimeter3/second 0.00105 mil........................................ micrometer 24.4000
gallon U.S./hour................ meter3/hour 0.00379 mile, nautical...................... kilometer 1.85200
gallon U.S./mile................. decimeter3/100 km 235.215 mile U.S. statute................. kilometer 1.60934
gallon U.S./minute............. decimeter3/second 0.06309 mile2 U.S. statue................. kilometer2 2.58999
gallon U.S./minute............. meter3/hour 0.22712 mile (U.S. stat.)/U.S. gal... kilometer/decimeter3 0.42514
gallon U.S./ton U.S............ decimeter3/tonne 4.1727 mile (U.S. stat.)/hour......... kilometer/hour 1.60934
grain..................................... milligram 64.7989 minute (angle)..................... radian 0.00029
grain/gallon U.S................. gram/meter3 17.1181 newton................................. pound force avg. 0.22481
grain/100 foot3.................... milligram/meter3 22.8835 ounce force avg.................. newton 0.27801
horsepower.......................... kilowatt 0.7457 ounce mass avg................... gram 28.3495
horsepower (boiler)............ kilowatt 9.8095 ounce mass avg................... kilogram 0.02835
horsepower/foot3................ kilowatt/meter3 26.3341 ounce U.S. fluid.................. centimeter3 29.5735
horsepower-hour................ kilowatt/hour 0.7457 ounce troy............................ gram 31.1035
horsepower-hour................ megajoule 2.68452 part/million (volume)........ centimeter3/meter3 1.00000
inch...................................... centimeter3/meter3 2.54 pascal................................... pound force/foot2 0.02089
inch...................................... millimeter3/joule 25.4 pascal................................... pound force/inch 2 0.00015
inch...................................... pica 6.0225 pica....................................... centimeter 0.42175
inch...................................... point 72.27 pica....................................... inch 0.16604
inch Hg (60oF).................... kilopascal 3.37685 pint U.S. dry........................ decimeter3 0.55061
inch H 2O (60oF).................. kilopascal 0.24884 pint U.S. liquid................... decimeter3 0.47318
inch/minute......................... centimeter/minute 2.54 point..................................... centimeter 0.03515
inch/second......................... centimeter/second 2.54 point..................................... inch 0.01384
inch/second......................... millimeter/second 25.4 pound force......................... newton 4.44822
inch/year.............................. millimeter/annum 254000 pound mass avg.................. kilogram 0.45359
inch 2..................................... centimeter2 6451630 pound mass troy................ kilogram 0.37324
inch 2..................................... millimeter2 645160 pound mol........................... kilomol 0.45359
inch 2/second........................ millimeter2/second 6145160 pound force/foot2............... pascal 47.8803
inch3..................................... centimeter3/meter3 16.3871 pound force/inch 2............... kilopascal 6.89476
inch4..................................... centimeter4 41.6231 pound force/inch 2/foot...... kilopascal/meter 22.6206
joule...................................... British thermal unit 0.00095 pound mass/barrel............. gram/decimeter3 2.85301
joule...................................... foot-point force 0.73756 pound mass/barrel............. kilogram/meter3 2.85301
kilogram.............................. pound mass avg. 2.20462 pound mass/foot................. kilogram/meter 1.48816
kilogram/meter3................. pound mass/foot3 0.06243 pound mass/foot2............... kilogram/meter2 4.88243
APPENDIX B 383

pound mass/foot3................ kilogram/foot3 16.0185 ton mass U.S./day............... kilogram/second 0.0105
pound mass/U.S. gallon.... gram/centimeter3 0.11983 ton mass U.S./hour............ kilogram/second 0.2512
pound mass/U.S. gallon.... kilogram-decimeter3 0.11983 ton mass U.S./minute........ kilogram/second 15.1197
pound mass/horsepower-hr. kilogram/kilowatt-hour 0.60828 ton mass U.S./year............. tonne-annum 0.90718
pound mass/horsepower-hr. kilogram/megajoule 0.16897 ton mass U.S./foot2............ tonne/meter2 9.76486
pound mass/horsepower-hr. milligram/joule 0.16897 torr........................................ pascal 133.322
pound mass/hour................ tonee/day 0.45359 watt...................................... Btu/minute 0.05687
pound mass/minute............ kilogram/minute 0.45359 watt...................................... joule/second 1.00000
pound mass/second............ kilogram/second 0.45359 watt-hour............................. joule 3600.0
pound mass/hour-foot....... gram/second-meter 0.41338 watt-second......................... joule 1.00000

pound mass/second-foot... kilogram/second-meter 1.48816 yar........................................ meter 0.91440
pound mass/second-foot... pascal-second 1.48816 yare2.................................... meter2 0.83613
pound mass/second-foot2.. kilogram/second-meter2 4.88243 yard 3..................................... meter3 0.76455
pound mol........................... kilomal 0.45359 year...................................... annum 1.00000
pound mol/foot3.................. kilomol/meter3 16.0185
pound mol/U.S. gallon...... kilomol/meter3 119.826 This times this give this
pound mol/hour.................. kilomol/hour 0.45359 Acre......................... 43560 sq. ft.
pound mol/second.............. kilomol/second 0.45359 Acre-feet................. 7757.8 bbl (42 gal)
pound force-foot................. joule 1.35582 Acre-feet................. 43560 cu. ft.
pound force-foot................. newton-meter 1.35582 Ampere-hours........ 3600 Coulombs
pound force-inch................ joule 0.11298 Angstroms.............. 0.0001 Microns
pound force-inch................ newton-meter 0.11298 Atm. At 32°F.......... 33.90 ft. of water
pound fource-foot2............. kilogram-meter2 0.04214 Atm. At 32°F.......... 1034 g./sq/cm
pound force-foot/inch........ newton-meter/meter 53.3787 Atm. At 32°F.......... 29.92 in. Hg
pound force-foot/inch........ newton-meter/meter 4.44822 Atm. At 32°F.......... 760.18 mm. Hg
pound force-foot/inch 2...... joule/centimeter 0.00210 Atm. At 32°F.......... 14.697 psi.
pound force-foot/second... kilogram-meter/second 0.13826 Bbl (42 gal)............. 5.6146 cu. ft.
pound force-second/foot2. pascal-second 47.8803 Bbl (42 gal)............. 9702.03 cu. In.
quart U.S............................. decimeter3 0.94635 Bbl/day (42 gal)...... 1.75 g.p.h.
radian (angle)...................... degree 57.2958 Bbl/day (42 gal)...... 0.0292 g.p.m.
radian (angle)...................... revolution 0.15915 Bbl/hr (42 gal)........ 0.0936 cu. ft./min.
radian (angle)/minute........ revolution/minute 0.15915 Bbl/hr (42 gal)........ 0.7 g.p.m.
°Rankine.............................. kelvin 0.55556 Board feet............... 144.0 cu. In.
revolution............................ radian (angle) 6.28319 Btu........................... 778 ft.-lb
revolution /minute.............. radian/minute 6.28319 Btu........................... 252 gram-cal.
section.................................. hectare 258.999 Btu........................... 0.0003927 hp.-hr
therm.................................... megajoule 105.506 Btu........................... 0.0002928 kw.-hr.
ton force U.S....................... kilonewton 8.89644 Btu/min................... 46681.68 ft.-lb/hr.
ton mass U.S. short............ kilogram 907.185 Btu/min................... 778 ft.-lb/min.
ton mass U.S. short............ tonne 0.90718 Btu/min................... 12.967 ft.-lb/sec.
tonne.................................... kilogram 1000.0 Btu/min................... 0.02356 hp.
tonne.................................... megagram 1.00000 Btu/min................... 0.01758 kw.
ton force U.S./foot2........... megapascal 0.09576 Btu/sec.................... 46681.68 ft.-lb/min.
ton force U.S./inch 2........... megapascal 13.7895 Btu/sec.................... 778 ft.-lb/sec.
ton force U.S./mile............. megajoule 14.3174 Btu/sec.................... 1.4146 hp.
ton mass U.S./day............... tonne/hour 0.03780 Btu/sec.................... 1.05487 kw.
ton mass U.S./hour............. tonne/day 0.90718 Bushels (U.S. std.). 1.2445 cu. ft.

This times this give this This times this give this
Bushels (U.S. std.). 2150 cu. In. Dyne-cm................. 7.3760000000E-08 ft.-lb.
Candles/sq. in......... 452.39 ft.-Lamberts Dyne-cm................. 0.0010197 g.-cm.
Candles/sq. in......... 0.48695 Lamberts Ems.......................... 0.1666 in.
Candlepower (sph.) 12.566 lumens Ergs......................... 1 dyne-cm.
Carat (Intl.)............. 3.08647 grains Faradays.................. 26.8 amp.-hr.
Carat (Intl.)............. 0.2 g. Fathoms................... 6 ft.
Carat (Intl.)............. 200 mg. Feet.......................... 30.48 cm.
Centimeters............ 0.03281 ft. Feet.......................... 0.16667 fathoms
Centimeters............ 0.3937 in. Hg Feet.......................... 0.000164468 mile(U.S. naut.)
Centimeters............ 393.7 mils Feet.......................... 0.000189394 mile(U.S. stat.)

Cm. of mercury...... 0.01316 atm. Feet per minute...... 0.5080 cm./sec.
Cm. of mercury...... 0.4461 ft. of water Feet per minute...... 0.00987 knots/hr.
Cm. of mercury...... 27.85 lb./sq. ft. Feet per minute...... 0.01136 m.p.h.
Cm. of mercury...... 0.1934 psi. Feet per second...... 0.68121 m.p.h.
Cm. per second...... 1.9685 ft./min. Feet per second...... 0.01136 miles/min.
Cm. per second...... 0.03281 ft./sec. Feet of water........... 0.02950 atm.
Cm. per second...... 0.02237 m.p.h. Feet of water........... 0.4335 psi.
Centipoise............... 1.0000 g./cm.-sec Foot-Candles.......... 1 lumens/sq. ft.
Centipoise............... 0.00067197 lb./ft.-sec. Foot-Lamberts....... 0.0022105 candles/sq. in.
Circular mils.......... 0.7854 sq. mils Foot-Lamberts....... 1 lumens/sq. ft.
Coulombs................ 0.1 Abcoulombs Foot-pounds............ 0.0012853 Btu.
Coulombs................ 0.0002778 amp.-hr. Foot-pounds............ 0.000000505 hp-hr
Cubic centimeters.. 0.00003531 cu. Ft. Foot-pounds............ 1.35582 joules
Cubic centimeters.. 0.0002642 gal. (U.S. Liq.) Foot-pounds............ 0.003241 kg.-cal
Cubic centimeters.. 0.001 liters Foot-pounds............ 3.766E-07 kw.-hr.
Cubic feet................ 0.00002296 acre-ft. Foot-pounds/hour.. 0.001284 Btu/hr.
Cubic feet................ 0.1781 bbl. (42 gal) Foot-pounds/hour.. 0.00002141 Btu/min.
Cubic feet................ 0.80356 bu. Foot-pounds/hour.. 0.000000357 Btu/sec.
Cubic feet................ 28320 cc. Foot-pounds/hour.. 0.01666 ft.-lb./min.
Cubic feet................ 1728 cu. In. Foot-pounds/hour.. 0.000000505 hp.
Cubic feet................ 7481 gal. (U.S. Liq.) Foot-pounds/hour.. 3.766E-07 kw.
Cubic feet................ 28.32 liters Foot-pounds/min... 0.077118 Btu/hr.
Cu. ft., million....... 22.95 acre-ft. Foot-pounds/min... 0.001286 Btu/min.
Cu. ft. per min........ 10.686 bbl. (42 gal)/hr. Foot-pounds/min... 0.0000303 hp.
Cu. ft. per min........ 0.1781 bbl. (42 gal)/min. Foot-pounds/min... 0.00002256 kw.
Cu. ft. per min........ 1440 cu. Ft./day Foot-pounds/sec... 0.001285 Btu/sec.
Cu. ft. per min........ 7481 g.p.m. (U.S. liq.) Foot-pounds/sec... 0.001818 hp.
Cubic inches........... 0.000465 bu. Furlong.................... 660 ft.
Cubic inches........... 16.39 cc. Gal. (U.S. dry)........ 0.15556 cu. ft.
Cubic inches........... 0.0005787 cu. Ft. Gal. (U.S. dry)........ 1.637 gal. (U.S. liq)
Cubic inches........... 0.004329 gal. (U.S. Liq.) Gal. (U.S. liquid)... 0.02381 bbl. (42 gal)
Cubic inches........... 0.016387 liters Gal. (U.S. liquid)... 0.133681 cu.ft
Degrees of arc........ 60 minutes Gal. (U.S. liquid)... 231 cu. in.
Degrees of arc........ 0.017453 radians Gal. (U.S. liquid)... 0.859365 gal. (U.S. dry)
Dynes...................... 0.0010197 g. Gal. (U.S. liquid)... 3.7854 liters
Dynes...................... 0.000002248 lb. Gal. /hr. (U.S. liq.). 0.1337 cu. ft./hr
Dyne-cm................. 1 ergs Gal. /hr. (U.S. liq.). 0.002228 cu.ft./min.
APPENDIX B 385
This times this give this This times this give this
Gal./hr. (U.S. liq.). 0.01666 gpm,. (U.S. liq.) Knots....................... 101.34 ft/min
G.p.m. (U.S. liq.).... 34.2857 bbl/day (42 gal.) Knots....................... 1.152 m.p.h. (U.S. stat.)
G.p.m. (U.S. liq.).... 1.4286 bbl/hr. (42 gal.) Liters....................... 1000 cc
G.p.m. (U.S. liq.).... 0.02381 bbl/min (42 gal.) Liters....................... 0.03531 cu. ft.
G.p.m. (U.S. liq.).... 192.49 cu.ft./day Liters....................... 61.0271 cu. in.
G.p.m. (U.S. liq.).... 0.1337 cu. ft./min. Liters....................... 0.264 18 gal. (U.S. liq.)
G.p.m. (U.S. liq.).... 1440 gal/day Liters....................... 1.057 qt. (U.S. liq.)
Grains..................... 0.00014286 lb., avoir. Logarithm, com..... 2.3026 logarithm, Nap.
Grains/gal. (U.S. liq.) 0.01714 g/l. Logarithm, Nap..... 0.4343 logarithm, com
Grains/gal. (U.S. liq.) 17.118 ppm. Meters..................... 3.2808 ft.
Grams..................... 980.7 dynes Meters..................... 39.37 in.

Grams..................... 0.035274 oz., avoir. Meters..................... 1 000 000 microns
Grams..................... 0.0022046 lb., avoir Microns................... 10 000 angstroms
Grams-Calories..... 0.003968 Btu Microns................... 0.000 039 37 in.
Grams-Calories..... 3.0875 ft.-lb. Microns................... 0.001 mm
Grams per liter....... 58.418 grains/gal Mils......................... 0.002 54 cm
Grams per liter....... 1000 ppm, Mils......................... 0.001 in.
Grams per liter....... 0.0624 lb/cu. ft. Mils......................... 25.4 microns
Horsepower............ 2544 Btu/hr Miles (U.S. stat.).... 5280 ft.
Horsepower............ 42.44 Btu/min Miles (U.S. stat.).... 1.6093 km.
Horsepower............ 33 000 ft-lb/min Miles (U.S. naut.)... 6080 ft.
Horsepower............ 550 ft-lb/sec Miles per hour........ 44.704 cm/sec
Horsepower............ 745.70 joules/sec Miles per hour........ 88 ft/min
Horsepower............ 0.745 70 kw Miles per hour........ 1.4667 ft/sec
Horsepower-hours. 2544 Btu Miles per hour........ 0.016 66 miles/min
Horsepower-hours. 1 980 000 ft-lb Milliliters................ 0.061 cu. in.
Horsepower-hours. 0.7457 kw-hr Millimeters............. 0.039 37 in.
Inches...................... 2.54 cm Millimeters............. 39.37 mils
Inches...................... 0.08333 ft Minutes of arc........ 0.016 667 deg. of arc
Inches...................... 25 400.05 microns Ounces (avoir.)....... 28.35 g
Inches...................... 1000 mils Parts per million.... 0.053 85 grains/gal
Inches of Mercury. 0.03242 atm Parts per million.... 0.001 g/l
Inches of Mercury. 0.49116 psi Points...................... 0.013 889 in.
Joules...................... 0.000 948 6 Btu Pounds, avoir.......... 444 823 dynes
Joules...................... 0.239 ft-lb Pounds, avoir.......... 7000 grains
Joules...................... 0.737 56 ft-lb Pounds, avoir.......... 453.59 g
Kilograms............... 2.205 lb., avoir. Pounds, avoir.......... 1.215 lb., Troy, Apoth
Kilograms-calories 3.9683 Btu Pounds per gallon.. 7.4085 lb./cu. ft.
Kilograms-calories 3087.5 ft-lb Pounds per cu. ft.... 0.016 018 g/cc
Kilowatts................ 56.92 Btu/min Pounds per cu. ft.... 0.133 68 lb/gal (U.S. liq.)
Kilowatts................ 0.948 Btu/sec Pounds per sq. in... 0.068 04 atm
Kilowatts................ 44 253 ft-lb/min Pounds per sq. in... 5.1715 cm. Hg
Kilowatts................ 1.341 hp Pounds per sq. in... 2.307 ft. of water
Kilowatts hours...... 3415 Btu Pounds per sq. in... 2.036 in. Hg
Kilowatts hours...... 2 655 199 ft-lb Pounds per sq. in... 144 lb/sq. ft.
Kilowatts hours...... 1341 hp-hr Quarts..................... 0.946 liters
Knots (naut. mile).. 6080 ft Radians................... 57.2958 deg. of arc
Knots (naut. mile).. 1.152 mile (U.S. stat.) Radians per sec...... 9.549 r.p.m.

This times this give this

Rods........................ 16.5 ft.
Rods........................ 5.5 yd
Sections................... 640 acres
Sections................... 1 sq. mile
Square feet.............. 0.000 022 96 acres
Square feet.............. 144 sq. in.
Square mils............. 1.2732 circular mils
Township................ 23 040 acres
Township................ 36 sections
Township................ 36 sq. miles
Vara......................... 2.7777 ft.
APPENDIX B 387
Temperature Temperature Temperature Temperature Temperature
oC oC or oF oF oC oC or oF oF oC oC or oF oF oC oC or oF oF oC oC or oF oF
-459.69 to -4 -3 to 83 84 to 800 810 to 1670 1680 to 3000

-273.16 -459.69 -19.44 -3 26.6 28.9 84 183.2 432.2 810 1490 915.6 1680 3056.0
-267.78 -450 -18.89 -2 28.4 29.4 85 185.0 437.8 820 1508.0 921.1 1690 3074.0
-262.22 -440 -18.33 -1 30.2 30.0 86 186.8 443.3 830 1526.0 926.7 1700 3092.0
-256.67 -430 -17.8 0 32.0 30.6 87 188.6 448.9 840 1544.0 932.2 1710 3110.0
-251.11 -420 -17.2 1 33.8 31.1 88 190.4 454.4 850 1562.0 937.8 1720 3128.0
-245.56 -410 -16.7 2 35.6 31.7 89 192.2 460.0 860 1580.0 943.3 1730 3146.0
-240.00 -400 -16.1 3 37.4 32.2 90 194.0 465.6 870 1598.0 948.9 1740 3164.0
-234.44 -390 -15.6 4 39.2 32.8 91 195.8 471.1 880 1616.0 954.4 1750 3182.0
-228.89 -380 -15.0 5 41.0 33.3 92 197.6 476.7 890 1634.0 960.0 1760 3200.0
-223.33 -370 -14.4 6 42.8 33.9 93 199.4 482.2 900 1652.0 965.6 1770 3218.0
-217.78 -360 -13.9 7 44.6 34.4 94 201.2 487.8 910 1670.0 971.1 1780 3236.0
-212.22 -350 -13.3 8 46.4 35.0 95 203.0 493.3 920 1688.0 976.7 1790 3254.0
-206.67 -340 -12.8 9 48.2 35.6 96 204.8 498.9 930 1706.0 982.2 1800 3272.0
-201.11 -330 -12.2 10 50.0 36.1 97 206.6 504.4 940 1724.0 987.8 1810 3290.0
-195.56 -320 -11.7 11 51.8 36.7 98 208.4 510.0 950 1742.0 993.3 1820 3308.0
-190.00 -310 -11.1 12 53.6 37.2 99 210.2 515.6 960 1760.0 998.9 1830 3326.0
-184.44 -300 -10.6 13 55.4 37.8 100 212.0 521.1 970 1778.0 1004.4 1840 3344.0
-178.89 -290 -10.0 14 57.2 43.3 110 230.0 526.7 980 1796.0 1010.0 1850 3362.0
-173.33 -280 -9.44 15 59.0 48.9 120 248.0 532.2 990 1814.0 1015.6 1860 3380.0
-169.53 -273.16 -459.7 -8.89 16 60.8 54.4 130 266.0 537.8 `1000 1832.0 1021.1 1870 3398.0
-168.89 -272 -457.6 -8.33 17 62.6 60.0 140 284.0 543.3 1010 1850.0 1026.7 1880 3416.0
-167.78 -270 -454.0 -7.78 18 64.4 65.6 150 302.0 548.9 1020 1868.0 1032.2 1890 3434.0
-162.22 -260 -436.0 -7.22 19 66.2 71.1 160 320.0 554.4 1030 1886.0 1037.8 1900 3452.0
-156.67 -250 -418.0 -6.67 20 68.0 76.7 170 338.0 560.0 1040 1904.0 1043.3 1910 3470.0
-151.11 -240 -400.0 -6.11 21 69.8 82.2 180 356.0 565.6 1050 1922.0 1048.9 1920 3488.0
-145.56 -230 -382.0 -5.56 22 71.6 87.8 190 374.0 571.1 1060 1940.0 1054.4 1930 3506.0
-140.00 -220 -364.0 -.500 23 73.4 93.3 200 392.0 576.7 1070 1958.0 1060.0 1940 3524.0
-134.44 -210 -346.0 -4.44 24 75.2 98.9 210 410.0 582.2 1080 1976.0 1065.6 1950 3542.0
-128.89 -200 -328.0 -3.89 25 77.0 104.4 220 428.0 587.8 1090 1994.0 1071.1 1960 3560.0
-123.33 -190 -310.0 -3.33 26 78.8 110.0 230 446.0 593.3 1100 2012.0 1076.7 1970 3578.0
-117.78 -180 -292.0 -2.78 27 80.6 115.6 240 464.0 598.9 1110 2030.0 1082.2 1980 3596.0
-112.22 -170 -274.0 -2.22 28 82.4 121.1 250 482.0 604.4 1120 2048.0 1087.8 1990 3614.0
-106.67 -160 -256.0 -1.67 29 84.2 126.7 260 500.0 610.0 1130 2066.0 1093.3 2000 3632.0
-101.11 -150 -238.0 -1.11 30 86.0 132.2 270 518.0 615.6 1140 2084.0 1098.9 2010 3650.0
-95.56 -140 -220.0 -0.56 31 87.8 137.8 280 536.0 621.1 1150 2102.0 1104.4 2020 3668.0
-90.00 -130 -202.0 0 32 89.6 143.3 290 554.0 626.7 1160 2120.0 1110.0 2030 3686.0
-84.44 -120 -184.0 0.56 33 91.4 148.9 300 572.0 632.2 1170 2138.0 1115.6 2040 3704.0
-78.89 -110 -168.0 1.11 34 93.2 154.4 310 590.0 637.8 1180 2156.0 1121.1 2050 3722.0
-73.33 -100 -148.0 1.67 35 95.0 160.0 320 608.0 643.3 1190 2174.0 1126.7 2060 3740.0
-70.56 -95 -139.0 2.22 36 96.8 165.6 330 626.0 648.9 1200 2192.0 1132.2 2070 3758.0
-67.78 -90 -130.0 2.78 37 98.6 171.1 340 644.0 654.4 1210 2210.0 1137.8 2080 3776.0
-65.00 -85 -121.0 3.33 38 100.4 176.7 350 662.0 660.0 1220 2228.0 1143.3 2090 3794.0
-62.22 -80 -112.0 3.89 39 102.2 182.2 360 680.0 665.6 1230 2246.0 1148.9 2100 3812.0
-59.45 -75 -103.0 4.44 40 104.0 187.8 370 698.0 671.1 1240 2264.0 1154.4 2110 3830.0
-56.67 -70 -94.0 5.00 41 105.8 193.3 380 716.0 676.7 1250 2282.0 1160.0 2120 3848.0
-53.89 -65 -85.0 5.56 42 107.6 198.9 390 734.0 682.2 1260 2300.0 1165.6 2130 3866.0
-51.11 -60 -76.0 6.11 43 109.4 204.4 400 752.0 687.8 1270 2318.0 1171.1 2140 3884.0
-48.34 -55 -67.0 6.67 44 111.2 210.0 410 770.0 693.3 1280 2336.0 1176.7 2150 3902.0
-45.56 -50 -58.0 7.22 46 113.0 215.6 420 788.0 698.9 1290 2354.0 1182.2 2160 3920.0
-42.78 -45 -49.0 7.78 46 114.8 221.1 430 806.0 704.4 1300 2372.0 1187.8 2170 3938.0
-40.00 -40 -40.0 8.33 47 116.6 226.7 440 824.6 710.0 1310 2390.0 1193.3 2180 3956.0
-39.45 -39 -38.2 8.89 48 118.4 232.2 450 842.0 715.6 1320 2408.0 1198.9 2190 3974.0
-38.89 -38 -36.4 9.44 49 120.2 237.8 460 860.0 721.1 1330 2426.0 1204.4 2200 3992.0
-38.34 -37 -34.6 10.0 50 122.0 243.3 470 878.0 726.7 1340 2444.0 1210.0 2210 4010.0
-37.78 -36 -32.8 10.6 51 123.8 248.9 480 896.0 732.2 1350 2462.0 1215.6 2220 4028.0
-37.23 -35 -31.0 11.1 52 125.6 254.4 490 914.0 737.8 1360 2480.0 1221.1 2230 4046.0
-36.67 -34 -29.2 11.7 53 127.4 260.0 500 932.0 743.3 1370 2498.0 1226.7 2240 4064.0
-36.12 -33 -27.4 12.2 54 129.2 265.6 510 950.0 748.9 1380 2516.0 1232.2 2250 4082.0
-35.56 -32 -25.6 12.8 55 131.0 271.1 520 968.0 754.4 1390 2534.0 1237.8 2260 4100.0
-35 -31 -23.8 13.3 56 132.8 276.7 530 986.0 760.0 1400 2552.0 1243.3 2270 4118.0
-34.44 -30 -22.0 13.9 57 134.6 282.2 540 1004.0 765.6 1410 2570.0 1248.9 2280 4136.0
-33.89 -29 -20.2 14.4 58 136.4 287.8 550 1022.0 771.1 1420 2588.0 1254.4 2290 4154.0
-33.33 -28 -18.4 15.0 59 138.2 293.3 560 1040.0 776.7 1430 2606.0 1260.0 2300 4172.0
-32.78 -27 -16.6 15.6 60 140.0 298.9 570 1058.0 782.2 1440 2624.0 1265.6 2310 4190.0
-32.22 -26 -14.8 16.1 61 141.8 304.4 580 1076.0 787.8 1450 2642.0 1271.1 2320 4208.0
-31.67 -25 -13.0 16.7 62 143.6 310.0 590 1094.0 793.3 1460 2660.0 1276.7 2330 4226.0
-31.11 -24 -11.2 17.2 63 145.4 315.6 600 1112.0 798.9 1470 2678.0 1282.2 2340 4244.0
-30.56 -23 -9.4 17.8 64 147.2 321.1 610 1130.0 804.4 1480 2696.0 1287.8 2350 4262.0
-30.00 -22 -7.6 18.3 65 149.0 326.7 620 1148.0 810.0 1490 2714.0 1293.3 2360 4280.0
-29.45 -21 -5.8 18.9 66 150.8 332.2 630 1166.0 815.6 1500 2732.0 1298.9 2370 4298.0
-28.89 -20 -4.0 19.4 67 152.6 337.8 640 1184.0 821.1 1510 2750.0 1304.4 2380 4316.0
-28.34 -19 -2.2 20.0 68 154.4 343.3 650 1202.0 826.7 1520 2768.0 1310.0 2390 4334.0
-27.78 -18 -0.4 20.6 69 156.2 248.9 660 1220.0 832.2 1530 2786.0 1343.3 2450 4442.0
-27.23 -17 1.4 21.1 70 158.0 354.4 670 1238.0 837.8 1540 2804.0 1371.1 2500 4532.0
-26.67 -16 3.2 21.7 71 159.8 360.0 680 1256.0 843.3 1550 2822.0 1398.9 2550 4622.0
-26.12 -15 5.0 22.2 72 161.6 365.6 690 1274.0 848.9 1560 2840.0 1426.7 2600 4712.0
-25.56 -14 6.8 22.8 73 163.4 371.1 700 1292.0 854.4 1570 2858.0 1454.4 2650 4802.0
-25.00 -13 8.6 23.3 74 165.42 376.7 710 1310.0 860.0 1580 2876.0 1482.2 2700 4892.0
-24.44 -12 10.4 23.9 75 167.0 382.2 720 1328.0 865.6 1590 2894.0 1510.0 2750 4982.0
-23.89 -11 12.2 24.4 76 168.8 387.8 730 1346.0 871.1 1600 2912.0 1537.8 2800 5072.0
-23.33 -10 14.0 25.0 77 170.6 393.3 740 1364.0 876.7 1610 2930.0 1565.1 2850 5162.0
-22.78 -9 15.8 25.6 78 172.4 398.9 750 1382.0 882.2 1620 2948.0 1593.3 2900 5252.0
-22.22 -8 17.6 26.1 79 174.2 404.4 760 1400.0 887.8 1630 2966.0 1621.1 2950 5342.0
-21.67 -7 19.4 26.7 80 176.0 410.0 770 1418.0 893.3 1640 2984.0 1648.9 3000 5432.0
-21.11 -6 21.2 27.2 81 177.8 415.6 780 1436.0 898.9 1650 3002.0
-20.56 -5 23.0 27.8 82 179.6 421.1 790 1454.0 904.4 1660 3020.0
-20.00 -4 24.8 28.3 83 181.4 426.7 800 1472.0 910.0 1670 3038.0

APPENDIX C – THERMODYNAMIC DATA
THERMODYNAMIC DATA
Both SI and FPS unit data are shown. The H-S diagram for steam is from the reference shown in
the title block.

All other P-H diagrams, and the thermodynamic data tables have been generated from the REFPROP
software developed by the National Institute of Standards and Technology.
APPENDIX C 389
390
Enthalpy - Entropy Diagram
For Steam - SI
Prepared by: D. C. Hickson and F. R. Taylor
and drawn by: E. A. Ayers
Source of data: National Engineering Laboratory, Steam Tables 1964

(by courtesy of the Controller of Her Majesty’s Stationery Office).
For use with: Thermodynamic and Transport Properties of fluids,
arranged by Y. R. Mayhew and G. F. C. Rogers.
THERMODYNAMIC DATA
APPENDIX C — THERMODYNAMIC DATA

g-K
30
20
J/k
°C
k
°C
10
-20
2.5
°C
°C
10 000
³ ³ ³ ³
³
120
³
³
³
/m
³
³
³
m /m g/m g/m / m³ °C
³
/
m³
8000 80 k 60 kg
/m
/m³
110
kg g /m 0 kg 20 kg 100 k
1
g
k
kg ³
kg/m
k 14
kg/
kg/m
kg/m
80 60 °C
kg/m
0
0
0k
1 1
0k
100°
³
20 g/m
26
22 /m³
6000 C
340
280
320
24 g/m³
360
40 kg/m
380 kg
300
90°C
APPENDIX C
400 kg/m³
440 kg/m³
420 kg/m
5000
80°C
70°C
60°C
4000
50°C
-90°C 20 kg/m³
40°C
3000
30°C
20°C
-100°C
10°C
0°C
-10°C
2000
-20°C
-110°C 10 kg/m³
-30°C
-80
-50°
°
-40°C
-70
C
C
-60°C
8 kg/m³
°C
g-K
-0.5 kJ/kg-K
-120°C
J/k
6 kg/m³
4k
55
-K
5
1000
44..22
kg
5 kg/m³
g-K
3.7
kg-K
J/
5
800
5k
5
kJ/k
-130°C
4.
3 kJ/
4 kg/m³
3.2
4.7
K
3.5
-0.25
g-
2.75
600
J/k
3 kg/m³
5k
500
/kg-K
-140°C 5
400 5.2
2.5 kJ
K 2 kg/m³
g-
J/k
2.25
Melting Line
300 5k
5.
g-K
5
0 kJ/kg-K
-150°C
5.7
2 kJ/k
200
Pressure (kPa)
-K 1 kg/m³
J /kg
6k
1.75
5
THERMODYNAMIC DATA
-160°C 6.2
100 K
1.5 kJ/kg-K
g- 0.5 kg/m³
kJ /k
Methane Pressure Enthalpy Diagram - SI
80 5
6.
1.25
60 5
6.7
50 -170°C
K 0.25 kg/m³
1 kJ/kg-K
40 k g-
0.75
7 kJ/
30 5
7.2
-K
0.5 kJ/kg-K
kg
5 kJ/
20
0.25
7.
-180°C 5
7.7 K
g-
J/k
Triple Point Line: 11.7 kPa, -182.46 °C 8k 5
8.2
10
10.0
-100
-100. 0.0
0.000 100
100. 200
200. 300
300. 400
400. 500
500. 600
600. 700 800
800. 900
900. 1000
1000. 1100
1100.
"Setzmann, U. and Wagner, W., "A New Equation of State and Tables of Enthalpy (kJ/kg)
391
Thermodynamic Properties for Methane Covering the Range from the Melting Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Line to 625 K at Pressures up to 1000 MPa," J. Phys. Chem. Ref. Data, 20(6):1061-1151, 1991." Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
Reference State: Enthalpy, Entropy = 0 for the saturated liquid at the normal boiling point (NBP) Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (kJ/kg)
³
/f t
³ / f t³
/f t
m
lb
lbm lbm
24
18
/ f t³
22
lbm
3
Specific Entropy = Btu/lbm-°R, Density = lbm/ft , Temperature = °F
280
26
2000
°F
80
392
³
22
240
°F
60
³ /ft /ft³
°F
t³
°
°F
/ft
16
40
m/f
200
0°F
bm lbm 260 F
³
l
180
m 20
°F
10 8 lb
14
°F
/ft
lb 12 °F
0°F
°F
12
0°
14 F
0°F
10
bml
-20
0°F
/ft³
°F /ft³
0°F
16
1000 -40 4 lbm
t³
/ft³
ft³
°F
t³
m
lbm
6 lb -6
0°
/ft³
F
18
800 /ft³ 2 lbm/ft³
bm/
-8 3 lbm
0°
-1 F
20 l
26 lbm/f
-120°F 00
28 lbm/ft³
600
24 lbm/f
°F
22 lbm
500
-140°F
400 1 lbm/ft³
300 -160°F 0.75 lbm/ft³
200 -180°F 0.5 lbm/ft³

0.4 lbm/ft³
-0.1 Btu/lbm-°R
-200°F 0.3 lbm/ft³
100
80 0.2 lbm/ft³
-220°F
60
ting Line
50
Melting
Mel
40 0.1 lbm/ft³
-240°F
30
Pressure (psia)
°RR
20 //llbb
mm--° 0.05 lbm/ft³
ttuu
-260°F
BB
THERMODYNAMIC DATA
1.22
10
Methane Pressure Enthalpy Diagram - FPS
8
--°°R
R
mm
°RR
--°°R
//llbb
bmm
m--°
6
m
/llb
R
ttuu
utu/
-°°RR
--°°R
u//llbb
5
4 BB
Bt
m-
-280°F bmm
bm
8B
1.4
BBttu
u//lbl R
//lbl
RR
R
1..5
-°°R
-°R
°R
utu
4 R Btut mm-
BBt
1.38
78 B
-°R
m-°-°RR
m-°-°RR
m-°R
66
m--°R
m-°-°RR
m--°°R
1. /l/blb
m--°°R
m--°°R
t u
m--°°R
u
1..
t
m-°°R
bm
bm
BB
lbm
/lbm
lbm
/lbbm
/lbm
/lb
//llbbm
/lb
3 1..88
u/l/lb
tu/l/lb
/lbm-°R
tu//llbbm
tu/l/lbm-°
tu/lb
u//llb
Btu/l
8 BBtutu
Btu/lbm
1
3 BBtu
.
8 Bttu
.6 BBtu
.
.7 Bttu
.5 BBtu
8 Bttu
1 BBttu
0.2Btu
1
0.8
0.6
0.
0.2
0 Btu
0.1 Btu/lb
0.8
0.8
00.8
00..8
00.4.4 BBtu
00..9
2 m -°R
Triple Point Line: 1.7 psia, -296.42 °F /lb
Btu
1.9
-300 °F
1
-50 0 50 100 150 200 250 300 350 400 450
"Setzmann, U. and Wagner, W., "A New Equation of State and Tables of
Thermodynamic Properties for Methane Covering the Range from the Melting Enthalpy (Btu/lbm) Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Line to 625 K at Pressures up to 1000 MPa," J. Phys. Chem. Ref. Data, 20(6):1061-1151, 1991." Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National

-90 °C
100 °C
10 000
17
13 14 16 0°
12 C
/m³
11 0 15 0°
8000 0 0° 0° C
-90 °C
-80 °C
C C
-70 °C
°C 0°
100
°C C
APPENDIX C
³
°C
600 k g
m³
³
³
6000 m³ ³
kg/
g/m
³
kg/
/m
k kg/m
kg/m
150
/m
kg
2 50 200 g/m³
400
100 k
kg
5000
00
450
3
0
35
500 kg/m³
4000
90 °C
g-K
550 kg/m³
³
kJ/k
3000 80 °C 50 kg/m
5
³
1.4
2
40 kg/m
70 °C ³
40 kg/m
2000 60 °C
30 kg/m³
50 °C
40 °C
20 kg/m³
30 °C
1000
-K
800 20 °C
K
J/kg
Pressure (kPa)
kg-
g-K
.65 k
10 kg/m³
kJ/
21
10 °C
5
8
600
.
kJ/k
21
5
g-K
THERMODYNAMIC DATA
2.2
1
kJ/kg-K
g-K
500
J/k
0.2 kJ/kg-K
kJ/kg-K
0 °C
K
0.4 kJ/kg-K
0.5
3k
g--K
0.6 kJ/kg-K
0.5
1 kJ/k
2
Propane Pressure Enthalpy Diagram - SI
400
-K
0.8 kJ/kg-K
-10 °C
.5 kJ/k
5 kg/m³
1.8
300 .5 kJ/kg
1.6
4 kg/m³
-20 °C
200 .5 kJ/kg-K
1.4 3 kg/m³
20 °C
°C
-30 °C -30 °C
110 °C
100 °C
90 °C
60 °C
80 °C
0.5 kJ/kg-K
1.2
50 °C
40 °C
-50 °C
-80 °C
-70 °C
-80 °C
-70 °C
-50 °C
-60 °C
-60 °C
30 °C
10 °C
0 °C
1 kJ/kg-K
70 °C
130 °C
120 °C
-10 °C
-20 °C
-40 °C -40 °C
100
0 100
100. 200
200. 300
300. 400
400. 500
500. 600 700 800
800.
393
III. A Reference Equation of State for Temperatures from the Melting Line to 650 K Enthalpy (kJ/kg) Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Reference State: Enthalpy = 200 kJ/kg, Entropy = 1 kJ/kg•K for the saturated liquid at 0°C Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (kJ/kg)
28
0°
240
F
-60 °F
°F
26
-120 °F
-100 °F
Specific Entropy = Btu/lbm-°R, Density = lbm/ft3, Temperature = °F 0°
F
1000 ³ ³
/ f t³
/f t
t³
32
/ f t³
³ /f t
/ f t³
³
m
/ft³
394
lb ³ /f t lbm
0°
F
/f t
lbm
bm
/f t bm 12 / f t³ 30
m / f t³
lbm
m-°R
800 20 bm
bm
4l
24
bm 1 0°
10 l f t³ F
26 l
8l
22
1 6l m/
34 lbm/ft³
32 lbm/f
30 lbm
tu/lb
28 lb
28
8 lb
0°
F
600 t³
0.6 B
200°F m/f
6 lb
0.15 Btu/lbm-°R
26
500 0°F
180°F ³
m/f t
0.1 Btu/lbm-°R
0.05 Btu/lbm-°R
4 lb
-°R
400
240
160°F
°F
lbm
220
tu/
°F
B
300 140°F
0 .65
36 lbm/ft³
2 lbm/ft³
120°F
38 lbm/ft³
200
100 °F
1 lbm/ft³
80°F
-°R
lbm
60 °F
/
100
Btu
0.7
80 40 °F
³
Pressure (psia)
0.5 lbm/ft
0.4 lbm/ft³
R
60
20 °F
°R-°
50
mlb-m
-°R
t³
-°R
0.3 lbm/f
°R
THERMODYNAMIC DATA
°R
°R
Bt ut/ulb/
lb-m
b-m
mR-°R
Propane Pressure Enthalpy Diagram - FPS
B
m-
40
5
b-°
0 °F
/lb
ut/ulb/lm
tut/lub/m
tu
/lb/lm
Bt
0..555
0
tu
5B
.455BB
m/ft³
0..55B
30
0.7
.4BBtu
0.4
0
0.2 lb
0
0.4
-°R
/lbm-°R
-20 °F
20
0.35 Btu
0.3 Btu/lbm
-40 °F
-°R
0.25 Btu/lbm-°R
0.1 lbm/ft³
-80°F
-60°F
-120°F
-100°F
/ lbm
0.2 Btu/lbm-°R
Btu
0.8
10
0 50 100 150 200 250 300 350
III. A Reference Equation of State for Temperatures from the Melting Line to 650 K

Reference State: Enthalpy = 200 kJ/kg, Entropy = 1 kJ/kg-K for the saturated liquid at 0°C

50 000
³
³
/m ³
g/m
³
40 000 0 kg 250 kg/m
/m
-
0k K
50
0
kJ
kg
g/m³
6 /kg-
0
g-K
³ 300 k
25 120 °C
55
30 000 ³
J/k
g/m
-0.
APPENDIX C
k g/m 0k
0k
40 ³ 200 kg/m³
4 50 g/m
k
3 50
20
19
³
0°
18
20 000 150 kg/m
0°
-110 °C
0
C
15
0
°C
17
0
14
°C
0
13
16
°C
0
°C
1
0°
°C
C
90 11 20 °
°C 0 C 100 kg/m³
80 10 °C
°C 0°
70
°C C
10 000
60
°C
8000 50
°C
40
°C 50 kg/m³
6000 30
°C
20 °
C 40 kg/m³
5000 10 °C
4000 0 °C 30 kg/m³
3000 -10 °C
20 kg/m³
-20 °C
2000
-30 °C
Pressure (kPa)
-40 °C
10 kg/m³
0.25 kJ/kg-K
1000 -50 °C
THERMODYNAMIC DATA
800
-60 °C
5 kg/m³
Ethylene Pressure Enthalpy Diagram - SI
600
4 kg/m³
500 -70 °C
K
kg-
400
kJ/
3 kg/m³
5
2.7
-80 °C
-K
300
/kg
g-K
-K
K
kJ
2 kg/m³
g-
-K
J/k
/ kg
75
J/k
3.
kJ
3k
k
kJ/kg
3.5
-90 °C
3. 2
200
K
g-K
g-K
1.75
g-
/kg-K
/kg-K
K J/ k
g-
/kg-K
kJ/k
kJ/k
kJ/k 5k
4.2
1 kJ/kg-K
2.5
4
2 kJ
1.5 kJ
1 kg/m³
0.75 kJ/kg-K
0.5 kJ/kg-K
2.25
1.25 kJ
-100 °C
100
0 100 200 300 400 500 600 700 800 900 1000
Smukala, J., Span, R. and Wagner, W., "A New Equation of State for Enthalpy (kJ/kg)
395
Ethylene Covering the Fluid Region for Temperatures from the Melting Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Line to 450 K at Pressures up to 300 MPa," J. Phys. Chem. Ref. Data, 29(5):1053-1122, 2000. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
Specific Entropy = Btu/lbm-°R, Density = lbm/ft3, Temperature = °F

10000. 10 000
396
/ft³
/f t
8000 20 lbm
m
³
B
ft / f t³
lb m-°R
m
2
-°R
0
m/
4 tu/lb
0 lb
-0.
lb 3
F
6000 35
/lbm
/ f t³
lbm ³
25
Btu
5000 15 lbm/ft
1
-2
0 .
- 00 °
40
38
4000
0°
36
22
0°
34
F
32
0°
0°
10 lbm/ft³
0°
F
20
F
0°
F
30
F
0°
3000
28
18
26
F
0
°F
16
0°
°F
24
F
0 °F
0°
F
°F
14
0
°F
2000 12
R
0°
10 F 5 lbm/ft³
0°
F
-180 °F
80 4 lbm/ft³
°F
0 Btu/lbm-°
1000
1000. 60 3 lbm/ft³
°F
800
40 °F 2 lbm/ft³
600
500 20 °F
400 0 °F
1 lbm/ft³
300 -20 °F
-40 °F
Pressure (psia)
200
-60 °F 0.5 lbm/ft³
Pressure (psia)
0.4 lbm/ft³
100 -80 °F 0.3 lbm/ft³

THERMODYNAMIC DATA
100.
80
Ethylene Pressure Enthalpy Diagram - FPS
-100 °F 0.2 lbm/ft³

60
50
-°R
m
-°R
40 -120 °F
u /lb
/lbm
Bt
tu
0.1 lbm/ft³
9
0.
-°R
30
7B
bm
0.
-°R
R
t u/l
m-°R
-°R
-°
-°R
-140 °F m
8B
u /lb
0.
tu/lb
/lbm-°R
/lbm
20 Bt
tu/lbm
1
Btu
0.2 Btu/lbm
0.5 B
0.1 Btu/lbm-°R
0.6
0.4 B
0.3 Btu
-°R
-160 °F bm
u/l
Bt
10 1.1
10.0 0 25 50 75 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475
-25.00.000 25.0 50.0 75.0 100. 125. 150. 175. 200.
Smukala, J., Span, R. and Wagner, W., "A New Equation of State for
225. 250. 275. 300. 325. 350. 375. 400. 425. 450.
Ethylene Covering the Fluid Region for Temperatures from the Melting
Line to 450 K at Pressures up to 300 MPa," J. Phys. Chem. Ref. Data, 29(5):1053-1122, 2000. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National

Enthalpy (Btu/lbm)

100 000
³ ³
80 000 kg/m /m³ 550 kg/m ³
900 g/m³ g/m³ 650 kg /m³ 500 kg/m ³
³ 750 k 700 k 600 k g 450 kg/m 400 kg/m³
g/m
60 000 8 00 k 350 kg/m³
50 000 ³ 300 kg/m³
APPENDIX C
g/m
40 000 0k
85 250 kg/m³
30 000 ³
200 kg/m
20 000
40 °
C
200 °C
20
50 °
160 °C
150 °C
°
140 °C
60 ° C
70 °C
C
130 °C
30 °
120 °C
80 °C
-10
-20
110 °C
10 °
C
°
190 °C
C
90 °C
100 °C
0 °C
170 °C
°C
C
10 000 g/m³
150 k
ne
/m³
180 °C
8000 100 k g
6000 50 kg/m³
40 kg/m³
Melting Li
-50
-11
-30 °C
-60
5000
-40 °
-8
-1
0
C
2
-70
°C
°C
0
°C
4000
-1
-14
-90
°C
0
3
-1
30 kg/m³
°C
°C
0
°C
0
°C
°C
3000 -150 °C
0 °C
20 kg/m³
2000
-160 °C
10 kg/m³
2.5 kJ/kg-K
1000 -170 °C
800
5 kg/m³
600
Pressure (kPa)
500 4 kg/m³
-180 °C
400 3 kg/m³
300
THERMODYNAMIC DATA
2 kg/m³
200
-190 °C
K
Nitrogen Pressure Enthalpy Diagram - SI
g-K
/kg-K
/kg-
1 kg/m³
5 kJ
4 kJ/k
4.5 kJ
100
80
60 -200 °C
g-K 0.5 kg/m³
50
J/k
K
g-
40
6k
/k
-K
kJ
5
6.
30
J/kg
3.5 kJ/kg-K
g-K
J/k
3 kJ/kg-K
7k -K
20 5.5 k 7.5
kJ/kg
Triple Point Line: 12.5 kPa, -210.0 °C -210 °C

10
0 50 100 150 200 250 300 350 400 450 500 550 600 650
397
Span, R., Lemmon, E.W., Jacobsen, R.T, Wagner, W., and Yokozeki, A. "A Reference Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Equation of State for the Thermodynamic Properties of Nitrogen for Temperatures
Enthalpy (kJ/kg) Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
from 63.151 to 1000 K and Pressures to 2200 MPa," J. Phys. Chem. Ref. Data, 29(6):1361-1433, 2000. Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (kJ/kg)

10 000
10000. / f t³ ³
8000 lbm m/ft³ 25 lbm/ft 20 lbm/ft³
35 lb
398
55 /ft³
6000 ³ m / f t³ m / f t³ 30 lbm 15 lbm/ft³
/f t
lbm 4 5 lb 4 0 lb
5000
50
4000 10 lbm/ft³
280 °F
260 °F
240 °F
2
220 °F
200 °F
0
140 °
180 °F
3000
160 °F
1 °
F
100 °
80 °
F
m-°R
F
60 °
F
40 °
400 °F
20 °
380 °F
F
360 °F
320 °F
-20
340 °F
tu/lb
300 °F
0 °F
2000
-40
-60
°F
5 lbm/ft³
°F
-80
°F
0.6 B
-10
-1
°F
2
0°
0
4 lbm/ft³
-1
F
-18
40
°F
-1
0° 6
°F
1000 F 0°
1000. -20 F 3 lbm/ft³
0 °F
800
-220
600
°F 2 lbm/ft³
500 °R
m-
/lb
400 -240 °F Btu
1.4
1 lbm/ft³
300
-260 °F -°R
200 /lbm
Btu
1.5 0.5 lbm/ft³
Melting Line
0.4 lbm/ft³
-280 °F ³
100
100. 0.3 lbm/ft
80 R
/lb m-°
Btu 0.2 lbm/ft³
60 1.6
Pressure (psia)
50
-300 °F
40
30 0.1 lbm/ft³
20 -°R
THERMODYNAMIC DATA
/lbm
Btu
-320 °F 1.7
Nitrogen Pressure Enthalpy Diagram - FPS
10
10.0
8
-°R
m-°R
-°R
m-°R
-°R
6 -°R
/lbm
tu/lbm
lbm
Btu
tu/lbm
5 1.8
1 Btu/lb
Btu/
0.7 Btu/lbm-°R
0.9 Btu/lb
1.1 B
0.8 Btu/lbm-°R
4
1.2 B
1.3
3 -340 °F
2
Triple Point Line: 1.8 psia, -346 °F
1.001 0 25 50 75 100 125 150 175 200 225 250 275 300
-75.0 -50.0 -25.0 0.000 25.0 50.0 75.0 100. 125. 150. 175. 200. 225.
Span, R., Lemmon, E.W., Jacobsen, R.T, Wagner, W., and Yokozeki, A. "A Reference Enthalpy (Btu/lbm) Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Equation of State for the Thermodynamic Properties of Nitrogen for Temperatures Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National

from 63.151 to 1000 K and Pressures to 2200 MPa," J. Phys. Chem. Ref. Data, 29(6):1361-1433, 2000. Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (Btu/lbm)

100 000
/m³ ³
80 000 700 k g 650 kg/m ³
600 kg/m
m³ m³ ³ ³
kg/ kg/ g/m /m³ 550 kg/m
g/ m³ 050 000 95 0k ³ / m³ 0 kg
60 000 1 1 m³ 0 kg 75
0 0k kg/ kg/m 80 ³
11 900 850 500 kg/m
50 000 450 kg/m³
APPENDIX C
³
40 000 400 kg/m
³
350 kg/m
24 ³
0
30 000 30 0 kg/m
°C
0
10 11 ³
23
0 15 250 kg/m
°C
0°
C 0
0°
90 °C 12 14
C
°C 0 °C
22 0 °C
20 000 0° 16
C 13 0 ³
21 0 °C
80 0 ° °C °C 200 kg/m
°C C 0
20 0 °C
1
70
19 °C
°C 18 70
60 ° ³
°C
C 150 kg/m
K
50 °
C
10 000 ³
40 °C
100 kg/m
0.7 kJ/kg-
8000
30 °C
6000
20 °C
5000
10 °C 50 kg/m³
4000
0 °C 40 kg/m³
3000
Melting Line
-10 °C 30 kg/m³
Pressure (kPa)
2000 -20 °C
20 kg/m³
-K
kg
-K
-30 °C
kJ/
/kg
-K
K
2.1
kJ
0.6 kJ/kg-K
K
K
g-K
J/kg
kg-
-K
2.2
kg-
THERMODYNAMIC DATA
J/kg-
-40 °C
kJ/
1000
kJ/k
J/kg-
kJ/
J/kg
1.5 k
10 kg/m³
1.9
1.3 k
1.7
1.8
g-K
/kg-K
-K
/kg-K
1.4 k
800
1.6 k
J/k
J/kg
-50 °C
2k
1 kJ/kg-K
Carbon Dioxide Pressure Enthalpy Diagram - SI
3k
1.1 kJ
0.9 kJ/kg-K
1.2 kJ
0.8 kJ/kg-K
2.
600
500 Triple Point Line: 518 kPa, -56.6 °C
-K
/kg
K
5 kg/m³
g-
kJ
400
-K
J/k
2.4
k
4 kg/m³
/kg
kJ
2.5
6
-K
300
2.
/kg
3 kg/m³
kJ
-K
7
/kg
2.
kJ -K
8 -K /kg
200 2. J
-60 °C
/kg 3k 2 kg/m³
kJ
2. 9 -K
/kg
kJ
3. 1
-70 °C
100
50 100 150 200 250 300 350 400 450 500 550 600 650 700
50. 100. 150. 200. 250. 300. 350. 400. 450. 500. 550. 600. 650. 700.
Span, R. and Wagner, W., "A New Equation of State for Carbon Dioxide Covering Enthalpy (kJ/kg)
the Fluid Region from the Triple-Point Temperature to 1100 K at Pressures up to Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
399
800 MPa," J. Phys. Chem. Ref. Data, 25(6):1509-1596, 1996. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
Reference State: Enthalpy = 200 kJ/kg, Entropy = kJ/kg-K for hte saturated liquied at 0°C Enthalpy (kJ/kg) Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.

50 000
40 000
400
60 lbm/ft³
30 000
55 lbm/ft³
20 000 50 lbm/ft³
/ft³ ³
7 5 lbm /f t /ft³
7 0 lbm 65 lbm 45 lbm/ft³
³
40 lbm/ft
10 000
10000. 35 lbm/ft³
t³
8000 30 lbm/f
³
6000 25 lbm/ft
5000 44 20 lbm/ft³
0
4000 40 °
0°42 F
F 0
36 3 °F 15 lbm/ft³
3000 32 0 8
0° 34 °F 0 °F
F 0
°F
30 10 lbm/ft³
2000 1 26 0°
200
°F 22 0° 28 F
160 80 °F 24 F 0
140 °
F °F 0° 0° °F
120 °F F F
100 °F
5 lbm/ft³
1000
1000. 80 °F
800 4 lbm/ft³
60 °F
600 3 lbm/ft³
40 °F
500
20 °F 2 lbm/ft³
-°R
400
Pressure (psia)
lbm
/
-°R
-°R
tu
0 °F
B
300
Melting Line
5
Pressure (psia)
/lbm
0.
-°R
tu/lbm
-°R
Btu
-20 °F m
-°R
200 lb 1 lbm/ft³
°R
u/
0.3 B
tu/lbm
0.35
/lbm
Bt
m-
0.15 Btu/lbm-°R
tu
-°R
/lb
55
THERMODYNAMIC DATA
0.
tu
-40 °F
.4 B
0.25 B
0
5B -°R
100 0.4 lbm
0.5 lbm/ft³
tu/
Carbon Dioxide Pressure Enthalpy Diagram - FPS
100. -60 °F B
0.2 Btu/lbm
80 0.6 0.4 lbm/ft³
Triple Point (75.122 psia, -69.804 °F
60 0.3 lbm/ft³
50
40 -°R 0.2 lbm/ft³
lbm
Line
u/ °R
30 5 Bt m-
0.6 /lb
Btu
0.7
20 0.1 lbm/ft³
-°R
lbm
-80 °F
Sublimation
B tu/
5
0.7
10
10.0 25 50 75 100 125 150 175 200 225 250 275 300
25.0 50.0 75.0 100. 125. 150. 175. 200. 225. 250. 275. 300.
Span, R. and Wagner, W., "A New Equation of State for Carbon Dioxide Covering Enthalpy (Btu/lbm)
the Fluid Region from the Triple-Point Temperature to 1100 K at Pressures up to Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
800 MPa," J. Phys. Chem. Ref. Data, 25(6):1509-1596, 1996. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National

Reference State: Enthalpy = 200 kJ/kg, Entropy = kJ/kg-K for hte saturated liquied at 0°C Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (Btu/lbm)

100 000
100000.
80 000 g/m³ 350 kg
/m³
³ ³ 400 k
/m ³ g/m
25
m³
³
m³ /m³
0
kg /m g/ 4 50 k
23
60 000 g/ 300 k g
/m
0 0k
0
kg
³
°C
0 0k 50
kg
75 55
°C
24
0
50 000 65 g/m³
g/m
0°
C 250 k
60
22
APPENDIX C
/m³
0k
0°
40 000 C 200 k g
70
17
200 210
°C °C ³
30 000 0° 19 150 kg/m
16 C 180 0 °C
0° °C
15 C 100 kg/m³
20 000 0°
C
140
°C
130 °C 50 kg/m³
10 000
10000. 120 °C
8000 ³
110 °C 40 kg/m
6000 100 °C ³
30 kg/m
5000 90 °C
80 °C 20 kg/m³
4000
70 °C
3000
60 °C
50 °C
0.5 kJ/kg-K
2000 10 kg/m³
40 °C
30 °C 5 kg/m³
1000
1000. 20 °C ³
800 4 kg/m
3 kg/m³
600 10 °C
Pressure (kPa)
500
0 °C 2 kg/m³
400
300 -10 °C
THERMODYNAMIC DATA
1 kg/m³
200 -20 °C
Ammonia Pressure Enthalpy Diagram - SI
-K
/ kg
-30 °C kJ 0.5 kg/m³
5
7.
100
100.
80
-40 °C
60
-K
50 /kg
kJ
-50 °C 8
g-K
40
g-K
K
30 g-
-K
J/ k
kg
k
g-K
2.5 kJ/k
g-K
kg-
2 kJ/kg-K
3 kJ/k
kJ/
8.5
J/kg-K
/kg-
J/k
kJ/
-60 °C
/kg-K
kJ/k
6.5
20
6k
5 kJ
5.5
3.5 k
g-K
4.5
g-K
4 kJ
1.5 kJ/kg-K
kJ/k
J/k
1 kJ/kg-K
9
7k
-70 °C
10
10. 0.0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
0.00 200. 400. 600. 800. 1000. 1200. 1400. 1600. 1800. 2000. 2200.
401
Enthalpy (kJ/kg) Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
Tillner-Roth, R., Harms-Watzenberg, F., and Baehr, H.D., "Eine neue Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
Fundamentalgleichung fuer Ammoniak," DKV-Tagungsbericht, 20:167-181, 1993. Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (kJ/kg)

10000. 10 000
402
8000 ³
m/f t
20 lb
m/ft³
6000 15 lb
³
/f t
lbm
5000
-80 °F
-100 °F
/ft³
30
10 lbm
³
/f t
4000
-60 °F
³
lbm
m/ft³
25
m/f t
3000
40 lb
3
35 lb
360 80 °F 40 /ft³
300 °F 320 °F 340 °F 0° 5 lbm
°F F
2000 280 °F t³
4 lbm/f
260 °F /ft³
3 lbm
0.2 Btu/lbm-°R
240 °F
0.1 Btu/lbm-°R
1000 220 °F
1000.
800 200 °F /ft³
2 lbm
180 °F
600
500 160 °F
45 lbm/ft³
/ft³
1 lbm
400 140 °F
300 120 °F
/ft³
0.5 lbm
100 °F
200
Pressure (psia)
/ft³
0.4 lbm
80 °F /ft³
0.3 lbm
60 °F
100
THERMODYNAMIC DATA
100. /ft³
0.2 lbm
80
Ammonia Pressure Enthalpy Diagram - FPS
40 °F
60
0.3 Btu/lbm-°R
50 20 °F /ft³
0.1 lbm
-°R
R
40
R
m-°R
-°R
-°R
-°
/lbm
-°R
°R
tu
-°R
/lbm
/lbm-°R
/lbm-°
0 °F
/lbm
-°R
/lbm
bm
30
tu/lbm
°R
.4 B
Btu
lbm-
-°R
u/l
1
t
Btu
m
m-
0.6 Btu/lb
1 Btu
1.3
/lb
7B
Btu/
/lb
0.7 Btu
0.9 B
0.8 Btu
u
1.2
1.
tu
Bt
1.1
8
-°R
6B
20
1.
0.5 Btu/lbm
1.
-20 °F
-°R
/lbm
m
/lb
Btu
u
0.4 Btu/lbm-°R
Bt
1.5
9
1.
-40 °F
10
10.0 0.0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900
0.000 50.0 100. 150. 200. 250. 300. 350. 400. 450. 500. 550. 600. 650. 700. 750. 800. 850. 900.
Tillner-Roth, R., Harms-Watzenberg, F., and Baehr, H.D., "Eine neue Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National

Fundamentalgleichung fuer Ammoniak," DKV-Tagungsbericht, 20:167-181, 1993. Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
Enthalpy (Btu/lbm)

20 000
g/m³ 100 kg/m³
40
500 k
65 kJ/kg-K
0.55
300 kg/m³
APPENDIX C
10 000
10000.
³
³
24
³
/m³
g/m
22
g/m³
g/m
8000 g/m
0°
k
0k 100 kg/m³
20
0k
0k
20
C
0°
0 kg
690
18
70
890
0
0°
1010
1100
C
°C
6000
260
³
14
°C
5000
0.75 kJ/kg-K
120 0°
C
kg/m
°C
60
4000 100 kg/m³
900
100 °C
C
3000 50 kg/m³
75
80 °C
50 kg/m³
2000
60 °C
1500 kg/m³
1200
1000 50 kg/m³
25
1000. 40 °C
800
g-K
/kg-
K
kJ/k
600 15 kg/m³
kg-
g-K
5 kJ
20 °C
kJ/
1.75
/kg-K
J/k
-K
1. 8
500
J
5
5k
1300 kg/m³
50 kg/m³
10
2.0
0.65 kJ/kg-K
1.9
kJ/kg
400
K
K
1.45 k
-K
kg-
1.55
K
kJ/
300
5
0 °C
kJ/kg
Pressure (kPa)
2.1
1.25 kJ/kg-
1.65
Pressure (kPa)
5 kg/m³
200
1.35 kJ/kg-
1500 kg/m³
1400
g-K
3 kg/m³
4
J/k
1.15 kJ/kg-K
k
THERMODYNAMIC DATA
1500 kg/m³
.25
3 kg/m³
2
-20 °C
-K
100
/kg
100.
R134a Pressure Enthalpy Diagram - SI
kJ
3 kg/m³
2
5
K
80
g-
2. 3
-K
J/k
k
/kg
60
kJ
. 55
1.05 kJ/kg-K
5
2
50 -40 °C
2.4
1 kg/m³
0.95 kJ/kg-K
40
-K
/kg
kJ
30
2. 6
160
1 kg/m
0.5 ³ ³
kg/m
140 °C
120 °C
140 °C
100 °C
80 °C
60 °C
20
0.85 kJ/kg-K
40 °C
20 °C
0 °C
-60 °C
-40
-20 °C
260
180
240
220
200
-20 °C
140 °C
140 °C
140 °C
140 °C
140 °C
10
10.0
100
100. 200
200. 300
300. 400
400. 500
500. 600
600. 700
700.
Tillner-Roth, R. and Baehr, H.D., "An international standard formulation of the Enthalpy (kJ/kg)
403
thermodynamic propertiesof 1,1,1,2-tetrafluoroethane (HFC-134a) for temperatures Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
from 170 K to 455 K at pressures up to 70 MPa," J. Phys. Chem. Ref. Data, 23:657-729, 1994. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National
Reference State: IIR: Enthalpy = 200 kJ/kg, entropy = 1 kJ/kg-K for saturated liquid at 0°C
Enthalpy (kJ/kg)
13: Pressure vs. Enthalpy plot: R134a

Specific Entropy = Btu/lbm-°R, Density = lbm/ft3 , Temperature = °F
3000
/ft³
/ft³
t³ ³ 30 lbm
404
m/ft³
-°R
³ / f t³ lb m/f m/f t m/ft³
/f t bm 40 lb 35 lb t³
45
90 lb
lbm 0l 25 lbm/f
95 lbm
5
2000 55
48
t³
20 lbm/f
0°
0.16 Btu/lbm
F
44
36
46
0
-80 °F
0°
500
0°
°F ³
40
F
32 34 15 lbm/ft
0.18 Btu/lbm-°R
°F
38
0°
0
0
42
0°
F
30 F °F
°F
0°
0°
F
F
1000
1000. 28
900 260 0°
F 10 lbm/ft³
m/ft³
°F
220
-60 °F
800
°F
240
60 lb
°F
80 lbm/ft³
700
70 lbm/ft³
³
75 lbm/ft³
600
-40 °F
R
500 200 °F 5 lbm/ft³
65 lbm/ft
bm-°
400 180 °F 4 lbm/ft³
Btu/l
0.42
300 160 °F
3 lbm/ft³
140 °F
200 2 lbm/ft³
120 °F
-°R
-°R
-°R
-°R
/lbm
-°R
lbm
/lbm
/lbm
Btu
/lbm
100 °F
Btu
Btu/
Btu
0.5
4
Btu
Pressure (psia)
2
0.22 Btu/lbm-°R
0.48
0.46
0.5
0.2 Btu/lbm-°R
0.5
°R
1 lbm/ft³
Pressure (psia)
100
100. 80 °F
lbm-
90
80 tu/
44 B
70 60 °F
0.
THERMODYNAMIC DATA
60
R134a Pressure Enthalpy Diagram - FPS
-°R
85 lbm/ft³
50 40 °F 0.5 lbm/ft³
m-°R
tu/lbm
°R
40
m-
-°R
R
b
0.38 B
tu/l
20 °F
0.32 Btu/lb
6B
/lbm-°
R
30
0.5
0.3 Btu/lbm
0.25 lbm/ft³
0.4 Btu
tu/lbm-°
/lbm-°R
0 °F
-°R
20
°R
bm
0.36 B
0.26 Btu/lbm-°R
0.28 Btu/lbm-°R
m-
tu/l
B
/lb
0.34 Btu
tu
.58
0
6B
0.
-20 °F
0.24 Btu/lbm-°R
10
10.050
50.0 100
100. 150
150. 200
200. 250
250. 300
300.
Tillner-Roth, R. and Baehr, H.D., "An international standard formulation of the Enthalpy (Btu/lbm)
thermodynamic propertiesof 1,1,1,2-tetrafluoroethane (HFC-134a) for temperatures Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23:
from 170 K to 455 K at pressures up to 70 MPa," J. Phys. Chem. Ref. Data, 23:657-729, 1994. Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 9.0, National

Reference State: IIR: Enthalpy = 200 kJ/kg, entropy = 1 kJ/kg-K for saturated liquid at 0°C Enthalpy (Btu/lbm) Institute of Standards and Technology, Standard Reference Data Program, Gaithersburg, 2010.
THERMODYNAMIC DATA
REFERENCES
1C.1 Lemmon, E.W., Huber, M.L., McLinden, M.O. NIST Standard Reference Database 23: Reference Fluid Thermodynamic
and Transport Properties-REFPROP, Version 9.0, National Institute of Standards and Technology, Standard Reference
Data Program, Gaithersburg, (2010).
1C.2 Wagner, W. and Pruss, A., "The IAPWS Formulation 1995 for the Thermodynamic Properties of OrdinaryWater Substance
for General and Scientific Use," J. Phys. Chem. Ref. Data, 31(2):387-535, (2002).
1C.3 "Setzmann, U. and Wagner, W., "A New Equation of State and Tables of Thermodynamic Properties for Methane Covering
the Range from the Melting Line to 625 K at Pressures up to 1000 MPa," J. Phys. Chem. Ref. Data, 20(6):1061-1151,
(1991).
1C.4 Lemmon, E.W., McLinden, M.O., Wagner, W., "Thermodynamic Properties of Propane. III. A Reference Equation of State
for Temperatures from the Melting Line to 650 K and Pressures up to 1000 MPa," J. Chem. Eng. Data, 54:3141-3180,
(2009).
1C.5 Smukala, J., Span, R. and Wagner, W., "A New Equation of State for Ethylene Covering the Fluid Region for Temperatures
from the Melting Line to 450 K at Pressures up to 300 MPa," J. Phys. Chem. Ref. Data, 29(5):1053-1122, (2000).
1C.6 Buecker, D. and Wagner, W. "A Reference Equation of State for the Thermodynamic Properties of Ethane for Temperatures
from the Melting Line to 675 K and Pressures up to 900 MPa," J. Phys. Chem. Ref. Data, 35(1):205-266, (2006).
1C.7 Span, R., Lemmon, E.W., Jacobsen, R.T, Wagner, W., and Yokozeki, A., "A Reference Equation of State for the Thermo-
dynamic Properties of Nitrogen for Temperatures from 63.151 to 1000 K and Pressures to 2200 MPa," J. Phys. Chem.
Ref. Data, 29(6):1361-1433, (2000).
1C.8 Span, R. and Wagner, W., "A New Equation of State for Carbon Dioxide Covering the Fluid Region from the Triple-Point
Temperature to 1100 K at Pressures up to 800 MPa," J. Phys. Chem. Ref. Data, 25(6):1509-1596, (1996).
1C.9 Tillner-Roth, R., Harms-Watzenberg, F., and Baehr, H.D., "Eine neue Fundamentalgleichung fuer Ammoniak," DKV-Ta-
gungsbericht, 20:167-181, (1993).
1C.10 Tillner-Roth, R. and Baehr, H.D., "An international standard formulation of the thermodynamic properties of 1,1,1,2-tet-
rafluoroethane (HFC-134a) for temperatures from 170 K to 455 K at pressures up to 70 MPa," J. Phys. Chem. Ref. Data,
23:657-729, (1994).
APPENDIX C 405
406
API 14E...................................................................... 245, 297
INDEX API 520 Part 1............................................................ 360, 362
API 521....................................................................... 368-371
API 526.............................................................................. 360
In searching for a given item in this book, please also refer to the
Table of Contents, List of Figures, and List of Table in the front API barrel (bbl).............................................................. 17, 67
of this book. The latter two are particularly useful since they API Gravity.................................................. 17, 45, 66, 67, 72,
show the content of the accompanying material. The reader is
API Method, liquid density............................................ 70, 71
advised that this index only covers Volume 1 of the “Gas Condi-
tioning and Processing” series. Volume 2 has a separate index. API MPMS 5.8.................................................................. 343
API RP 520 Part 2.............................................................. 364
API RP 576........................................................................ 364
A
Aromatic hydrocarbons (BTEX)............................ 7, 8, 17, 63

Absorption ASME Section VIII Boiler & Pressure
Glycol Dehydration...................................................... 36 Vessel Code........................................................ 363, 375
Lean Oil....................................................................... 40 Atomic Weight....................................................................... 3
Accumulation Pressure...................................................... 363 Avogadro’s number................................................................ 3
Acentric Factor......................................................... 55, 57, 62
Acetylene (C2H2).................................................................... 7 B
Acid Gases............................................................................. 9
Back pressure, relief valves....................................... 361, 368
Acids .................................................................................... 11
Balanced Bellows Relief Valve.......................................... 360
Activity Coefficients.......................................................... 106
Balanced, control valves.................................................... 333
Actuators..................................................................... 332-336
Bases .................................................................................... 11
Adiabatic..................................................................... 206-210
Basic Equation, See Gas Flow................................... 258, 260
Adsorption
Beggs & Brill..................................................................... 279
Gas Dehydration.......................................................... 36
Benedict-Webb-Rubin (BWR)............................................. 55
Gas Sweetening............................................................ 35
Benedict-Webb-Rubin-Starling (BWRS)....................... 49, 72
Liquid Product Treating............................................... 41
Benzene, (C6H6), see aromatic hydrocabons.......................... 7
Silica Gel...................................................................... 40
Bernouilli’s equations........................................................ 240
AGA Report No. 8............................................................... 59
BETX See Aromatic hydrocarbons
AGA REPORT NO. 9........................................................ 343
Bias .................................................................................. 321
Alcohols............................................................................... 10
Binary Interaction Parameter.................................. 58, 71, 116
Alkanes.................................................................................. 5
Bingham Plastic, fluid flow................................................ 243
Alkenes.................................................................................. 6
Black Oil Model, multiphase floor..................................... 301
Alkyne ...................................................................................... 7
Black Oil Reservoirs............................................................ 97
Amagat’s Law................................................................ 67, 72
Blowdown Valves............................................... 358, 376, 377
Amalgam corrosion (Mercury)............................................ 37
Boyle-Charles Laws............................................................. 48
Amines .............................................................................. 10, 35
Brill .......................................................................... 291, 292
Ammonia........................................................................ 10, 44
BS&W specifications........................................................... 42
Angle Valve................................................................ 251, 330
Bubble, flow regime............................................ 274-275, 290
Annular Mist, flow regime............................ 279, 284, 290, 297
Bubblepoint............................................................. 89, 91, 113
ANSI B16.5....................................................................... 304
Buckling Pin Valves........................................................... 361
ANSI B31.3....................................................................... 303
Bundled flowlines...................................................... 271, 274
ANSI B31.4....................................................................... 303
Buoyancy seals................................................................... 369
ANSI B31.8....................................................................... 303
Butadiene (C4H6).................................................................... 7
ANSI/ISA S.75.01.............................................................. 376
Butane (C4).............................................. 56, 25-26, 29, 33, 45
Antiagglomerants, hydrate inhibition....................171, 187, 189
INDEX 407
Butene (C4H8)......................................................................... 7 Conversion Factors.................... 22-23, 74, 124, 381-388
Butterfly Valve............................................................ 331-332 Coriolis Meters............................................................ 341-342
Corresponding States Concept............................................. 56
C Corresponding States Correlations, liquid density.......... 70-72
C6+ Characterization......................................... 13, 62, 93, 107 Corrosion................................ 28, 37, 185, 187, 297, 300, 303
Cage-guided Control Valves...................................... 331, 333 COS See Carbonyl Sulfide
Calcium Chloride (CaC12), gas dehydration........................ 36 COSTALD method, liquid density....................................70-72
Capacitance.......................................... 317-319, 322-324, 339 Cricondenbar....................................... 91-92, 95, 98, 100, 299
Carbon-12.............................................................................. 3 Cricondentherm..................................... 32, 91-92, 97, 99, 100
Carbon dioxide........... 9, 29, 32, 35, 46, 95, 131-132, 151, 164 Critical Compressibility....................................................... 57
Carbon Disulfide........................................................ 9, 14, 35 Critical Locus....................................................................... 92
Carbon Number “cut”.................................................. 12, 107 Critical Point.............................. 56, 88-89, 91-93, 97-98, 101
Carbonyl Sulfide........................................................ 9, 14, 35 Critical Pressure (Pc)..................................... 47-48, 88-89, 92
Cascade Control.................................................. 328-329, 349 Critical Temperature (Tc)................................... 47, 88, 97, 107
Causes of Over-pressure, relief systems............................ 356 Crude Oil.............................. 42, 61-74, 92, 117-121, 125-129
Centripetal Force, flow splitting................................. 301-302 Crude Oil Vapor Pressure Specification.............. 118, 125-129
Characterized Ball Valve............................................. 331-332 CS2 See Carbon Disulfide
Chattering Relief Valves.................................................... 359 Cunliffe, multiphase flow........................................... 289, 294
Chemical Absorption Cycling, control stability....................................... 98, 323, 325
see Sweetening............................................................. 35 Cyclohexane........................................................................... 8
Chilled Mirror, water content measurement...................... 155 Cyclopentane.......................................................................... 8
Chromatograph................................................. 12-13, 94, 156

Clathrate, gas hydrate......................................................... 156
D
Closed System, thermodynamic concepts.......................... 204 Dalton’s Law...................................................................... 104
CO2, H2S, and N2 Effect on Darcy equation.................................................... 239, 244, 248
Reservoir Phase Behavior....................................... 95-96 Datum Point............................................................... 208, 216
Water Content..................................................... 151-153 Deadtime, control........................................ 317, 319, 322, 325
Coalbed Methane................................................................. 27 Decane (C10)........................................................................... 5
Colebrook-White equation.......................................... 261-262 Dehydration (Gas)..................................... 11, 36-37, 153, 170
Combination Rules, see Mixing Rules................................. 58 Delivery point, gas sales...................................................... 32
Commercial Steel, pipe wall roughness............................. 244 Dense Fluid or Phase...................... 88, 95, 100-101, 217, 298
Compositional Models, multiphase floor........................... 301 Density
Compounds............................................................................ 3 Definition & units........................................................ 17
Compressibility Factor................................ 49-53, 59, 81, 259 Gas..................................................... 17, 48, 49, 54, 81-85
Compression Ratio, in stage separation............................. 119 Hydrocarbon liquid........................................ 17, 61-72, 86
Compressor Scrubber Liquids............................................ 119 Inhibitor...................................................................... 173
Condensate....................................... 29, 33, 40, 66-67, 97, 125 Depressurization or Blowdown........................... 368, 376-377
Continuous Phase, multiphase flow............ 274-275, 278, 290 Derivative action, control............................. 320, 325-326, 341
Control Design Pressure.......................................................... 363, 365
Controlled Variable....... 316-317, 323-324, 327-329, 349 Dewpoint
Controller............................................. 316-330, 337, 349 Hydrocarbon (HCDP).......... 29, 32, 39-40, 89, 91, 94, 98,
....................................................................... 100, 114-115
Control Loop................................ 316-320, 326-330, 349
Water................................. 29, 40, 147-156, 160, 174-190
Control Modes.................................................... 320-326
Diaphragm.................................................... 332-333, 336-337
Control System Block Diagram................................. 317
Diatomic Molecule............................................................. 3, 4
Control Valve........................ 316-317, 327, 330-337, 349

Diethanolamine (DEA).................................................. 10, 35 Feedback Control Systems................... 316-320, 328-330, 350
Diethylene Glycol (DEG) See Glycols Feedback Trim................................................................... 330
Dilatant, fluid flow............................................................. 243 Feed Forward Control................................................. 328-330
Diolefins................................................................................. 7 Field Condensate See Condensate
Direct Acting............................................................... 326-327 Fire Relief........................................................... 356, 363, 377
Distillation Curves.......................................................... 61-62 Flanges 304
Double Ported Control Valves........................................... 333 Flanigan Correlation, multiphase flow........................ 283-286
Drager Tube....................................................................... 155 Flare Systems
Dry Gas Reservoir........................................................... 97-98 Flare Gas Recovery System....................................... 371
Duns and Ros...................................................... 289-290, 301 Flare Headers...................................... 358, 359, 368, 370
Flare Ignition.............................................................. 371

E Flare KO Drum................................... 358, 359, 360, 370
Eaton Liquid Holdup Correlation............................... 285-287 Flare Radiation.................................................... 371-374
Eccentric Rotating Plug Contorl Valve.............................. 331 Flare Stack........................................... 358-359, 369-373
Economic Pipe Diameter................................................... 252 Flare Tip...................................................... 358, 368-370
Elements................................................................................. 3 Flash Calculation........................................................ 115-116
Emergency Shutdown Systems (ESD)....................... 355, 374 Flow Control........................................ 318-319, 327, 329-331
Energy Balance............................................ 203-206, 239, 269 Flow Measurement....................................................... 341347
Enthalpy........................................ 204-211, 215-228, 269-270 Flow Regimes....................... 274-275, 279-280, 286, 289, 345
Entropy................................................. 206-211, 216-218, 239 regimes that occur in vertical flow............................. 275
Equal percentage, control valves................................ 332-335 Fluid Head............................................................................ 18
Equation of State (EOS).......... 47-49, 55-58, 72, 105, 116-117, Force .................................................................................... 16
170 FPS .................................................................................... 14
Equilibrium Friction-dominated, multiphase flow......................... 277, 294
Vapor Liquid Hydrocarbons..................... 88, 91, 103-145 Friction Factor, f........... 239-241, 244, 248, 258-262, 275, 278
Water Content, Hydrates....... 147-154, 159, 170-172, 174, Froude Number, multiphase flow....................................... 277
...................................................................................... 183
Fugacity...................................................................... 105, 106
Equilibrium Vaporization Ratio See K-value
Fully Turbulent........................................................... 260-262
Equivalent Diameter, pipe............................ 255-257, 266-267
Equivalent Length, pipe................ 249-251, 255-257, 266-267 G
Erosional Velocity.............................................................. 297
Gas Chromatography See Chromatograph
Error Signal.......................................... 316, 320-321, 323-324
Gas Condensate, see Condensate......................................... 25
Ethane (C2)................................... 5, 6, 33, 41, 92-93, 116, 158
Gas Conditioning...................................................... 25, 34-40
Ethylbenzene (C8H10)............................................................. 7
Gas Flow Equations..................................... 248-249, 258-268
Ethylene (C2H4).............................................................. 67, 33
Gas Holdup, multiphase flow............................................. 277
Ethyl Mercaptan (C2H5SH).................................................... 9
Gas Hydrates, beginning page........................................... 156
Euler Number Multiphase Flow......................................... 278
Gas Injection...................................................................... 297
Excessive Velocity, piping................................................. 253
Gas Line Looping....................................................... 265-267
Expanders.............................................................. 40, 206, 209
Gas Oil Ratio (GOR)............................... 97-98, 107, 300, 346
Extended Analyses.................................................... 12-13, 94
Gas Processing................................................................ 26-41
F Gas Sweetening............................................................... 35-36

Gas-to-Liquids (GTL).......................................................... 44
Fail Closed (FC), control valves......................... 327, 333, 336
Gas Volume Fraction, multiphase flow............... 276, 345-346
Fail Open (FO), control valves........................... 327, 333, 336
Gibbs Free Energy (G)....................................................... 208
“Fanning” Friction Factor................................... 239, 258, 263
Globe Control Valve................................................... 330-331
INDEX 409
Glycol Dehydration see Gas Hydrates........................................................ 158
see Absorption.............................................................. 36 Hydrogen Sulfide... 9, 26, 27, 28, 29, 35, 36, 41, 42, 57, 77-80,
83, 84, 95, 96, 158, 161, 166-170
Glycols ......................................................................... 11, 173
Diethylene Glycol................................................ 10, 171
Monoethylene Glycol.............................. 10, 36, 171-187
I
Triethylene Glycol.......................................... 10, 36, 154 Ideal Gas “Law”........................................................... 48, 104
Gravitational Force........... 16, 18, 203, 240, 289-290, 301-302 Inhibition
See Hydrate Inhibition
Gravity Dominated, multiphase flow......................... 277, 294
Instrumentation........................................................... 337-346
Gross Heating
Instrumented Protective Function...................................... 356
see Heating Valve......................................................... 30
Insulation, Fluid Flow................................................. 271-274

Ground Flare, see Flare Systems....................................... 368
Integral Action, control............................................... 324-325
Guest Molecules................................................................. 156
Internal Energy............................................................ 204-205
H I/P Transducer.................................................................... 337

Isentropic.................................................................... 207, 209
H2O See Water
ISO 12213............................................................................ 59
H2S See Hydrogen Sulfide
ISO 17089-1:2010.............................................................. 343
Hammerschmidt.................................................. 171, 180, 181
Isobutane (iC4)......................................................... 6, 33, 157
Hankisnon, Brobst, Thomson See COSTALD
Isomers................................................................................... 6
Head ................................ 18, 99, 240, 254, 264, 278-279, 284
Isothermal, flow......................................................... 258, 259
Heat Capacity (Cp) of........................................................ 210
Hydrocarbon Liquids................................................. 214
J
Natural Gas......................................................... 212-213
Joule-Thomson coefficient................................................. 269
Heating Value.................................................................. 30-31
Joule Thomson (J-T) expansion............................ 40, 259, 270
Heat of Fusion...................................................................... 88
Heat (Q)................................................. 19, 205-207, 209-210
Helium (He)........................................................................... 9
K
Helmholtz Free Energy (A)............................................... 208 Katz Correlation
Heptane (C7H16)...................................... 56, 12 ,13, 66, 93, 98 Compressibility factors............................... 54, 59, 81-83
Hexane (C6H14)...................................................... 5, 6, 13, 107 Hydrate Prediction.............................................. 160-165
Hold-up See Liquid Hold-up Kay’s Rule..................................................... 54, 67, 71, 81-83
Homologous Series.......................................................... 5, 47 Kilogram (kg), definition..................................................... 16
Horsepower (hp).................................................................. 18 Kilopascal (kPa), definition................................................. 18
Hydrates Kinematic Viscosity See Viscosity
Formation Conditions and Prediction.. 159-170, 192-200 Kinetic Energy (KE)............................ 203-205, 208, 239-240
History and Structure.......................................... 156-158 Kinetic Hydrate Inhibitors (KHIs)...................... 171, 187-189
Inhibition............................................................. 171-187 K Value Charts............................................................ 130-146
Prevention............................................................ 36, 170 K Values....................................................... 103-117, 161-165
Saturated H20 Content................................................ 154
L
Hydrocarbon Dewpoint (HCDP)
see Dewpoint-Hydrocarbon Lean-oil Process................................................................... 40
Hydrocarbon Gas Viscosity................................................. 60 Length, definition................................................................. 16
Hydrocarbons...................................................... 57, 12, 13, 33 Level Measurement..................................................... 337-338
Physical Properties of............................................. 77-80 Linear Control Valve................................................... 333-335
Hydrodynamic Slugs.................................................. 290, 291 Line Pack, fluid flow................................................... 254-255
Hydrogen Bond Liquid Density See Density Hydrocarbon Liquid

Liquid Head Factor............................................................ 284 Mixture Combination Rules................................................. 58
Liquid Holdup....................... 275-279, 282, 286-289, 294-298 Modified Flanigan Correlation See Flanigan Correlation
Liquid Holdup Fraction............................................... 276-277 Modified Rackett Equation............................................ 70, 71
Liquid Hydrocarbon Products......................................... 33-34 Mol ...................................................................................... 4
Liquid Line Looping................................................... 255-258 Molecular Sieve................................................................... 36
Liquid metal embrittlement (LME), corrosion.................... 37 Molecular Weight.................................................. 4, 63-65, 66
Liquid Physical Properties.............................................. 61-74 Molecules............................................................................... 3
Liquid Product Treating....................................................... 41 Mol Percent........................................................................ 122
Liquid Viscosity See Viscosity Monoethanol Amine (MEA).......................................... 10, 35
Liquid Volume Fraction (LVF).......................................... 276 Monoethylene Glycol (MEG)
See Glycol Monoethylene Glycol

Liquid Volume Percent....................................................... 122
Moody Chart...................................................................... 244
Liquified Natural Gas (LNG)......................................... 29, 44
Moody Friction Factor................................. 239, 241, 261-262
Liquified Petroleum Gas (LPG)............................... 29, 33, 41
Multiphase Flow......................................................... 274-301
Load Changes, control............................................... 317, 328
Multiphase Flow Correlations..................................... 278-290
Loop Gain................................................................... 318-319
Multiphase Flow Measurement................................... 344-346
Lost Work................................................................... 239, 275
Multiphase Flow Meter Operational Ranges..................... 346
Low Dosage Hydrate Inhibitors (LDHI)
See Hydrates Inhibition Multiphase Flow Splitting.......................................... 301-302
M.W. Kellogg.............................................................. 245-248
M
Manipulated Variable................................... 316-317, 327-328
N
Mass Balance..................................................................... 202 NaCl .................................................................................. 174
Mass, definition.................................................................... 15 Naphthene........................................................................ 8, 12
Mass Percent...................................................................... 122 Natural Gas.............. 25-33, 34-37, 40-41, 44, 91-94, 148, 151,
Master Loop, control.......................................................... 329 ................................................................... 161, 211-213
Maximum Allowable Working Pressure (MAWP)............ 363 Natural Gas Liquids (NGLs)........ 26, 29, 33, 34, 37-41, 45-46
Maximum Velocity............................................................. 263 Newtonian Fluids....................................................... 243, 249
Mechanical Design if Piping....................................... 302-304 Newton (N), definition......................................................... 16
Mechanical Refrigeration..................................................... 39 NGL Extraction............................................. 26, 28, 30, 36-41
Mechanistic Model............................................................. 279 Nielsen Bucklin Method, hydration inhibition.......... 172, 181
MEG See Glycols, Monethylene Glycol Nitrogen (N2)................... 3, 26, 28-29, 32, 41, 95-96, 153, 161
Megapascal (MPa)............................................................... 18 Nominal Diameter.............................................................. 243
Membranes..................................................................... 36, 41 Nonane (Cg)........................................................................... 5
Mercaptans (RSH).......................................... 9, 28, 35, 41, 42 Non-Newtonian Liquids.............................................. 243-244
Mercury (Hg)............................................................. 9, 32, 37 Normal Butane (nC4)............................................. 5, 6, 33, 45
Metastable Water Dewpoint....................................... 154, 183 Normal Cubic Meter (Nm3)................................................. 19
Methane.................................................................... 5, 29, 159 NORM, naturally occurring radioactive materials............... 10
Methanol.................................................... 10, 36, 44, 171-185 No “Slip”.................................................................... 277, 286
Methylcyclohexane (C7H14)................................................... 8
Methylcyclopentane (C6H12).................................................. 8
O
Methyldiethanol Amine (MDEA).................................. 10, 35 Octane (C8)............................................................................. 5
Methyl Mercaptan (CH3SH).................................................. 9 Offset, control............................................................ 323, 324
Midstream...................................................................... 25, 27 Olefin ................................................................................... 6
Miscible Flood..................................................................... 95 On-off Control.................................................... 320-321, 326
Mixture................................................................................... 4 Open-loop Control............................................................. 329
INDEX 411
Open System, thermodynamic concepts............................ 204 Surge................................................................... 254-255
Orifice Meters............................................................. 341-343 Process Control See Control
Overall Heat Transfer Coefficient (Uo)....................... 270-272 process Gain, (Kp)............................................................. 318
Over Pressure............................................... 355-357, 358, 365 process safety system......................................................... 355
Oxygen (O2)................................................................... 10, 32 Produced Water.................................................................... 42
Propane (C3).................................................. 56, 26, 29, 33, 45
P Proportional Band....................................................... 322-324
Panhandle A equation.......................................... 259-261, 283 Proportional Control................................................... 321-326
Panhandle B equation................................................. 259-261 Proportional Plus Derivative (P+D)................................... 325
Paraffin Hydrocarbon....................................................... 5, 63 Proportional Plus Integral (P+I)......................................... 324

Partially Turbulent, AGA equation............................. 260-261 Proportional Plus Integral Plus Derivative........................ 326
Partial Pressure........................................................... 104, 147 Propylene (C3H6).................................................................... 6
Partial Pressure and Fugacity PRV coefficient........................................................... 362-363
see Water Content of Gases....................................... 147 Pseudocomponents................................................ 62, 107, 108
Pascal (Pa), definition.......................................................... 18 Pseudocritical
Peng-Robinson (PR) EOS................................. 55, 58, 72, 117 Pressure (Pc’)......................................... 58, 59, 71, 81-85
Pentane (C5)........................................................... 5, 6, 26, 29 Temperature (Tc’).................................. 58, 59, 71, 81-85
pH ................................................................................. 11 Pseudoplastic, fluid flow.................................................... 243
Phase Behavior Purge Gas............................................................ 358, 368, 369
Multicomponent Systems....................................... 91-96 P-V-T equation of state See Equation of State (EOS)
Single Component Systems.................................... 87-90

Phase Envelopes
Q
Application of....................................................... 97-101 Quadruple Line.................................................................. 160
Effect of Composition............................................. 92-96 Quality Lines........................................................................ 91
P-H Diagrams............................................... 216-217, 219-220 Quick Opening, control valves................................... 333-334
Physical Absorption, sweetening......................................... 35
Physical Properties, see Hydrocarbons........................... 77-80 R
Pigging.................................................. 277, 286, 294, 298-300 Rackett Method See Modified Rackett Equation
Pilot Operated Relief Valves (PORV)................................ 361 Radicals.......................................................................... 11, 12
Pipeline Efficiency (E)................................................ 259-260 Raoult’s Law.............................................................. 104, 147
Pipe Wall Roughness........................... 240, 244, 248, 260-262 Ratio Contraol.................................................................... 330
Pneumatic Piston Acutator................................................. 336 Reduced Pressure.......................................... 48, 56, 71, 81-85
Pneumatic Spring and Diaphragm Actuator...................... 336 Reduced Temperature................................... 48, 56, 71, 81-85
Polytropic........................................................................... 209 Reid Vapor Pressure (RVP)................................... 42, 125-129
Porcess Control See Control Relative Density....................................... 17, 21, 63, 66, 68-69
Positive Displacement Meters............................................ 344 Relative Roughness See Pipewall Roughness
Potential Energy (PE)......................................... 203-205, 208 Relief Devices.................................................................... 356
Pound Force, definition........................................................ 16 Relief Systems
Pound Mass, definition........................................................ 16 Devices................................................................ 358-361
Pour Point.................................................................... 73, 274 Scenarios.................................................................... 357
Pressure, definition............................................................... 18 Systems............................................................... 358-359
Drop, fluid flow..................... 240, 245-249, 252, 278-280 Valves.................................................................. 359-367
Measurement....................................................... 341-345 Reset, control..................................................................... 324
Pressure Valve, see relief valve Residue Gas See Sales Gas

Retrograde Condensation............................ 91, 92, 97, 98, 100 Stabilizing Crude Oil................................................... 34, 117
Reverse Acting, control...................................................... 327 Stage Separation System............................................. 118-121
Reversible Process..................................................... 207, 209 Standard Cubic Foot (scf), definition................................... 19
Reynolds Number......................... 240, 244-245, 248, 261-262 Standard Cubic Meter (std m3), definition.......................... 19
Rheopectic Liquid.............................................................. 244 Steady State................................................. 202, 205, 206, 258
Rotary Control Valves................................................ 330, 332 Stock Tank..............................................................117, 118, 129
Rupture Discs..................................................................... 362 “stock tank”................................................................ 118
Stranded Gas........................................................................ 44
S Stratified, flow regime......................................... 275, 281, 286
Safety Instrumented Functions (SIF)................................. 374 Stratified Wavy, flow regime............................... 280-281, 286
Safety Instrumented System (SIS)..................................... 374 Structure II (sII)
Safety Integrity Level (SIL)............................................... 374 see Gas Hydrates................................................. 157-158
Sales Gas Specifications................................................. 29-33 Structure I (sI)
Salts, inhibition effect........................................................ 174 see Gas Hydrates........................................................ 157
SDV (Shutdown Valve)...................................................... 374 Sub-cooling, Kinetic Inhib.......................................... 187-189
Sensible Heat..................................................................... 211 Subsonic, flare and relief..................................... 361, 370, 377
Set Point Control.................................. 316-321, 324, 326-327 Sulfur Content, sales gas specification........................... 32, 42
Set Pressure Relief Valve............................................ 363-365 Sulfur Recovery Unit (SRU)........................................ 36, 330
Severe Slugging.......................................................... 292-294 Sweetening...................................................................... 35-36
Shale Gas............................................................................. 27 System See Thermodynamics
Shrinkage........................................................................ 37-39 System Gain, control.......................................................... 318
Shut-In Tubing Head Pressure (SITHP)............................ 356 System Internationale (SI), definition.................................. 14
Signal Booster.................................................................... 337

Silica Gel........................................................................ 36, 40
T
Single Component Systems See Phase Behavior Tail Gas Unit (TGU)............................................................ 36
Slave Controller, control.................................................... 329 Taitel-Duckler Correlation, multiphase flow..................... 280
Sliding Stem....................................................................... 330 Temperature.................................................. 18, 319, 328-330
Sliding Vane Meters........................................................... 344 Temperature Measurement.......................................... 340-341
Slip ....................................................................... 277, 345 Terrain Induced Slugs........................................................ 290
Slug ............................................................................... 345 Test Separator Recombination.................................... 122-123
Slug Catchers...................................................... 294, 297, 299 Thermodynamic Inhibitors See Hydrate Inhibition
Slug Flow.................................................................... 290-292 Thermodynamics
Slugging....................................................... 276, 282, 290-300 Applications........................................................ 209-210
Smokeless Flaring.............................................................. 370 Basic Concepts.................................................... 201-202
Snap-acting, control........................................................... 321 First Law.................................................................... 205
Soave-Redlich-Kwong (SRK)....................................... 55, 58 Relationships.............................................................. 208
Sonic Tip, flare........................................................... 369, 370 Second Law................................................................ 206
Sonic/Ultrasonic Flow Meter..................................... 339, 342 Thermometers See Temperature Measurement
Sour ................................................................................ 9, 35 Thiophene.............................................................................. 9
Sour Natural Gas............................................................ 54, 84 Third Parameters, EOS........................................................ 56
Specific Volume (v)............................................................ 211 Thixotropic, fluid flow....................................................... 243
Split-Range Control.................................................... 327-328 Time Constant, control....................................................... 318
Spring and Diaphragm....................................................... 336 Toluene (C7H8)....................................................................... 7
Stability....................................................................... 319-320 Transducer, control............................................................ 339
Stabilization / Fractionation........................................... 34, 40 Transmitter, control.................................................... 315, 326
INDEX 413
Transportation Lag See Deadtime Weymouth Equation.................................................... 259-262
Trekell-Campell Correlation............................... 165, 192-200 Wichert Aziz, compressibility factor....................... 54, 84, 86
Trim, control valve............................................................. 332 Wobbe number................................................................ 30-31
Turbine Meters................................................................... 343 Work and Power, definition.................................................. 18
Work (W) See Thermodynamics, First Law
U
Ultrasonic Meters....................................................... 341, 342
X
Unbalance Force, control valve................................. 332, 333 Xylene ................................................................................... 7
Unconventional Gas............................................................. 27
Unsaturated Hydrocarbons................................................. 6, 7 Y
Y-grade................................................................................. 33
V
Valence................................................................... 4, 5, 11, 12
Valve Gain (Kv), control..................................................... 318
Valve Positioners................................................................ 337
Valves and Fittings...................................................... 249-251
Van der Waals................................................................. 54, 58
Vapor Liquid Equilibrium (VLE)................................ 103-118
Vapor Pressure of Hydrocarbons.................................... 89-90
Vapor Pressure Specifications............................... 42, 125-128
Vapor Solid Equilibrium Constants................................... 161
Velocity Seals..................................................................... 369
Vertical Flare Stack............................................................ 370
Vertical Two-Phase Flow.................................... 275, 289-290
Viscosity
Dynamic Viscosity............................................... 19, 243
Gas............................................................................... 60
Kinematic Viscosity............................................... 19, 73
Liquids.................................................................... 73-74
Volatile Oil Reservoir..................................................... 97-98
Volume, definition................................................................ 16
W
Water
Content in Gases................................................. 147-154
Measurement (Dewpoint)............................. 32, 155-156
Sales Specification................................................. 29, 36
Water cut............................................................................ 345
Water Seal, flare system..................................................... 369
Watson Characterization Factor, Kw............................. 62, 65
Weber Number, multiphase flow........................................ 278
Weight, definition................................................................. 16
Wet Gas Reservoir.......................................................... 97-98

JOHN M. CAMPBELL | PETROSKILLS BOOKS
GAS CONDITIONING AND PROCESSING “SERIES”
The first of a two volume series, this book has been published for the natural gas processing industry
for over 45 years. Volumes 1 and 2 of “Gas Conditioning and Processing”, used in the Campbell Gas
Course® (G-4), are the most “borrowed” books from many engineers’ shelves. This edition has been
edited to reflect continuing changes in technology and the manner in which it is practiced. This book
addresses material and energy balances; phase behavior; physical properties; water-hydrocarbon equilib-
rium; hydrates; applied thermodynamics; process control; and flow of fluids.
VOLUME 2: THE EQUIPMENT MODULES

The second of a two volume series, this book is a continuation of the material presented in The Basic
Principles. This edition includes information for applying today’s technology and the current business
requirements to selecting and operating gas processing and production facilities. This book aids in deci-
sions relating to separation; heat transfer; pumps; compressors; refrigeration; fractionation and absorp-
tion; glycol and solid bed dehydration.
ADDITIONAL BOOK PUBLICATIONS

VOLUME 4: GAS TREATING AND SULFUR RECOVERY
This book concentrates on problems associated with treating and removing CO2 and sulfur compounds
often associated with natural gas production. A detailed view of commercial amine type processors;
carbonate processes; physical absorption methods; solid bed sweetening; sulfur production; and tail gas
conditioning is presented.
APPLIED WATER TECHNOLOGY

This book focuses on water handling and disposal problems for produced water associated with natural
gas and oil production. The subjects covered include: water sampling and analysis; water formed scales;
corrosion control; microbiology; water processing equipment; water injection system; water treatment for
EOR; boiler water and cooling water treatment.
COMPUTER PROGRAMS
GCAP ® 9th EDITION
This software is a companion to the latest edition of Volumes 1 and 2 of our Gas Conditioning and Pro-
cessing series. It is based on the equations and correlations referenced in the textbook. This software is
designed to aid the facilities engineer, process engineer, and manager with a quick review of detailed
calculations to check for accuracy. It is not designed to replace process simulators or equipment manu-
facturer’s verification. So the next time someone asks you, “Is this separator properly sized?”, amaze your
manager by using GCAP™.
To order our books, please visit our website at www.petroskills.com or contact us at +1-918-828-2500. A
price list for all books is available upon request. Professional training courses using these books also are
available exclusively through John M. Campbell | PetroSkills.
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GAS CONDITIONING AND PROCESSING

Volume 1: The Basic Principles

© 2017 PetroSkills, all rights reserved PetroSkills, LLC.

3rd Printing, June 2017

Published by: PetroSkills, LLC.

Special Thanks: Illustrators: Amy Ashby – Graphics Specialist

Relative Atomic Mass (Weight)...........................................................................................................................................3

Gas Processing / NGL Extraction......................................................................................................................................37

ii VOLUME 1: THE BASIC PRINCIPLES

TABLE OF CONTENTS iii

Inhibition in the Presence of Salts in Produced Water.................................................................................................... 174

iv VOLUME 1: THE BASIC PRINCIPLES

Pressure Surges ...............................................................................................................................................................254

vi VOLUME 1: THE BASIC PRINCIPLES

TABLE OF CONTENTS vii

viii VOLUME 1: THE BASIC PRINCIPLES

4.19 Process Flow Diagram for an Amine System Inlet...........................................................................................................100

6.18b Methanol K-Values in Natural Gas, FPS Units................................................................................................................ 175

x VOLUME 1: THE BASIC PRINCIPLES

7A.6(a) Enthalpy, kJ/kg Hydrocarbon Gas P = 2.8 MPa..............................................................................................................230

8.22 Flanigan’s Liquid Head Factor.........................................................................................................................................284

xii VOLUME 1: THE BASIC PRINCIPLES

9.28 Sliding Vane Meter.......................................................................................................................................................... 344

TABLE OF CONTENTS xiii

2.8 NGL Product and Markets.................................................................................................................................................33

xiv VOLUME 1: THE BASIC PRINCIPLES

SOME CAMPBELL LAWS OF ENGINEERING

• The physical properties of the fluids and solids

• The vapor-liquid-solid behavior of a substance as a function of pressure, temperature, and

• The concept of equilibrium

2 VOLUME 1: THE BASIC PRINCIPLES

Elements and Atoms

Chemical Compounds and Molecules

Relative Atomic Mass (Weight) Table 1.1

Relative Molecular Mass (Weight)

atoms, molecules, ions, electrons, etc.

4 VOLUME 1: THE BASIC PRINCIPLES

BASIC HYDROCARBON NOMENCLATURE

Paraffin Series (Alkanes) Formula: CnH2n+2

Methane, CH4 Ethane, C2H6 Propane, C3H8

Figure 1.1 Methane, Ethane, and Propane

Name Formula Mol. Wt. Name Formula Mol. Wt.

designate a molecule with the carbon atoms in a straight line.

Olefin or Ethylene Series (Alkenes) Formula: CnH2n

6 VOLUME 1: THE BASIC PRINCIPLES

These molecules possess many different properties. They

This series is of basic importance only in certain refining

and petrochemical applications. Acetylene is the most important

Diolefins Formula: CnH2n-2 H H

Diolefins are primarily of concern in petrochemical plants. Butadiene Butadiene, C4H6

Aromatic (Benzene) Series Formula: CnH2n-6

Benzene, C6H6 Ethylbenzene, C6H5CH2CH3 Toluene, C6H5CH3 Para-Xylene, C6H4(CH3)2

Figure 1.7 BETX Compounds (Benzene, Ethylbenzene, Toluene, Xylene)

H H Naphthene Series Formula: CnH2n

TYPICAL COMPOUNDS IN PRODUCTION/PROCESSING SYSTEMS

8 VOLUME 1: THE BASIC PRINCIPLES

Common Contaminants Found in Natural Gas