B.E. Sem.

VII (Chemical)

Chapter 3
Synthesis of Separation Trains
from the subject

Computer Aided Process Synthesis

(3170507)

by

Dr. Vyomesh M. Parsana

Assistant Professor,
Chemical Engineering Department
V. V. P. Engineering College, Rajkot
 Teaching and Examination Scheme

Teaching Credits Examination Marks

Scheme
Total
Theory Marks Practical Marks Marks
L T P C
ESE (E) PA (M) ESE (V) PA (I)
3 0 2 4 70 30 30 20 150

 Chapter 3: Synthesis of Separation Trains (8 hrs)

 Chapter 4: Synthesis of Heat Exchanger Networks (16 hrs)
 Chapter 5: Energy Integrated Distillation Processes (6 hrs)
 Detailed Syllabus
Chap. Content Total
No. hrs
3 Synthesis of Separation Trains: 8
Objectives, Introduction, Phase Separation of Reactor Effluent,
Criteria for Selection of Separation Methods, Selection of
Equipment, Sequencing of Ordinary Distillation for the Separation
of Nearly Ideal Fluid Mixtures, Heuristics for Determining
Favourable Sequences, Marginal Vapour Rate Method, Complex and
thermally coupled distillation, Sequencing of Ordinary Distillation
for the Separation of nearly Non-Ideal fluid mixtures

4 Synthesis of Heat Exchanger Networks: 16

Objectives, Basic Heat Exchanger Network Synthesis (HENS),
Minimum Utility Targets, Temperature Interval Method,
Hohmann / Lochart Composite Curves (HCC), Grand Composite
Curves (GCC), Pinch Design Approach to Inventing a Network,
Networks for Maximum Energy Recovery, Minimum Number of
Exchangers, Stream Splitting, Threshold and Optimum Approach
Temperature, Derivation of Network Superstructures for
Minimization of Annual Costs, Multiple Utility Design Problems
 Detailed Syllabus
Chap. Content Total
No. hrs
5 Energy Integrated Distillation Processes: 6
Heat Integrated Distillation Trains, Impact of Pressure, Multi Effect
Distillation, Heat Pumping, Vapour Recompression and Reboiler
Flashing, Positioning of Heat Engines and Heat Pumps
 Reference Books
1. Lorens T. Biegler, E. Ignacio grossmann, Arthur W. Westerberg,
Systematic Methods of Chemical Process Design, Prentice Hall
International.
2. Warren D. Seider, J. D. Seader, Daniel R. Lewin, Product and
Process Design Principles: Synthesis, Analysis, and Evaluation,
2nd Edition, Wiley.
3. Robin Smith, Chemical Process: Design and Integration, Wiley.
4. James M. Douglas, Conceptual Design of Chemical Processes,
McGraw Hill International, 1988
 Course Outcomes – CAPS (3170507)
At the end of the course, students will be able to:
CO
number Course Outcomes Level
C70507.1 Describe environment protection, safety consideration & U
engineering ethics in product process design.
C70507.2 Establish the reactor network using the attainable Ap
region concept of reactor network synthesis.
C70507.3 Determine an optimal sequence of distillation type Ap
separations with knowledge of separation factor.
C70507.4 Develop the heat exchanger networks for energy C
integration.
C70507.5 Recognize an approach of designing energy-efficient U
distillation trains and positioning of heat engines and
heat pumps.
C70507.6 Use scheduling of batch plants for the production of Ap
single and multiple products.
 Synthesis of Separation Trains
Chap. Content Total
No. hrs
3 Synthesis of Separation Trains: 8
Objectives, Introduction, Phase Separation of Reactor
Effluent, Criteria for Selection of Separation Methods,
Selection of Equipment, Sequencing of Ordinary
Distillation for the Separation of Nearly Ideal Fluid
Mixtures, Heuristics for Determining Favourable
Sequences, Marginal Vapour Rate Method, Complex and
thermally coupled distillation, Sequencing of Ordinary
Distillation for the Separation of nearly Non-Ideal fluid
mixtures
Introduction
 Introduction
• Almost all chemical processes require the separation of
chemical species (components), to:
 Purify a reactor feed
 Recover unreacted species for recycle to a reactor
 Separate and purify the products from a reactor

• Frequently, the major investment and operating costs of a

process will be associated with separation equipment
• For a binary mixture, it may be possible to select a
separation method that can accomplish the separation
task in just one piece of equipment.

• More commonly, the feed mixture involves more than two

components, involving more complex separation systems.
 Instructional Objectives

When you have finished studying this unit, you should:

 Be familiar with the more widely used industrial

separation methods and their basis for separation.
 Understand the concept of the separation factor and be
able to select appropriate separation methods for vapor
and liquid mixtures.
 Understand how distillation columns are sequenced and
how to apply heuristics to narrow the search for a near-
optimal sequence.
 Be able to apply algorithmic methods to determine an
optimal sequence of distillation-type separations.
Phase Separation of Reactor Effluent
Examples of Phase Separation Devices
 Example: Butenes Recovery
Species b.pt.(C) Tc (C) Pc, (MPa)
Propane A -42.1 97.7 4.17
1-Butene B -6.3 146.4 3.94
n-Butane C -0.5 152.0 3.73
trans-2-Butene D 0.9 155.4 4.12
cis-2-Butene E 3.7 161.4 4.02
n-Pentane F 36.1 196.3 3.31
 Example: Butenes Recovery

100-tray column
C3 & 1-Butene in
distillate

Propane and
1-Butene recovery
Pentane withdrawn
as bottoms n-C4 and 2-C4=s
cannot be
separated by
ordinary distillation
(=1.03), so 96%
furfural is added as
2-C4=s withdrawn as an extractive agent
distillate. Furfural is (  1.17).
recovered as bottoms n-C4 withdrawn as
and recycled to C-4 distillate.
 Separation is Energy Intensive
• Unlike the spontaneous mixing of chemical species, the
separation of a mixture of chemicals requires an
expenditure of some form of energy

• Separation of a feed mixture into streams of differing

chemical composition is achieved by forcing the different
species into different spatial locations, by one or a
combination of four common industrial techniques:
 The creation by heat transfer, shaft work, or pressure reduction
of a second phase that is immiscible with the feed phase (ESA –
energy separating agent)
 Introduction into the system of a second fluid phase (MSA –
mass separating agent). This must be subsequently removed.
 Addition of a solid phase upon which adsorption can occur
 Placement of a membrane barrier
 Common Separation Methods

Separation Phase of Separation Developed or Separation

Method the feed agent added phase principle
Equilibrium L and/or V Pressure V or L difference
reduction or
flash heat transfer
in volatility
Distillation L and/or V Heat transfer V or L difference
or shaft work
in volatility
Gas V Liquid L difference
absorbent
Absorption in volatility
Stripping L Vapor stripping V difference
agent
in volatility
Extractive L and/or V Liquid solvent V and L difference
and heat
Distillation transfer
in volatility
Azeotropic L and/or V Liquid V and L difference
entrainer and
Distillation heat transfer
in volatility
 Common Separation Methods

Separation Phase of Separation Developed Separation

Method the feed agent or added principle
phase
Liquid-liquid L Liquid Second Difference in
Extraction solvent liquid solubility

Crystalli- L Heat Solid Difference in

zation transfer solubility or
m.p.
Gas V Solid Solid difference in
adsorption adsorbent adsorbabililty

Liquid L Solid Solid difference in

adsorption adsorbent adsorbabililty

Membranes L or V Membrane Membrane difference in

permeability
and/or
solubility
 Common Separation Methods

Separation Phase of Separation Developed Separation

Method the feed agent or added principle
phase
Supercritical L or V Supercritical Supercritical Difference
extraction solvent fluid in solubility
Leaching S Liquid L Difference
solvent in solubility
Drying S and L Heat V Difference
transfer in volatility
Criteria of Selection of Separation Methods
• The development of a separation process requires the
selection of:
 Separation methods
 ESAs and/or MSAs
 Separation equipment
 Optimal arrangement or sequencing of the equipment
 Optimal operating temperature and pressure for the equipment

• Selection of separation method depends on feed condition:

• Vapor Partial condensation, distillation, absorption,
adsorption, gas permeation (membranes)
• Liquid Distillation, stripping, LL extraction, supercritical
extraction, crystallization, adsorption, and dialysis or
reverse osmosis (membranes)
• Solid If wet  drying, if dry  leaching
 Separation Method Selection
• The separation factor, SF, defines the degree of separation
achievable between two key components of the feed. This
factor, for separation of component 1 from component 2
between phases I & II, for a single stage of contacting, is:

C = composition
variable, I, II = phases (8.1)
rich in components 1
and 2.
• SF is generally limited by thermodynamic equilibrium. For
example, in the case of distillation, using mole fractions as the
composition variable and letting phase I be the vapor and phase
II be the liquid, the limiting value of SF is given in terms of
vapor-liquid equilibrium ratios (K-values) as:

(8.2), (8.3)
 Separation Method Selection
• For vapor-liquid separation operations that use an MSA that
causes the formation of a non-ideal liquid solution (e.g.
extractive distillation):

(8.
5)
• If the MSA is used to create two liquid phases, such as in liquid-
liquid extraction, the SF is referred to as the relative selectivity,
β , where:
(8.
6)

• In general, MSAs for extractive distillation and liquid-liquid

extraction are selected according to their ease of recovery for
recycle and to achieve relatively large values of SF.
 Equal Cost Separators
Liquid-Liquid Extraction
should NOT be used
when α for ordinary
distillation is greater
than 3.2

Extractive distillation
should NOT be used
when α for ordinary
distillation is
greater than 2

Ref: Souders (1964)

 Summary – Separation Trains

On completion of this part, you should:

 Be familiar with the more widely used industrial separation

methods and their basis for separation.

 Understand the concept of the separation factor and be

able to select appropriate separation methods for liquid
mixtures.
 Objectives

 Understand how distillation columns are sequenced and

how to apply heuristics to narrow the search for a near-
optimal sequence.

 Be able to apply systematic methods to determine an

optimal sequence of distillation-type separations.
 Sequencing OD Columns
• Use a sequence of ordinary distillation (OD) columns to
separate a multicomponent mixture provided:

  in each column is > 1.05.

 The reboiler duty is not excessive.
 The tower pressure does not cause the mixture to approach the
TC of the mixture.
 Column pressure drop is tolerable, particularly if operation is
under vacuum.
 The overhead vapor can be at least partially condensed at the
column pressure to provide reflux without excessive refrigeration
requirements.
 The bottoms temperature for the tower pressure is not so high
that chemical decomposition occurs.
 Azeotropes do not prevent the desired separation.
Pressure/Condenser Algorithm
 Number of Sequences of Ordinary Distillation Columns

• Number of different sequences of P –1 ordinary distillation

(OD) columns, NS, to produce P products:

 P # of Separators  Ns
2 1 1
3 2 2
4 3 5
5 4 14
6 5 42
7 6 132
8 7 429
Thomson and King Formula
Example: 4 Components
Example: 4 Components
 Best Sequence using Heuristics
• The following guidelines are often used to reduce the
number of OD sequences that need to be studied in detail:
 Remove thermally unstable, corrosive, or chemically reactive
components early in the sequence.
 Remove final products one-by-one as distillates (the direct sequence).
 Sequence separation points to remove, early in the sequence, those
components of greatest molar percentage in the feed.
 Sequence separation points in the order of decreasing relative
volatility so that the most difficult splits are made in the absence of
other components.
 Sequence separation points to leave last those separations that give
the highest purity products.
 Sequence separation points that favor near equimolar amounts of
distillate and bottoms in each column. The reboiler duty should not be
excessive.
 Class Exercise

Design a sequence
of ordinary
distillation columns
to meet the given
specifications.
Exercise – Possible Solution

Guided by Heuristic 4, the first

column in position to separate the
key components with the greatest
SF.

 Sequence separation points in the

order of decreasing relative volatility
so that the most difficult splits are
made in the absence of other
components.
 Exercise – Possible Solution

a = 1.5

a = 3.6 a = 2.8

a = 1.35
 Marginal Vapor Rate Method

When the number of products is more than four, using the annualized
cost method is very difficult and time-consuming. One of the less rigorous
method for OD that can produce good results is Marginal Vapor Rate
(MV) that proposed by Modi and Westerberg (1992).

 The difference in costs between the separation in the absence of

nonkey components and the separation in the presence of nonkey
components, defined as Marginal Annualized Cost (MAC).
 A good approximation of MAC is the MV, which is the corresponding
difference in molar vapor rate passing up the column. The sequence
with the minimum sum of column MVs is selected.
 Vapor rate is a good measure of cost because it is a major factor in
determining column diameter, reboiler and condenser areas, and
reboiler and condenser duties.
 Estimating Marginal Vapor Rate, MV
 For each separation, MV is estimated assuming feed at
bubble point and 99.9 mol % recovery of light key and heavy
key in distillate and bottom, respectively. The following steps
are followed:

1. Set distillate and bottoms column pressures using

2. Estimate distillate rate (D), by using a short-cut distillation method

(e.g., DSTWU in Aspen plus with R=1.2 Rmin).

3. Calculate the up column vapor rate as V=D(R+1).

4. Calculate the MV (The difference in vapor rate between the

separation in the absence of nonkey components and the
separation in the presence of nonkey components)
 Example
 Use the marginal vapor rate (MV) method to determine a
sequence for the hydrocarbon specified in the figure, except:
1. Ignore the given temperature and pressure of the feed
2. Assume a recovery of 99.9% in each column
 Example 4
A=isobutane, B= n-butane, C=isopentane, D= n-
pentane
 Minimum and Marginal vapor flow
Underwood's method for minimum vapor flow

Marginal vapor flow calculation

(a simplified formula)
5 components Alcohol Mixture

Marginal vapor flows

Total Marginal vapor flows
Possible Sequences
 Complex Columns
• In some cases, complex rather than simple distillation
columns should be considered when developing a
separation sequence.

Ref: Tedder and Rudd (1978)

 Regions of Optimality
• As shown below, optimal regions for the various
configurations depend on the feed composition and the
ease-of-separation index (ESI):
ESI = AB/
BC

ESI  1.6 ESI  1.6

 Introduction
• Separation sequences are complicated by the presence of
azeotropes, often involving mixtures of oxygenated
organic compounds:
 Alcohols
 Ketones
 Ethers
 Acids
 Water

• In these cases, distillation boundaries limit the product

compositions of a column to lie within a bounded region.

• This prevents the removal of certain species in high

concentrations.
Homogeneous Azeotropes 1:4

At equilibrium:

At fixed temperature
Homogeneous Azeotropes 2:4

Example – Phase diagrams for benzene-

toluene mixture at 90 oC
 Homogeneous Azeotropes 3:4

For non-ideal mixtures, the

activity coefficients are
different from unity:

If the mixture has a minimum-boiling

azeotrope

Example – Phase diagrams for Isopropyl ether-Isopropyl alcohol

 Homogeneous Azeotropes 4:4

For non-ideal mixtures, the

activity coefficients are
different from unity:

If the mixture has a maximum-boiling azeotrope

Example – Phase diagrams for Acetone-Chloroform

 Heterogeneous Azeotropes

For a minimum-boiling azeotrope with large deviation from

Raoult’s law ( ), phase splitting may occur and a
minimum-boiling heterogeneous azeotrope forms, having a
vapor phase in equilibrium with two liquid phases.

Homogeneous Azeotrope Heterogeneous Azeotrope

 Residue Curves 1:3

Simple Distillation

Mass balance on species j:

Rearranging:
 Residue Curves 2:3
• Residue Curves  Liquid Compositions at Total Reflux

Residue curves for

zeotropic system
Residue curves for
Azeotropic system