AES Notes

Advanced Engineering
Separations
2019-2020
Thomas Rodgers
UG Notes
Contents
List of Figures vii
List of Tables ix
Nomenclature xi
Course Information xiii
1 Industrial Separations 1
1.1 Chapter 1 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Basic Separation Techniques . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Separations by Phase Addition or Creation . . . . . . . . . . . . . . . . . 5
1.5 Separations by Barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.6 Separations by Solid Agents . . . . . . . . . . . . . . . . . . . . . . . . 14
1.7 Separations by External Field or Gradient . . . . . . . . . . . . . . . . . 16
1.8 Component Recoveries . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.8.1 Split Fractions and Split Ratios . . . . . . . . . . . . . . . . . . 19
1.8.2 Separation Factor . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.10 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2 Liquid-Liquid Extraction 27
2.1 Chapter 2 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2.1 Partition coefficient . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2.2 Solvent Selection . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.3 General Design Considerations . . . . . . . . . . . . . . . . . . . . . . . 32
2.4 Representation of Multi-phase Liquid-Liquid Systems . . . . . . . . . . . 33
2.5 Single Stage Liquid-Liquid Extraction . . . . . . . . . . . . . . . . . . . 34
2.6 Lever-Arm Rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.7 Hunter-Nash Graphical Equilibrium-Stage Method . . . . . . . . . . . . 37
2.7.1 Step 1 - Calculation of the Mixing Point . . . . . . . . . . . . . . 38
2.7.2 Step 2 - Product Mass Balance . . . . . . . . . . . . . . . . . . . 38
2.7.3 Step 3 - Calculation of the Operating Lines . . . . . . . . . . . . 39
2.7.4 Step 4 - Tie Lines and Equilibrium Lines . . . . . . . . . . . . . 40
2.8 Minimum and Maximum Solvent-to-Feed Flow-Rate Ratios . . . . . . . 41
2.8.1 Minimum Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
i
2.8.2 Maximum Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.9 Equipment for Solvent Extraction . . . . . . . . . . . . . . . . . . . . . 45
2.9.1 Mixer-Settlers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.9.2 Spray Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.9.3 Packed Columns . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.9.4 Plate Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.9.5 Columns with Mechanically Assisted Agitation . . . . . . . . . . 48
2.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.11 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3 Multi-Component Distillation 59
3.1 Chapter 3 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3 Vapour-Liquid Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.4 Short-cut methods for multi-component distillation . . . . . . . . . . . . 64
3.4.1 Relative volatility . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.4.2 The Fenske equation . . . . . . . . . . . . . . . . . . . . . . . . 65
3.4.3 The Hengstebeck-Geddes Method . . . . . . . . . . . . . . . . . 67
3.4.4 The Underwood Equation . . . . . . . . . . . . . . . . . . . . . 69
3.4.5 The Gilliland correlation . . . . . . . . . . . . . . . . . . . . . . 72
3.4.6 The Erbar-Maddox correlation . . . . . . . . . . . . . . . . . . . 73
3.4.7 The Kirkbride Correlation . . . . . . . . . . . . . . . . . . . . . 74
3.4.8 Procedures of the short-cut design . . . . . . . . . . . . . . . . . 74
3.5 Rigorous Model for Multi-component Distillation . . . . . . . . . . . . . 75
3.6 Considerations in Multi-component Distillation . . . . . . . . . . . . . . 77
3.6.1 Choice of distillation operating parameters . . . . . . . . . . . . 77
3.6.2 Choice of reflux ratio . . . . . . . . . . . . . . . . . . . . . . . . 80
3.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.8 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4 Distillation Sequencing 91
4.1 Chapter 4 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.3 Sequencing Simple Distillation Columns . . . . . . . . . . . . . . . . . . 93
4.4 Distillation Columns Sequencing Heuristics . . . . . . . . . . . . . . . . 95
4.5 Performance Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5.1 Vapour load . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5.2 Energy demand . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.5.3 Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.6 Distillation Sequencing with Complex Columns . . . . . . . . . . . . . . 98
4.6.1 Side-Steam Columns . . . . . . . . . . . . . . . . . . . . . . . . 98
4.6.2 Side-stripper arrangement . . . . . . . . . . . . . . . . . . . . . 99
4.6.3 Side-rectifier arrangement . . . . . . . . . . . . . . . . . . . . . 100
4.6.4 Pre-fractionation arrangements . . . . . . . . . . . . . . . . . . . 101
4.7 Utility Considerations with Thermally Coupled Columns . . . . . . . . . 103
4.8 Decomposition of Complex Columns for Design . . . . . . . . . . . . . 105
4.8.1 Side-stripper decomposition . . . . . . . . . . . . . . . . . . . . 105
4.8.2 Side-rectifier decomposition . . . . . . . . . . . . . . . . . . . . 106
4.8.3 Pre-fractionator decomposition . . . . . . . . . . . . . . . . . . . 106
4.8.4 Extension to Underwood Equations for Side Stream Columns . . 106
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4.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4.10 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5 Azeotropic Distillation 115

5.1 Chapter 5 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5.2 Azeotropic mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.3 Triangular Graphs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.3.1 Residue-Curve Maps . . . . . . . . . . . . . . . . . . . . . . . . 122
5.3.2 Distillation-Curve Maps . . . . . . . . . . . . . . . . . . . . . . 124
5.3.3 Approximate Residue-Curve Maps . . . . . . . . . . . . . . . . . 126
5.3.4 Feasible Product-Composition Regions at Total Reflux . . . . . . 130
5.3.5 Extension to Short-cut Equations for Azeotropic Systems . . . . . 132
5.4 Separations for Azeotropes . . . . . . . . . . . . . . . . . . . . . . . . . 134
5.4.1 Pressure Swing Distillation . . . . . . . . . . . . . . . . . . . . . 135
5.4.2 Extractive Distillation . . . . . . . . . . . . . . . . . . . . . . . 136
5.4.3 Homogeneous Azeotropic Distillation . . . . . . . . . . . . . . . 139
5.4.4 Heterogeneous Azeotropic Distillation . . . . . . . . . . . . . . . 139
5.4.5 Reactive Distillation . . . . . . . . . . . . . . . . . . . . . . . . 140
5.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
6 Revision 151
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.2 Flash Equlibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.3 McCabe-Thiele Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.4 Ponchon-Savarit Method . . . . . . . . . . . . . . . . . . . . . . . . . . 158
6.5 Absorption/Desorption . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.5.1 Scrubbing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.5.2 Stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.6 Liquid-Liquid Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . 165
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List of Figures
1.1 Example of a simple chemical process. . . . . . . . . . . . . . . . . . . . 3

1.2 Basic separation techniques. . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1 Common liquid-liquid extraction cascade configurations. . . . . . . . . . 32

2.2 Ternary phase diagram for a 2 phase liquid-liquid system. . . . . . . . . . 34
2.3 Some examples of liquid-liquid systems . . . . . . . . . . . . . . . . . . 34
2.4 Single stage liquid-liquid extraction. . . . . . . . . . . . . . . . . . . . . 34
2.5 Ternary phase diagram for a general system. . . . . . . . . . . . . . . . . 35
2.6 Counter-current flow liquid-liquid extraction cascade. . . . . . . . . . . . 37
2.7 Construction 1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.8 Construction 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.9 Construction 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.10 Construction for minimum solvent to feed ratio. . . . . . . . . . . . . . . 42
2.11 Construction of the minimum solvent to feed ratio. . . . . . . . . . . . . 43
2.12 Determination of Mmin . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.13 Determination of Mmax . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.14 Mixer-Settler equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.15 Spray columns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.16 Efficiency of liquid-liquid packed column. . . . . . . . . . . . . . . . . . 47
2.17 Commercial extractor with mechanically assisted agitation. . . . . . . . . 48
3.1 Multi-component distillation. . . . . . . . . . . . . . . . . . . . . . . . . 62

3.2 Vapour-liquid equilibrium of Benzene-Toluene mixture. . . . . . . . . . . 64
3.3 Simple distillation column for deriving the Fenske equation. . . . . . . . 65
3.4 The Hengstebeck-Geddes relation. . . . . . . . . . . . . . . . . . . . . . 68
3.5 Pinch point condition for a binary system. . . . . . . . . . . . . . . . . . 69
3.6 Graphical solution to the first Underwood equation. . . . . . . . . . . . . 72
3.7 The Gilliland correlation. . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.8 The Erbar-Maddox correlation. . . . . . . . . . . . . . . . . . . . . . . . 74
3.9 Mass and Energy Flow in the Top of a Distillation Column. . . . . . . . . 76
3.10 Condenser options. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.11 The effects of pressure of distillation. . . . . . . . . . . . . . . . . . . . 79
3.12 The effect of temperature on utility costs. . . . . . . . . . . . . . . . . . 79
3.13 Effect of reflux ratio on the number of theoretical stages. . . . . . . . . . 80
3.14 Trade-offs between the capital and energy costs. . . . . . . . . . . . . . . 80
3.15 Heating duty against feed position. . . . . . . . . . . . . . . . . . . . . . 82
4.1 A simple column. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
v
4.2 The direct and indirect sequences. . . . . . . . . . . . . . . . . . . . . . 94
4.3 Alternative sequences for separating a five component mixture. . . . . . . 95
4.4 Schematic representation of the vapour load. . . . . . . . . . . . . . . . . 97
4.5 Energy demand for condensers. . . . . . . . . . . . . . . . . . . . . . . . 98
4.6 Side-stream distillation columns. . . . . . . . . . . . . . . . . . . . . . . 99
4.7 Thermally coupled distillation configurations. . . . . . . . . . . . . . . . 100
4.8 Thermal coupling for indirect sequences. . . . . . . . . . . . . . . . . . . 100
4.9 Energy Savings for using a Side-Stripper System. . . . . . . . . . . . . . 101
4.10 Thermal coupling for direct sequences. . . . . . . . . . . . . . . . . . . . 101
4.11 Thermal coupling for pre-fractionation sequences. . . . . . . . . . . . . . 102
4.12 Conventional sequence for separating a three component mixture. . . . . 103
4.13 Composition profile of component B in the pre-fractionation arrangement. 103
4.14 Comparison of temperature range. . . . . . . . . . . . . . . . . . . . . . 104
4.15 The decomposition of a side-stripper. . . . . . . . . . . . . . . . . . . . . 105
4.16 The decomposition of a side-rectifier. . . . . . . . . . . . . . . . . . . . 106
4.17 The decomposition of a pre-fractionator. . . . . . . . . . . . . . . . . . . 107
4.18 A side stream column. . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.1 Minimum-boiling-point azeotrope. . . . . . . . . . . . . . . . . . . . . . 117

5.2 Maximum-boiling-point azeotrope. . . . . . . . . . . . . . . . . . . . . . 118
5.3 Minimum-boiling-point azeotrope. . . . . . . . . . . . . . . . . . . . . . 118
5.4 Stichlmair ternary diagram. . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.5 Residue curves for liquid-phase compositions of ternary systems. . . . . . 120
5.6 Distillation sequences for ternary zeotropic mixtures. . . . . . . . . . . . 121
5.7 Distillation sequences for ternary azeotropic mixtures. . . . . . . . . . . 122
5.8 Residue-curve patterns. . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
5.9 Comparison of residue curves to distillation curves. . . . . . . . . . . . . 125
5.10 Actual distillation plotted on a residue curve plot. . . . . . . . . . . . . . 126
5.11 Product-composition regions for a zeotropic system. . . . . . . . . . . . . 130
5.12 Product-composition regions for given feed compositions. . . . . . . . . 131
5.13 Transformation for short-cut method for azeotropes. . . . . . . . . . . . . 132
5.14 Ternary transformation for short-cut method for azeotropes. . . . . . . . . 133
5.15 Pressure swing to break a minimum boiling binary azeotrope. . . . . . . . 136
5.16 Typical 3 column extractive distillation sequence. . . . . . . . . . . . . . 137
5.17 Typical 3 column distillation sequence in ternary space. . . . . . . . . . . 137
5.18 Vapour-Liquid equilibrium for Butadiene and Butane. . . . . . . . . . . . 138
5.19 Distillation sequence for homogeneous azeotropic distillation. . . . . . . 140
5.20 Distillation sequence for heterogeneous azeotropic distillation. . . . . . . 141
5.21 Typical 2 column distillation sequence in ternary space. . . . . . . . . . . 141
6.1 Flash Vessel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

6.2 Mass balance around the top of distillation column. . . . . . . . . . . . . 155
6.3 Mass balance on the enrichment section of a distillation column. . . . . . 155
6.4 Mass balance on the feed section of a distillation column. . . . . . . . . . 156
6.5 Graphical McCabe-Thiele Operating lines. . . . . . . . . . . . . . . . . . 157
6.6 Graphical McCabe-Thiele Stages. . . . . . . . . . . . . . . . . . . . . . 158
6.7 Mass and energy balance around the top of distillation column. . . . . . . 159
6.8 Graphical Ponchon-Savarit Operating points. . . . . . . . . . . . . . . . 161
6.9 Graphical Ponchon-Savarit Stages. . . . . . . . . . . . . . . . . . . . . . 162
6.10 Absorption Column Mass Balance. . . . . . . . . . . . . . . . . . . . . . 163
6.11 Graphical Scrubbing Operating lines. . . . . . . . . . . . . . . . . . . . . 164
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6.12 Graphical Stripping Operating lines. . . . . . . . . . . . . . . . . . . . . 165
6.13 Liquid-Liquid Extraction Column Mass Balance. . . . . . . . . . . . . . 166
6.14 Graphical Liquid-Liquid Extraction Operating lines. . . . . . . . . . . . . 166
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viii
List of Tables
1.1 Separation Operations Based on Phase Creation or Addition. . . . . . . . 8

1.2 Separation Operations Based on a Barrier. . . . . . . . . . . . . . . . . . 12
1.3 Separation operations based on solid agents. . . . . . . . . . . . . . . . . 15
1.4 Separation operations by external field or gradient. . . . . . . . . . . . . 17
2.1 Example solubility parameters . . . . . . . . . . . . . . . . . . . . . . . 31
3.1 Representative commercial distillation operations. . . . . . . . . . . . . . 81
4.1 Number of sequences changes with the number of components. . . . . . . 94
5.1 Example relative volatilities for a ternary system. . . . . . . . . . . . . . 133

5.2 Example transposed relative volatilities for a ternary system. . . . . . . . 134
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x
Nomenclature
Roman
B Bottom product flow mol s−1
D Distillate flow mol s−1
E Extract kg s−1
EA Extraction factor −
F Mass flow rate kg s−1
f Fugacity Pa
KD Partition coefficient −
L Liquid flow mol s−1
N Number of stages −
n Molar flow rate mol s−1
n Stage number −
−1
R Raffinate kg s
R Reflux ratio −
SF Split fraction −
SP Separation factor −
SR Split ratio −
−1
V Vapour flow mol s
x Mole fraction −
Greek
α Relative volatility −
γ Activity coefficient −
µ Chemical potential J mol−1
φ Fugacity coefficient −
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Course Information
Separations have been a key step in processing for thousands of years. Separations are
crucial in chemical engineering; a typical chemical plant is a chemical reactor surrounded
by separators. Raw materials are pre-purified in separation devices and fed to the chem-
ical reactor; unreacted feed is separated from the reaction products and recycled back
to the reactor. Products must be further separated and purified before they can be sold.
Chemical plants commonly have from 40% to 70% of both capital and operating costs in
separations.
This course has been developed to cover some of the widely used separation methods in
industries and link fundamental theory to design. The course ILOs are:
ILO 1. Classify separation processes by type and select suitable separations for mixtures
based on the properties of the components.
ILO 2. Design liquid-liquid extraction columns for ternary systems using the Hunter-
Nash method.
ILO 3. Calculate the approximate design of multi-component distillation columns using
short-cut models.
ILO 4. Assess simple and complex distillation column sequences using heuristic rules to
find the optimal options.
ILO 5. Construct azeotropic distillation sequences using residue curve for ternary sys-
tems.
The course is built around this handbook, and the content within is supported by the lec-
tures, tutorial questions, past exam papers, key concept videos, and a selection of online
formative questions. Key videos can be accesed by scanning the QR codes found in these
notes, or following the weblinks on blackboard. For a complete set of all the videos follow
the AdvancedEngineeringSeparations channel on YouTube.
The tutorial questions are listed in 3 classifications,
R for revision questions. These refer to topics from previous courses, but will help your
understanding of this course.
E for exam style questions. These are questions in the style which may appear in the
exam.
D for design style questions. These are questions that may require you to look up more
information, use a computer, or go beyond the core course.
For discussion of specific topics regarding this course with your fellow students or to
communicate with the module leader, please use the Discussion Board and post your
threads. The module leader will look on the board regularly and answer those uncleared
questions, or come to the drop in session.
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Chapter 1
Industrial Separations
Contents
1.1 Chapter 1 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Basic Separation Techniques . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Separations by Phase Addition or Creation . . . . . . . . . . . . . . 5
1.5 Separations by Barriers . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.6 Separations by Solid Agents . . . . . . . . . . . . . . . . . . . . . . 14
1.7 Separations by External Field or Gradient . . . . . . . . . . . . . . 16
1.8 Component Recoveries . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.8.1 Split Fractions and Split Ratios . . . . . . . . . . . . . . . . . 19
1.8.2 Separation Factor . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.10 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1
CHAPTER 1. INDUSTRIAL SEPARATIONS
1.1 Chapter 1 ILOs

.
ILO 1.1. Classify separation processes by general separation method.
ILO 1.2. Select suitable separations for mixtures based on the properties of the compo-
nents.
ILO 1.3. Define the quality of a separation process using key separation metrics.
Chapter Video
2 T.L.
c Rodgers 2019
1.2. INTRODUCTION
1.2 Introduction
Separations have been a key step in processes for thousands of years, those developed by
early civilisations include extraction of metals from ores[5], evaporation of sea water to
obtain salt[1], and the distillation of alcohol[3, 8].
Separations are crucial in chemical engineering; a typical chemical plant is a chemical
reactor surrounded by separators, as shown by the schematic flow sheet of Figure 1.1. Raw
materials are prepurified in separation devices and fed to the chemical reactor; unreacted
feed is separated from the reaction products and recycled back to the reactor. Products
must be further separated and purified before they can be sold. Chemical plants commonly
have from 40% to 70% of both capital and operating costs in separations[4].
Product
Unreacted Feed
Feed
Separator Reactor Separator Separator
Byproduct
Unreacted Feed
Product
Byproduct
Figure 1.1: Example of a simple chemical process.
The exploitation and selection of the separation methods depends on the nature of the
mixture but will be based on largely the so called phase separation. If the mixture is in
a homogenous form, then another phase will have to be created, e.g. if the mixture is a
vapour phase, then by a condenser a liquid phase can be created. However, if the mixture
is in a heterogeneous form or the so called multiphase form, then the separation can be
carried out relatively easily by exploiting the density difference between those multiple
phases. It should be pointed out that any heterogeneous separation should be considered to
be carried out first before any homogeneous separation, as the already existing advantages
can be exploited.
1.3 Basic Separation Techniques

The creation of a mixture of chemical species from separate species is a spontaneous
process that requires no energy input (though can take long amounts of time). The inverse
process, separation of a chemical mixture into pure components, is not a spontaneous
process and thus requires energy. A mixture to be separated may be single or multiphase.
If it is multiphase, it is usually advantageous to first separate the phases.
In a general separation process both species and phase separation can occur; the feed and
products may be vapour, liquid, or solid; one or more separation operations may be taking
place; and the products differ in composition and may differ in phase. In each separation
operation, the mixture components are induced to move into different, separable spatial
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locations or phases by any one or more of the five basic separation methods shown in Fig-
ure 1.2. However, in most instances, the separation is not perfect, and if the feed contains
more than two species, two or more separation operations may be required.
Phase 1 Phase 1
Feed
Feed Phase Phase
Creation MSA Addition
Phase 2 Phase 2
(a) Separation by phase creation (b) Separation by phase addition
Phase 1
Feed
Barrier
Phase 2
(c) Separation by barrier
Feed Phase 1
Solid Phase 1 Feed Force Field

Agent or Gradient
Phase 2 Phase 2
(d) Separation by solid agent (e) Separation by force field or gradient
Figure 1.2: Basic separation techniques: (a) separation by phase creation; (b) separation
by phase addition;(c) separation by barrier; (d) separation by solid agent; (e) separation
by force field or gradient.
The most common separation technique, shown in Figure 1.2(a), creates a second phase,
immiscible with the feed phase, by energy (heat and/or shaft-work) transfer or by pressure
reduction. Common operations of this type are distillation, which involves the transfer of
species between vapour and liquid phases, exploiting differences in volatility (e.g. vapour
pressure or boiling point) among the species; and crystallisation, which exploits differ-
ences in melting point. A second technique, shown in Figure 1.2(b), adds another fluid
phase, which selectively absorbs, extracts, or strips certain species from the feed. The
most common operations of this type are liquid-liquid extraction, where the feed is liquid
and a second, immiscible liquid phase is added; and absorption, where the feed is vapour,
and a liquid of low volatility is added.
In both cases, species solubilities are significantly different in the added phase. Less
common, but of growing importance, is the use of a barrier (shown in Figure 1.2(c)), usu-
ally a polymer membrane, which involves a gas or liquid feed and exploits differences in
species permeabilities through the barrier. Also of growing importance are techniques that
involve contacting a vapour or liquid feed with a solid agent, as shown in Figure 1.2(d).
Most commonly, the agent consists of particles that are porous to achieve a high surface
area, and differences in species adsorbability are exploited. Finally, external fields (cen-
trifugal, thermal, electrical, flow, etc.), shown in Figure 1.2(e), are applied in specialised
4 T.L.
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1.4. SEPARATIONS BY PHASE ADDITION OR CREATION
cases to liquid or gas feeds, with electrophoresis being especially useful for separating
proteins by exploiting differences in electric charge and diffusivity.
For the techniques of Figure 1.2, the size of the equipment is determined by rates of mass
transfer of each species from one phase or location to another, relative to mass transfer
of all species. The driving force and direction of mass transfer is governed by the depar-
ture from thermodynamic equilibrium, which involves volatilities, solubilities, etc. Fluid
mechanics and heat transfer play important roles in separation operations. The extent of
separation possible depends on the exploitation of differences in molecular, thermody-
namic, and transport properties of the species. Properties of importance are:
1. Molecular properties
Molecular weight Polarizability
van der Waals volume Dielectric constant
van der Waals area Electric charge
Molecular shape (acentric factor) Radius of gyration
Dipole moment
2. Thermodynamic and transport properties

Vapour pressure Adsorptivity
Solubility Diffusivity
Values of these properties appear in handbooks, reference books, and journals. Many can
be estimated using process simulation programs. When property values are not available,
they must be estimated or determined experimentally if a successful application of the
separation operation is to be achieved.
1.4 Separations by Phase Addition or Creation

If the feed is a single-phase solution, a second separable phase must be developed before
separation of the species can be achieved. The second phase is created by an energy-
separating agent (ESA) and/or added as a mass-separating agent (MSA). An ESA involves
heat transfer or transfer of work to or from the mixture. An example of work is the
creation of vapour from a liquid phase by reducing the pressure. An MSA may be partially
immiscible with one or more mixture components and frequently is the constituent of
highest concentration in the added phase. Alternatively, the MSA may be miscible with
a liquid feed mixture, but may selectively alter partitioning of species between liquid and
vapour phases.
When immiscible fluid phases are contacted, intimate mixing is used to enhance mass-
transfer rates so that the maximum degree-of-partitioning of species can be approached
rapidly. After phase contact, the phases are separated by employing gravity and/or an
enhanced technique such as centrifugal force. Table 1.1 includes the most common sepa-
ration operations based on interphase mass transfer between two phases, one of which is
created by an ESA or added as an MSA.
The equipment symbols shown in Table 1.1 correspond to the simplest configuration for
each operation. More complex versions are frequently desirable. For example, a more
complex version of the absorber could have a reboiler and several feeds. Design pro-
cedures must handle such complex equipment. Also, it is possible to conduct chemical
reactions within separation equipment, e.g. reactive distillation[9].
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When the feed mixture includes species that have widely different vapour pressures (boil-
ing points) then partial condensation or partial vapourisation could be adequate to achieve
the desired separation. The second phase is created when a vapour feed is partially con-
densed by removing heat or a liquid feed is partially vapourised by adding heat. Alterna-
tively, partial vapourisation can be initiated by reducing the feed pressure with a valve or
turbine (flash vapourisation). In both operations, the resulting vapour phase is enriched
with the more easily vapourised species, while the liquid phase is enriched with respect
to the less-volatile species. The two phases are then separated by gravity.
Often, the separation achieved by a single stage process is inadequate because the volatil-
ity differences among the species are not sufficiently large. In that case, multiple par-
tial condensation and vapourisation stages can be used, distillation. Distillation is the
most commonly used industrial separation process and involves multiple contacts be-
tween counter-currently flowing liquid and vapour phases.
When the volatility difference between species is so small as to necessitate more than
about 100 trays extractive distillation can be considered. Here, a miscible MSA, acting as
a solvent, increases the volatility difference among species in the feed, thereby reducing
the number of trays. This MSA can also increase relative volatilities of species enough to
break azeotropes.
If it is difficult to condense the vapour leaving the top of a distillation column, a liquid
MSA, called an absorbent, can be fed to the top tray in place of reflux. If the feed is a
vapour then the stripping section of the column is not needed, and the operation is referred
to as absorption. Absorbers generally do not require an ESA and are frequently conducted
at ambient temperature and elevated pressure. Species in the feed vapour dissolve in the
absorbent depending on their solubility.
The inverse of absorption is stripping, where a liquid mixture is separated, often at ele-
vated temperature and ambient pressure, by contacting the feed with a vapour stripping
agent. If trays are needed above the feed tray to achieve the separation, a condenser with
reflux can be used at the top of the column to produce a refluxed stripper, often called
steam distillation if the MSA used is steam. Additional separation operations may be
required to recover MSAs for recycling.
Liquid-liquid extraction is typically used when distillation is impractical, especially when
the mixture is temperature sensitive. One or two solvents are added (potentially at dif-
ferent locations) which selectively dissolve only one or a fraction of the components in
the feed. Several counter-currently arranged stages may be necessary. As with extractive
distillation, additional operations are required to recover solvent from the streams leaving
the extraction operation.
Since many chemicals are processed wet but sold as dry solids, a common manufacturing
step is drying. Although the only requirement is that the vapour pressure of the liquid to
be evaporated from the solid be higher than its partial pressure in the gas stream, dryer
design and operation represents a complex problem. In addition to the effects of such
external conditions as temperature, humidity, air flow, and degree of solid subdivision
on drying rate, the effects of internal diffusion conditions, capillary flow, equilibrium
moisture content, and heat sensitivity must be considered.
Evaporation is defined as the transfer of volatile components of a liquid into a gas by
heat transfer. Applications include humidification, air conditioning, and concentration of
aqueous solutions.
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Crystallisation is carried out in some organic, and in almost all inorganic, chemical plants
where the desired product is a finely divided solid. Crystallisation is a purification step,
so the conditions must be such that impurities do not precipitate with the product. In
solution crystallisation, the mixture, which includes a solvent, is cooled and/or the solvent
is evaporated. In melt crystallisation, two or more soluble species are separated by partial
freezing.
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8
Table 1.1: Separation Operations Based on Phase Creation or Addition. Greyed rows are not covered by this course.
Created or Added Separating Agent /

Separation Operation Symbol Feed Phase Industrial Example Course
Phase Property
Partial condensation or Vapour and/or liquid Liquid or vapour Heat transfer (ESA) Recovery of H2 and CHEN10082
V
vaporisation Vapour pressure N2 fromammonia by Engineering
V /L (Relative volatility) partial condensation Thermodynam-
and high-pressure ics
L phase separation
Flash vaporisation V Liquid Vapour Pressure reduction Recovery of water CHEN10082

Vapour pressure from sea water Engineering
L (Relative volatility) Thermodynam-
ics
L
Distillation Liquid and/or Vapour Vapour and liquid Heat transfer (ESA) Purification of CHEN20072
L
and sometimes work styrene Distillation and
V /L Relative volatility Absorption
This course
L will cover mul-
ticomponent
and distillation
sequencing
Extractive distillation Liquid and/or Vapour Vapour and liquid Liquid solvent Separation of ethanol This course
MSA (MSA) and heat from water[7]
L
V /L
transfer (ESA)
c
Modified relative
T.L.
L volatility / Solubility
Continued on next page
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c
Table 1.1 – Continued from previous page
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Phase Property
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Absorption V Vapour Liquid Liquid absorbent Separation of car- CHEN20072
MSA
(MSA) bon dioxide from Distillation and
Solubility combustion products Absorption
V by absorption with
L aqueous solutions of
an ethanolamine
Stripping V Liquid Vapour Stripping vapour Stream stripping of CHEN20072
L
(MSA) naphtha, kerosene, Distillation and
Solubility and gas oil side cuts Absorption
MSA from crude distilla-
L tion unit to remove
light ends
Liquid-liquid extraction L0 Liquid Liquid Liquid solvent Recovery of peni- This course
MSA
(MSA) cillin from aque-
Solubility ous fermentation
L0 medium by methyl
L00 isobutyl ketone. Re-
covery of aromatics
Drying Liquid and often solid Vapour Gas (MSA) and/or Removal of water
(V )
heat transfer (ESA) from polyvinylchlo-
V
L(+S) S Vapour pressure ride with hot air in a
fluid-bed dryer
Evaporation V Liquid Vapour Heat transfer (ESA) Evaporation of wa- CHEN10082
L Vapour pressure ter from a solution of Engineering
urea and water Thermodynam-
ics
L
9

10
Phase Property
Crystallisation (V ) Liquid Solid (and vapour) Heat transfer (ESA) Recovery of a pro- CHEN40052
L L Solubility tease inhibitor from Interface and
an organic solvent. Colloid Science
Crystallisation of p-
S
xylene from a mix-
ture with m-xylene
Leaching S
Solid Liquid Liquid solvent Removal of caffeine
MSA L (MSA) from coffee beans
Solubility of solid with methylene
S components chloride
Coagulation Liquid/solid Polymers and salts (MSA) Removal of small

Flocculation L/ L van der Waals force particulates from
sewage in waste
S
water treatment
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1.5. SEPARATIONS BY BARRIERS
1.5 Separations by Barriers

Use of microporous and nonporous membranes as semipermeable barriers for selective
separations is gaining adherents. Membranes are fabricated mainly from natural fibers and
synthetic polymers, but also from ceramics and metals. Membranes are fabricated into flat
sheets, tubes, hollow fibers, or spiral-wound sheets, and incorporated into commercial
modules or cartridges. For microporous membranes, separation is effected by rate of
species diffusion through the pores; for nonporous membranes, separation is controlled by
differences in solubility in the membrane and rate of species diffusion. The most complex
and selective membranes are found in the trillions of cells in the human body.
Table 1.2 lists the main membrane-separation operations. Osmosis involves transfer, by
a concentration gradient, of a solvent through a membrane into a mixture of solute and
solvent. This membrane is almost impermeable to the solute. In reverse osmosis the
transport of solvent is forced in the opposite direction by imposing a pressure, higher than
the osmotic pressure, on the feed side.
Dialysis is the transport by a concentration gradient of small solute molecules through
a porous membrane. The molecules unable to pass through the membrane are small,
insoluble, non-diffusible particles. Microporous membranes selectively allow small so-
lute molecules and/or solvents to pass through the membrane, while preventing large dis-
solved molecules and suspended solids from passing through, these filtration separations
are generally classified by the size of the particles. Microfiltration refers to the retention
of molecules from 0.02 to 10 mm Ultrafiltration, refers to the retention of molecules that
range from 1 to 20 nm To retain molecules down to 0.1 nm , nonporous membranes can
be used in hyperfiltration. Gases can be separated in a similar manor by selective gas
permeation.
Pervaporation involves the transport of evaporated material through a nonporous mem-
brane. This method, which can be used to separate azeotropic mixtures, uses much lower
pressures than reverse osmosis and filtration, but the heat of vaporization must be sup-
plied.
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12
Table 1.2: Separation Operations Based on a Barrier. Greyed rows are not covered by this course.
Separation Operation Symbol Feed Phase Separating Agent Industrial Example Course
Osmosis Liquid Nonporous mem-

brane
Reverse osmosis L
Liquid Nonporous mem- Desalinization of sea
L brane with pressure water
gradient
L
Dialysis L
Liquid Porous membrane Recovery of caustic
L with pressure gradi- from hemicellulose
ent
L
Filtration Liquid and Solid Porous film or bead Removal of crystals CHEN20061
L/S of granular material from feed stock liquid Solid Fluid
L Systems
Microfiltration L
Liquid Microporous mem- Removal of bacteria
L brane with pressure from drinking water
gradient
L
c
T.L.
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c
T.L.
Separation Operation Symbol Feed Phase Separating Agent Industrial Example Course
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Ultrafiltration L
Liquid Microporous mem- Separation of whey
L brane with pressure from cheese
gradient
L
Gas permeation Vapour Nonporous mem- Hydrogen enrichment

V
V brane with pressure
gradient
V
Pervaporation Liquid Nonporous mem- Separation of

L
L brane with pressure azeotropic mixtures
gradient
V
13
1.5. SEPARATIONS BY BARRIERS
1.6 Separations by Solid Agents

Separations that use solid agents are listed in Table 1.3. The solid, in the form of a granular
material or packing, is the adsorbent itself, or it acts as an inert support for a thin layer
of adsorbent. The separation is achieved by selective adsorption or chemical reaction
with species in the feed. Adsorption is confined to the surface of the solid adsorbent,
unlike absorption, which occurs throughout the absorbent. The active separating agent
eventually becomes saturated with solute and must be regenerated or replaced. Such
separations are often conducted batchwise or semicontinuously; however, equipment is
available to simulate continuous operation.
Adsorption is generally used to remove species in low concentrations and is followed
by desorption to regenerate the adsorbents, which include activated carbon, aluminum
oxide, silica gel, and synthetic sodium or calcium aluminosilicate zeolites (molecular
sieves). The sieves are crystalline and have pore openings of fixed dimensions, making
them very selective. Equipment consists of a cylindrical vessel packed with a bed of
solid adsorbent particles through which the gas or liquid flows. Because regeneration is
conducted periodically, two or more vessels are used, one desorbing while the other(s)
adsorb(s). If the vessel is vertical, gas flow is best employed downward. With upward
flow, movement can cause particle attrition, pressure-drop increase, and loss of material.
However, for liquid mixtures, upward flow achieves better flow distribution. Regeneration
occurs by one of four methods:
1. vapourisation of the adsorbate with a hot purge gas (thermal-swing adsorption),
2. reduction of pressure to vapourise the adsorbate (pressure-swing adsorption),
3. inert purge stripping without change in temperature or pressure, and
4. displacement desorption by a fluid containing a more strongly adsorbed species.
Chromatography separates gas or liquid mixtures by passing them through a packed bed.
The bed may be solid particles (gas-solid chromatography or a solid-inert support coated
with a viscous liquid (gas-liquid chromatography). Because of selective adsorption on the
solid surface, or absorption into liquid absorbents followed by desorption, components
move through the bed at different rates, thus effecting the separation.
Ion exchange resembles adsorption in that solid particles are used and regenerated. How-
ever, a chemical reaction is involved.
14 T.L.
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Table 1.3: Separation operations based on solid agents. Greyed rows are not covered by this course.
T.L.
Separating Agent /
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Property
Adsorption V /L V /L Vapour or liquid Solid adsorbent Purification of p-xylene CHEN40061
Adsorbance Adsorption &
Ion Exchange
V /L
Chromatography V /L
Vapour or liquid Solid adsorbent or Separation and pu- CHEN40061
liquid adsorbent on a rification of proteins Adsorption &
solid support from complex mix- Ion Exchange
Adsorbance tures. Separation of
V /L
xylene isomers and
ethylbenzene
Ion exchange L L Liquid Resin with ion- Demineralization of CHEN40061
active sites water Adsorption &
Adsorbance Ion Exchange
15
1.6. SEPARATIONS BY SOLID AGENTS
1.7 Separations by External Field or Gradient

External fields can take advantage of differing degrees of response of molecules and ions
to force fields. Table 1.4 lists common techniques and combinations.
When feed mixtures have different densities then gravity settling could be adequate to
achieve the desired separation. The more dense material settles to the bottom of the settler
and the less dense material rises to the top. This allows dense material to be taken from
the bottom and the light material from the top. This separation can be used to separate
gas-liquid, gas-solid, liquid-liquid, and liquid-solid systems.
If the difference in densities the only small this separation can take a long time. Therefore,
the separation force can be increased by exchanging gravity for rotational inertia. The two
main options for this are centrifugation and cyclones. In centrifugation the contents are
rotated at high speed in a rotating container, where as in cyclones the material is rotated
due to its own inertia.
Electrolysis is the passage of a direct electric current through an ionic substance that is
either molten or dissolved in a suitable solvent, resulting in chemical reactions at the
electrodes and separation of materials. Electrolysis requires an electrolyte, substance
containing free ions which are the carriers of electric current in the electrolyte; a direct
current (DC) supply, provides the energy necessary to create or discharge the ions in the
electrolyte; and two electrodes, an electrical conductor which provides the physical inter-
face between the electrical circuit providing the energy and the electrolyte. A permeable
membrane can be added to the system preventing migration of species of like charge, this
is called electrodialysis.
In field-flow fractionation an electrical or magnetic field or thermal gradient is established
perpendicular to a laminar-flow field. Components of the mixture travel in the flow direc-
tion at different velocities, so a separation is achieved. A related device is a small-particle
collector where the particles are charged and then collected on oppositely charged metal
plates.
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Table 1.4: Separation operations by external field or gradient. Greyed rows are not covered by this course.
T.L.
Force Field or
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Gradient
Less
Gravity Settling dense
Vapour or liquid or Gravity CHEN20061
Feed solid Solid Fluid
systems
More
dense
Less
Flotation dense
Solid in Liquid Gravity Removal of
Feed Reduction in density precious metals
from gas bubbles from waste ores
More
V dense
in mining
Centrifugation V /L Vapour or liquid Centrifugal force Separation of uranium CHEN20061
field isotopes Solid Fluid
V /L
Systems
V /L
Cyclone S(V ) Solid (and vapour) Centrifugal force Remove sawdust from CHEN20061
S(V )
field air at Saw mills Solid Fluid
Systems
S(V )
Hydrocyclone S(L) Solid (and Liquid) Centrifugal force Remove sand, staples,
S(L)
field and plastics from paper
pulp
S(L)
17
1.7. SEPARATIONS BY EXTERNAL FIELD OR GRADIENT

18
Force Field or
Gradient
Electrolysis Liquid Electrical force field Concentration of heavy
L L(V ) water
Electrodialysis Liquid Electrical force field Desalinization of sea

L L and membrane water [6]
Field-flow fractionation Liquid Laminar flow in Separation of cells and

L
L force field [2] platelets from blood

L
Magnetic Separation Solids in solids or Magnetic force Ferrous scrap are to

S liquid be separated from other
S
S waste from recycling
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1.8. COMPONENT RECOVERIES
1.8 Component Recoveries

If no chemical reaction occurs and the process operates in a
continuous, steady-state fashion, then for each component i, in
a mixture of C components, the molar (or mass) flow rate in
(F )
the feed, ni , equals the sum of the product molar (or mass)
(p)
flow rates, ni , for that component in the N product phases, p,.
N
X
(F ) (p)
ni = ni (1.8.1)
p=1 Summary Video
(p) (F )
To solve equation 1.8.1 for values of ni from specified values of ni an additional N −1
(p)
independent expressions involving ni are required. This gives a total of N C equations
in N C unknowns. If a single-phase feed containing C components is separated into N
products, C(N − 1) additional expressions are needed. If more than one stream is fed to
(F )
the separation process, ni is the summation for all feeds.
1.8.1 Split Fractions and Split Ratios
Chemical plants are designed and operated to meet specifications given as component
recoveries and product purities. For each separation process, feed components are parti-
tioned between the outlets (often 2) according to a split fraction or split ratio that depends
on the properties of the components and the separator. The split fraction, SF , for compo-
nent i in separator k is the fraction found in the product, p,
(p)
ni,k
SFi,k = (F )
(1.8.2)
ni,k
Alternatively, a split ratio, SR, between two products, p1 and p2 , is,

(p )
ni,k1 SFi,k
SRi,k = (p )
= (1.8.3)
ni,k2 (1 − SFi,k )
SF may be a better degree-of-separation indicator than SR because SF is bounded be-

tween 0 and 1, while SR can range from 0 to a large value. Two other measures of success
can be applied to each separation or to an entire process. One is the percent recovery of a
designated product. The other is product purity.
1.8.2 Separation Factor
Some separation operations are incapable of making a sharp split between key compo-
nents and can effect the desired recovery of only a single component. For these, either a
single separation stage is utilised, or the feed enters at one end (not near the middle) of a
multistage separator. The split ratio (SR), split fraction (SF ), recovery, or purity that can
be achieved for the single key component depends on a number of factors. For these, a
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measure of the relative degree of separation between two key components, i and j, is the
separation factor or power, SP , defined in terms of the component splits as measured by
the compositions of the two products, (1) and (2),
(1)
Ci
(2)
Ci
SPi,j = (1)
(1.8.4)
Cj
(2)
Cj
where C is some measure of composition. SP is readily converted to the following forms

in terms of split fractions or split ratios,
SRi
SPi,j = (1.8.5)
SRj
SFi
SFj
SPi,j = (1.8.6)
(1 − SFi )
(1 − SFj )
1.9 References
[1] Flad, R., Zhu, J., Wang, C., Chen, P., von Falkenhausen, L., Sun, Z. and Li, S.
[2005], ‘Archaeological and chemical evidence for early salt production in china’,
Proceedings of the National Academy of Sciences of the United States of America
102(35), 12618–12622.
[2] Giddings, J. C. [1984], ‘Field-flow fractionation’, Separation Science and Technol-
ogy 19, 831–847.
[3] Haw, S. G., ed. [2006], Marco Polo’s China, Routledge, chapter 10, p. 147.
[4] Humphrey, J. L. and Keller II, G. E., eds [1997], Separation Process Technology,
McGraw-Hill, New York.
[5] Reardon, A., ed. [2011], Metallurgy for the Non-Metallurgist, 2nd edn, ASM Inter-
national, chapter 4, pp. 73–84.
[6] Sadrzadeh, M. and Mohammadi, T. [2008], ‘Sea water desalination using electro-
dialysis’, Desalination 221, 440–447.
[7] Tassios, D., ed. [1974], Extractive and Azeotropic Distillation, American Chemical
Society, chapter 1, pp. 1–15.
[8] Taylor, F. S. [1945], ‘The evolution of the still’, Annals of Science 5(3), 185–202.
[9] Taylor, R. and Krishna, R. [2000], ‘Modelling reactive distillation’, Chemical Engi-
neering Science 55, 5183–5229.
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1.10. PROBLEMS
1.10 Problems
E1 How can we separate a mixture of 10 vol% ethanol in water to produce
(a) 50 vol% ethanol in water?
(b) 99 vol% ethanol in water?
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E2 For each of the following binary mixtures, a separation operation is suggested. Ex-
plain why the operation will or will not be successful.
(a) Separation of air into oxygen-rich and nitrogen-rich products by distillation.
(b) Separation of m-xylene from p-xylene by distillation.
(c) Separation of benzene and cyclohexane by distillation.
(d) Separation of isopropyl alcohol and water by distillation.
(e) Separation of penicillin from water in a fermentation broth by evaporation of
the water.
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1.10. PROBLEMS
E3 The system of 3 distillation columns below are used to separate a mixture of hydro-
carbons with stream compositions given in the table. Calculate the split fraction,
SF , split ratio, SR, and the recovery of C3 H8 .
3 4 6
C3 iC4
1
Feed C1 C2 C3
C+
5 -rich nC4 -rich
2 5 7
lbmol h−1 in Stream
1 2 3 4 5 6 7
Component Feed to C1 C+5 Feed to C2 C3 Feed to C3 iC4 nC4 -rich
C2 H6 0.60 0.00 0.60 0.60 0.00 0.00 0.00
C3 H8 57.00 0.00 57.00 54.80 2.20 2.20 0.00
iC4 H10 171.80 0.10 171.70 0.60 171.10 162.50 8.60
nC4 H10 227.30 0.70 226.60 0.00 226.60 10.80 215.80
iC5 H12 40.00 11.90 28.10 0.00 28.10 0.00 28.10
nC5 H10 33.60 16.10 17.50 0.00 17.50 0.00 17.50
C+
6 205.30 205.30 0.00 0.00 0.00 0.00 0.00
Total 735.60 234.10 501.50 56.00 445.50 175.50 270.00
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E4 For the system shown in E3 also calculate the

(a) recovery of iC4 H10 .
(b) split fraction of C3 H8 in column 1.
(c) purity of the C3 H8 product.
(d) split ratio of iC4 H10 in column 3.
(e) separation factor between C3 H8 and iC4 H10 in column 2.
24 T.L.
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1.10. PROBLEMS
E5 A feed, F , of 100 kmol h−1 of air containing 21 mol% O2 and 79 mol% N2 is to be

partially separated by a membrane unit according to each of four sets of specifica-
tions. Compute the amounts, in kmol h−1 , and compositions, in mol%, of the two
products (retentate, R, and permeate, P ). The membrane is more permeable to O2 .
(a) 50% recovery of O2 to the permeate and 87.5% recovery of N2 to the retentate.
(b) 50% recovery of O2 to the permeate and 50 mol% purity of O2 in the permeate.
(c) 85 mol% purity of N2 in the retentate and 50 mol% purity of O2 in the perme-
ate.
(d) 85 mol% purity of N2 in the retentate and a split ratio of O2 in the permeate to
the retentate equal to 1.1.
T.L.
c Rodgers 2019 25
26
Chapter 2
Liquid-Liquid Extraction
Contents
2.1 Chapter 2 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2.1 Partition coefficient . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2.2 Solvent Selection . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.3 General Design Considerations . . . . . . . . . . . . . . . . . . . . . 32
2.4 Representation of Multi-phase Liquid-Liquid Systems . . . . . . . . 33
2.5 Single Stage Liquid-Liquid Extraction . . . . . . . . . . . . . . . . . 34
2.6 Lever-Arm Rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.7 Hunter-Nash Graphical Equilibrium-Stage Method . . . . . . . . . 37
2.7.1 Step 1 - Calculation of the Mixing Point . . . . . . . . . . . . . 38
2.7.2 Step 2 - Product Mass Balance . . . . . . . . . . . . . . . . . . 38
2.7.3 Step 3 - Calculation of the Operating Lines . . . . . . . . . . . 39
2.7.4 Step 4 - Tie Lines and Equilibrium Lines . . . . . . . . . . . . 40
2.8 Minimum and Maximum Solvent-to-Feed Flow-Rate Ratios . . . . . 41
2.8.1 Minimum Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.8.2 Maximum Ratio . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.9 Equipment for Solvent Extraction . . . . . . . . . . . . . . . . . . . 45
2.9.1 Mixer-Settlers . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.9.2 Spray Columns . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.9.3 Packed Columns . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.9.4 Plate Columns . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.9.5 Columns with Mechanically Assisted Agitation . . . . . . . . . 48
2.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.11 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
27
CHAPTER 2. LIQUID-LIQUID EXTRACTION
2.1 Chapter 2 ILOs

.
ILO 2.1. Choose suitable solvents and explain why they are suitable for the separation.
ILO 2.2. Use the lever-arm rule to calculate flow rates on ternary diagrams.
ILO 2.3. Demonstrate knowledge of general design considerations for liquid-liquid ex-
traction.
ILO 2.4. Calculate single stage liquid-liquid equilibrium using ternary diagrams
ILO 2.5. Apply the Hunter-Nash method to allow calculation of the number of equilib-
rium stages needed for a single section liquid-liquid extraction system.
ILO 2.6. Recall the types of equipment used for liquid-liquid extraction.
Chapter Video 1
Chapter Video 2
28 T.L.
c Rodgers 2019
2.2. INTRODUCTION
2.2 Introduction
In liquid-liquid extraction (also called solvent extraction or extraction), a liquid feed of
two or more components is contacted with a second liquid phase, called the solvent, which
is immiscible or only partly miscible with one or more feed components and completely
or partially miscible with one or more of the other feed components. Thus, the solvent
partially dissolves certain species of the liquid feed, effecting at least a partial separation
of the feed components.
The solvent may be a pure compound or a mixture. If the feed is an aqueous solution,
an organic solvent is used; if the feed is organic, the solvent is often water. Important
exceptions occur in metallurgy for the separation of metals and in bioseparations for the
extraction from aqueous solutions of proteins that are denatured or degraded by organic
solvents.
Extraction has been practiced since the time of the Romans, who used molten lead to
separate gold and silver from molten copper by extraction[3]. However, it was not until
the early 1930s that Lazăr Edeleanu invented the first large-scale extraction process. The
Edeleanu process[1] is used in the petroleum refining industry, whereby liquid sulphur
dioxide is used to extract aromatics from liquid kerosene at around −20 ◦ C. Liquid SO2
selectively dissolves the aromatics leaving behind the low aromatic content kerosene as
the finished product, resulting in cleaner-burning kerosene. Liquid-liquid extraction has
grown in importance since then because of the demand for temperature-sensitive products,
higher-purity requirements, better equipment, and availability of solvents with higher se-
lectivity, and is an important method in bioseparations.
This chapter covers the simplest liquid-liquid extraction, which involves only a ternary
system consisting of two miscible feed components — the carrier, C, and the solute, A
— plus solvent, S, a pure compound. Components C and S are at most only partially
soluble, but solute A is completely or partially soluble in S. During extraction, mass
transfer of A from the feed to the solvent occurs, with less transfer of C to the solvent, or
S to the feed. Nearly complete transfer of A to the solvent is seldom achieved in just one
stage. Therefore, in practice, a number of stages are used.
In general, extraction is preferred over distillation for:
1. Dissolved or complexed inorganic substances in organic or aqueous solutions
2. Removal of a contaminant present in small concentrations
3. A high-boiling component present in relatively small quantities in an aqueous waste
stream
4. Recovery of heat-sensitive materials, where extraction may be less expensive than
vacuum distillation
5. Separation of mixtures according to chemical type rather than relative volatility
6. Separation of close-melting or close-boiling liquids, where solubility differences
can be exploited.
7. Separation of mixtures that form azeotropes.
T.L.
c Rodgers 2019 29
2.2.1 Partition coefficient
The solute in the mixture is separated by its different solubility in the 2 immiscible sol-
vents. This difference in solubility can be represented by the distribution (partition) coef-
ficient,
(S)
xA
KDA = (C) (2.2.1)
xA
This value should be greater than one, or a large a solvent-to-feed ratio will be required.
The partition coefficient is an equilibrium constant, and this equilibrium is based on the
chemical potential, µ, of the solute being equal in each phase,
(S) (C)
µA = µA
0,(S) (S) 0,(C) (C)
µA + RT ln xA = µA + RT ln xA
!
(S) 0,(C) 0,(S)
xA µA − µA
(C)
= exp = KD A (2.2.2)
xA RT
The standard chemical potential can be represented in terms of the molar volumes as the
solubility parameter, so that,[2]
!
vA (δA − δC )2 − vA (δA − δS )2
KDA = exp (2.2.3)
RT
An example of some solubility parameters of commonly used liquid-liquid extraction

materials are given in Table 2.1.
The separation can also be represented by the extraction factor, which takes into account
the flow rates of the solvent and carrier,1
0
KD F
A S
EA = (2.2.4)
FC
When the degree of solute extraction is not particularly high and/or when a large extrac-
tion factor can be achieved, an extractor will not require many stages. This is fortunate
because mass-transfer resistance in liquid-liquid systems is high and stage efficiency is
low in contacting devices, even if mechanical agitation is provided.
2.2.2 Solvent Selection
The key to an effective extraction process is a suitable solvent. The ideal solvent should
have,
1. High selectivity for the solute relative to the carrier to minimize the need to recover
carrier from the solvent
2. High capacity for dissolving the solute to minimize solvent-to-feed ratio
1 0
KDA is the distribution or partition coefficient in terms of mass or mole ratios (instead of mass or
mole fractions). FS and FC are the flow rate of the solvent and carrier respectively.
30 T.L.
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2.2. INTRODUCTION
Table 2.1: Some example solubility parameters of common liquid-liquid extraction

materials[4].
Solvent δ / cal1/2 cm−3/2

Amyl acetate 8.32
Benzene 9.15
Butanol 11.30
Butyl acetate 8.46
Carbon disulphide 9.97
Carbon tetrachloride 8.65
Chloroform 9.21
Cyclohexane 8.18
Ethanol 12.92
Hexane 7.24
Hexanol 10.7
Acetone 9.77
Perfluorohexane 5.9
Toluene 8.91
Water 23.5
3. Minimal solubility in the carrier

4. A volatility sufficiently different from the solute that recovery of the solvent can be
achieved by distillation, but not so high that a high extractor pressure is needed, or
so low that a high temperature is needed if the solvent is recovered by distillation
5. Stability to maximise the solvent life and minimise the solvent makeup requirement
6. Inertness to permit use of common materials of construction
7. Low viscosity to promote phase separation, minimise pressure drop, and provide a
high-solute mass-transfer rate
8. Nontoxic and nonflammable characteristics to facilitate its safe use
9. Availability at a relatively low cost
10. Moderate interfacial tension to balance the ease of dispersion and the promotion of
phase separation
11. Large difference in density relative to the carrier to achieve a high capacity in the
extractor
12. Compatibility with the solute and carrier to avoid contamination
13. Lack of tendency to form a stable scum layer at the phase interface
14. Desirable wetting characteristics with respect to extractor internals
Solvent selection is a compromise among all the properties listed above. However, initial
consideration is usually given to selectivity and environmental concerns, and second to
capacity and cost.
T.L.
c Rodgers 2019 31
2.3 General Design Considerations

Liquid-liquid extractors involve more variables than vapour-liquid operations because liq-
uids have more complex structures than gases. To determine stages, one of the three cas-
cade arrangements in Figure 2.1, or an even more complex arrangement, must be selected.
Solvent-free Solvent-free
extract Solvent product A Solvent S
SR SR
Solvent T
Extract
Feed Feed Feed

A, B
Solvent S
Solvent-free
Raffinate Solvent Raffinate Solvent Solvent T product B
SR
(a) Single-section cascade (b) Two-section cascade (c) Dual solvent with two section cas-
cade
Figure 2.1: Common liquid-liquid extraction cascade configurations: (a) single-section

cascade;(b) two-section cascade; (c) dual solvent with two section cascade.
The single-section cascade of Figure 2.1(a), which is similar to that used for absorption
and stripping, will transfer solute in the feed to the solvent. The two-section cascade of
Figure 2.1(b) is similar to that used for distillation. Solvent enters at one end and re-
flux, derived from the extract, enters at the other end. The feed enters in between. With
two sections, depending on solubilities, it is sometimes possible to achieve a separation
between feed components; if not, a dual-solvent arrangement with two sections, as in Fig-
ure 2.1(c), with or without reflux at the ends, may be advantageous. The configurations in
Figure 2.1 are shown with packed sections, but any extraction equipment may be chosen.
Operative factors are:
1. Entering feed flow rate, composition, temperature, and pressure
2. Type of stage configuration (one- or two-section)
3. Desired degree of recovery of one or more solutes for one-section cascades
4. Degree of feed separation for two-section cascades
32 T.L.
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2.4. REPRESENTATION OF MULTI-PHASE LIQUID-LIQUID SYSTEMS
5. Choice of solvent(s)
6. Operating temperature
7. Operating pressure (greater than the bubble point)
8. Minimum-solvent flow rate and actual-solvent flow rate as a multiple of the min-
imum rate for one-section cascades or reflux rate and minimum reflux ratio for
two-section cascades
9. Number of equilibrium stages
10. Emulsification and scum-formation tendency
11. Interfacial tension
12. Phase-density difference
13. Maximum residence time to avoid degradation
14. Type of extractor
15. Extractor cost and power requirement
2.4 Representation of Multi-phase Liquid-Liquid Systems

Extraction calculations of liquid systems are most conveniently carried out with ternary
equilibrium diagrams; this is due to the fact that 3 liquids are generally in equilibrium
with each other.
In Figure 2.2, for a general system, the bold line is the equilibrium curve, also called the
binodal curve because the plait point separates the curve into an extract to the left and
a raffinate to the right. Mixtures of the 3 liquid system inside the equilibrium curve are
not stable and separate into two immiscible phases. The red lines are tie-lines connecting
compositions of these equilibrium phases.
Figure 2.3 shows some of the key different types of multi-phase systems found for 3
liquid systems. Type 1 has one pair of partially immiscible liquids with both of these
miscible in the third liquid, e.g. Figure 2.3(a) where liquids A and B are immiscible in
each other but both are miscible in liquid C. Type 2 has two pairs of partially immiscible
liquids with two of the liquids being miscible, e.g. Figure 2.3(b) where liquids A and B
are immiscible in each other and liquids B and C are also immiscible in each other but A
and C are miscible.
If the two 2 phase boundaries are large enough then they can meet creating a large 2 phase
region, e.g. Figure 2.3(c). The two 2 phase boundaries can also join and form a 3 phase
region, e.g. Figure 2.3(d) where any total composition falling inside the middle triangle
separates into 3 liquid phases with the compositions of a, b, and c.
T.L.
c Rodgers 2019 33
0
100
20
80
Ma
n
tio
ss
40
rac
Fra
60
F
ctio
ss
Ma
Plait point
nA
60 • 40
80
20
100
0
0 20 40 60 80 100
Mass Fraction C
Figure 2.2: Example ternary phase diagram for a 2 phase liquid-liquid system.
C C C C
c•
•
a• b
A B A B A B A B
(a) (b) (c) (d)
Figure 2.3: Some examples of liquid-liquid system, (a) Type 1, (b) Type 2 non-meeting,
(c) Type 2 meeting, and (d) 3 liquid phases.
2.5 Single Stage Liquid-Liquid Extraction

Adding a solvent, S to a mixture of a solute, A, and a carrier, C, allows the solute to
dissolve into the solvent, producing two output streams; the extract, E, and the raffinate,
R; Figure 2.4.
E S
M
F R
Figure 2.4: Single equilibrium stage liquid-liquid extraction.
An overall total mass balance can be generated for the system, as we know that the total
amount of material entering the system must equal that exiting the system. We can also
refer to the total amount in the system as M , i.e. the total mixture,
F +S =M =E+R (2.5.1)
34 T.L.
c Rodgers 2019
2.5. SINGLE STAGE LIQUID-LIQUID EXTRACTION
As well as an overall total mass balance we can also produce an overall mass balance for
each component in the mixture,
(xA )F F + (xA )S S = (xA )M M = (xA )E E + (xA )R R

(xC )F F + (xC )S S = (xC )M M = (xC )E E + (xC )R R
(xS )F F + (xS )S S = (xS )M M = (xS )E E + (xS )R R (2.5.2)
This process can be represented on a ternary diagram. For example, the following feed
and solvent specifications,
Feed (F) Solvent (S)

F = 400 kg S = 100 kg
(xA )F = 0.25 (xA )S = 0.00
(xC )F = 0.75 (xC )S = 0.00
(xS )F = 0.00 (xS )S = 1.00
can be taken and plotted in Figure 2.5.
0
100
20
80
nS
Ma
ctio
ss
40
Fra
60
Fra
ctio
ss
Ma
nA
60 E
40
F
80 M
20
R
100 S
0
0 20 40 60 80 100
Mass Fraction C
Figure 2.5: Ternary phase diagram for a general solute-carrier-solvent system.
By material balances (equations 2.5.1 and 2.5.2), the composition of M is,
M = F + S = 400 + 100 = 500 kg

(xA )M M = 0.25 · 400 + 0 · 100 = 100 kg
(xA )M = 100/500 = 0.20 = 20.0 %
(xC )M M = 0.75 · 400 + 0 · 100 = 300 kg
(xC )M = 300/500 = 0.60 = 60.0 %
(xS )M M = 0 · 400 + 1 · 100 = 100 kg
(xS )M = 100/500 = 0.20 = 20.0 %
T.L.
c Rodgers 2019 35
This mixing point, M , can be located on Figure 2.5. It can be seen that is point, M , is
located on the straight line connecting F and S (red line). Therefore, M could be located
knowing just one value of (xi )M , say, (xS )M .
With point M located, the composition of exiting extract, E, and raffinate, R, is deter-
mined from the equilibrium tie line that the mixing point lies on (blue line),
Raffinate Product Extract Product

(xA )R = 0.100 (xA )E = 0.400
(xC )R = 0.861 (xC )E = 0.110
(xS )R = 0.039 (xS )E = 0.490
From the material balances (equations 2.5.1 and 2.5.2) the flow rates of the extract and
raffinate can then be calculated. With M = 500 kg this means that the mass of the extract
and raffinate are, R = 322 kg and E = 178 kg.
2.6 Lever-Arm Rule

As noted when the feed, solvent, and mixing point were plotted
on Figure 2.5; they all lie on a straight line. Taking the material
balances for two of the components (equation 2.5.2),
(xA )F F + (xA )S S = (xA )M M .

(xC )F F + (xC )S S = (xC )M M
these can be combined with the overall total mass balance, F + Summary Video
S = M , to give,
F (xA )S − (xA )M (xC )S − (xC )M

= = (2.6.1)
S (xA )M − (xA )F (xC )M − (xC )F
The points must therefore lie on a straight line with the mixing position set by the amounts
of the solvent and the feed1 , as the differences can be thought of as vector line lengths,
F SM
= (2.6.2)
S FM
So in our previous example we could have found the position of M by taking,
400 kg SM
=
100 kg FM
SM = 4F M
and measuring the line lengths.
1
As proof equation 2.6.1 can then be rearranged into the form of an equation for a straight line,
(xC )S − (xC )F (xC )F (xA )S − (xC )S (xA )F

(xC )M = (xA )M +
(xA )S − (xA )F (xA )S − (xA )F
36 T.L.
c Rodgers 2019
2.7. HUNTER-NASH GRAPHICAL EQUILIBRIUM-STAGE METHOD
2.7 Hunter-Nash Graphical Equilibrium-Stage Method

For a single stage system the extract and raffinate compositions
are limited by the liquid-liquid equilibrium tie lines. Often
these compositions are not suitable for the separation that is
needed. To improve the separation a multi-stage method can
be used. .
Stagewise extraction calculations for Type I and Type II sys-
tems are most conveniently carried out with ternary equi-
librium diagrams. Consider a counter-current flow, N -
equilibrium-stage extractor operating isothermally in steady- Summary Video
state, continuous flow, as in Figure 2.6.
Stages are numbered from the feed end. Thus, the final extract is E1 and the final raffinate
is RN . Equilibrium is assumed at each stage, so for any stage n, the components in extract
En and raffinate Rn are in equilibrium.
E2 E3 En En+1 EN −1 EN
E1 S
1 2 n N −1 N
F RN
R1 R2 Rn−1 Rn RN −2 RN −1
Figure 2.6: Counter-current flow, N -equilibrium-stage liquid-liquid extraction cascade.
Mass transfer of all species occurs at each stage. The feed, F , contains the carrier, C, the
solute, A, and potentially the solvent, S, up to the solubility limit. Entering solvent, S, can
contain C and A, but preferably contains little of either. Most liquid-liquid equilibrium
data are listed and plotted in mass rather than mole concentrations, therefore we can say
that F is the mass flow rate of feed to the cascade, S is the mass flow rate of solvent to
the cascade, En is the mass flow rate of extract leaving stage n, Rn is the mass flow rate
of raffinate leaving stage n, (yi )n is the mass fraction of species i in extract leaving stage
n, and (xi )n is the mass fraction of species i in raffinate leaving stage n.
Although Figure 2.6 implies that the extract is the light phase, either phase can be the
light phase. Phase equilibrium is represented on an equilateral-triangle diagram, e.g. Fig-
ure 2.5. In this case the ternary system is A (solute), C (carrier), and S (solvent) at a
temperature, T . The tie lines slope upward from the C side toward the S side, at equilib-
rium, A has a concentration higher in S than in C. Thus, in this example, S is an effective
solvent for extracting A from C.
In general when designing liquid-liquid extraction equipment to determine the number
of stages several specifications are made; typically these are F , (xi )F , (yi )S , T , S, and
(xi )RN . Although other options can be used e.g. F , (xi )F , (yi )S , T , (xi )RN , and (yi )E1 if
the exit compositions are important, or F , (xi )F , (yi )S , T , (xi )RN , and N if the design is
for a retrofit of existing equipment. All the exiting phases, (xi )RN , and (yi )E1 , lie on the
equilibrium curve.
For example we will consider the typical set of specifications, with the procedures for
the other sets being minor modifications, e.g. calculation of S from a suitable mixing
point, and an iterative procedure with a given N . The technique, sometimes called the
Hunter-Nash method[5], involves three kinds of constructions on the triangular diagram,
T.L.
c Rodgers 2019 37
and is more difficult than the McCabe-Thiele staircase method for distillation. Although
the procedure below is illustrated here only for a Type I system, parallel principles apply
to a Type II system. The construction steps are shown as follows.
2.7.1 Step 1 - Calculation of the Mixing Point
As in the single stage separation an overall total mass balance can be written for the whole
system,
F + S = RN + E1 = M (2.7.1)
and for the an overall component mass balance can be written too,
F (xi )F + S (xi )S = RN (xi )RN + E1 (xi )E1 = M (xi )M (2.7.2)
The first step is the same a in the single stage extraction, which is to calculate the mixing
point, M , which can be calculated from equations 2.7.1 and 2.7.2 or using the lever-arm
rule.
Assuming the same feed and solvent specifications as in section 2.5,
Feed Solvent
F = 400 kg S = 100 kg
(xA )F = 0.25 (xA )S = 0.00
(xC )F = 0.75 (xC )S = 0.00
(xS )F = 0.00 (xS )S = 1.00
we can plot the feed, F , solvent, S, and mixing point, M , on Figure 2.7.
2.7.2 Step 2 - Product Mass Balance
The difference from the single stage extraction is that the final extract, E1 , and the final
raffinate, RN , now do not need to be based on the equilibrium tie line (as we will have
multiple equilibrium stages). The position of either product is specified and then the other
calculated by a mass balance (equations 2.7.1 and 2.7.2), i.e. a straight line which passes
between E1 , M , and RN .
In this example, we will specify (xA )RN = 0.025 = 2.5 %, i.e. the desired exit concen-
tration. As this point lies on the equilibrium curve, RN can be located and the values
of (xC )RN = 92.8 % and (xS )RN = 4.7 % can be read from Figure 2.7. A straight line
drawn from RN through M locates E1 at the equilibrium-curve intersection, from which
the composition of E1 can be read. Values of the flow rates RN and E1 can then be de-
termined from the overall material balance equations, or from Figure 2.7 by the lever-arm
rule.
With M = 500 kg; by either method the results are,
Raffinate Product Extract Product

RN = 295.5 kg E1 = 204.5 kg
(xA )R = 0.025 (xA )E = 0.457
(xC )R = 0.928 (xC )E = 0.126
(xS )R = 0.047 (xS )E = 0.417
38 T.L.
c Rodgers 2019
2.7. HUNTER-NASH GRAPHICAL EQUILIBRIUM-STAGE METHOD
0
100
Ma
20
ss
80
r
ate
Fra
nW
ctio
40
ctio
nE
60
thy
Fr a
E1
len
ss
60
Ma
eG
40
lyc
F
l o
80 M
20
100 S RN
0
0 20 40 60 80 100
Mass Fraction Furfural
Figure 2.7: Construction 1: Location of product points.
2.7.3 Step 3 - Calculation of the Operating Lines
For vapour-liquid cascades, e.g. distillation and absorption, an operating line can be de-
termined that is the locus of passing streams in a the cascade. Referring to Figure 2.6, a
material balance can be generated around stage n,
Rn−1 + En+1 = Rn + En = M (2.7.3)
This can be rearranged to give the difference in flows, ∆, at both sides of the stage,
Rn−1 − En = Rn − En+1 = ∆ (2.7.4)
This value of ∆ must be the same for every stage including the first the last stage such
that,
F − E1 = RN − S = ∆ (2.7.5)
This process can be repeated for each component around stage n,

Rn−1 (xi )Rn−1 + En+1 (xi )En+1 = Rn (xi )Rn + En (xi )En = M (xi )M (2.7.6)
which means that the difference in component flows is,

Rn−1 (xi )Rn−1 − En (xi )En = Rn (xi )Rn − En+1 (xi )En+1 = ∆ (xi )∆ (2.7.7)
Because the passing streams are differenced, ∆ defines a difference point, not a mixing
point, M . From the same geometric considerations that apply to a mixing point, a dif-
ference point also lies on a line through the points involved1 . However, whereas M lies
1
The component balance equation can be rearranged for that of a straight line,
Rn−1 (xi )Rn−1 − En (xi )En Rn (xi )Rn − En+1 (xi )En+1
(xi )∆ = = .
Rn−1 − En Rn − En+1
T.L.
c Rodgers 2019 39
inside the diagram and between the two end points, ∆ usually lies outside the triangular
diagram along an extrapolation of the line through two points such as F E1 , SRN .
To locate this difference point, two straight lines are drawn through the passing-stream
point pairs (E1 , F ) and (S, RN ) (equation 2.7.5) established from Figure 2.7 and shown
in Figure 2.8. These lines are extrapolated until they intersect at the difference point ∆.
These lines and point ∆ are shown in Figure 2.8.
0
100
Ma
20
ss
80
r
ate
Fra
nW
c
tio
40
tio
nE
60
rac
thy
F
E1
len
ss
60
Ma
eG
40
lyc
F
ol
80
20
100 S •
RN 0 ∆
0 20 40 60 80 100
Figure 2.8: Construction 2: Location of operating points. Red line is the F −E1 operating
line and the blue line is the RN − S operating line.
Straight lines drawn through points for any other pair of passing streams, such as (En , Rn−1 ),
must also pass through point ∆. Thus, the difference point becomes an operating point
for the extraction, and lines drawn through pairs of points for passing streams and extrap-
olated to point ∆ are operating lines.
The operating point, ∆, lies on the feed or raffinate side of the diagram in Figure 2.8.
Depending on the relative amounts of feed and solvent and the slope of the tie lines,
point ∆ may lie on the solvent or feed side of the diagram, and inside or outside of the
diagram.
2.7.4 Step 4 - Tie Lines and Equilibrium Lines
The next part of the construction involves the tie lines that define the equilibrium curve,
which is divided into the two sides (raffinate and extract) by the plait point. A material
balance around stage n for any of the three components is,
(xi )n−1 Rn−1 + (yi )n+1 En+1 = (xi )n Rn + (yi )n En (2.7.8)
Because Rn and En are in equilibrium, their composition points are at the two ends of a
tie line. Typically, a diagram will not contain all tie lines needed; they may be added by
centering them between existing tie lines.
40 T.L.
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2.8. MINIMUM AND MAXIMUM SOLVENT-TO-FEED FLOW-RATE RATIOS
Equilibrium stages are stepped off by alternate use of tie lines and operating lines, as
shown in Figure 2.9, where constructions have been employed to locate the stages points.
Starting at the feed end from point E1 and referring to Figure 2.9, it is seen that R1
is in equilibrium with E1 . R1 passes E2 . Therefore, E2 lies at the intersection of the
straight operating line drawn through points R1 and ∆, and back to the extract side of the
equilibrium curve. From E2 , R 2 is located with a tie line (equilibrium).
Continuing in this fashion by alternating between equilibrium tie lines and operating lines,
the specified point RN is reached or passed. In Figure 2.9, 4 equilibrium stages are re-
quired, where equilibrium stages are counted by the number of equilibrium tie lines used.
0
100
Ma
20
ss
80
r
ate
Fra
nW
ctio
40
ctio
nE
60
thy
Fra
E1
len
ss
60
Ma
eG
40
lyc
E2 F
ol
80
E3 R1 20
E4 R2
100 S R3 •
RN 0 ∆
0 20 40 60 80 100
Figure 2.9: Construction 3: Determination of the extraction stages. Red lines are the
equilibrium tie lines, blue lines are the operating difference lines between equilibrium
stages.
2.8 Minimum and Maximum Solvent-to-Feed Flow-Rate

Ratios
The procedure above for determining the number of equilibrium stages needed to achieve
a desired solute extraction for a given solvent-to-feed ratio presupposes that this ratio
is,
• greater than the minimum ratio, which corresponds to an infinite number of stages,
and
• less than the maximum ratio that would prevent the formation of the required second
liquid phase.
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2.8.1 Minimum Ratio
In practice, one usually determines the minimum ratio first. This is done by solving with
N = ∞, where, as in distillation, absorption, and stripping, the infinity of stages occurs
at an equilibrium-curve and operating-line pinch point. In ternary systems, the pinch
point occurs when a tie line coincides with an operating line. The calculation is involved
because the pinch point is not always at the feed end of the cascade.
Each tie line is assumed to be a pinch point by extending each tie line until it intersects
the line SR. In this manner, a sequence of intersections ∆1 , ∆2 , etc., is found. If these
points lie on the raffinate side of the diagram, the pinch point corresponds to the point
∆min located at the greatest distance from RN , Figure 2.10.
0
100
20 Ma
80 ss
r
ate
Fra
nW
c
tio
40
ctio
nE
60
thy
Fra
len
ss
60
Ma
eG
40
lyc
F
ol
80
20
100 S ∆min
•
RN 0
0 20 40 60 80 100
Figure 2.10: Construction to find the minimum solvent to feed ratio for equilibrium lines
slopping towards the raffinate side.
If the intersection points lie on the extract side of the diagram, the pinch point corresponds
to the point ∆min located at the closest distance to S, Figure 2.11.
Joining the ∆min to the feed point, F , we can get the Emin value. Joining the Emin to
R gives the mixing point, Mmin . The (S/F )min value can be calculated by the lever-arm
rule, Figure 2.12.
2.8.2 Maximum Ratio
If M in Figure 2.12 is moved along the F S line towards S, the intersection for (S/F )max
occurs at the point shown on the extract side of the binodal curve, Figure 2.13. This is the
maximum about of solvent that can be added with the mixture composition within the 2
phase region. If the mixture falls outside the 2 phase region there is only one phase, so
there can’t be any extraction.
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2.8. MINIMUM AND MAXIMUM SOLVENT-TO-FEED FLOW-RATE RATIOS
0
100
Ma
r
ate
20
ss
nW
80
Fra
ctio
40
c
tio
60
Fra
nA
60
ss
cet
40
Ma
one
80 F
20
100 RN
S 0
• 0 20 40 60 80 100
∆min
Mass Fraction Acetate
Figure 2.11: Construction to find the minimum solvent to feed ratio for equilibrium lines
slopping towards the extract side.
0
100
20
Ma
80
r
te
ss
Wa
Fra
ion
40
ctio
60
t
rac
nA
F
ss
cet
60
Ma
40
one
F
80 Emin
Mmin 20
To ∆
100 R
R0
S 0
0 20 40 60 80 100
Figure 2.12: Determination of Mmin .
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0
100
20 Ma
80
r
ate
ss
nW
Fra
40
ctio
60
tio
Fra
nA
ss
cet
60
Ma
40
one
F
80
20
100 Mmax R
R0
S 0
0 20 40 60 80 100
Figure 2.13: Determination of Mmax .
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2.9. EQUIPMENT FOR SOLVENT EXTRACTION
2.9 Equipment for Solvent Extraction

Equipment similar to that used for absorption, stripping, and distillation is sometimes
used for extraction, but such devices are inefficient unless liquid viscosities are low and
differences in phase density are high. Generally, centrifugal and mechanically agitated
devices are preferred. Regardless of the type of equipment, the number of equilibrium
stages required is computed first. Then the size of the device is obtained from experimen-
tal HETP or mass-transfer-performance-data characteristic of that device. In extraction,
some authors use the acronym HETS, height equivalent to a theoretical stage, rather than
HETP. Also, the dispersed phase, in the form of droplets, is referred to as the discontinu-
ous phase, the other phase being the continuous phase.
2.9.1 Mixer-Settlers
In mixer-settlers, the two liquid phases are first mixed in a vessel (Figure 2.14(a)) by
one of several types of impellers, and then separated by gravity-induced settling (Fig-
ure 2.14(b)). Any number of mixer-settler units may be connected together to form a
multistage, countercurrent cascade.
Turbine
Spacer
Scum tap
Baffle Light liquid
Plate
Mix in Heavy liquid
(a) Mixing Vessel (b) Gravity settler
Figure 2.14: Mixer-Settler equipment (a) Compartmented mixing vessel with turbine ag-
itators, (b) Horizontal gravity-settling vessel.
During mixing, one of the liquids is dispersed in the form of small droplets into the
other liquid. The dispersed phase may be either the heavier or the lighter phase. The
mixing is commonly conducted in an agitated vessel with sufficient residence time so that
a reasonable approach to equilibrium (e.g. 80% to 90%) is achieved. The vessel may
be compartmented as in Figure 2.14(a). If dispersion is easily achieved and equilibrium
rapidly approached, as with liquids of low interfacial tension and viscosity, the mixing
step can be achieved by alternative, more energy efficient means, e.g. impingement in a jet
mixer, by turbulence in a nozzle mixer, orifice mixer, or other in-line mixing device.
The settling step is by gravity in a settler (decanter). In Figure 2.14(b) a horizontal vessel,
with an impingement baffle to prevent the jet of the entering two-phase dispersion (emul-
sion) from disturbing the gravity-settling process, is used. Vertical and inclined vessels
are also common. A major problem in settlers is emulsification in the mixing vessel,
which may occur if the agitation is so intense that the dispersed droplet size falls below 1
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to 1.5 µm (micrometers). When this happens, coalescers, separator membranes, meshes,

electrostatic forces, ultrasound, or chemical treatment are required to speed settling. If
the phase-density difference is small, the rate of settling can be increased by substituting
centrifugal for gravitational force.
Each mixer-settler can be thought of as one theoretical stage.
2.9.2 Spray Columns
The simplest and one of the oldest extraction devices is the spray column. Either the
heavy phase or the light phase can be dispersed, as seen in Figure 2.15. The droplets of
the dispersed phase are generated at the inlet, usually by spray nozzles.
Light Light
liquid liquid
Heavy Heavy
liquid liquid
Light Light
liquid liquid
Heavy Heavy
liquid liquid
(a) (b)
Figure 2.15: Spray columns: (a) light liquid dispersed, heavy liquid continuous; (b) heavy
liquid dispersed,light liquid continuous.
Because of lack of column internals, throughputs are large, depending upon phase-density
difference and phase viscosities. As in gas absorption, axial dispersion (backmixing) in
the continuous phase limits these devices to applications where only one or two stages
are required. Axial dispersion is so serious for columns with a large diameter-to-length
ratio that the continuous phase is completely mixed, and spray columns are thus rarely
used, despite their low cost. The HETP for spray towers depends on the properties of the
liquids and the dimensions of the column[6–9].
Spray towers can be used e.g. when there is an irreversible reaction occurring in one of
the phases. Spray towers are thus used in waste acid neutralisation. In these cases the
column volume may be set by the reaction rate, not the mass transfer, and the height is
not designed only based on HETP.
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2.9. EQUIPMENT FOR SOLVENT EXTRACTION
2.9.3 Packed Columns
Axial dispersion in a spray column can be reduced, but not eliminated, by packing the
column. This also improves mass transfer by breaking up large drops to increase interfa-
cial area, and promoting mixing in drops by distorting droplet shape. With the exception
of Raschig rings, the packings used in distillation and absorption are suitable for liquid-
liquid extraction, but choice of packing material is more critical.
A material preferentially wetted by the continuous phase is preferred. Figure 2.16 shows
performance data, in terms of HTU, for Intalox saddles in an extraction service as a func-
tion of continuous, UC , and discontinuous, UD , phase superficial velocities. Because of
backmixing, the HETP is generally larger than for staged devices; hence packed columns
are suitable only when few stages are needed.
2.5
UD = 17.2 m hr−1
2 UD = 7.5 m hr−1
HTU / m
1.5
0.5
0
0 20 40 60 80
Continuous phase velocity, UC / m hr−1
Figure 2.16: Efficiency of 1-inch Intalox saddles in a column 60 inches high with
MEK–water–kerosene [10]. UD is the dispersed phase velocity.
2.9.4 Plate Columns
Sieve plates reduce axial mixing and promote a stagewise type of contact. The dispersed
phase may be the light or the heavy phase. For the former, the dispersed phase, analogous
to vapour bubbles in distillation, flows up the column, with redispersion at each tray. The
heavy phase is continuous, flowing at each stage through a downcomer, and then across
the tray like a liquid in a distillation tower. If the heavy phase is dispersed, upcomers are
used for the light phase. Columns have been built with diameters larger than 4.5 m. Holes
from 0.64 to 0.32 cm in diameter and 1.25 to 1.91 cm apart are used, and tray spacings
are closer than in distillation - 10 to 15 cm for low-interfacial-tension liquids. Plates are
usually built without outlet weirs on the downspouts.
If operated properly, extraction rates in sieve-plate columns are high because the dispersed-
phase droplets coalesce and re-form on each sieve tray. This destroys concentration gradi-
ents, which develop if a droplet passes through the entire column undisturbed. Sieve-plate
extractors are subject to the same limitations as distillation columns: flooding, entrain-
ment, and, to a lesser extent, weeping. An additional problem is scum formation at phase
interfaces due to small amounts of impurities.
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2.9.5 Columns with Mechanically Assisted Agitation
If interfacial tension is high, the density difference between liquid phases is low, and/or
liquid viscosities are high, gravitational forces are inadequate for proper phase dispersal
and turbulence creation. In that case, mechanical agitation is necessary to increase interfa-
cial area per unit volume, thus decreasing mass-transfer resistance. For packed and plate
columns, agitation is provided by an oscillating pulse to the liquid, either by mechanical
or pneumatic means.
The most prevalent agitated columns are those that employ rotating agitators, such as
those in Figure 2.17, driven by a shaft extending axially through the column. The agitators
create shear mixing zones, which alternate with settling zones.
Light liquid out

Heavy liquid in
Packing
Feed (optional)
Turbine agitator
Light liquid in
Heavy liquid out
Figure 2.17: Commercial extractor with mechanically assisted agitation.
2.10 References
[1] Brandt, R. L. [1930], ‘The edeleanu process for refining petroleum’, Industrial &
Engineering Chemistry 22(3), 218–223.
[2] Davis, S. [1970], ‘Molar attraction constants applied to structure activity relation-
ships’, Experientia 26, 671–672.
[3] Derry, T. K. and Williams, T. I., eds [1961], A Short History of Technology, Oxford
University Press, New York.
[4] Hansen, C. M. [1967], The Three Dimensional Solubility Parameter and Solvent
Diffusion Coefficient, Danish Technical Press.
[5] Hunter, T. G. and Nash, A. W. [1934], ‘The application of physico-chemical princi-
ples to the design of liquid-liquid contact equipment, part ii: Application of phase-
rule graphical method’, Journal of the Society of Chemical Industry 53, 95T–102T.
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2.10. REFERENCES
[6] Keith, F. W. and Hixson, A. N. [1955], ‘Liquid-liquid extraction spray columns -

drop formation and interfacial transfer area’, Industrial & Engineering Chemistry
47(2), 258–267.
[7] Kumar, A. and Hartland, S. [1999], ‘Correlations for prediction of mass transfer
coefficients in single drop systems and liquid-liquid extraction columns’, Chemical
Engineering Research and Design 77(5), 372–384.
[8] Licht, W. and Conway, J. B. [1950], ‘Mechanism of solute transfer in spray towers’,
Industrial & Engineering Chemistry 42(6), 1151–1157.
[9] Mixon, F. O., Whitaker, D. R. and Orcutt, J. C. [1967], ‘Axial dispersion and heat
transfer in liquid-liquid spray towers’, AIChE Journal 13(1), 21–28.
[10] Neumatis, R., Eckert, J., Foote, E. and Rollinson, L. [1971], Chemical Engineering
Progress 67, 60.
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50
2.11. PROBLEMS
2.11 Problems
R1 Plot the points that refer to
(a) Pure B
(b) 70% B and 20% A
(c) A composition of 0.1 A, 0.5 B, 0.4 C
0C
100
10
90
20
80
30
70
40
60
50
50
60
40
70
30
80
20
90
10
100
A 0
0 10 20 30 40 50 60 70 80 90 100 B
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E1 Determine the composition of the equilibrium phases produced when a 45 % w/w

ethylene glycol and 55 % water solution is contacted with twice its weight of pure
furfural solvent at 25 ◦ C and 101 kPa. [Phase 1 - 32.0 wt% Ethylene Glycol, Phase
2 - 8.5 wt% Ethylene Glycol].
Furfural (w/w %) Ethylene Glycol (w/w %) Water (w/w %)

95.0 0.0 5.0
90.3 5.2 4.5
86.1 10.0 3.9
75.1 20.0 4.9
66.7 27.5 5.8
49.0 41.5 9.5
34.3 50.5 15.2
27.5 52.5 20.0
13.9 47.5 38.6
11.0 40.0 49.0
9.7 30.0 60.3
8.4 15.0 76.6
7.7 0.0 92.3
Equilibrium miscibility data
EG in Water (w/w %) EG in Furfural (w/w %)

41.5 41.5
52.5 27.5
51.5 20.0
47.5 15.0
40.0 10.0
30.0 7.5
20.0 6.2
15.0 5.2 Solution Video
7.3 2.5
Mutual Equilibrium (Tie Line) data.
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2.11. PROBLEMS
0
100
10
90
20
80
30
70
40
60
50
50
60
40
70
30
80
20
90
10
100
0
0 10 20 30 40 50 60 70 80 90 100
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E2 A feed with a flow rate of 1000 kg h−1 contains 30 %wt acetic acid in isopropyl
ether. The acetic acid is to be extracted with water. Equilibrium data are given
in the table, in which it can be seen that water and ether have significant mutual
solubility.
Mass fraction in water phase Mass fraction in ether phase

Acetic acid water Isopropyl ether Acetic acid water Isopropyl ether
0.0069 0.981 0.012 0.0018 0.005 0.993
0.0141 0.971 0.015 0.0037 0.007 0.989
0.0289 0.955 0.016 0.0079 0.008 0.984
0.0642 0.917 0.019 0.0193 0.010 0.971
0.1330 0.844 0.023 0.0482 0.019 0.933
0.2550 0.711 0.034 0.1140 0.039 0.847
0.3670 0.589 0.044 0.2160 0.069 0.715
(a) Represent the equilibrium data in the table in composition space (e.g. mass
fraction acetic acid vs mass fraction water).
(b) Estimate the flow rate and composition of the two liquid phases obtained if
2500 kg h−1 water is mixed with the feed. Represent the single-stage phase
separation in the composition space diagram. [Phase 1 - 9.86 wt% Acetic
acid, Phase 2 - 3.35 wt% Acetic acid]
0
100
10
90
20
80
30
70
40
60
50
50
60
40
70
30
80
20
90
10
100
0
0 10 20 30 40 50 60 70 80 90 100
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2.11. PROBLEMS
E3 A process produces a stream consisting of 20 mol% ethanol and 80 mol% n-pentane.

This is to be separated into a product of n-pentane with only 5 mol% ethanol present
using a solvent of water. If the flow rate of the feed is 720 kmol hr−1 and the flow
rate of the solvent is 100 kmol hr−1 how many stages are needed for the separation?
[3 stages]
0
100
10
90
20
80
30
70
ane
Mo
ent
40
le %
60
n-p
le %
eth
50
50
ano
Mo
l
60
40
70
30
80
20
90
10
•
100
0
0 10 20 30 40 50 60 70 80 90 100
Mole % water
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E4 Acetone is to be extracted from a 30 wt% acetone (A) and 70 wt% ethyl acetate (C)
feed at 30 ◦ C, using pure water (S) as the solvent. The final raffinate is to contain
5 wt% acetone on a water-free basis.
(a) Find the actual raffinate composition. [4.725 wt% acetone, 5.5 wt% water]
(b) Determine the minimum and maximum solvent-to-feed ratios (NB. you might
need to use some extra paper to draw the lines). [min = 1, max = 10]
(c) Find the number of equilibrium stages required if S/F = 3. [3 stages]
0
100
10
90
20
80
30
70
Wt
)
r (S
40
%
te
60
ace
wa
ton
50
%
50
e
Wt
(A
60
)
40
70
30
80
20
90
10
100
• 0
0 10 20 30 40 50 60 70 80 90 100
Wt % acetate (C)
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2.11. PROBLEMS
D1 In question E4 above, a feed of 30 wt% acetone and 70 wt% ethyl acetate was ex-
tracted with pure water in a single-section, counter-current cascade to obtain a raf-
finate of 5 wt% acetone on a water (solvent-free basis).
An enrichment section can be added to the system to allow less

water content in the extract. Use the equilibrium diagram over
the page to calculate the number of stages to produce an extract
of only 50 wt% water with a S/F ratio of 1.43.
Method Video
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58
0
100
10
90
20
80
30
70
Wt
(S)
40
%
60
ter
ac
wa
eto
50
%
n
50
e(
Wt
A)
60
40
70
30
80
20
90
10
100
c
• 0
T.L.
0 10 20 30 40 50 60 70 80 90 100
Wt % acetate (C)
Rodgers 2019
Chapter 3
Multi-Component Distillation
Contents
3.1 Chapter 3 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.3 Vapour-Liquid Equilibrium . . . . . . . . . . . . . . . . . . . . . . . 62
3.4 Short-cut methods for multi-component distillation . . . . . . . . . 64
3.4.1 Relative volatility . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.4.2 The Fenske equation . . . . . . . . . . . . . . . . . . . . . . . 65
3.4.3 The Hengstebeck-Geddes Method . . . . . . . . . . . . . . . . 67
3.4.4 The Underwood Equation . . . . . . . . . . . . . . . . . . . . 69
3.4.5 The Gilliland correlation . . . . . . . . . . . . . . . . . . . . . 72
3.4.6 The Erbar-Maddox correlation . . . . . . . . . . . . . . . . . . 73
3.4.7 The Kirkbride Correlation . . . . . . . . . . . . . . . . . . . . 74
3.4.8 Procedures of the short-cut design . . . . . . . . . . . . . . . . 74
3.5 Rigorous Model for Multi-component Distillation . . . . . . . . . . 75
3.6 Considerations in Multi-component Distillation . . . . . . . . . . . . 77
3.6.1 Choice of distillation operating parameters . . . . . . . . . . . 77
3.6.2 Choice of reflux ratio . . . . . . . . . . . . . . . . . . . . . . . 80
3.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.8 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
59
CHAPTER 3. MULTI-COMPONENT DISTILLATION
3.1 Chapter 3 ILOs

.
ILO 3.1. Define the average relative volatility for components in a multi-component mix-
ture.
ILO 3.2. Explain the key assumptions used in the short-cut design equations.
ILO 3.3. Use the short-cut design equations to approximately design multi-component
distillation columns.
ILO 3.4. Assess considerations for multi-component distillation design.
Chapter Video
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3.2. INTRODUCTION
3.2 Introduction
In a brief statement, distillation is a method of separating homogeneous mixtures based
on the difference in volatilities of the components in the mixtures. Distillation is a unit
operation, or a physical separation process, and not a chemical reaction. Distillation often
produces an overhead distillate (can be either vapour or liquid) and a bottom product
(almost always liquid), whose compositions differ from that of the feed.
Unlike absorption and stripping, the second phase created in distillation is normally by
thermal vaporisation or condensation rather than by introducing a second phase that may
contain an additional component or components not present in the feed mixture.
Distillation normally requires repeated vaporisation and condensation and is the most
common method for the separation of fluid mixtures with fluid products. The driving force
for such a separation is the difference between the compositions of the vapour and liquid
phases at equilibrium. Distillation is suitable for a wide range of throughputs and feed
concentration and can produce high product purity, e.g. in the industry of recovering and
purifying small biomolecules such as ethanol, acetone, and n-butanol, and solvent (e.g.
organic alcohols, acids, and ketones) in biochemical industry. However, in bioseparation
of large biological metabolites, polymers or the products that are thermolabile, distillation
is not often seen.
Multistage distillation is the most widely used industrial method for separating chemical
mixtures. However, it is a very energy-intensive technique, especially when the relative
volatility of the key components being separated is low (< 1.5). About two-thirds of the
distillation energy was consumed by petroleum refineries, where distillation is used to
separate crude oil into petroleum chemicals.
Even distillation is widely used in the chemical industry, but it may not be suitable
for:
• Low molecular weight materials.
• High molecular weight heat-sensitive materials.
• Components with a low concentration.
• Classes of components.
• Mixtures with low relative volatility or which exhibit azeotropic behaviour.
• Mixtures of condensable and non-condensable components.
As for binary mixtures, vapour-liquid equilibrium is governed by equation 3.3.2, when
there are more than two components in the mixture as in Figure 3.1, the calculations
become more complicated. In principle, the design equations for binary distillation still
apply but N − 1 balance equations in an N component mixture make solutions harder to
obtain. It is also worth noting that short-cut distillation models are useful for initialising
more rigorous models and design methods.
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A
B
C
A (D)
B
C
D
(B)
C
D
Figure 3.1: Multi-component distillation, where B and D are light and heavy key compo-
nents and C is the intermediate boiling component.
3.3 Vapour-Liquid Equilibrium

The status of a matter existing in our physical world is determined by pressure and tem-
perature. At the right temperature and pressure, a matter can be solid, liquid or vapour.
In thermodynamics, the three phases can coexist - interpreted as phase equilibrium at a
particular point of temperature and pressure. In distillation, we are normally concerned
with the vapour-liquid equilibrium in multi-component mixtures.
We first introduce a concept - fugacity. In a pure liquid, the vapour generated by its
escaping molecules necessarily has the same composition as that of the liquid. However,
in a mixture, the composition of the vapour is not the same as that of the liquid, the vapour
is richer in that component whose molecules have greater tendency to escape from the
liquid phase. This tendency is measured by fugacity. Therefore, fugacity is a measure of
the tendency of a component of a liquid mixture to escape, or vaporize, from the mixture.
The fugacity of a component in a mixture is essentially the pressure that it exerts in the
vapour phase when in equilibrium with the liquid mixture. It is the effective pressure of a
real gas that differs from the behaviour of an ideal gas.
Thus, for each component in the mixture, when the vapour and liquid are in thermody-
namic equilibrium, we have:
fiV = fiL (3.3.1)
where fiV is the fugacity of component i in the vapour phase and fiL is the fugacity of the
component i in the liquid phase.
Defining the vapour phase fugacity coefficient φVi and the liquid phase fugacity coefficient
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3.3. VAPOUR-LIQUID EQUILIBRIUM
φLi and activity coefficient γi , when the system pressure is P , we have:
fiV = φVi yi P
fiL = φLi xi P
or
fiL = γi xi f0 (3.3.2)
where f0 is the standard state fugacity of component i at the temperature of the system,
xi and yi are the molar fractions of component i in liquid and vapour phases, respec-
tively.
For moderate pressures f0 is usually taken to be the saturated vapour pressure p0I
fiL = γi xi Pi0 (3.3.3)
The above equations can be combined (using equation 3.3.1) to give an expression for the
equilibrium ’constant’ or K-value, Ki ,
yi φL γi P 0
Ki = = Vi = V i (3.3.4)
xi φi φi P
At moderate pressure, φVi → 1

γi Pi0
Ki = (3.3.5)
P
When the liquid phase behaves as an ideal solution (γi → 1), this expression simplifies
to
Pi0
Ki = (3.3.6)
P
which is the so called Raoult’s Law.
Figure 3.2 shows an example of the vapour-liquid equilibrium in an ideal binary mixture:
Benzene-Toluene mixture at 1 atm.
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120 1
Mole fraction of Benzene

110 0.8
Temperature / ◦ C
(Vapour Phase)
Vapour
100 0.6
90 0.4
80 Liquid 0.2
70 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Mole fraction of Benzene Mole fraction of Benzene
(Liquid Phase) (Liquid Phase)
Figure 3.2: Vapour-liquid equilibrium of Benzene-Toluene mixture at 1 atm. The same

equilibriumpair is shown in both styles of plot.
3.4 Short-cut methods for multi-component distillation

In short-cut design for multi-component distillation, the basic assumptions include,
1. constant relative volatility, which is the most important assumption for most prob-
lems although not often a good assumption for mixtures with non-ideal behaviour,
and
2. constant molar overflow i.e. constant molar vapour and liquid flowrates.
There are a number of short-cut methods for simple columns including,
• Fenske equation: Minimum number of stages, Nmin .
• Hengstebeck-Geddes method: Distribution of non-key components.
• Underwood equations: Minimum reflux ratio, Rmin .
• Gilliland correlation: Actual number of stages, given the actual reflux ratio, Rmin
and Nmin .
It should be pointed out that all these methods have approximations that the designer
must understand. Otherwise, incorrect preliminary decisions on the choice of separator
and operating conditions might be made.
3.4.1 Relative volatility
We first introduce relative volatity - a ratio of the K-values of two components:

yi
Ki x
αij = = yji (3.4.1)
Kj
xj
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3.4. SHORT-CUT METHODS FOR MULTI-COMPONENT DISTILLATION
The geometric mean of the top and bottom product α values is most commonly used in
the short-cut calculations,
q
(αij )mean = (αij )top (αij )bottom (3.4.2)
From equation 3.4.1, it is clear that the relative volatilities of distillate and bottom product
depend on product compositions, but normally product compositions are not known and
an iterative procedure may be required to estimate them using short-cut models.
3.4.2 The Fenske equation
The Fenske equation[5] is used to estimate the minimum number of the theoretical stages,
Assumptions:
• Total Reflux
Figure 3.3 shows two stages in a simple distillation column, where yL and yH refer to the
compositions of light and heavy components in the vapour and xL and xH refer to the
compositions of light and heavy components in the liquid.
y1
1 x0
y2
x1
2
..
.
N −1
yN
xN −1 yN +1
N
xN
Figure 3.3: Simple distillation column for deriving the Fenske equation.
According to the definition of the relative volatity, equation 3.4.1, on each stage,

yL,n
xL,n
αLH,n =
yH,n
xH,n
yL,n xH,n
αLH,n = (3.4.3)
yH,n xL,n
which can be transformed into:

yL xL
= αLH,n (3.4.4)
yH n xH n
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At the bottom of the column the mass balance is given by the stripping section operating
line (remembering the assumption of constant L/V ),
L B
yn+1 = xn − xD (3.4.5)
V V
As the column is run under total reflux there is no bottom product, i.e. B = 0, there-
fore,
L
yn+1 = xn (3.4.6)
V
This is true for all components in the system, which means that,

L
xL,n
yL,n+1 V
=
yH,n+1 L
xH,n
V

yL xL
= (3.4.7)
yH n+1 xH n
Combining equation 3.4.7 with 3.4.4 (taken for n + 1) gives,

xL yL xL
αLH,n+1 = = (3.4.8)
xH n+1 yH n+1 xH n
For the each stage in the column we therefore have,

xL xL
= αLH,N
xH N −1 xH N
.. ..
. .
xL xL
= αLH,2
x
H 1 xH 2
xL xL
= αLH,1 (3.4.9)
xH 0 xH 1
Combining equation 3.4.9 produces,

N
xL Y xL
= αLH,n (3.4.10)
xH 0 n=1
xH N
As the composition of the liquid entering the column at the top is equal to the distillate
composition, and that leaving the column at the bottom is equal to the bottoms composi-
tion, then,
N
xL Y xL
= αLH,n (3.4.11)
xH D n=1 xH B
If we then define,
N
!1/N
Y
ᾱLH = αLH,n (3.4.12)
n=1
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Which can be approximated by equation 3.4.2. Therefore,

N
xL Y xL
= αLH,n
xH D n=1
xH B

xL N xL
= ᾱLH
xH D xH
B
N xL xH
ᾱLH = (3.4.13)
xH D xL B
As this analysis is for total reflux this means that the number of stages is the minimum
number, Nmin ,
xL xH
log
x H D xL B
Nmin = (3.4.14)
log ᾱLH
or equivalently,
DL BH
log
DH BL
Nmin = (3.4.15)
log ᾱLH
If can also be expressed in terms of the recovery of the key components, r,

rD,L rB,H
log
1 − rD,L 1 − rB,H
Nmin = (3.4.16)
log ᾱLH
Equation 3.4.14 is the original form of the Fenske equation for calculating the minimum
number of theoretical stages. When ᾱ is extended to be the geometric mean of the relative
volatilities of the light and heavy key components in a multiple component system. Equa-
tion 3.4.14 are still approximately valid and largely useful for estimating the minimum
number of the theoretical stages.
3.4.3 The Hengstebeck-Geddes Method
All components distribute between distillate and bottoms at total reflux; while at minimum
reflux conditions, none or only a few of the nonkey components distribute. Distribution
ratios for these two limiting conditions are given in Figure 3.4 [11].
For total reflux, the Fenske equation results in a plot as a straight line on log-log coordi-
nates. Such that taking equation 3.4.15 for to general components, i and j,

Di Bi
log
Dj Bj
Nmin =
log αi,j

Di Dj
Nmin log αi,j = log − log
Bi Bj

Di Dj
log = log + Nmin log αi,j (3.4.17)
Bi Bj
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Total Reflux
High L/D (~5Rmin )
Low L/D (~1.1Rmin )
Minimum Reflux
Light key
Log di /bi
Heavy key
Log αi,HK
Figure 3.4: The Hengstebeck-Geddes relation (adapted from [11]).
As it can be said that αi,j = αi,r αr,j , where r refers to a reference component, equa-
tion 3.4.17 can be rearanged to be,

Di Dj
log = log + Nmin log αi,r + Nmin log αr,j
Bi Bj

Di Dj
log = log + Nmin log αi,r − Nmin log αj,r
Bi Bj

Di Dj −Nmin
log = log α + Nmin log αi,r (3.4.18)
Bi Bj j,r
which is known as the Hengstebeck-Geddes method [6]. If we take the heavy key, H, as
the reference component, then the straighline equation can be written for each component,
i, in the system as,
Di
log = A + C log αi,H (3.4.19)
Bi
where C is equal to Nmin and A can be conveniently obtained from the heavy key com-
ponent as,
DH
A = log (3.4.20)
BH
For minimum reflux, the Underwood equations (below) can be used to estimate the com-
ponent distributions. Product-distribution curves for a given reflux might be expected to
lie between the lines for total and minimum reflux. However, this is not the case, and
product distributions are complex. Near Rmin , product distribution (curve 3) lies between
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the two limits (curves 1 and 4). However, for a high reflux ratio, non-key distributions
(curve 2) may lie outside the limits, thus causing inferior separations.
As the reflux ratio is decreased from total reflux while maintaining the key-component
splits, stage requirements increase slowly at first, but then rapidly as minimum reflux is
approached. Initially, large decreases in reflux cannot be compensated for by increasing
stages. This causes inferior nonkey distributions. As Rmin is approached, small decreases
in reflux are compensated for by large increases in stages; and the separation of non-key
components becomes superior to that at total reflux.
It appears reasonable to assume that, at a near-optimal reflux ratio of 1.3, nonkey-component
distribution is close to that estimated by the Fenske equation for total-reflux conditions.
3.4.4 The Underwood Equation
The Underwood equation[12, 13] is widely used in estimating the minimum reflux ra-
tio for multiple component systems even though it usually underestimates the minimum
reflux ratio.
At the point of the minimum reflux ratio, there is a pinch point in the system, Figure 3.5
1.0
Mole fraction in vapour, y
Pinch point
stage j •
0.0 zf
0.0 1.0
Mole fraction in liquid, x
Figure 3.5: Pinch point condition for a binary system.
At this pinch point the concentration at stage j stays the same on the plates above and
below,
xj−1 = xj = xj+1
yj−1 = yj = yj+1 (3.4.21)
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The pinch point is also on the equilibrium curve such that,
yj,i = Ki xj,i (3.4.22)
Taking a mass balance over the rectifing section (i.e. pinch point up to the distillate)
gives,
Vmin yj+1,i = Lmin xj,i + DxD,i (3.4.23)
Substituting equation 3.4.22 into equation 3.4.23 gives,

yj,i
Vmin yj+1,i = Lmin + DxD,i (3.4.24)
Ki
and from equation 3.4.21,

yj,i
Vmin yj,i = Lmin + DxD,i (3.4.25)
Ki
This can be rearranged for yj,i as,

yj,i
Vmin yj,i − Lmin = DxD,i
Ki

Lmin
yj,i Vmin − = DxD,i
Ki
DxD,i
yj,i = (3.4.26)
Lmin
Vmin −
Ki
As we don’t know the position of the pinch point, we don’t know the individual com-
positions of yj,i , however we do know that the sum of the vapour fractions of all the
components is equal to one, so that,
X DxD,i
1= (3.4.27)
Lmin
Vmin −
Ki
The equilibrium constant for any component can be given by the relative volatility and
the equilibrium constant of the reference component Ki = αi,r Kr , so that,
X DxD,i
1= (3.4.28)
Lmin
Vmin −
αi,r Kr
This can now be rewritten as in a simplified form as an expression for Vmin ,

X xD,i
1=D
Vmin Lmin
αi,r −
αi,r Vmin Kr
X αi,r xD,i
Vmin = D (3.4.29)
Lmin
αi,r −
Vmin Kr
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This same method analysis can also be performed on the stripping section of the column
to produce,
0
X αi,r xB,i
− Vmin =B (3.4.30)
L0min

αi,r − 0
Vmin Kr0
Under the assumptions of constant molar overflow and constant relative volatility it can
be proved that,
Lmin L0
= 0 min 0 = φ (3.4.31)
Vmin Kr Vmin Kr
Substituting equation 3.4.31 into equations 3.4.29 and 3.4.30 produces to key linked equa-
tions for the minimum vapour flows,
X αi,r xD,i
Vmin = D (3.4.32)
(αi,r − φ)
X αi,r xB,i
0
Vmin = −B (3.4.33)
(αi,r − φ)
(3.4.34)
These key equations allow us to generate the two underwood equations. For the first
equation, a mass balance around the feed stage gives,
0
Vmin − Vmin = F (1 − q) (3.4.35)
Substituting equations 3.4.32 and 3.4.33 in this gives,

X αi,r DxD,i X αi,r BxB,i
+ = F (1 − q)
(αi,r − φ) (αi,r − φ)
X αi,r (DxD,i + BxB,i )
= F (1 − q) (3.4.36)
(αi,r − φ)
From an overall column mass balance,
DxD,i + BxB,i = F zF,i (3.4.37)
Substituting this into equation 3.4.36 gives, the first Underwood equation,
X αi,r zF,i
1−q = (3.4.38)
(αi,r − φ)
As this only contains information about the feed it allows us to calculate φ. Note, there
are multiple roots to this equation, Figure 3.6; each root of φ lies between an adjacent
pair of relative volatilities of distributing species. Generally the root we are looking for is
αHK < φ < αLK if the heavy key is the reference for the volatility.
The value of φ can then be used to find the minimum reflux ratio, Rmin from,
Vmin
Rmin = −1 (3.4.39)
D
Substituting Vmin from equation 3.4.32 gives the second Underwood equation,
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α1 α2 αH αL α5 α6
5
4
3
2
1
f (φ)
0
−1
−2
−3
−4
−5
10−1 100 101
φ
Figure 3.6: Graphical solution to the first Underwood equation for an example of 6 com-
ponents.
X αi,r xD,i
Rmin + 1 = (3.4.40)
(αi,r − φ)
The Underwood minimum reflux equations are widely used, but often without examining
the possibility of non-key distributions. In addition, the assumption is frequently made
that Rmin equals the reflux ratio without pinch points of the non-key components.
When the Underwood assumptions appear valid and a negative minimum reflux ratio is
computed, a rectifying section may not be needed for the separation. The Underwood
equations show that the minimum reflux depends mainly on feed condition and α and,
to a lesser extent, on degree of separation, as is the case with binary distillation. As
with binary distillation, a minimum reflux ratio exists in a multi-component system for a
perfect separation between the LK and HK. The Underwood method can also be extended
for use with multiple feeds [2].
For calculations at actual reflux conditions with a process simulator by the computer pro-
grams knowledge of Rmin is not essential, but Nmin must be known if the split between
two components is to be specified.
3.4.5 The Gilliland correlation
The Gilliland correlation[7] is probably the most widely used empirical relation in prac-
tical distillation design for the calculation of the number of the theoretical stages under a
given reflux ratio.
As shown in Figure 3.7, the correlation was established between Y = (N −Nmin )/(N +1)
and X = (R − Rmin )/(R + 1). As the minimum number of theoretical stages, Nmin and
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100
N −Nmin
N +1
10−1
10−2 −2
10 10−1 100
R−Rmin
R+1
Figure 3.7: The Gilliland correlation. Data plotted: from Gilland [7, 10], from van
Winkle and Todd [14], and 4 from Brown-Martin [3]. Line plotted from equation 3.4.41
by Molokanov [9].
minimum reflux ratio, Rmin can be obtained from Fenske equation and the Underwood
equation, respectively, as long as the actual reflux ratio, R, is given, then the actual num-
ber of the theoretical stages, N , can be calculated according to the values given in the
correlation. The data used covers the range of parameters,
• Number of components: 2 to 11
• α: 1.11 to 4.05
• q: 0.28 to 1.42
• Rmin : 0.53 to 9.09
• Pressure: vacuum to 600 psig
• Nmin : 3.4 to 60.3
It is worth noting that the Gilliland correlation presents a graphical correlation, using
the design data. This correlation is effectively accurate for X < 0.17. This graphical
correlation has been fitted to an equation [9],

N − Nm 1 + 54.5Ψ Ψ−1 R − Rm
= 1 − exp 0.5
where Ψ=
N +1 11 + 117.2Ψ Ψ R+1
(3.4.41)
A more accurate correlation should utilize a parameter involving the feed condition, q. As
feed conditions range from subcooled liquid to superheated vapour the number of stages
required for the separation decreases. However, this effect is small unless αLK,HK is
high.
3.4.6 The Erbar-Maddox correlation
Similar to the Gilliland correlation, the Erbar-Maddox correlation [4] also relates the ac-
tual number of theoretical stages to the actual reflux ratio, the minimum reflux ratio and
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the minimum number of theoretical stages.

This is also an empirical correlation, it is sometimes considered more reliable than the
Gilliland correlation, but its use is not as widespread as the latter, Figure 3.8.
1
0.9
0.8 0.8
0.7
0.6 0.6
R+1
0.5
R
0.4
0.4
0.3
0.2 Rmin
0.2 Rmin +1
0
0 0.2 0.4 0.6 0.8 1
Nmin
N
Figure 3.8: The Erbar-Maddox correlation [4] using prediction equations from [1].
3.4.7 The Kirkbride Correlation
Implicit in the application of the Gilliland correlation is the specification that stages be
distributed optimally between the rectifying and stripping sections. The optimal feed
stage can be located by assuming that the ratio of stages above the feed to stages below is
the same as the ratio determined by applying the Fenske equation to the separate sections
at total reflux conditions.
Unfortunately, this is not reliable except for fairly symmetrical feeds and separations.
A better approximation of the optimal feed-stage location can be made with the Kirkbride
empirical equation [8],
" 2 #
Nr B xHK,f xLK,b
log = 0.206 log (3.4.42)
Ns D xLK,f xHK,d
where Nr is the number of stages in the rectifying section (above feed stage), Ns is the
number of stages in the stripping section (below feed stage), xHK,f is the mole fraction of
heavy key component in feed, xLK,f is the mole fraction of light key component in feed,
B and D are the distillate and bottoms flow rates respectively, xLK,b is the mole fraction
of light key component in bottom product, and xHK,d is the mole fraction of heavy key
component in distillate.
3.4.8 Procedures of the short-cut design
For shortcut distillation design, several commercial software packages are available for
simulations, optimizations, and optimal controls. Most of these packages are usually
limited to conventional systems as they were developed in early or late 1980s.
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3.5. RIGOROUS MODEL FOR MULTI-COMPONENT DISTILLATION
Normally, in the use of the shortcut design, the following steps are required, for a feed of
known composition, flow rate, thermal condition and pressure,
1. Specify top product phase, i.e. total or partial condenser.
2. Select light and heavy key components.
3. Specify mole fraction of light key in the bottoms and heavy key in the distillate.
4. Specify pressure of condenser and reboiler.
5. Estimate the relative volatilities for the top, bottom and feed point of the column.
6. Use the Fenske equation to calculate Nmin .
7. Use the Hengstebeck-Geddes method to estimate the split of the non-key compo-
nents.
8. Repeat steps 5 to 7 until Nmin doesn’t change.
9. Use the Underwood equations to calculate Rmin .
10. Pick a R/Rmin value.
11. Use the Gilliland correlation to calculate the actual number of stages, N .
12. Use the Kirkbride correlation to calculate the ratio of the rectifying to stripping
number of stages.
3.5 Rigorous Model for Multi-component Distillation

A common design for distillation columns is that the condenser at the top of the column
is assumed to be a complete condenser (i.e. all the vapour that enters the condenser leaves
as a liquid at the same temperature with no-sub-cooling). This means that this does not
represent an equilibrium stage. The first plate below the condenser is where the final stage
of the enrichment occurs.
Calculation of Plate Vapour-Liquid Equilibrium
The composition of the vapour on the plate, yj , is known from calculation of the previous
plate1 . Therefore it is possible to calculate the composition of the liquid on the same tray,
xj , as it is in equilibrium.
The temperature of the plate is calculated using a mole weighted vapour pressure2 ,
X yi
=1 (3.5.1)
Ki
The values of yi /Ki produced are then the values of xi for that plate, the xj s.
1
In the case of the first plate the composition of y1 is of course equal to that of the distillate, xd , which
is also equal to x0
2
The pressure at this point can be considered constant throughout the column and equal to that of the
feed
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V1 T0
j−1=0
Hj
Lj−1 xj−1 L0
Vj yj D
hj−1
j=1 Tj
Hj+1
Lj xj Vj+1 yj+1
hj
j+1 Tj+1
Hj+2
Lj+1 xj+1 V
j+2 yj+2
hj+1
Figure 3.9: Mass and energy flow in the top of a distillation column.
Plate Mass and Energy Balance
The second step for calculating the plate is to make an estimate for the composition of
the vapour arriving from the next plate, yj+1 . Assuming that there is no chemical reaction
then the molar flow from each plate should equal that to each plate,
Lj + Vj = Lj−1 + Vj+1 (3.5.2)

and the flow of each component should also be constant,
xj Lj + yj Vj = xj−1 Lj−1 + yj+1 Vj+1 (3.5.3)
Combining these two equation gives yj+1 ,
(Lj−1 + Vj+1 − Vj ) xj + yj Vj − xj−1 Lj−1

yj+1 = (3.5.4)
Vj+1
At this point however the value of Vj+1 is unknown, but as an initial guess assumed to be
equal to Vj . The values of Lj−1 and Vj are known from the previous plate balance1 .
1
The value of V1 and L0 can be calculated from the distillate flow rate, D, and the reflux ratio , R,
calculated from the short cut calculation,
V1 = (R + 1) D
L0 = RD
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3.6. CONSIDERATIONS IN MULTI-COMPONENT DISTILLATION
The liquid flow down from the plate, Lj , and the vapour flow rate up from the next plate,
Vj+1 can also be calculated using a heat balance,
hj Lj + Hj Vj = hj−1 Lj−1 + Hj+1 Vj+1 (3.5.5)

where H is the vapour enthalpy and h is the liquid enthalpy calculated from the calculated
plate temperature and the estimate of yj+1 .
Rearranging this equation in terms of Lj and combining with the molar flow balance
(equation 3.5.2) gives,
Hj Vj − hj−1 Lj−1 + Hj+1 (Lj−1 − Vj )

Lj = (3.5.6)
Hj+1 − hj
Also from the molar flow balance (equation 3.5.2),
Lj = Lj−1 + Vj+1 − Vj (3.5.7)

therefore iterating the value of Vj+1 until the values of Lj calculated by the last two
equation are equal solves the plate.
3.6 Considerations in Multi-component Distillation

There are some general considerations in designing a multi-component distillation. As
many components are present in the feed, fixing the recovery or mole fraction of a single
component does not specify the product composition or temperature; also, the selection
of the key components is a process engineering decision, usually based on the objectives
of the separation. Mass and energy balances are solved iteratively. It is useful to use
commercial process simulation software to carry out the calculations. The short-cut de-
sign equations allow initial estimates of design variables and column performance to be
obtained prior to rigorous simulation. Practical experience shows that convergence of
rigorous simulation can be facilitated by good initial estimates.
3.6.1 Choice of distillation operating parameters
In determining the distillation operating parameters, usually the feed composition and
flow rate are considered fixed. The product specifications are usually given in the design
problem statement and may be expressed in terms of recovery of certain components,
product purities or specific compositions.
The operating parameters to be selected by the design engineer would normally include,
• Operating pressure.
• Reflux ratio.
• Feed condition.
• Feed stage location.
• Type of condenser.
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In the preliminary distillation design, it is necessary for the design to be on the basis of the
whole system rather than a specific part as distillation columns are energy-intensive any
heat integration of distillation columns can significantly reduce the energy costs.
The heat integration opportunities for heat recovery in distillation columns can be cre-
ated and the operating pressure, reflux ratio and feed condition can have effects on those
opportunities thus their selection should be carefully considered.
Operating pressure
It is clear that the condenser temperature sets the distillation operating pressure as the
vapour comes out of the top of the column. There are two types of condensers: total and
partial condensers, Figure 3.10.
(a) Total condenser (b) Partial condenser
Figure 3.10: Condenser options.
A total condenser means all the vapour is to be condensed leaving only liquid as the
top product, in such cases, pressure should be fixed. Additionally, if cooling water is to
be used as the heat transfer agent, the bubble point of the overhead product should be
typically 10 ◦ C above the summer cooling water temperature. If air cooling is to be used,
the bubble point of the overhead product should be typically 20 ◦ C above the summer air
temperature.
For a partial condenser: vapour is taken as the top product. The above criteria for the total
condenser are applied to the dew point of the vapour top product.
There are exceptions for determining operating pressure in a distillation column, e.g.
• In the separation of gases and light hydrocarbons, a very high operating pressure
may be required as a result of trying to operate the condenser against cooling water
or air cooling, therefore, a combination of high operating pressure and low temper-
ature condensation using refrigeration may be needed.
• For distilling high molecular weight materials, process constraints may restrict the
maximum temperature of the distillation to avoid product decomposition, a vacuum
operation must be used to reduce the boiling temperature.
• In a sequence of columns, the condenser of one operating at a high pressure may
provide heat to the reboiler of another operating at a lower pressure thus heat re-
covery opportunities can be created.
The effect of pressure on distillation is shown in Figure 3.11 in an example of separating
a benzene-toluene-ethylbenzene-styrene mixture.
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2 6 16
1.75 5 14
Nmin
Rmin
1.5
α 1.25 4 12
1 3 10
1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
P / bar P / bar P / bar
(a) Relative volatility decreases (b) Reflux requirement increase (c) No. stages required increases
250 34
λ / MJ kg−1
200 TReboiler
T / ◦C
32
150
TCondenser 30
100
50 28
1 2 3 4 5 1 2 3 4 5
P / bar P / bar
(d) Reboiler and condenser tempera- (e) Latent heat of vapourisation de-
ture increases creases
Figure 3.11: The effects of pressure on (a) relative volatility of components, (b) reflux, (c)
number of theoretical stages, (d) reboiler and condenser temperatures, and (e) the latent
heat of the vaporisation.
Effect of temperature on utility costs
The temperature of a distillation column has significant effects on utility costs as the typ-
ical utility costs depend on the temperature and source of heating or cooling. Figure 3.12
shows such effects.
4
Cost / $ GJ−1
0
40 barg 10 barg 4 barg Cooling 0 ◦C −20 ◦ C −40 ◦ C
Steam water Refrigeration
High temperature Low temperature
heating is expensive cooling is expensive
Figure 3.12: The effect of temperature on utility costs.
As seen from Figure 3.12, water used as the cooling agent would lower the costs signifi-
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cantly thus is the most economic source of creating condensation. This result is also based
on a simulation of separating a benzene-toluene-ethylbenzene-styrene mixture.
3.6.2 Choice of reflux ratio
The reflux ratio has a direct effect on the number of theoretical stages. There are two
extreme situations: minimum and total reflux ratio.
In the case of the minimum refux ratio, an infinite number of stages would be required
which would incur a very high capital cost but minimise the energy requirements thus
the operating cost is low. However, in case of total reflux ratio, a minimum number of
stages is required, which means low capital cost but needs to maintain high energy supply
resulting in high operating costs. Figure 3.13 shows the variation of the number of stages
with the reflux ratio for the same benzene-toluene-ethylbenzene-styrene mixture.
50
Rmin
40
30
N
20
10 Nmin
0
0 10 20 30 40 50
R
Figure 3.13: Effect of reflux ratio on the number of theoretical stages.
To avoid the two extremes, the actual reflux will lie between the minimum and the total
ratio. Figure 3.14 illustrates that there are capital-energy trade-offs, to lower the total cost,
and that there is often an optimum reflux ratio.
Rmin Ropt
Total
Energy
Cost
Capital
Figure 3.14: Trade-offs between the capital and energy costs.
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The Rule of thumb for the choice of the optimum reflux ratio can be expressed as within
the range of 1.1 to 1.3 times of the minimum reflux ratio. This rule of thumb assumes
that heating and cooling duties will be provided by the utility system. Also, the reflux
ratio should only be optimised in the context of the overall process heating and cooling
requirements. Table 3.1 shows some industrial examples and the conditions used; this
shows that the guide reflux ratio is not always the optimum for a variety of reasons.
Table 3.1: Representative commercial distillation operations.
Binary Mixture Average Relative Number of Typical Operating Reflux to Minimum

Volatility Pressure / psia Reflux Ratio
1,3-Butadiene/vinyl acetylene 1.16 130 75 1.70
Vinyl acetate/ethyl acetate 1.16 90 15 1.15
o-Xylene/m-xylene 1.17 130 15 1.12
Isopentane/n-pentane 1.30 120 30 1.20
Isobutane/n-butane 1.35 100 100 1.15
Ethylbenzene/styrene 1.38 34 1 1.71
Propylene/propane 1.40 138 280 1.06
Methanol/ethanol 1.44 75 15 1.20
Water/acetic acid 1.83 40 15 1.35
Ethylene/ethane 1.87 73 230 1.07
Acetic acid/acetic anhydride 2.02 50 15 1.13
Toluene/ethylbenzene 2.15 28 15 1.20
Propane/1,3-butadiene 2.18 40 120 1.13
Ethanol azeotrope/water 2.21 60 15 1.35
Isopropanol/water 2.23 12 15 1.28
Benzene/toluene 3.09 34 15 1.15
Methanol/water 3.27 60 45 1.31
Cumene/phenol 3.76 38 1 1.21
Benzene/ethylbenzene 6.79 20 15 1.14
HCN/water 11.20 15 50 1.36
Ethylene oxide/water 12.68 50 50 1.19
Formaldehyde/methanol 16.70 23 50 1.17
Water/ethylene glycol 81.20 16 4 1.20
Choice of feed condition and feed stage location
The feed condition and feed stage location are two other important factors that would
affect the heating duty energy cost significantly.
The feed condition, q, value affects the vapour and liquid flow rates in the column. A
simple rule is that the feed temperature usually lies between the extreme temperatures of
the column (condenser and reboiler temperatures).
• q = 1, (saturated liquid feed) is preferred. This makes the column pressure easy to
control by pumping the liquid to the correct pressure.
• If q = 0 (saturated vapour feed), a compressor, rather than a pump, is needed, as it
is harder to adjust the pressure of a vapour feed than a liquid feed.
• Superheated or subcooled feeds cannot participate in the separation process until
thermal equilibrium is achieved
• In columns with multiple feeds, it is not unusual to use feeds with q < 0 or q > 1,
which would be determined by the practical needs.
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Therefore, heating or cooling the feed can reduce overall energy costs. Preheating the
feed typically decreases the reboiler duty and may increase the condenser duty. Cooling
the feed, conversely, tends to decrease the condenser duty and may increase the reboiler
duty. The best feed condition can only be determined by considering heat recovery op-
portunities with the overall process.
The choice of feed stage location should follow the best match with the feed stage in terms
of composition and temperature or using the Kirkbride equation to provide an initial esti-
mate. It should be noted that poor matches are thermodynamically unfavourable, leading
to higher energy requirements. In multi-component distillation, it is highly unlikely that
the composition of all components can be matched.
Again, in the simulation of separating a Benzene-toluene-ethylbenzene-styrene mixture,
a comparison shown in Figure 3.15 between different feeding stages is made to highlight
the fact that heating duty depends on the match between the feed compositions and that
of the components on a particular stage.
5.8
5.6 Reboiler
Duty / GJ hr−1
5.4
5.2 Condenser
5
4.8
5 6 7 8 9 10 11 12 13 14 15
Feed Tray
(a) Change in duty of the condenser and reboiler with feed stage
Mole fraction (liquid) Mole fraction (liquid) Mole fraction (liquid)

0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
0 0 0
5 5 5
Stage number
10 10 10
15 15 15
Benzene
20 Styrene 20 20
Ethylbenzene
Toluene
25 25 25
(b) Composition with feed at (c) Composition with feed at (d) Composition with feed at
stage 8 stage 10 stage 13
Figure 3.15: Heating duty depending on the match between the feed condition and the-
composition of the component on the stage. (a) Variation in heat duty, (b)-(d) composition
of compentents on the stages with different feed stage positions.
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3.7. REFERENCES
Note in Figure 3.15, when the feed composition and feed stage composition are not well
matched, significant disruptions to the composition profiles have been observed.
Type of condenser
As shown in Figure 3.10, there are two types of condensers: total and partial condensers.
The total condenser produces liquid product for intermediate or final product storage or
the top product is to be fed to another distillation at a higher pressure. The partial con-
denser reduces the condenser duty and avoid expensive refrigeration as not all vapour is
condensed.
3.7 References
[1] Bahadori, A. and Vuthaluru, H. B. [2010], ‘Simple equations to correlate theoretical
stages and operating reflux in fractionators’, Energy 35, 1439–1446.
[2] Barnes, F. J., Hanson, D. N. and King, C. J. [1972], ‘Calculation of minimum reflux
for distillation columns with multiple feeds’, Industrial & Engineering Chemistry
Process Design and Development 11, 136–140.
[3] Brown, G. G. and Martin, H. Z. [1939], ‘An empirical relationship between reflux
ratio and the number of equlibrium plates for fractionating columns’, Transactions
of the AIChE 35, 679–708.
[4] Erbar, J. H. and Maddox, R. N. [1961], ‘Latest score: Reflux vs trays’, Petroleum
Refiner 40(5), 183.
[5] Fenske, M. R. [1932], ‘Fractionation of straight-run pennsylvania gasoline’, Indus-
trial & Engineering Chemistry 24(5), 482–485.
[6] Geddes, R. L. [1958], ‘A general index of fractional distillation power for hydrocar-
bon mixtures’, AIChE Journal 4(4), 389–392.
[7] Gilliland, E. R. [1940], ‘Multicomponent rectification estimation of the number of
theoretical plates as a function of the reflux ratio’, Industrial & Engineering Chem-
istry 32(9), 1220–1223.
[8] Kirkbride, C. G. [1944], ‘Process design procedure for multicomponent fractiona-
tors’, Petroleum Refiner 23, 321–336.
[9] Molokanov, Y. K., Korabline, T. R., Mazuraina, N. I. and Nikiforov, G. A. [1972],
‘An approximate method for calculating the basic parameters of multicomponent
fractionation’, International Chemical Engineering 12, 209–212.
[10] Robinson, C. S. and Gilliland, E. [1950], Elements of Fractional Distillation, 4th
edn, McGraw-Hill.
[11] Stupin, W. and Lockhart, F. [1968], The distribution of non-key components in mul-
ticomponent distillation, in ‘61st Annual Meeting of the AIChE’, Los Angeles, CA.
[12] Underwood, A. J. V. [1948], ‘Fractional distillation of multicomponent mixtures’,
Chemical Engineering Progress 44, 603–614.
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[13] Underwood, A. J. V. [1949], ‘Fractional distillation of multicomponent mixtures’,

Industrial & Engineering Chemistry 41(12), 2844–2847.
[14] van Winkle, M. and Todd, W. G. [1971], ‘Columns optimum fractionation design by
simple graphical methods’, Chemical Engineering 78, 136–148.
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3.8. PROBLEMS
3.8 Problems
R1 A mixture of 44 mol% Benzene and 56 mol% Toluene needs to be separated into a
product of at least 98 mol% Benzene and one of at least 98 mol% Toluene. It has
been suggested by the plant engineer that this could be achieved using a distillation
column at 1 atm with a Reflux ratio twice the minimum reflux ratio and a saturated
liquid feed. How many stages are needed for this distillation column? [13 trays
plus partial reboiler]
x y
0.0 0.00
0.1 0.21
0.2 0.38
0.3 0.51
0.4 0.62
0.5 0.71
0.6 0.78
0.7 0.85
0.8 0.91 Solution Video
0.9 0.96
1.0 1.00
VLE Data for benzene with toluene at 1 atm.
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E1 A de-ethaniser is to be designed for the separation summarised in the table below.

Estimate the minimum number of stages required for the separation. [12 stages]
Component Feed flow rate Specified recovery to Average volatility

(kmol h−1 ) distillate (kmol h−1 )
methane 160 8.22
ethane 370 368 2.42
propane 240 2 1.00
n-butane 25 0.378
n-pentane 5 0.150
Feed temperature (◦ C) 32
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3.8. PROBLEMS
E2 A distillation column is used to separate a mixture of 30% mol propane in propylene

to obtain 99% mol propylene and 98% mol propane.
(a) Calculate the column pressure if the reboiler is temperature is 370 K and the
condenser temperature is 317 K. [18 bar]
(b) Calculate Rmin if the feed condition at a column operating pressure is
i. saturated liquid, [φ = 1.25,Rmin = 0.65]
ii. saturated vapour, [φ = 1.61,Rmin = 1.09]
iii. 50% mol vapour. [φ = 1.38,Rmin = 0.79]
(c) Calculate the reboiler duty for the case that the feed flow rate is 500 kmol h−1
and the reflux ratio is 1.1 times Rmin . Take the heat of vapourisation of
the bottom product to be 11330 kJ kmol−1 . [3053.6 MJ h−1 , 6768.9 MJ h−1 ,
4573.5 MJ h−1 ]
Use the Antoine equation to estimate relative volatilities,

0 Bi
pi = exp Ai −
T + Ci
where: p0i is the saturated vapour pressure in bar and T is the temperature in K.
Component Ai Bi Ci
Propane 9.1058 2154.9 −25.16
Propylene 9.5749 1999.1 −17.61
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E3 A distillation column is to be designed to separate Hexane from Cyclohexane.

The feed consisting of 50 mol% Hexane enters the column as a saturated liquid at
346.77 K. The distillate consisting of 95 mol% Hexane exits the column at 342.38 K
and the bottom product consisting of 5 mol% Hexane exits the column at 352.97 K.
What is the minimum number of stages and the minimum reflux ratio needed for
the separation.
The saturated vapour pressure of the components can be given by:

Bi
Ai −
p0i = 10 Ci + T
with parameters of:

Component A B C Tmin Tmax
Hexane (H) 4.1297 1246.33 −40.162 178 508
Cyclohexane (C) 3.9706 1206.47 −50.014 280 354
The activity coefficient for each component can be given by:

Λij Λji
ln γi = − ln [xi + Λij (1 − xi )]+(1 − xi ) −
xi + Λij (1 − xi ) (1 − xi ) + Λji xi
with parameters of:
ΛHC = 0.8276
ΛCH = 1.1103
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3.8. PROBLEMS
D1 Use the short-cut method to design a distillation column to separate the mixture in
the table below, with a recovery of 95% of C5 to the distillate and 97% of C6 to the
bottom product. Use a saturated liquid feed at 298 K with a column pressure equal
to the feed pressure.
Alkane mol fraction

C3 0.05
C4 0.10
C5 0.40
C6 0.35
C7 0.10
The saturation pressure in kPa for any straight chained hydro-
carbon length n can be approximated toa ,
Pi0 = 1.78382 × 104 φn

1 −3 Solution Video
φ = exp −427.248 − 1.029807 × 10
T
a
L. Caldwell and D.S. van Vuuren, (1986), On the formation and com-
position of the liquid phase in Fischer-Tropsch reactors, Chemical Engi-
neering Science, 41:89-96
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90
Chapter 4
Distillation Sequencing
Contents
4.1 Chapter 4 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.3 Sequencing Simple Distillation Columns . . . . . . . . . . . . . . . . 93
4.4 Distillation Columns Sequencing Heuristics . . . . . . . . . . . . . . 95
4.5 Performance Indicators . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5.1 Vapour load . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.5.2 Energy demand . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.5.3 Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.6 Distillation Sequencing with Complex Columns . . . . . . . . . . . . 98
4.6.1 Side-Steam Columns . . . . . . . . . . . . . . . . . . . . . . . 98
4.6.2 Side-stripper arrangement . . . . . . . . . . . . . . . . . . . . 99
4.6.3 Side-rectifier arrangement . . . . . . . . . . . . . . . . . . . . 100
4.6.4 Pre-fractionation arrangements . . . . . . . . . . . . . . . . . . 101
4.7 Utility Considerations with Thermally Coupled Columns . . . . . . 103
4.8 Decomposition of Complex Columns for Design . . . . . . . . . . . 105
4.8.1 Side-stripper decomposition . . . . . . . . . . . . . . . . . . . 105
4.8.2 Side-rectifier decomposition . . . . . . . . . . . . . . . . . . . 106
4.8.3 Pre-fractionator decomposition . . . . . . . . . . . . . . . . . . 106
4.8.4 Extension to Underwood Equations for Side Stream Columns . 106
4.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4.10 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
91
CHAPTER 4. DISTILLATION SEQUENCING
4.1 Chapter 4 ILOs

.
ILO 4.1. Appraise simple distillation sequences using heuristic rules to find optimal se-
quences.
ILO 4.2. Compare distillation sequences with the calculation of key performance indica-
tors.
ILO 4.3. Develop distillation sequences using complex distillation columns.
ILO 4.4. Analyse the reasons for the advantages of complex distillation columns.
Chapter Video
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4.2. INTRODUCTION
4.2 Introduction
In almost any chemical industry, the mixtures intended to be separated are not simple
binary mixtures, they normally contain more than two components. If the mixture is
homogeneous as discussed in the previous chapters, distillation would be the most com-
monly used method for separating those multiple components. However, if the products
required are not only two but more than that, then generally a separation sequence is
needed to make the separation of the components in a viable and economic way. This is
called distillation sequencing; the separations carried out based on distillation does not
have only one sequence but other alternatives. The problem then becomes how to sieve
those sequences and choose the best option.
4.3 Sequencing Simple Distillation Columns

A simple distillation column means that a single feed, two products, the key components
are adjacent in volatility and the column has a reboiler and a condenser as shown in
Figure 4.1.
Decreasing
volatility A
B (light key)
A (C)
B
C
D
E
(B)
C (heavy key)
D
E
Figure 4.1: A simple column.
Suppose there is a homogeneous mixture with three components, A, B and C in which

A is the lightest component and C is the heaviest component, to be separated, we can
show there are in fact two alternative sequences - a direct sequence and an indirect se-
quence.
A direct sequence means in each column, the lightest component is taken as the over-
head product.
An indirect sequence means the heaviest component is taken as the bottom product in
each column.
The two sequences are illustrated in Figure 4.2.
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A
A A
B B
C C A
A
B
A A A B
B
B B B
B C C C
C
B
C C
(a) Direct Sequence A/BC - B/C (b) Indirect Sequence AB/C - A/B
Figure 4.2: The direct and indirect sequences.
As seen in Figure 4.2, in the two sequences, each column has a reboiler and a condenser.
It is worth noting that the direct sequence often requires less energy than the indirect one;
this is because the light component is only vaporised once. However, the indirect sequence
can be quite energy efficient compared to the direct one if the light component in the feed
has a low flowrate but the heavy component has a high flowrate. This is because feeding
a high flowrate of heavy component to both of the columns in the direct sequence is more
important than vaporising the light component twice in the indirect sequence.
In a three component mixture, there are only two sequences. When the number of compo-
nents in a mixture increases, the number of sequences increases dramatically. Figure 4.3
shows the alternative sequences for the separation of a five-component mixture.
Table 4.1 shows how dramatic the number of sequences changes with the increase of the
number of the components in the mixture.
Table 4.1: Number of sequences changes with the number of components.
Number of components Number of possible sequences

2 1
3 2
4 5
5 14
.. ..
. .
10 4862
As seen from Table 4.1, as the number of components increases to 10, the number of se-
quences increases to 4862. It is almost impossible to try so many sequences. Therefore,
the problem becomes: how do we screen for the best few sequences and what criteria
should we use to choose between alternative sequences? The way forward is to use sim-
plified methods to identify several promising sequences and then evaluate these options
further through rigorous simulations.
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4.4. DISTILLATION COLUMNS SEQUENCING HEURISTICS
C/DE D/E
B/CDE
CD/E C/D
A/BCDE BC/DE B/C D/E
B/CD C/D
BCD/E
BC/D B/C
C/DE D/E
AB/CDE A/B
CD/E C/D
ABCDE
A/BC B/C
ABC/DE D/E
AB/C A/B
B/CD C/D
A/BCD
BC/D B/C
ABCD/E AB/CD A/B C/D
A/BC B/C
ABC/D
AB/C A/B
Figure 4.3: Alternative sequences for separating a five component mixture.
4.4 Distillation Columns Sequencing Heuristics

Certainly, not every sequence is to be feasible, there are practical constraints to sequencing
columns including,
• Remove early: hazardous component, reactive and heat-sensitive components and
corrosive components.
• Decomposition in the reboilers would contaminate products, which means no fin-
ished products should be taken from bottoms of columns.
• For those compounds which polymerise when distilled would require chemicals
added to inhibit polymerisation but they tend to be involatile and end up in the
column bottoms, so it would be necessary to take finished products overhead.
• For those components that are difficult to condense, a total condensation would nor-
mally be required under low-temperature refrigeration and/or very high operating
pressures. The light components are normally removed from the top of the first
column to minimise use of refrigeration and high pressures.
However, there are some heuristics developed for sequencing columns, they are useful as
a guide line.
Heuristic 1 Separations where the relative volatility of the key components is close to
unity or which exhibit azeotropic behaviour should be performed in the absence of
non-key components (Difficult separations typically require large reflux ratios - by
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removing extraneous components, the internal flows in the column are reduced.) -
Do the most difficult separation last.
Heuristic 2 Sequences which remove the lightest components alone by one in column
overheads should be favoured. In other words, favour the direct sequence (Less
material is vaporised if only the lightest component is removed overhead, as in
Figure 4.9(a).)
Heuristic 3 A component comprising a large fraction of the feed should be removed first
(The inventory in subsequent columns is kept to a minimum.)
Heuristic 4 Favour near equimolar splits between top and bottom products in individual
columns (The mass load in subsequent columns will be more evenly distributed in
the sequence.)
However, difficulties can arise when those heuristics are in conflict with each other.
Heuristics can be contradictory to each other but they do have advantages such as they
incorporate engineering experience and insights and the designer stays in control (com-
pared to automated screening techniques). However, they are still qualitative guidance, it
is thus necessary to have some quantitative measures to classify the relative performance
of the sequences.
4.5 Performance Indicators

Some quantitative performance indicators are proposed for screening distillation sequences.
These are,
• Total vapour load.
• Total energy demand.
• Operating cost.
• Capital cost.
• Total annualised cost including capital, energy trade-offs, and the consideration of
heat integration.
4.5.1 Vapour load
Vapour load of a column is a meaningful performance indicator, as it relates to heat duties

in the reboiler and condenser (operating costs tend to dominate overall costs), size of
reboiler and condenser also the column diameter.
Vapour load can be calculated using short-cut methods (e.g. Underwood Equation). The
sum of the vapour loads for the sequence would provide a quantitative indicator of the
performance of the sequence. However, it has limitations such as it is not directly related
to energy demand or operating costs and the capital costs are only partially accounted for.
The calculation of vapour load can be made using the reflux ratio as shown in Figure 4.4.
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4.5. PERFORMANCE INDICATORS
D
R = L/D
L V
Figure 4.4: Schematic representation of the vapour load.
As the minimum reflux ratio Rmin can be calculated from the Underwood equation and
the minimum vapour load Vmin based on Rmin is,
Vmin = (Rmin + 1) D (4.5.1)
The typical values of R (1.1 - 1.3 times of Rmin ) have implicitly accounted for a capital-
energy trade-offs.
The total vapour load in a distillation sequence is thus the addition of the vapour load for
each column.
4.5.2 Energy demand
Energy demand is another useful indicator and allows total energy cost to be estimated.
The energy demand can be calculated from the energy balances effectively from the
vapour load. It should be pointed out that the heat of vaporisation depends on compo-
sition and temperature of stream (use product composition).
For a total condenser shown in Figure 4.5(a), the vapour to be condensed is V , thus the
energy needed for the condensation is,
Qcondenser = V · ∆ H vap (4.5.2)
where ∆ H vap is the enthalpy of vaporisation.

Similarly, for a partial condenser, Figure 4.5(b),
Qcondenser = L · ∆ H vap (4.5.3)
where L = RD.
4.5.3 Costs
• Operating costs. This can be determined by knowing the reboiler, condenser and
preheat duties, and given costs of utilities (e.g. steam, cooling water, refrigeration
power). It should be noted that costs of utilities are highly site-specific and vary
significantly from time to time.
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D
Qcondenser
Qcondenser
D
R = L/D R = L/D
L V L V
(a) Total condenser (b) Partial condenser
Figure 4.5: Energy demand for condensers.
• Capital costs. This can also be estimated, based on short-cut design results, e.g.
using the Fenske equation to calculate the minimum number of theoretical stages
(Nmin ) then using the Gilliland correlation to relate reflux ratio and number of
stages to Rmin and Nmin . However, the capital cost models are typically highly
inaccurate (±30-50%) and the actual cost of a installed equipment is typically 4
times purchase cost of the equipment.
• Total annualised costs account for both operating and capital costs.
4.6 Distillation Sequencing with Complex Columns

In addition to simple distillation columns, complex distilla-
tion columns can be considered. These can have more than
2 product streams, or have linking between columns by two-
directional flows with one column having no condenser, or
no reboiler - often referred to as thermally coupled distillation.
columns.
In sequencing distillation with complex columns, heuristics for
simple columns are still available and useful as they provide
qualitative guidance with insights; however, extra heuristics for Summary Video
the complex columns are also available.
4.6.1 Side-Steam Columns
A side-stream distillation column may replace two simple columns for some applica-
tions, sometimes at considerable savings in energy and investment. Intuitively, the side
stream should contain primarily middle boiling components from a multicomponent mix-
ture. Side streams may be useful when the middle boilers are the main product, as in a
pasteurization column where the lighter trace components leave overhead.
Based on experience of using these column types, and simulations of ideal systems [2]
heuristics have been suggested for when these columns provide a potential economic
advantage.
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4.6. DISTILLATION SEQUENCING WITH COMPLEX COLUMNS
Heuristic 1 For a pure sidestream product, for a three component mixture, A-B-C, if
the feed has B > 50% and and C < 5%, use a vapour sidestream, as B is more
volatile than the other dominant component, C, at the draw stage. As shown in
Figure 4.6(a).
Heuristic 2 For a pure sidestream product, for a three component mixture, A-B-C, if
the feed has B > 50% and and A < 5%, use a liquid sidestream, as B is less
volatile than the other dominant component, A, at the draw stage. As shown in
Figure 4.6(b).
A A
A A B
(Liquid sidestream)
B B
(Vapour sidestream)
C B C
C C
(a) (b)
Figure 4.6: (a) Vapour side-stream for separating middle and heavy components, (b) Liq-
uid side-stream for separating middle and light components.
4.6.2 Side-stripper arrangement
The use of complex nonstandard distillation columns can sometimes lead to substantial
savings in capital costs as well as in energy consumption in comparison with conventional
one-feed two-product distillation columns. Complex columns are also suitable for retrofit
design, since they can often be implemented with only small modifications to existing
columns.
As can be seen from Figure 4.7(a), for the side-stripper arrangement, the column on the
right hand side effectively takes liquid from and feeds vapour to the left column. For the
right column a condenser is saved.
The side-stripper sequence is a reconfiguration for the indirect sequence, Figure 4.2(b).
As in the indirect sequences Figure 4.8(a), the left hand column produces only the bottom
product and has part of the condensed liquid being fed into the right column and part
of the liquid being refluxed. The idea was to remove the total condenser from the left
column and to connect two streams to the right column, therefore to take liquid from the
right column but feed vapour to it as needed (Figure 4.8(b)), which was then rearranged
to become Figure 4.8(c).
Based on experience of using side-strippers, and calculations on energy use [1] heuristics
have been suggested for when these columns provide a potential economic advantage.
Figure 4.9(b) shows the percent savings when using a side stripper over the equivalent
two simple column system.
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A
A A B
B
A C
B
C
C B C
(a) Side-Stripper (b) Side-Rectifier
Figure 4.7: Thermally coupled distillation configurations, (a) side-stripper and (b) side-
rectifier.
A A 3 A
A 1 3 A 1 3
B B A 1
C 2 4 C 2 4 B 4
C 2
C B C B C B
(a) (b) (c)
Figure 4.8: Thermal coupling for indirect sequences, (a) the indirect sequence, (b) the
thermally-coupled indirect sequence, and (c) side-stripper arrangement.
Heuristic For a three component mixture, A-B-C, if the feed has B < 30% and there is
more C than A, use a side-stripper. As shown in Figure 4.8.
4.6.3 Side-rectifier arrangement
As can be seen from Figure 4.7(b), for the side-rectifier arrangement, the column on the
right hand side effectively takes vapour from and feeds liquid to the left column. For the
right column a reboiler is saved.
The side-rectifier sequence is a reconfiguration for the direct sequence, Figure 4.2(a). As
in the direct sequences Figure 4.10(a), the left hand column produces only the top product
and has part of the bottom liquid being fed into the right column and part of the liquid
reboiled into the column. The idea was to remove the reboiler from the left column and to
connect two streams to the right column, therefore to take vapour from the right column
but feed liquid to it as needed (Figure 4.10(b)), which was then rearranged to become
Figure 4.10(c).
Based on experience of using side-rectifiers, and calculations on energy use [1] heuristics
have been suggested for when these columns provide a potential economic advantage, this
is essentially the inverse of Figure 4.9(b).
Heuristic For a three component mixture, A-B-C, if the feed has B < 30% and there is
more A than C, use a side-rectifier. As shown in Figure 4.10.
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4.6. DISTILLATION SEQUENCING WITH COMPLEX COLUMNS
0 0
1 1
0.2 0.2
0.8 0.8
xC 0.4 0.4
xC
xB
xB
0.6 0.6
VI = VD
xC > xA
0.6 0.6
0.4 0.4
0.8 D 0.8 xB = 0.3
0.2 0.2
I 20
1 1 30 10
0 • 0
0 0.2 0.4 0.6 0.8 1 0 0.250 0.4 0.6 0.8 1
xA xA
(a) (b)
Figure 4.9: Energy savings for using a side-stripper system based on the assumption of
ideal separation following the calculations of [1]. (a) Comparison of energy use for the di-
rect vs indirect sequence, section marked D is where the energy use of the direct sequence
is less, and section marked I is where the energy use of the indirect sequence is less. (b)
Comparison of the energy use in a side stripper arrangement versus the lowest energy two
column system, the contour lines are percent energy saving and the grey shaded is the best
region for the use a side-stripper.
A
A B A B 1 A B
A 1 3 A 1 3 B 3
B B C 2
C 2 4 C 2 4
4
C C C
(a) (b) (c)
Figure 4.10: Thermal coupling for direct sequences, (a) the direct sequence, (b) the
thermally-coupled direct sequence, and (c) the side-rectifier arrangement.
4.6.4 Pre-fractionation arrangements
The pre-fractionation arrangement is also a type of thermal coupling for distillation se-
quences. In such cases, the products are taken from the column on the right (Figure 4.11(a)),
the left column has non-adjacent key components separated and fitted with a partial con-
denser and a partial reboiler, in such a connection, the column on the right has two feeds
and three products. Similar considerations as to the side-stripper and side-rectifier ar-
rangements can be made for rearranging such a connection to remove the condenser and
the reboiler from the left column but to connect two streams on both top and bottom of
it to the right column. This has been shown in Figure 4.11(b) also called the Petlyuk
arrangement.
Figure 4.11(c) further simplifies the connection in Figure 4.11(b) by combining the two
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A A A
A A A
B B B B B B
C C C
C C C
(a) (b) (c)
Figure 4.11: Thermal coupling for pre-fractionation sequences, (a) two columns with par-
tial condenser on first column, (b) thermally-coupled pre-fractionator (Petlyuk column),
and (c) dividing wall column.
columns into one so-called dividing wall column. The three arrangements have equal
mass balances for all components but in the dividing column, the capital cost may be
reduced significantly as not only does it remove the condenser and the reboiler but it is
in a combined single shell structure. The disadvantages in such dividing wall columns
are it may be sometimes difficult to cope with the differences in temperature and pressure
operated in the combined two columns.
Heuristic For a three component mixture, A-B-C, when the middle-boiling component
comprises a large fraction of the feed and αAB is similar to αBC , it is then useful to
consider a pre-fractionator arrangement. As shown in Figure 4.11.
The condition αAB is similar to αBC is important as B is then more uniformly distributed
in the A and C streams fed into the right column. The pre-fractionator arrangement typi-
cally requires 30% less energy than conventional column arrangements, due to the com-
position profile.
Figure 4.12(a) is the conventional direct sequence arrangement for separating a three com-
ponent mixture. The composition profile for the middle boiling product B is shown in
Figure 4.12(b). As seen from Figure 4.12(b), the top product in Column 1 is only A and
the bottom stream has a high concentration of B, when this stream is fed into Column 2,
as B is the product in the top of the column so B will experience a process called remixing
to reach the top of Column 2 as the product being taken out from this column. This means
that it is highly possible that the composition of the bottom stream from Column 1 as the
feed into Column 2 is not matching the composition of the stage at the feeding location.
A mismatching between the feed composition and that of the feeding stage will require
more energy consumption for the fact of remixing - concentration redistribution.
However, in the pre-fractionation arrangement, the energy loss for remixing can be sig-
nificantly reduced, this is due to a uniform distribution of the middle boiling component
in the top and bottom streams of the left column as feeds to the right column. This is
illustrated in Figure 4.13.
As no product has been taken from the left column, component B would be uniformly dis-
tributed in the top and bottom streams into the right column, thus there is no redistribution
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4.7. UTILITY CONSIDERATIONS WITH THERMALLY COUPLED COLUMNS
Top
A
A A
Column Position
B B
C C
B
B
B C
C Re-mixing
F1 F2 in column 1
Bottom
C 0 Mole fraction of B 1
(a) (b)
Figure 4.12: Separating a three component mixture with the (a) conventional direct se-
quence and (b) the composition profile of component B.
Top
A
Column Position
F1
A
B B
C
F2,bottom F2,top
B
Bottom
C 0 Mole fraction of B 1
(a) (b)
Figure 4.13: Composition profile of component B in the pre-fractionation arrangement.
of B taking place in the right column. This then gives a considerably greater freedom to
match the composition of the feed streams from the left column with that of the feeding
stages in the right column thus reduces energy consumption in remixing. In fact, the im-
proved thermodynamic efficiency (heat duties reduced) in pre-fractionation arrangements
is essentially due to reduced vapour load.
4.7 Utility Considerations with Thermally Coupled Columns

As been discussed in the last section, thermal coupling arrangements have great capabili-
ties to reduce energy consumption compared to that from the conventional arrangements.
Thus, it is necessary in the design distillation sequences, to take this into account. Such
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thermal coupling would result in the side-stripper, side-rectifier and Petlyuk configura-
tions and the pre-fractionation arrangement.
In thermally coupled arrangements, heating and/or cooling is provided to an upstream
column directly by a process stream from the downstream column, rather than indirectly
through a heat exchanger. Therefore, thermal coupling leads to energy savings as re-
mixing is reduced such as in the pre-fractionator arrangement compared to conventional
column arrangements, a reduction in total vapour flow is expected.
However, those thermally coupled arrangement have larger temperature ranges than sim-
ple column sequences as shown in Figure 4.14.
1 2 1 2
Temperature
Temperature
2 2
1 1
Enthalpy Enthalpy
(a) (b)
Figure 4.14: Comparison of temperature range between (a) the direct sequence and (b)
the side rectifier arrangement.
It should be noted in the thermally coupled arrangement, although less energy is required
in a single reboiler, all it is running at higher temperatures. Whether operating costs are
reduced depends on which utilities are required, and on their relative costs, thus the heat
integration opportunities created may be compromised.
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4.8. DECOMPOSITION OF COMPLEX COLUMNS FOR DESIGN
4.8 Decomposition of Complex Columns for Design

When it comes to mass and energy balance analysis, it is
practically useful to decompose complex columns into mul-
tiple columns so that short-cut calculations can be carried out
relatively easily. Thermally coupled columns can be decom-
posed into a combination of side stream columns and simple
columns. The mass and energy balances are equivalent for.
the complex column configurations and the decomposed multi-
column sequence. However, the capital costs would then de-
pend on the actual configurations used. Generally speaking, Summary Video
the cost of complex column configuration is less than that of
the equivalent sequence of columns.
There are mainly two steps used for the modelling. First, design the upstream column
using a hypothetical reboiler or condenser to obtain approximate flow rates and composi-
tions of the linking streams. Second, model the downstream column(s) as a side-stream
column using the extended Underwood equation for a side-stream columns.
4.8.1 Side-stripper decomposition
It is always the case that a side-stripper arrangement is for an indirect sequence. Thus, the
decomposition of a side-stripper would follow that two condensers are needed for the top
of the two columns, and, the right column takes vapour from the left column and feeds
liquid into it. Such decomposition is shown in Figure 4.15.
3 A A
A 1 b 3
1 B a Liquid
A Vapour b
B 4 C 2 4
C 2
C B C B
(a) (b)
Figure 4.15: The decomposition of a side-stripper; (a) original side-stripper and (b) the
decomposed sequence of a simple column with theoretical condenser and liquid side-
stream column.
The right column in Figure 4.15 indicates that the side stream column is a liquid and the
side stream should be one plate above feed plate. This is because this is the equivalent of
one stage of equilibrium. The added partial condenser on the left column is equivalent to
this one stage in the right column.
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4.8.2 Side-rectifier decomposition
The side-rectifier decomposition is similar to that of the side-stripper decomposition. The

difference is that a side-rectifier arrangement is for a direct sequence thus two reboilers
are needed for the bottom of the two columns, and, the right column takes liquid from the
left one and feeds vapour into it. This is shown in Figure 4.16.
A A B
1 A B A 1 3
B 3
C B Liquid b
2 a Vapour
C 2 b 4
4
C a C
(a) (b)
Figure 4.16: The decomposition of a side-rectifier; (a) original side-rectifier and (b)
the decomposed sequence of a simple column with theoretical reboiler and vapour side-
stream column.
If in the decomposition, a vapour side stream is needed from the right column, the side
stream should be taken from a plate below the feed plate. This is because this is the
equivalent of one stage of equilibrium. The added partial reboiler on the left column is
equivalent to this one stage in the right column.
4.8.3 Pre-fractionator decomposition
In the decomposition for a pre-fractionation arrangement, as no product would be taken

from the left column, it is relatively simpler. It can be made by adding a partial condenser
and a partial reboiler to the left column and feeding the top and bottom streams into the
right column. If there are also side streams being drawn from the right column, based on
the phase status, the drawing stage should also follow that explained for the side-stripper
and side-rectifier decompositions, Figure 4.17.
4.8.4 Extension to Underwood Equations for Side Stream Columns
As the Underwood equation is used to calculate the minimum reflux ratio under the con-
ditions of given the feed composition, feed condition and relative volatilities of the com-
ponents, the vapour flow in the column at minimum reflux, Vmin , can also be determined
[3],
n
X αi,R xi,M
Vmin = M (4.8.1)
i=1
α i,R − θ
where M is the flow of net overhead product as shown in Figure 4.18(a) and θ is calculated
according to equation 3.4.38 with αA,R > θ > αB,R .
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4.8. DECOMPOSITION OF COMPLEX COLUMNS FOR DESIGN
Side-stripper
A
decomposition 3
a Vapour
a Liquid
A b
4
A A b
B
B B B +
C C B
d
3
c Liquid d
c Vapour
Side-rectifier 4
C
decomposition
. C
(a) (b)
Figure 4.17: The decomposition of a pre-fractionator; (a) original pre-fractionator and

(b) the decomposed sequence of a simple column with theoretical condenser and reboiler,
and vapour side-stream and liquid side-stream columns.
A A
M
A B A
B B
C C B
H
C C
.
(a) (b)
Figure 4.18: A side stream column (a) with the net overhead product and (b) with the net
bottom product.
Similarly, for a side-stream below the feed as shown in Figure 4.18(b), the minimum
vapour flow can also be calculated as,
n
X αi,R xi,H
− Vmin = H (4.8.2)
i=1
αi,R − θ
where H is the flow of the net bottom product and αB,R > θ > αC,R .
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4.9 References
[1] Glinos, K. and Malone, M. F. [1988], ‘Optimality regions for complex column
alternatives in distillation systems’, Chemical Engineering Research and Design
66, 229–240.
[2] Rooks, R. E., Malone, M. F. and Doherty, M. F. [1996], ‘A geometric design method
for side-stream distillation columns’, Industrial & Engineering Chemistry Research
35, 3653–3664.
[3] Triantafyllou and Smith [1992], Chemical Engineering Research and Design
70, 118–132.
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4.10. PROBLEMS
4.10 Problems
E1 The mixture of A, B, C and D shown in the table below is to be separated into pure
component products using a sequence of distillation columns.
Apply heuristics to identify one or two promising se-

quences of simple distillation columns, as well as one or
two sequences including complex distillation configura-.
tions, to carry out the desired separation. Assume that the
relative volatilities are constant.
Solution Video
Component Molar composition Relative volatility between
adjacent components
A 0.20 2.33
B 0.50 2.33
C 0.25 1.148
D 0.05 −
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E2 The mixture of benzene, toluene and xylene isomers shown in the table below is to
be separated into pure component products using a sequence of distillation columns.
Three sequences are proposed,
• Sequence 1: B / T pX oX − T / pX oX − pX / oX (direct sequence)
• Sequence 2: B T / pX oX − B / T − pX / oX
• Sequence 3: B T pX / oX − B T / pX − B / T (indirect sequence)
Component Molar composition Relative volatility at 1 atm

Benzene 0.40 6.215
Toluene 0.35 2.673
p-Xylene 0.20 1.148
o-Xylene 0.05 1
Total flow rate 180 kmol h−1

Temperature 99.2 ◦ C (saturated liquid)
Pressure 1 atm
Use the total vapour load and reboiler duty to compare the proposed sequences.
Identify the most promising sequence. The reflux ratio is assumed to be 1.1 times
of the Rmin for each column. Short-cut distillation models are used to simulate
the individual simple distillation columns that are used in the distillation sequences
proposed. The table below presents the results of these simulations, where complete
separation of the key components is assumed in each column. The feeds to all
columns are saturated liquids; all columns are assumed to operate at a constant
pressure of 1 atm.
Separation Rmin Nmin ∆ Hfvap

eed Tcondenser Treboiler
−1
(kJ kmol ) (◦ C) (◦ C)
B / T pX oX 1.49 19.7 35170 80.2 120.1
B T / pX oX 0.63 19.6 35170 91.2 139.8
B T pX / oX 1.96 111.3 35170 97.4 143.6
B / T pX 1.50 19.8 34764 80.2 118.6
B T / pX 0.61 19.5 34764 91.2 139.0
T / pX oX 1.43 22.1 35476 110.3 139.8
T pX / oX 3.74 129.3 35476 118.6 143.6
B/T 1.36 20.0 32599 80.2 110.3
T / pX 1.34 22.8 35182 110.3 139.0
pX / oX 10.31 151.2 36349 138.9 143.6
B: Benzene; T: Toluene; pX: p-Xylene; oX: o-Xylene
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4.10. PROBLEMS
E3 Discuss the difference between simple distillation sequencing and thermally cou-
pled sequencing in the aspects,
(a) Operating lines
(b) Middle boiling component distribution
(c) Configuration
(d) Total vapour load
(e) Energy consumption and capital cost
(f) Feed composition requirement
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E4 Discuss any restrictions for dividing wall columns.
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4.10. PROBLEMS
D1 For the options you have identified in question E1 design the best distillation se-
quence using the short-cut design rules if the total feed is 300 kmol h−1 . Some
useful information,
Component Boiling point / ◦ C Liquid density / kg m−3 Molecular weight / Da

A 36 0.5 72
B 68 0.6 86
C 98 0.7 100
D 151 0.8 128
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114
Chapter 5
Azeotropic Distillation
Contents
5.1 Chapter 5 ILOs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5.2 Azeotropic mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.3 Triangular Graphs . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.3.1 Residue-Curve Maps . . . . . . . . . . . . . . . . . . . . . . . 122
5.3.2 Distillation-Curve Maps . . . . . . . . . . . . . . . . . . . . . 124
5.3.3 Approximate Residue-Curve Maps . . . . . . . . . . . . . . . . 126
5.3.4 Feasible Product-Composition Regions at Total Reflux . . . . . 130
5.3.5 Extension to Short-cut Equations for Azeotropic Systems . . . . 132
5.4 Separations for Azeotropes . . . . . . . . . . . . . . . . . . . . . . . 134
5.4.1 Pressure Swing Distillation . . . . . . . . . . . . . . . . . . . . 135
5.4.2 Extractive Distillation . . . . . . . . . . . . . . . . . . . . . . 136
5.4.3 Homogeneous Azeotropic Distillation . . . . . . . . . . . . . . 139
5.4.4 Heterogeneous Azeotropic Distillation . . . . . . . . . . . . . . 139
5.4.5 Reactive Distillation . . . . . . . . . . . . . . . . . . . . . . . 140
5.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
115
CHAPTER 5. AZEOTROPIC DISTILLATION
5.1 Chapter 5 ILOs

.
ILO 5.1. Explain the presence of different azeotrope types using the modified Raoult’s
law.
ILO 5.2. Demonstrate the use of ternary diagrams to represent distillation columns.
ILO 5.3. Analyse residue curve maps to find feasible distillation column separations.
ILO 5.4. Construct approximate residue curve maps on ternary diagrams.
ILO 5.5. Design azeotropic distillation sequences using ternary diagrams.
Chapter Video 1
Chapter Video 2
Chapter Video 3
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5.2. AZEOTROPIC MIXTURES
5.2 Azeotropic mixtures

Departures from Raoult’s law commonly manifest themselves in the formation of azeotropes.
Many close boiling, non-ideal mixtures form azeotropes, particularly those of different
chemical types. Azeotropic-forming mixtures exhibit either maximum- or minimum-
boiling points at some composition, corresponding, respectively, to negative and posi-
tive deviations from Raoult’s law. Vapour and liquid compositions are identical for an
azeotrope; thus, all K values are 1, αAB = 1, and no separation can take place,
yi P = xi γi P 0 (5.2.1)
with xi = yi at the non-trivial solutions of 0 and 1.

If only one liquid phase exists, it is a homogeneous azeotrope; if more than one liquid
phase is present, the azeotrope is heterogeneous. By the Gibbs phase rule, at constant
pressure in a two-component system, the vapour can coexist with no more than two liquid
phases; in a ternary mixture, up to three liquid phases can coexist with the vapour, and so
on.
Figures 5.1, 5.2, and 5.3 show three types of azeotropes. The most common by far is
the minimum-boiling homogeneous azeotrope, e.g. isopropyl ether-isopropyl alcohol,
shown in Figure 5.1. At a temperature of 70◦ C, the maximum total pressure is greater
than the vapour pressure of either component, as shown in Figure 5.1(a), because activity
coefficients are greater than 1. The y-x diagram in Figure 5.1(b) shows that for a pressure
of 1 atm, the azeotropic mixture is at 78 mol% ether. Figure 5.1(c) is a T -x diagram at
1 atm, where the azeotrope is seen to boil at 66◦ C. In Figure 5.1(a), for 70◦ C, the azeotrope
occurs at 123 kPa, for 72 mol% ether. Thus, the azeotropic composition and temperature
shift with pressure. In distillation, minimum-boiling azeotropic mixtures are approached
in the overhead product.
125 1 100
P
100 p1 0.8 90 Vapour
P / kPa
T / ◦C
75 0.6 80
y1
50 p2 0.4 70
25 0.2 60 Liquid
0 0 50
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1 x1
(a) (b) (c)
Figure 5.1: Minimum-boiling-point azeotrope, isopropyl ether (1) - isopropyl alcohol (2)
system: (a) partial and total pressures at 70◦ C; (b) vapour-liquid equilibria at 101 kPa; (c)
phase diagram at 101 kPa.
For the maximum-boiling homogeneous azeotropic acetone-chloroform system in Fig-

ure 5.2(a), the minimum total pressure at 60◦ C is below the vapour pressures of the pure
components because activity coefficients are less than 1. The azeotrope is approached in
the bottoms product in a distillation operation. Phase compositions at 1 atm are shown in
Figures 5.2(b) and (c).
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125 1 100
100 P 0.8 90 Vapour
P / kPa
p1
T / ◦C
75 0.6 80
y1
50 0.4 70
p2
25 0.2 60 Liquid
0 0 50
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1 x1
(a) (b) (c)
Figure 5.2: Maximum-boiling-point azeotrope, acetone (1) - chloroform (2) system: (a)
partial and total pressures at 60◦ C; (b) vapour–liquid equilibria at 101 kPa; (c) phase dia-
gram at 101 kPa pressure.
Heterogeneous azeotropes are minimum-boiling because activity coefficients must be

significantly greater than 1 to form two liquid phases. The grey region in Figure 5.2(a)
for the water-n-butanol system is a two-phase region, where total and partial pressures
remain constant as the amounts of the phases change, but phase compositions do not. The
y-x diagram in Figure 5.2(b) shows a horizontal line over the immiscible region, and the
phase diagram of Figure 5.2(c) shows a minimum constant temperature.
150 1 130
P Vapour
125 0.8 120
p1
100
P / kPa
T / ◦C
0.6 110
y1
75
0.4 100
50 p2
25 0.2 90 Liquid
0 0 80
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1 x1
(a) (b) (c)
Figure 5.3: Minimum-boiling-point (two liquid phases) water (1) - n-butanol(2) system:
(a) partial and total pressures at 100◦ C; (b) vapour-liquid equilibria at 101 kPa; (c) phase
diagram at 101 kPa pressure. Grey zone is the liquid 2-phase region.
To avoid azeotrope limitations, it is sometimes possible to shift the equilibrium by chang-

ing the pressure sufficiently to “break” the azeotrope, or move it away from the region
where the required separation is to be made. For example, ethyl alcohol and water form a
homogeneous minimum-boiling azeotrope of 95.6 wt% alcohol at 78.15◦ C and 101.3 kPa.
However, at vacuums of less than 9.3 kPa, no azeotrope is formed.
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5.3. TRIANGULAR GRAPHS
5.3 Triangular Graphs

In the distillation of a ternary mixture, possible equilibrium compositions do not lie
uniquely on a single, isobaric equilibrium curve because the Gibbs phase rule gives an
additional degree of freedom. The other compositions are determined only if the temper-
ature, pressure, and composition of one component in one phase are fixed.
The composition of a ternary mixture can be represented on a triangular diagram (like in
Chapter 2, either equilateral or right, where the three apexes represent pure components.
Although Stichlmair [4] shows that vapour-liquid phase equilibria at a fixed pressure can
be plotted by letting the triangular grid represent the liquid phase, with superimposing
lines of constant equilibrium-vapour composition for two of the three components, Fig-
ure 5.4, this representation is seldom used. It is more useful, when developing a feasible-
separation process for a ternary mixture, to plot only equilibrium-liquid-phase composi-
tions on the triangular diagram.
Nitrogen
0
1
0.1
0.9
0.2
0.8
0.3 0.1
0.1 0.7
0.4
0.6
0.5 0.2
0.2 0.5
0.6 0.3
0.4
0.7 0.3
0.4
0.3
0.4 0.5
0.8
0.5 0.2
0.9 0.7
0.7 0.1
1 0.9 0.9
Oxygen 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Argon
Figure 5.4: Example Stichlmair ternary diagram for a mixture of nitrogen, oxygen, and
argon [4], axis are xO2 , xN2 , and xAr while solid lines are yO2 and dashed lines are yAr .
Figure 5.5, where compositions are in mole fractions, shows plots of this type for three
different ternary systems. Each curve is the locus of possible equilibrium-liquid-phase
compositions during distillation of a mixture, starting from any point on the curve. The
boiling points of the three components and their binary and/or ternary azeotropes are
included on the diagrams.
The zeotropic system of Figure 5.5(a) does not form any azeotropes. If the mixture of
these three components is distilled, there is only one distillation region. Accordingly, the
distillate can be nearly pure A, or the bottoms can be nearly C. However, nearly pure
B, the intermediate-boiling component, cannot be produced as a distillate or bottoms.
To separate this ternary mixture into the three components, a sequence of two columns is
T.L.
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0A
1
0.2
0.8
0.4
0.6
0.6
0.4
0.8
0.2
1
C 0
0 0.2 0.4 0.6 0.8 1B
(a)
0A 0A
1 1
0.2 0.2
0.8 0.8
•
0.4 0.4
0.6 • 0.6
0.6 0.6
0.4 Region 1 0.4
0.8 0.8
0.2 Region 2 0.2
1 1
C 0 C • 0
0 0.2 0.4 0.6 0.8 1B 0 0.2 0.4 0.6 0.8 1B
(b) (c)
Figure 5.5: Residue curves for liquid-phase compositions of ternary systems. Lowest-
boiling component is A, the intermediate-boiling component is B, and the highest-
boiling component is C. (a) Mixture not forming an azeotrope, (b) Mixture forming one
minimum-boiling azeotrope, and (c) Mixture forming two minimum-boiling azeotropes.
used, as shown in Figure 5.6, where the feed, distillate, and bottoms product compositions
must lie on a straight, total-material balance line within the triangular diagram. In the
direct sequence of Figure 5.6(a), the feed, F, is first separated into distillate A and a
bottoms of B and C; then B is separated from C in the second column. In the indirect
sequence of Figure 5.6(b), a distillate of A and B and a bottoms of C are produced in
the first column, followed by the separation of A from B in the second column. When a
ternary mixture forms an azeotrope, the products from a single distillation column depend
on the feed composition, as for a binary mixture. However, unlike the case of the binary
mixture, where two distillation regions, are well defined, the determination of distillation
regions for azeotrope-forming ternary mixtures is complex. Consider the example of
Figure 5.5(b), for a mixture of A, B, and C, which are in the order of increasing boiling
point. The only azeotrope formed is a minimum-boiling binary azeotrope between A and
B.
For this type of system, no distillation boundaries for the ternary mixture exist, even
120 T.L.
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A B A+B A
A+B+C A+B+C
1 2 1 2
B+C C C B
(a) (b)
0A 0A
1 1
0.2 0.2
0.8 0.8
0.4 0.4 •A + B
0.6 0.6
F
•F •
0.6 0.6
0.4 0.4
0.8 0.8
0.2 0.2
1 B+C 1
C • 0 C 0
0 0.2 0.4 0.6 0.8 1B 0 0.2 0.4 0.6 0.8 1B
(c) (d)
Figure 5.6: Distillation sequences for ternary zeotropic mixtures, (a) and (c) Direct se-
quence, (b) and (d) Indirect sequence. Red is the first column material balance, blue is the
second column balance.
though an azeotrope is present. A feed composition located within the triangular diagram
can be separated into two binary products, consistent with the total-material-balance line.
Ternary distillate or bottoms products can be avoided if the column split is properly se-
lected, e.g. like the system in Figure 5.7(a).
The more complex case of the ternary mixture with 2 azeotropes is presented in Fig-
ure 5.5(c); A and B form a minimum-boiling binary azeotrope, and B and C do the same.
A triangular diagram for this system is separated by a distillation boundary into Regions
1 and 2. A column material-balance line connecting the feed to the distillate and bottoms
cannot cross this distillation boundary, thus restricting the possible distillation products.
For example, a mixture with a feed composition inside Region 2 cannot produce a bot-
toms of C, the highest-boiling component in the mixture. It can be distilled to produce
a distillate of the A-B azeotrope and a bottoms of a mixture of B and C, or a bottoms of
B and a distillate of all three components. If the feed lies in Region 1 of Figure 5.5(c),
it is possible to produce the A-B azeotrope and a bottoms of a mixture of A and C, or a
bottoms of C and a distillate of an A and B mixture, e.g. Figure 5.7(b). Thus, each region
produces unique products1 .
1
It should be noted that if the distillation boundary is very curved it is in fact possible to cross for
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A B A+B A
A+B+C A+B+C
1 2 1 2
B+C C C A+B
(a) (b)
0A 0A
1 1
0.2 0.2
0.8 0.8
•
0.4 0.4 •A + B
0.6 • 0.6
F
•F •
0.6 0.6
0.4 0.4
0.8 0.8
0.2 0.2
1 B+C 1
C • 0 C • 0
0 0.2 0.4 0.6 0.8 1B 0 0.2 0.4 0.6 0.8 1B
(c) (d)
Figure 5.7: Distillation sequences for ternary azeotropic mixtures, (a) Direct sequence for
a single azeotrope system, (b) Indirect sequence for a two azeotrope system. Red is the
first column material balance, blue is the second column balance.
5.3.1 Residue-Curve Maps
Consider the simple batch distillation (no trays, packing, or reflux). For any ternary mix-
ture component, a material balance for its vapourisation from the still, assuming that the
liquid is perfectly mixed and at its bubble point, can be written as,
d xi 1 dW
= (yi − xi ) (5.3.1)
dt W dt
where xi is the mole fraction of component i in W moles of a perfectly mixed liquid

residue in the still, and yi is the mole fraction of component i in the vapour leaving the
still (instantaneous distillate) in equilibrium with xi . As W decreases with time, t, it is
possible to combine W and t into a single variable, ξ 1 . As W (t) decreases monotonically
certain situations.
1
dξ 1 dW
=− (5.3.2)
dt W dt
Let the initial condition be ξ = 0 and W = W0 at t = 0. Then the solution to equation 5.3.2 for ξ at time
122 T.L.
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with time, ξ (t) must increase monotonically with time and is considered a dimensionless
time. Thus, for the ternary mixture, the distillation process can be modelled by,
d xi
= (xi − yi ) , i = 1, 2 (5.3.4)
dξ
If equation 5.3.4 is written in a forward-finite-difference form, the following set of differential-

algebraic equations can be used to solve the residue curves, assuming that a second liquid
phase does not form,
xi,ξ+∆ ξ − xi,ξ
= xi,ξ − yi,ξ , i = 1, 2 (5.3.5)
∆ξ
X3
xi = 1 (5.3.6)
i=1
y i = Ki x i , i = 1, 2, 3 (5.3.7)
and the bubble-point-temperature equation,

3
X
K i xi = 1 (5.3.8)
i=1
where, in the general case, Ki = Ki (T, P, x, y).

Thus, the system consists of seven equations in nine variables, P , T , x1 , x2 , x3 , y1 ,
y2 , y3 , and ξ. With the pressure fixed, the next seven variables can be computed from
equations 5.3.5 to 5.3.8 as a function of the ninth variable, ξ, from a specified initial
condition. The calculations can proceed in the forward or backward direction of ξ. The
results, when plotted on a triangular graph, are residue curves because the plot follows,
with time, the liquid-residue composition in the still. A collection of residue curves, at a
fixed pressure, is a residue curve map.
On a triangular diagram, all pure-component vertices and azeotropic points - whether
binary azeotropes on the borders of the triangle or a ternary azeotrope within the triangle
- are singular or fixed points of the residue curves because at these points, d x = d ξ =
0.
In the vicinity of these points, the behaviour of a residue curve depends on the two eigen-
values of equation 5.3.4. At each pure-component vertex, the two eigenvalues are identi-
cal. At each azeotropic point, the two eigenvalues are different. Three cases, illustrated
by each of three pattern groups in Figure 5.8, are possible,
Case 1, both eigenvalues are negative. This is the point reached as ξ tends to ∞, and is
where all residue curves in a given region terminate. Thus, it is the component or
azeotrope with the highest boiling point in the region. This point is a stable node.
Case 2, both eigenvalues are positive. This is the point where all residue curves in a
region originate, and is the component or azeotrope with the lowest boiling point in
the region. This point is an unstable node.
t is,
w0
ξ (t) = ln (5.3.3)
W (t)
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Unstable node Stable node
Saddle Saddle
(a)
• •
Unstable node Stable node
• •
Saddle Saddle
(b)
• • •
Unstable node Stable node Saddle

(c)
Figure 5.8: Residue-curve patterns, (a) near pure-component vertices, (b) near binary
azeotropes, and (c) near ternary azeotropes.
Case 3, one eigenvalue is positive and one is negative. Residue curves within the triangle
move toward and then away from such saddle points. For a given region, all pure
components and azeotropes intermediate in boiling point between the stable node
and the unstable node are saddles.
5.3.2 Distillation-Curve Maps
A residue curve represents the changes in residue composition with time as the result
of a simple, one-stage batch distillation. The curve points in the direction of increasing
time, from a lower-boiling state to a higher-boiling state. An alternative representation for
distillation on a ternary diagram is a distillation curve for continuous, rather than batch,
124 T.L.
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distillation. The curve is most readily obtained for total reflux at a constant pressure (like
for the derivation of the Fenske equation, section 3.4.2). The calculations are made down
or up the column, starting from any composition. Consider making the calculations by
moving up the column, starting from a stage designated as Stage 1. Between equilib-
rium stages j and j + 1, at total reflux, passing vapour and liquid streams have the same
composition. Thus,
xi,j+1 = yi,j (5.3.9)
Also, liquid and vapour streams leaving the same stage are in equilibrium,
yi,j = Ki,j xi,j (5.3.10)
To calculate a distillation curve, an initial liquid-phase composition, xi,1 , is assumed. This

liquid is at its bubble-point temperature, which is determined from equation 5.3.8, which
also gives the equilibrium-vapour composition, yi,1 in agreement with equation 5.3.10.
The composition, xi,2 , of the passing liquid stream is equal to yi,1 by equation 5.3.9.
The process is then repeated to obtain xi,3 , then xi,4 , and so forth. The sequence of liquid-
phase compositions, which corresponds to the operating line for the total-reflux condition,
is plotted on the triangular diagram. The distillation curve is analogous to the 45◦ line on
a McCabe–Thiele diagram.
Distillation curves can be computed more rapidly than residue curves, and closely approx-
imate them. A collection of distillation curves, including lines for distillation boundaries,
is a distillation-curve map, an example of which is given in Figure 5.9. The dashed lines
are the distillation curves, which approximate the solid-line residue curves. This system
has two minimum-boiling binary azeotropes, one maximum-boiling binary azeotrope, and
a ternary saddle azeotrope. The map shows four distillation boundaries, designated by A,
B, C, and D. These computed boundaries, which define four distillation regions (1 to 4),
are all curved lines rather than the approximately straight lines.
Chloroform,
0 61.8 ◦ C
• 1
0.2
0.8
53.80.4◦ C • • 65.6 ◦ C
0.6
1
0.6
0.4
D
A
0.8 2 • 57.6 ◦ C
B 4 0.2
C
1 3
Methanol, 64.5 ◦ C • •◦ • Acetone,
0 66.1 ◦ C
0 0.2 0.4 0.6 55.3
0.8 C 1
Figure 5.9: Comparison of residue curves (solid lines) to distillation curves (dashed lines).
Figure 5.10 shows an example of an actual distillation column with a finite reflux ratio
(R = 1) plotted on a residue curve plot for Hexane, Octane, and Decane. The rectifying
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c Rodgers 2019 125
section (red dots) approximately follows the residue curve that D is on. The stripping
section (blue dots) also follows the same residue curve from the other direction, starting
at B. There is some deviation around the feed point (stage 11), due to the fact that the
feed addition affects the equilibrium in column. The green line is the approx mass balance
between the feed (green dot), and the trays in the rectifying and stripping sections.
Decane
0
B 1
0.2
0.8
0.4
0.6
0.6
F• 0.4
0.8
D 0.2
1
0
Hexane0 0.2 0.4 0.6 0.8 1 Octane
Figure 5.10: Actual distillation column plotted on a residue curve plot for Hexane, Octane,
and Decane. Column has 20 stages, a reflux ratio of 1, and feed stage 11. Green line is
the balance on the feed stage with the rectifying section (red dots), the stripping section
(blue dots), and the feed (green dot).
5.3.3 Approximate Residue-Curve Maps
Calculation of a residue-curve map requires a considerable effort. However, process sim-

ulators such as ASPEN PLUS can compute residue maps. Alternatively, the classification
of singular points as stable nodes, unstable nodes, and saddles provides a rapid method
for approximating a residue-curve map, including approximate distillation boundaries,
from just the pure component boiling points and azeotrope boiling points and composi-
tions. Boiling points of pure substances are available in handbooks and databases, and
extensive listings of binary azeotropes are found in many sources.
Based on experimental evidence for ternary mixtures, with very few exceptions there are
at most three binary azeotropes and one ternary azeotrope. Accordingly, the following set
of restrictions applies to a ternary system,
N1 + S1 = 3 (5.3.11)
N2 + S2 = B ≤ 3 (5.3.12)
N3 + S3 = 1 or 0 (5.3.13)
where N is the number of stable and unstable nodes, S is the number of saddles, B is
the number of binary azeotropes, and the subscript is the number of components at the
126 T.L.
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node (stable or unstable) or saddle. Thus, S2 is the number of binary azeotrope saddles.
A topological relationship among N and S is,
2N3 − 2S3 + 2N2 − B + N1 = 2 (5.3.14)
The topological relationships are useful for rapidly sketching, on a ternary diagram, an ap-
proximate residue-curve map, including distillation boundaries. The procedure involves
the following nine steps,
Step 1
Label the ternary diagram with the pure-
0 L
component, normal-boiling-point temperatures. • 901 ◦C
It is preferable to designate the top vertex of 0.2

0.8
the triangle as the low boiler (L), the bottom-
1150.4◦ C •
right vertex as the high boiler (H), and the • 800.6◦ C
bottom-left vertex as the intermediate boiler (I). 0.6

0.4
Plot the composition points for the binary and
◦
ternary azeotropes and add labels for their nor-
0.8 100 C
• 0.2
mal boiling points. This determines the value of 1
◦ ◦
B. In this example, two minimum-boiling and 110 CI0• 0.2 105 0.4
•◦
C0.6 0.8
• 120
1 H
0 C
one maximum-boiling binary azeotropes and one
ternary azeotrope. Thus, B = 3.
0 90
1
0.2
0.8
Step 2 115 •
0.4
Draw arrows on the edges of the triangle, in the • 80

0.6
0.6
direction of increasing temperature, for each pair 0.4
of adjacent species. 0.8 100
• 0.2
1
• 0
1100 0.2 0.4 105 0.6 0.8 1 120
0 90
Step 3 NS1
Determine the type of singular point for each 0.2
0.8
pure component vertex by using Figure 5.8 with
115
0.4 •
the arrows drawn in Step 2. This determines the • 800.6
values for N1 and S1 . In this example L is a sad- 0.6

0.4
dle because one arrow points toward L and one
points away from L; H is a stable node because
0.8 100
• 0.2
both arrows point toward H, and I is a saddle. 1
Therefore, N1 = 1 and S1 = 2. SN • N 0
1100 0.2 105 0.6 0.8
0.4 1 120
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Step 4 (for a ternary azeotrope only)

Determine the type of singular point for the
ternary azeotrope, if one exists. The point is
0 90
a node if (a) N1 + B < 4, and/or (b) ex- NS1
cluding the pure-component saddles, the ternary 0.2
0.8
azeotrope has the highest, second-highest, low-
115 •
0.4
est, or second-lowest boiling point of all species. • 800.6
Otherwise, the point is a saddle. This determines 0.6

0.4
the values for N3 and S3 .
In this example, N1 + B = 1 + 3 = 4. However,
0.8 100
N 0.2
excluding L and I because they are saddles, the 1
ternary azeotrope has the second lowest boiling 110 SN • N 0

0 0.2 105 0.6 0.8
0.4 1 120
point. Therefore, the point is a node, and N3 = 1
and S3 = 0. The type of node, stable or unstable,
is still to be determined.
Step 5 (for a ternary saddle only)
Connect the ternary saddle, by straight lines, to all binary azeotropes and to all pure-
component nodes (but not to pure-component saddles), and draw arrows on the lines to
indicate the direction of increasing temperature. Determine the type of singular point for
each binary azeotrope, by using Figure 5.8 with the arrows drawn in this step. This deter-
mines the values for N2 and S2 . These values should be consistent with equations 5.3.12
and 5.3.13. If N1 + B = 6, then special checks must be made [1, 2], or the residue-curve-
map structure should be computed by equations 5.3.4 to 5.3.8.
This completes the development of the approximate residue-curve map, with no further
steps needed. This step does not apply to the example, because the ternary azeotrope is
not a saddle.
Step 6
Determine the number of binary nodes, N2 , and binary saddles, S2 , from equations 5.3.12
and 5.3.14, where equation5.3.14 can be solved for N2 to give
2 − 2N3 + 2S3 + B − N1
N2 = (5.3.15)
2
For this example, N2 = (2 − 2 + 0 + 3 − 1) /2 = 1. From equation 5.3.12, S2 = 3 − 1 =
2.
Step 7
Count the binary azeotropes that are intermediate boilers (i.e., that are not the highest-
or the lowest-boiling species), and call that number Bib . Make the following two data-
consistency checks: (a) The number of binary azeotropes, B, less Bib , must equal N2 ,
and (b) S2 must be ≤ Bib . For the example system, these are the L-I and I-H azeotropes
so Bib = 2, B − Bib = 1, N2 = 1, and S2 = 2. If these two consistency checks are not
satisfied, one or more of the boiling points may be in error.
Step 8
If S2 6= Bib , this procedure cannot determine a unique residue-curve-map structure, which
therefore must be computed from equations 5.3.4 to 5.3.8. If S2 = Bib , there is a unique
structure, which is completed in Step 9. For this example, S2 = Bib = 2; therefore, there
is a unique map.
128 T.L.
c Rodgers 2019
Step 9
In this final step, the distillation boundaries (con-
nections), if any, are determined and entered on
the triangular diagram as straight lines, and, if de-
sired, one or more representative residue curves
are sketched as curved lines within each distilla-
tion region. This step applies to cases of S3 = 0,
0 90
N3 = 0 or 1, and S2 = Bib . In all cases, the num- N 1
ber of distillation boundaries equals the number 0.2
of binary saddles, S2 . 0.8
115
0.4 •
• Each binary saddle must be connected to a • 80 0.6
node (pure component, binary, or ternary). 0.6
• A ternary node must be connected to at 0.4
least one binary saddle. 0.8 100

0.2
• Thus, a pure-component node cannot be 1
connected to a ternary node, N • 0
1100 0.2 105 0.6 0.8
0.4 1 120
• and an unstable node cannot be connected (i)
to a stable node.
0 90
The connections are made by determining a con- N 1
nection for each binary saddle such that (a) a 0.2
0.8
minimum-boiling binary saddle connects to an
115 •
0.4
unstable node that boils at a lower temperature • 80 0.6
and (b) a maximum-boiling binary saddle con- 0.6

0.4
nects to a stable node that boils at a higher tem-
perature.
0.8 100
0.2
It is best to first consider connections with the 1
ternary node and then examine possible connec- 1100N 0.2 0.4105 • 0
0.6 0.8 1 120
tions for the remaining binary saddles. In this (ii)
example, S2 = 2, with these saddles denoted as
0 90
L-I, a maximum-boiling azeotrope at 115 ◦ C, and N 1
◦
as I-H, a minimum-boiling azeotrope at 105 C. 0.2
0.8
Therefore, two connections are made to establish 115
0.4 •
two distillation boundaries. The ternary node at • 80 0.6
◦ ◦
100 C cannot connect to L-I because 100 C is 0.6
0.4
not greater than 115 ◦ C. The ternary node can, 0.8 100
however, connect, as shown in (i), to I-H be- 0.2
cause 100 ◦ C is lower than 105 ◦ C. This marks 1

N • 0
the ternary node as unstable. 1100 0.2 105 0.6 0.8
0.4 1 120
The connection for L-I can only be to H, as (iii)

shown in (ii), because it is a node (stable), and
120 ◦ C is greater than 115 ◦ C. This completes the
connections.
Finally, as shown in (iii), three typical, but ap-
proximate, residue curves are added to the di-
agram. These curves originate from unstable
nodes and terminate at stable nodes.
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c Rodgers 2019 129
5.3.4 Feasible Product-Composition Regions at Total Reflux
The feasible-distillation regions for azeotrope-forming ternary mixtures are not obvious.
Fortunately, residue-curve maps can be used to make preliminary estimates of regions
of feasible-product compositions for non-ideal ternary systems. These regions are de-
termined by superimposing a column material-balance line on either type of curve-map
diagram. Consider first the simpler zeotropic ternary system in Figure 5.11(a), which
shows an isobaric residue-curve map with three residue curves. Suppose a ternary feed F
in Figure 5.11(a) is continuously distilled isobarically to produce distillate D and bottoms
B. A straight line that connects the distillate and bottoms compositions must pass through
the feed composition at some intermediate point to satisfy the material-balance equations.
Three random material-balance lines are included in the figure. For a given line, D and B
composition points, designated by coloured squares, must lie on the same residue curve.
This causes the material-balance line to intersect the residue curve at these two points and
be a chord to the residue curve.
0 H
1
0.2
0.8
0.4
0.6
0.6
0.4
0.8 F•
0.2
1
0
L0 0.2 0.4 0.6 0.8 1 I
(a)
0 H 0 H
1 1

0.2 0.2
0.8 0.8
0.4
0.6
B for pure 0.4 B
0.6
0.6 L distillate 0.6
0.4 0.4
0.8 F• 0.8 F•
0.2 0.2
.
1 1 D
0
0
L0 D0.2for pure
0.4 H0.6bottoms
0.8 1 I L0 0.2 0.4 0.6 0.8 1 I
(b) (c)
Figure 5.11: Product-composition regions for a zeotropic system. (a) Material-balance

lines and residue curves, (b) Residue curve through the feed point with the extream prod-
uct lines, and (c) Product-composition regions shown shaded.
The limiting distillate-composition point for this zeotropic system is pure low-boiling
component, L. From the material-balance line passing through F , shown as the red line
in Figure 5.11(b), the corresponding bottoms composition with the least amount of com-
ponent L is point B. At the other extreme, the limiting bottoms-composition point is
high-boiling component H. A material-balance line from this point, through feed point F ,
ends at D, shown as the blue line in Figure 5.11(b).
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These two lines and the residue curve define the feasible product-composition regions,
shown a the shaded regions in Figure 5.11(c). Note that, because for a given feed both
the distillate and bottoms compositions must lie on the same residue curve, the shaded
feasible regions lie between the feed residue curve and the side of the material balance
line oposite the exteam end of the residue curve, i.e. the bottom product side is bounded
by the material balance line from the extream distillate product, the red line. Because of
its appearance, the feasible-product-composition region is called a bow-tie region.
For azeotropes, where distillation boundaries are present, a feasible-product-composition
region exists for each distillation region. Two examples are shown in Figure 5.12. Fig-
ure 5.12 has two distillation regions caused by two minimum-boiling binary azeotropes.
A curved distillation boundary connects the minimum-boiling azeotropes. In the lower,
right-hand distillation region (1), the lowest-boiling species is the n-octane-2-ethoxy-
ethanol minimum-boiling azeotrope, while the highest-boiling species is 2-ethoxyethanol.
Accordingly, for feed F1 , straight lines are drawn from the points for each of these two
species, through the point F1 , and to a boundary (either a distillation boundary or a side of
the triangle). Shaded, feasible-product-composition regions are then drawn on the outer
side of the residue curve that passes through the feed point. The result is that distillate
compositions are confined to shaded region D1 and bottoms compositions are confined to
shaded region B1 . For a given D1 , B1 must lie on a straight line that passes through D1
and F1 . D1 and B1 must also lie on the same residue curve.
n-Octane
◦
125.8
0 C
• 1
0.2
0.8
0.4
• 116.1 ◦
D2 0.6 C
0.6 F2
• 0.4
B2
0.8 D1
0.2
• F1
1 B1
• • • 0
0 ◦C
136.2 0.2 127.1 ◦ C0.6
0.4 0.8 1 ◦C
135.1
Ethylbenzene 2-Ethoxy-
ethanol
Figure 5.12: Product-composition regions for given feed compositions. Ternary mixture
with two minimum-boiling binary azeotropes at 1 atm.
A complicated situation is observed in distillation Region 2 on the left side of Figure 5.12,
where the lowest-boiling species is the binary azeotrope of octane and 2-ethoxy-ethanol,
while the highest-boiling species is ethylbenzene. The complicating factor in Region 2
is that feed F2 lies on or close to an inflection point of an S-shaped distillation curve. In
this case feasible-product-composition regions may lie on either side of the residue curve
passing through the feed point; however, following the same rule of the region being
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between the residue curve and the material balance line with the extreme other product,
then the region is place correctly.
In Figures 5.11 and 5.12 each bow-tie region is confined to its distillation region, defined
by the distillation boundaries. In all cases, the feed, distillate, and bottoms points on
the material-balance line lie within a distillation region, with the feed point between the
distillate and bottoms points. The material-balance lines do not cross the distillation-
boundary lines.
5.3.5 Extension to Short-cut Equations for Azeotropic Systems
In Section 3.4 the short-cut method was discussed for multi-component distillation. One
of the key assumptions for this method is a constant relative volatility (or approximately
constant). When a system has an azeotrope it is clear that the relative volatility is not
constant. Take Figure 5.13(a) as an example system, at x1 = 0.05 α = 2.55 while at
x1 = 0.95 α = 0.47, this means that it is not possible to use the short-cut method. Taking
an average relative volatility from the feed, distillate, and bottom product composition
gives a value of α = 1.82, which would be represented by the red line, which is not
similar to the actual VLE.
1 1
0.8 0.8
0.6 0.6
y10
y1
0.4 0.4
0.2 0.2
xb xf xd x0b x0f x0d

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x01
(a) (b)
Figure 5.13: Example azeotropic system transformation using equation 5.3.16[5, 6]. (a)
The original azeotropic VLE in black, and a constant relative volatility system with the
same average as the large region in the original system in red. (b) The transformed system
for the large region VLE in black, and a constant relative volatility system with the same
average as the transformed region in red.
The short-cut method can still be used for systems of this type by transforming the region
of interest using the method of Vogelpohl[5, 6]. It should be noted that this method will
give results that are even more approximate than for zeotropic systems, but the key is the
consistency of the relative volatility.
This method transforms the co-ordinate system using:
xi yi
x0i = , yi0 = (5.3.16)
a a
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where a is the composition of the azeotrope. The new value of the relative volatility for
each pair of x0i and yi0 can be given by,
yi0 (1 − x0i )
α0 = (5.3.17)
x0i (1 − yi0 )
For example taking the large region in Figure 5.13(a), using equation 5.3.16 with the
azeotrope composition, a = 0.8, produces Figure 5.13(b). The average relatively volatil-
ity of the transformed system is then α0 = 2.54, which when plotted is very similar to the
transformed VLE.
This method has been extended to more components, by using a matrix transformation[3].
Take Figure 5.14(a) as an example system, the relative volatility for the feed (F), bottom
product (B), and distillate (D) are given by Table 5.1. However, the relative volatility of
the azeotrope is unknown and the distillation boundary makes the methyl acetate pure
component inaccessible from the region of the separation.
Table 5.1: Example ternary azeotropic system for methanol(M), ethanol (E), and methyl
acetate (MA)
Component B F D
MA 5.49 4.44 3.02
M 1.77 1.97 2.91
E 1.00 1.00 1.00
M
0 (3) M
0 (2)
1 1
0.2 0.2
0.8 0.8
B• B• 0
0.4 F• 0.4
0.6 0.6
F•0
0.6 0.6
0.4 0.4
D •• A (1)
0.8 0.8
0.2 0.2
1 1
0 D0 • 0
E (4)0 0.2 0.4 0.6 0.8 1 MA (2) E (3)0 0.2 0.4 0.6 0.8 1 A (1)
(a) (b)
Figure 5.14: Example ternary azeotropic system for methanol(M), ethanol (E), and methyl
acetate (MA); this system has one azeotrope (A). The numbers represent the order of
the boing points. (a) The original ternery azeotropic system with an example separa-
tion shown in red, the grey arrows show the vapour phase composition in equlibrium
with the liquid phase composition of the points. (b) The transformed system using equa-
tion 5.3.18[3] with the same separation shown in red, the grey arrows show the vapour
phase composition in equlibrium with the liquid phase composition of the points in the
transformed co-ordinate system.
This method transforms the co-ordinate system using:
X = MX0 (5.3.18)
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where X is the original liquid composition, in boiling point order, M is the singular point
matrix of the 3 corners of the region X is in, in boiling point order, and X0 is the translated
liquid composition. This can also be carried out for the vapour compositions.
The new value of the relative volatility for each pair of x0i and yi0 can be given by,
yi0 x0H
α0 = 0
(5.3.19)
yH x0i
For example taking the separation in the large region in Figure 5.14(a), using equa-
tion 5.3.18 with the azeotrope composition produces Figure 5.14(b) as,
−1 
x0A
   
0.6574 0 0 xMA
x0M  = 0.3426 1 0  xM 
x0E 0 0 1 xE
Where the M matrix is the three singular points of the separation region in boiling point
order (A, M, E) horizontally where the co-ordinates are in terms of the pure components
in boiling point order (MA, M, E) vertically. The transposed relative volatility for the feed
(F0 ), bottom product (B0 ), and distillate (D0 ) are given by Table 5.2. The short-cut method
can then be used with these new x0 values and the average relative volatilities.
Table 5.2: Example relative volatilities for the transposed ternary azeotropic system for
methanol(M), ethanol (E), and azeotrope (A) system
Component B0 F0 D0
A 5.49 4.44 3.02
M 1.72 1.46 1.10
E 1.00 1.00 1.00
Although this method provides an approximate design and will work with any number of
components, there are limitations. The first is if there are more singular points in a region
than original components the matrix M has no inverse. The second is that distillation
boundaries are approximated to be straight lines, if the boundaries are not straight lines
then the resulting approximation will be poor, and the order of the component relative
volatilites can change. Finally the more non-ideal the components the more inaccurate
the method will become as the relative volatilities will vary across the column.
5.4 Separations for Azeotropes

When α < 1.10, separation by ordinary distillation may be uneconomical, and even im-
possible if an azeotrope forms. In that event, the following techniques referred to as
enhanced distillation, should be explored,
Pressure-Swing Distillation (changing P ), Separates a mixture that forms a pressure-
sensitive azeotrope by utilizing two columns in sequence at different pressures.
Extractive Distillation (changing α), Uses large amounts of a relatively high-boiling
solvent to alter the liquid-phase activity coefficients so that the α of key compo-
nents becomes more favourable. Solvent enters the column a few trays below the
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5.4. SEPARATIONS FOR AZEOTROPES
top, and exits from the bottom without forming any azeotropes. If the column feed
is an azeotrope, the solvent breaks it. It may also reverse key-component volatili-
ties. A variant of this is salt distillation where a nonvolatile ionic salt, which stays
in the liquid phase as it passes down the column, is used to modify the α.
Homogeneous Azeotropic Distillation (changing α), A method of separating a mixture
by adding an entrainer that forms a homogeneous minimum- or maximum-boiling
azeotrope with feed component(s). Where the entrainer is added depends on whether
the azeotrope is removed from the top or the bottom of the column.
Heterogeneous Azeotropic Distillation (add secondary separation mechanism), A min-
imum boiling heterogeneous azeotrope is formed by the entrainer. The azeotrope
splits into two liquid phases in the overhead condenser. One liquid phase is sent
back as reflux; the other is sent to another separation step or is a product.
Reactive Distillation (changing species), A chemical that reacts selectively and reversibly
with one or more feed constituents is added, and the reaction product is then dis-
tilled from the non-reacting components. The reaction is later reversed to recover
the separating agent and reacting component. This operation, referred to as cat-
alytic distillation if a catalyst is used, is suited to reactions limited by equilibrium
constraints, since the product is continuously separated. Reactive distillation also
refers to chemical reaction and distillation conducted simultaneously in the same
apparatus.
If an azeotrope is formed in a process of separating a multiple component mixture, nor-
mally the azeotrope is isolated as a whole then separated separately. This way is treating
the azeotrope as a single component from other components. Normally, an azeotrope
is formed between two components - binary azeotrope, however, it is possible that an
azeotrope may contain multiple components.
5.4.1 Pressure Swing Distillation
If a binary azeotrope disappears at some pressure, or changes composition by 5 mol%

or more over a moderate range of pressure, consideration should be given to using two
ordinary distillation columns operating in series at different pressures. This process is
referred to as pressure-swing distillation.
Figure 5.15 illustrated this method for a minimum boiling binary azeotrope.
As seen from the right hand of Figure 5.15, the left column is operated at a lower pressure
P1 , as the boiling temperature of the azeotrope is lower than both A and B components,
so the bottom product would only be B but the top product is the azeotrope. This more
volatile azeotrope is then fed into the right column operating at a higher pressure, as seen
from the left graph of this figure, as the composition of A in the azeotrope at the higher
pressure is lower than that in higher pressure, when the azeotrope is fed into a column
operating at a higher pressure, part of A in the azoetrope from higher pressure would be
released, thus the bottom product from the right column would just be pure A.
Pressure swing distillation is a simple and effective way of overcoming the boundary
presented by a binary azeotrope, it requires two columns; a pump would need to be used
to elevate pressure and no additional material (i.e. entrainer or solvent) needed. However,
azeotropes are often insensitive to changes in pressure. Also, when the difference in
azeotrope compositions is small, large recycle flows are needed, which makes pressure
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c Rodgers 2019 135
P2 D1 D2
P1
D2 D1 F1 F2
A,B P1 P2
B1 B2
B1 F1 B2 B A
B x,y A .
(a) (b)
Figure 5.15: Pressure swing to break a minimum boiling binary azeotrope, (a) the VLE
data and (b) the distillation sequence.
swing method ineffective with some negative impact on capital and operating costs of
process, due to the high cost of gas compression.
5.4.2 Extractive Distillation
Extractive distillation is used to separate azeotropes and close-boiling mixtures. If the

feed is a minimum-boiling azeotrope, a solvent (the entrainer), with a lower volatility
than the key components of the feed mixture, is added to a tray just a few trays below the
top of the column so that,
• the solvent is present in the down-flowing liquid, and
• little solvent is stripped and lost to the overhead vapour.
If the feed is a maximum boiling azeotrope, the solvent enters the column with the
feed.
The components in the feed must have different solvent affinities so that the solvent causes
an increase in α of the key components, to the extent that separation becomes feasible and
economical. The solvent should not form an azeotrope with any components in the feed.
Usually, a molar ratio of solvent to feed on the order of 1 is required. The bottoms are
processed to recover the solvent for recycle and complete the feed separation.
In selecting a solvent for extractive distillation, a number of factors are considered, includ-
ing availability, cost, corrosivity, vapour pressure, thermal stability, heat of vapourisation,
reactivity, toxicity, infinite-dilution activity coefficients in the solvent of the components
to be separated, and ease of solvent recovery for recycle.
Initial screening is based on the measurement or prediction of infinite-dilution activity
coefficients. Generally successful solvents for extractive distillation are highly hydrogen-
bonded liquids such as water, amino-alcohols, amides, and phenols that form three-dim-
ensional networks of strong hydrogen bonds; and alcohols, acids, phenols, and amines
that are composed of molecules containing both active hydrogen atoms and donor atoms
(oxygen, nitrogen, and fluorine).
Figure 5.16 shows the typical three column extractive distillation sequence, consisting of
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ordinary distillation concentrating the feed to the azeotrope composition, followed by the
extractive distillation with the added solvent, and then ordinary distillation to recover the
solvent. Often a pre-concentration distillation column is used as this reduces the amount
of material passing through the two distillation columns with the solvent. This reduced
the size of these columns and the amount of solvent needed, thus the cost of the system is
reduced. If the feed composition is similar to the azeotrope the it may not be necessary to
have the pre-concentration distillation column - this is an economic balance.
D2 D3
D1
A+B Pre- F2 F3
F1 2 3
conc
B2 B3
B1
S
Figure 5.16: Typical 3 column extractive distillation sequence.
For the sequence shown in Figure 5.16 the columns can be represented on a ternary dia-
gram, Figure 5.17. This allows the compositions in the columns to be approximated and
used in short-cut calculations.
0A
D2 • 100
20
80
40
• 60
D1
Col 2
60
40
Mix • F Pre-
80 conc
20
100 Col 3 D3 B1
B3 • • • 0
E0 20 40 B2 60 80 100B
Figure 5.17: Typical 3 column extractive distillation sequence, Figure 5.16, shown on an
example ternary diagram with residue curves.
If the boiling point of the solvent is much higher than the boiling points of the compo-
nents in the feed, then a good approximation is that the solvent never vapourises, thus the
system can be though of as a binary system, but with a modified activity coefficient be-
tween the feed components. An example of this can be seen for the Butadiene and Butane
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c Rodgers 2019 137
system in Figure 5.18. At 1 atm there is an azeotrope between Butadiene (B.P. −4.4 ◦ C)
and Butane (B.P. −0.2 ◦ C) preventing separation via simple distillation, Figure 5.18(a).
Adding N-Methyl-2-pyrrolidone (NMP) (B.P. 202.0 ◦ C) to the mixture effects the activity
coefficient between Butadiene and Butane and removes the azeotrope producing the equi-
librium given by Figure 5.18(b). In fact, the activity coefficient is effected so much that
Butadiene becomes the least volatile component rather then the most volatile component.
As the boiling point of NMP is so much higher than that of the other two components, it
does not really vapourise in the distillation column and just passes down the column as a
liquid.
1 1
0.8 0.8
0.6 0.6
y1
y1
0.4 0.4
0.2 0.2
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1
(a) (b)
Figure 5.18: Vapour-Liquid equilibrium at 1 atm for (a) Butadiene(1) and Butane(2) and
(b) Butadiene(1) and Butane(2) in the presence of N-Methyl-2-pyrrolidone (NMP), 2 parts
NMP to 1 part Butadiene/Butane.
An alternative to adding a pure solvent is to add a salt solution or salt melt to the azeotropic
mixture (often called salt distillation). This allows a extra modification to the α. The
vapour pressure of the dissolved salt is so small that it never enters the vapour, provided
entrainment is avoided.
Salt distillation is accompanied by several problems. First and foremost is corrosion,
particularly with aqueous chloride-salt solutions, which may require stainless steel or a
more expensive corrosion-resistant material. Feeding and dissolving a salt into the reflux
poses problems as the solubility of salt will be low in the reflux because it is rich in the
more-volatile component, the salt being most soluble in the less-volatile component. Salt
must be metered at a constant rate and the salt-feeding mechanism must avoid bridging
and prevent the entry of vapour, which could cause clogging when condensed. The salt
must be rapidly dissolved, and the reflux must be maintained near the boiling point to
avoid precipitation of already-dissolved salt. In the column, presence of dissolved salt
may increase foaming, requiring addition of antifoaming agents and/or column-diameter
increase. There is also potential that the salt may crystallise within the column. However,
the concentration of the less-volatile component (e.g., water) increases down the column,
so the solubility of salt increases down the column while its concentration remains rela-
tively constant. Thus, the possibility of clogging and plugging due to solids formation is
unlikely.
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5.4.3 Homogeneous Azeotropic Distillation
As seen in the previous section, an azeotrope can be separated by extractive distillation,

using a solvent that has a higher boiling than the feed components and does not form any
azeotropes with either component. However, this restricts the number of solvents that can
be used.
Alternatively, the separation can be made by homogeneous azeotropic distillation, using
an entrainer not subject to such restrictions. Like extractive distillation, a sequence of
two or three columns can be used. For a suitable entrainer, E, the two components, A
and B, to be separated, or any product azeotrope, must lie in the same distillation region
of the residue-curve map. Thus, a distillation boundary cannot be connected to the A-B
azeotrope. Furthermore, A or B, but not both, must be a saddle.
Figure 5.19 shows a typical two column homogeneous azeotrope distillation sequence,
consisting of a distillation column with the added solvent, and then an ordinary distillation
to recover the solvent as an azeotrope.
5.4.4 Heterogeneous Azeotropic Distillation
For homogeneous azeotropic distillation it is required that A

and B lie in the same distillation region of the residue-curve
map as the residue forms an azeotrope with one of them. To
allow this to occur, one of the azeotropes formed needs to.
be a maximum-boiling azeotrope, which are much rarer than
minimum-boiling azeotropes. These constraints are often so
restrictive that it is often difficult to find a feasible entrainer. Summary Video
A better, alternative technique that finds wide use is heterogeneous azeotropic distillation
to separate close-boiling binaries and minimum-boiling binary azeotropes by employing
an entrainer that forms a binary and/or ternary heterogeneous (two-phase) azeotrope. A
heterogeneous azeotrope has two or more liquid phases. If it has two, the overall, two-
liquid-phase composition is equal to that of the vapour phase. Thus, all three phases
have different compositions. If the overhead vapour from the azeotropic column is close
to the composition of the heterogeneous azeotrope when condensed, two liquid phases
form in a decanter (a strenuous attempt is made to restrict the formation of two liquid
phases to the decanter because when two liquid phases form on a tray, the tray efficiency
decreases).
After separation, most or all of the entrainer-rich liquid phase is returned to the column
as reflux, while most or all of the other liquid phase is sent to the next column for further
processing, Figure 5.20(a). The distillation sequence can also include a separate precon-
centrater, Figure 5.20(b).
As the two liquid phases from the azeotropic column top product usually lie in different
distillation regions of the residue-curve map, the restriction that dooms homogeneous
azeotropic distillation is overcome. Thus, in heterogeneous azeotropic distillation, the
components to be separated need not lie in the same distillation region.
Figure 5.21 shows a typical two column heterogeneous azeotrope distillation sequence
plotted on a ternary diagram, consisting of an azeotropic distillation column with the het-
erogeneous azeotrope being condensed and separated settled into two liquid phases, L1
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0A
D2 • 100
20
• D1 80
Col 2
40
•• 60
Mix F
B2
60 •
Col 1 40
80
20
•
100 B1
• • 0
E0 20 40 60 80 100B
(a)
D1
D2
A+B
F 1 2
B1 B2
A-E azeotrope
(b)
Figure 5.19: Typical 2 column homogeneous azeotropic distillation sequence, shown on

an example ternary diagram with residue curves.
and L2 . The liquid phase with the most solvent tends to be fed back into the azeotropic
column. The other liquid phase is fed into a simple distillation column where the remain-
ing solvent is separated.
5.4.5 Reactive Distillation
Reactive distillation denotes simultaneous chemical reaction and distillation. The reaction
usually takes place in the liquid phase or at the surface of a solid catalyst in contact with
the liquid. The separation of a close-boiling or azeotropic mixture of components A and
B can be enhanced if a chemically reacting entrainer E is introduced into the column. If
A is the lower-boiling component, it is preferable that E be higher boiling than B and that
it react selectively and reversibly with B to produce reaction product C, which also has a
higher boiling point than component A and does not form an azeotrope with A, B, or E.
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Entrainer Make-up Entrainer Make-up

D1 D3
D1
D2 D2
L2 L2
L1 L3
2 1 F1 F1 1 2 3
F2
B2 B1 B1 B2 B3
(a) (b)
Figure 5.20: Distillation sequence for heterogeneous azeotropic distillation; (a) two col-
umn design, column 1 is the combined pre-concentrator/entrainer recovery column and
column 2 is the Azeotropic column;and (b) three column design, column 1 is the pre-
concentrator column, column 2 is the Azeotropic column, and column 3 is the entrainer
recovery column.
0A
B2 • 100
20
80
40
60
•
F• Col 2
60
D1 • 40
Mix
80
Col 1 20
Mix
100B1 D2 Top-up
•• •
N • • 0
B0 L1 20 40 LLE 60 80 L2 100E
Figure 5.21: Typical 2 column heterogeneous azeotropic distillation sequence, Fig-

ure 5.20(a), shown on an example ternary diagram with residue curves and liquid-liquid
equilibrium.
Component A is removed as distillate, and components B and C, together with any excess
E, are removed as bottoms. Components B and E are recovered from C in a separate
distillation, where the reaction is reversed (C −−→ B + E); B is taken off as distillate, and
E is taken off as bottoms and recycled to the first column.
Reactive distillation should be considered whenever the following hold,
1. The chemical reaction occurs in the liquid phase, in the presence or absence of a
homogeneous catalyst, or at the interface of a liquid and a solid catalyst.
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2. Feasible temperature and pressure for the reaction and distillation are the same.
That is, reaction rates and distillation rates are of the same order of magnitude.
3. The reaction is equilibrium-limited so that if one or more of the products can be
removed by distillation, the reaction can be driven to completion; thus, a large reac-
tant excess is not necessary for a high conversion. This is particularly advantageous
when excess reagent recovery is difficult because of azeotrope formation. For reac-
tions that are irreversible, it is more economical to take the reactions to completion
in a reactor and then separate the products in a distillation column. In general, reac-
tive distillation is not attractive for supercritical conditions, for gas-phase reactions,
and for reactions at high temperatures and pressures and/or that involve solids.
Careful consideration must be given to the configuration of reactive distillation columns.
Important factors are feed entry and product-removal stages, the possible need for inter-
coolers and interheaters when the heat of reaction is appreciable, and obtaining required
residence time for the liquid phase.
5.5 References
[1] Foucher, E. R., Doherty, M. F. and Malone, M. F. [1991a], ‘Automatic screening
of entrainers for homogeneous azeotropic distillation’, Industrial & Engineering
Chemistry Research 30, 760–772.
[2] Foucher, E. R., Doherty, M. F. and Malone, M. F. [1991b], ‘Automatic screening
of entrainers for homogeneous azeotropic distillation [erratum to document cited in
ca114(16):145978g]’, Industrial & Engineering Chemistry Research 30, 2364.
[3] Liu, G., Jobson, M., Smith, R. and Wahnschafft, O. M. [2004], ‘Shortcut design
method for columns separating azeotropic mixtures’, IndustIndus& Engineering
Chemistry Research 43(14), 3908–3923.
[4] Stichlmair, J. [1988], Ullmann’s Encyclopedia of Industrial Chemistry, Vol. B3,
5 edn, VCH Verlagsgesellschaft Weinheim, chapter Distillation and Rectification,
pp. 4–1–4–94.
[5] Vogelpohl, A. [1974], ‘Die näherungsweise berechnung der rektifikation von gemis-
chen mit binären azeotropen’, Chemie Ingenieur Technik 46(5), 195.
[6] Vogelpohl, A. [2002], ‘On the relation between ideal and real mixtures in multicom-
ponent distillation’, Chemical Engineering & Technology 25(9), 869–872.
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5.6. PROBLEMS
5.6 Problems
E1 Plot a portion of a residue curve for n-propanol (1), isopropanol (2), and benzene
(3) at 1 atm starting from a bubble-point liquid with 20 mol% each of 1 and 2, and
60 mol% of component 3 (78.67 ◦ C).
Use Raoult’s law with regular-solution theory for estimat-

ing the liquid-phase activity coefficients.
The normal boiling points of the three components in ◦ C.
are 97.3, 82.3, and 80.1, respectively.
Minimum-boiling azeotropes are formed at 77.1 ◦ C for
components 1, 3 and at 71.7 ◦ C for 2, 3.
Solution Video
Useful information:
R = 1.987 cal mol−1 K−1 .
γiL p◦i B
Ki = ln (p◦ [kPa]) = A − ◦
P !2 T [ C] + C
Xn
viL δi − Φj δj
j=1 xj vjL
ln γiL = Φj = n
RT X
xk vkL
k=1
Component δ / cal1/2 cm−3/2 v / cm3 mol−1 A B C

n-propanol 12.0 74.72 16.1154 3483.67 205.807
isopropanol 11.6 76.4 16.6796 3640.2 219.61
Benzene 9.2 89.04 13.7819 2726.81 217.572
T.L.
c Rodgers 2019 143
E2 For the feed positions below, find the feasible product regions.
0A 0A
1 1
0.2 0.2
0.8 0.8
•
0.4 0.4
0.6 0.6
0.6 0.6 F
0.4 • 0.4
0.8 F 0.8
• 0.2 0.2
1 1
C 0 C 0
0 0.2 0.4 0.6 0.8 1B 0 0.2 0.4 0.6 0.8 1B
(a) (b)
0A 0A
1 1
0.2 0.2
0.8 0.8
0.4 0.4 • F •
• 0.6 • 0.6
0.6 0.6
0.4 0.4
0.8 F 0.8 •
• 0.2 0.2
1 1
C • 0 C • 0
0 0.2 0.4 0.6 0.8 1B 0 0.2 0.4 0.6 0.8 1B
(c) (d)
144 T.L.
c Rodgers 2019
5.6. PROBLEMS
E3 For the normal hexane-methanol-methyl acetate system at 1 atm, sketch a residue-

curve map on a right-triangular diagram, and indicate the distillation boundaries.
Determine for each azeotrope and pure component whether it is a stable node, an
unstable node, or saddle.
Methanol - b.p. = 64.65 ◦ C
Methyl acetate - b.p. = 57.1 ◦ C
n-hexane - b.p. = 69.0 ◦ C
Methanol 18.7 wt%, Methyl acetate 81.3 wt% - b.p. = 53.8 ◦ C
Methanol 28.0 wt%, n-hexane 72.0 wt% - b.p. = 50.6 ◦ C
Methyl acetate 60.7 wt%, n-hexane 39.3 wt% - b.p. = 51.8 ◦ C
Methanol 14.0 wt%, Methyl acetate 27.0 wt%, n-hexane 59.0 wt% - b.p. = 45.0 ◦ C
0
100
10
90
20
80
30
70
40
60
50
50
60
40
70
30
80
20
90
10
100
0
0 10 20 30 40 50 60 70 80 90 100
T.L.
c Rodgers 2019 145
E4 A distillation column is to be designed to separate two components. The feed con-

sisting of 40 mol% component 1 enters the column as a saturated liquid. A distillate
consisting of 75 mol% component 1 and a bottom product consisting of 5 mol%
component 1 are produced. What is the minimum number of stages and the mini-
mum reflux ratio needed for the separation. The VLE for the system is:
x1 y1
0.000 0.000
0.050 0.118
0.100 0.215
0.200 0.368
0.300 0.483
0.400 0.573
0.500 0.646
0.600 0.706
0.700 0.757
0.750 0.779
0.800 0.800
0.900 0.850
0.950 0.900
1.000 1.000
146 T.L.
c Rodgers 2019
5.6. PROBLEMS
E5 Pressure swing distillation is used to separate 100 kmol hr−1 of a mixture of 40 mol%
ethanol with water into products with 99 mol% purity.
Based on the sequence and the VLE below,
(a) Identity the compositions of B1 , D1 , B2 and D2
(b) Determine the flowrates of B1 and B2
(c) Determine the flowrates of D1 and D2
D1 D2
F1 F2
E,W 1 atm 6 atm
B1 B2
1 1
1 atm 6 atm
0.8 0.8
0.6 0.6
yE
yE
1 1
0.95
0.4 0.95 0.4
0.9
0.9
0.2 0.2 0.85
0.85 0.8
0.85 0.9 0.95 1 0.8 0.85 0.9 0.95 1
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
xE xE
T.L.
c Rodgers 2019 147
E6 Forty mol s−1 of a bubble-point mixture of 75 mol% acetone and 25 mol% methanol
at 1 atm is separated by extractive distillation, using water as the solvent, to produce
an acetone product of not less than 95 mol% acetone, a methanol product of not
less than 98 mol% methanol, and a water stream for recycle of at least 99.9 mol%
purity. Prepare a preliminary process design using the traditional three-column
sequence consisting of ordinary distillation followed by extractive distillation, and
then ordinary distillation to recover the solvent, Figure 5.16.
MeOH
0 (I)
100
10
90
20
80
30
70
40
60
50
50
60
40
70
30
80 •Azeotrope
20
90
10
100
0
H2 O (H)0 10 20 30 40 50 60 70 80 90 100Acetone (L)
148 T.L.
c Rodgers 2019
5.6. PROBLEMS
E7 Design a two-column distillation sequence (Figure 5.20(a) to separate 150 mol/s of

an azeotropic mixture of ethanol and water at 1 atm into nearly pure ethanol and
nearly pure water using heterogeneous azeotropic distillation with benzene as the
entrainer.
0
100
10
78.2 ◦ C 90
20
80
30
70
Eth
l%
40
60
ano
mo
l/
r/
50
te
mo
50
Wa
l%
67.8 ◦ C
60
40
70
30
63.8 ◦ C
80
20
90
10
100 69.2 ◦ C
0
0 10 20 30 40 50 60 70 80 90 100
Benzene / mol %
T.L.
c Rodgers 2019 149
E8 Design a three-column distillation (Figure 5.20(b)) sequence to separate a feed of

20% ethanol in water into products of at least 99% purity using heterogeneous
azeotropic distillation with a pentane entrainer.
0
100
10 • 90
20
80
30
70
n e
Mo
nta
40
e
le %
60
n-p
le %
eth
50
50
ano
Mo
l
60
40
70
30
80
20
90
10
•
100 •
• 0
0 10 20 30 40 50 60 70 80 90 100
Mole % water
150 T.L.
c Rodgers 2019
Chapter 6
Revision
Contents
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.2 Flash Equlibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.3 McCabe-Thiele Method . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.4 Ponchon-Savarit Method . . . . . . . . . . . . . . . . . . . . . . . . 158
6.5 Absorption/Desorption . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.5.1 Scrubbing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.5.2 Stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.6 Liquid-Liquid Extraction . . . . . . . . . . . . . . . . . . . . . . . . 165
151
152
6.1. INTRODUCTION
6.1 Introduction
This section does not aim to provide the full information and detail for the separations
listed, it is simply there as revision of topics covered in previous courses, which could be
useful during this course.
6.2 Flash Equlibrium
For a vapour in equilibrium with a liquid the mole fraction in

the vapour, yi , and liquid, xi , phases are linked by,
.
P yi = xi γi Pio
γi Pio
yi = xi = K i xi (6.2.1)
P
Summary Video
For a non-condensible gas, i.e. a temperature far above the boiling point, this expression
doesn’t work and the solubility must be taken into account, e.g. oxygen dissolved in water,
with an expression like Henry’s Law,
P yi = Hi xi
Hi
yi = xi = K i xi (6.2.2)
P
A simple flash system can be represented by Figure 6.1.
T, P V , yi
F , zi
L, xi
Figure 6.1: Representation of a flash vessel separation.
A mass balance for a component i in this system can be given by,
F zi = Lxi + V yi (6.2.3)
Substituting yi from equation 6.2.1,
F zi = Lxi + V Ki yi
= (F − V ) xi + V Ki xi
= F xi + V xi (Ki − 1)
F zi
xi =
F + V (Ki − 1)
zi
= (6.2.4)
V
1 + (Ki − 1)
F
T.L.
c Rodgers 2019 153
CHAPTER 6. REVISION
P
The
P sum of the mole fractions of each component must add to 1 such that, xi = 1 and
yi = 1, therefore:
X X
0= yi − xi
i i
X
= (Ki xi − xi )
i
= xi (Ki − 1) (6.2.5)
Substituting xi from equation 6.2.4 produces the Rachford-Rice Flash equation,
X zi (Ki − 1)
=0 (6.2.6)
V
i 1 + (Ki − 1)
F
This equation can be solved iteratively to calculate the vapourised fraction, V /F , for the
given temperature and pressure of the system.
6.3 McCabe-Thiele Method

The main assumptions of the McCabe-Thiele method are:
• Constant Molar Overflow (CMO) - The flow rate of the
vapour and the liquid in the column sections are constant
and do not change from tray to tray.
• Adiabatic and Isobaric - There are no heat losses within
the system and the pressure doesn’t change in the col-.
umn.
• Parallel Enthalpy Lines (PEL) - The saturated liquid
and saturated vapour (molar) enthalpy curves, hL (x) and
hV (y) respectively, are parallel lines, i.e. the molar en- Summary Video
thalpy of vaporisation, λM , of the mixture is constant
and independent of composition.
Taking a mass balance on the top of the distillation column, Figure 6.2.
V yn = Lxn+1 + Dxd
L D
yn = xn+1 + xd
V V
L D
Yn − xn+1 = xd (6.3.1)
V V
Taking a mass balance on the enrichment section, Figure 6.3.
V yn−1 + Lxn+1 = V yn + Lxn

L L
yn−1 = xn + yn − xn+1 (6.3.2)
V V
154 T.L.
c Rodgers 2019
6.3. MCCABE-THIELE METHOD
V , yn+1
D, xd
L
V , yn n+1
L,
xn+1
V , yn−1 n
L,
xn
Figure 6.2: Mass balance around the top of distillation column.
V , yn+1
D, xd
L
V , yn n+1
L,
xn+1
V , yn−1 n
L,
xn
Figure 6.3: Mass balance on the enrichment section of a distillation column.
Substituting equation 6.3.1 into this equation gives,

L D
yn−1 = xn + xd
V V
L D
yn = xn+1 + xd (6.3.3)
V V
This is the enrichment section operating line (ESOL). Equation 6.3.3 can also be written
T.L.
c Rodgers 2019 155
CHAPTER 6. REVISION
in terms of the reflux ratio, R = L/D as,

L
L L R
= = D = (6.3.4)
V L+D L R+1
+1
D
D D 1 1
= = = (6.3.5)
V L+D L R+1
+1
D
Therefore,
R 1
yn = xn+1 + xd (6.3.6)
R+1 R+1
At the top of the column yn+1 = xn+1 = xd as the condenser is a complete condenser,
this means that,
R 1
yn = xd + xd
R+1 R+1
1
R+1 R+1
= xd = xd
R+1 R+1
= xd (6.3.7)
This process can also be repeated for the stripping section of the column which gives the
stripping section operating line (SSOL),
Lm B
ym = xm+1 − xb (6.3.8)
Vm Vm
At the bottom of the column xm+1 = xb , thus from equation 6.3.8 ym = xb .

A mass balance on the feed is shown in Figure 6.4.
Vf , yf
F , zf
Lf , xf
Figure 6.4: Mass balance on the feed section of a distillation column.
F zf = Vf yf + Lf xf
Vf yf = = F zf − Lf xf
Lf F
yf = − xf + zf (6.3.9)
Vf Vf
156 T.L.
c Rodgers 2019
6.3. MCCABE-THIELE METHOD
This is the feed operating line (FOL). Equation 6.3.9 can also be written in terms of the
feed quality, q = Lf /L as,
Lf
Lf Lf F q
− = − = = (6.3.10)
Vf F − Lf Lf q−1
−1
F
F F 1 1
= = = (6.3.11)
Vf F − Lf Lf 1−q
1−
F
Therefore,
q 1
yf = xf + zf (6.3.12)
q−1 1−q
Knowledge of VLE data along with equations 6.3.12 and 6.3.6 allows a graphical calcu-
lation of the number of stages needed for the separation. To do this the equality line is
plotted, y = x followed by the position of the top product, (xd , xd ); feed, (zf , zf ); and the
bottom product, (xb , xb ) shown as the red points in Figure 6.5.
y
•

zf
(xd , xd )
0, •
1−q
•
(zf , zf )

xd
0, •
R+1
• (xb , xb )
x
Figure 6.5: Graphical McCabe-Thiele operating lines. Feed line in green, enrichment
section operating line in blue, and stripping section operating line in purple.
The feed operating line, equation 6.3.12, can be plotted on the graph as it is known it starts
at the feed point, (zf , zf ), and at the y-axis (i.e. x = 0) the y coordinate is zf / (1 − q).
This is shown as the green line in Figure 6.5.
After the feed line, the enrichment section operating line, equation 6.3.6, can be plotted
on the graph as it is known it starts at the distillate product point, (xd , xd ), and at the
y-axis (i.e. x = 0) the y coordinate is xd / (R + 1). This is shown as the blue line in
Figure 6.5.
The stripping section operating line can then be drawn by joining the the bottom product
point, (xb , xb ), with the point where the feed operating line and the enrichment section
operating line meet. This is shown as the purple line in Figure 6.5.
T.L.
c Rodgers 2019 157
CHAPTER 6. REVISION
Now that the operating lines are draw, the stages can be calculated by drawing between
the operating lines and the equilibrium line as shown by the red lines in Figure 6.6. This
process is continued until the last red line is below the bottom product position.
y 1
2 •
(xd , xd )
•
(zf , zf )
• (xb , xb )
x
Figure 6.6: Graphical McCabe-Thiele equilibrium stages drawn on the operating lines.
6.4 Ponchon-Savarit Method
The Ponchon-Savarit method has advantages over the

McCabe-Thiele method as it doesn’t require the PEL or CMO
assumptions. .
Taking a mass and energy balance on the top of the distillation
column, Figure 6.7.
Summary Video
An energy balance around the top of the column is,
Vn hV,n = Ln+1 hL,n+1 + DhL,d + Q̇C (6.4.1)
Defining h0d = hL,d + Q̇C /D means that,
Vn hV,n = Ln+1 hL,n+1 + Dh0d (6.4.2)
From a total mass balance Ln+1 + D = Vn , therefore,
(Ln+1 + D) hV,n = Ln+1 hL,n+1 + Dh0d

Ln+1 (hV,n − hL,n+1 ) = D (h0d − hV,n )
Ln+1 h0d − hV,n
= (6.4.3)
D hV,n − hL,n+1
158 T.L.
c Rodgers 2019
6.4. PONCHON-SAVARIT METHOD
Q̇C
Vn+1 , hV,n+1 , yn+1

D, hL,d , xd
L
Vn , hV,n , yn n+1
Ln+1 ,
hL,n+1 ,
xn+1 n
Vn−1 , hV,n−1 , yn−1
Ln ,
hL,n ,
xn
Figure 6.7: Mass and energy balance around the top of distillation column.
A mass balance for the top of the column is,

Vn yn = Ln+1 xn+1 + Dxd
(Ln+1 + D) yn = Ln+1 xn+1 + Dxd
Ln+1 (yn − xn+1 ) = D (xd − yn )
Ln+1 xd − y n
= (6.4.4)
D yn − xn+1
Comparing equations 6.4.3 and 6.4.4 produces,

h0d − hV,n xd − y n
=
hV,n − hL,n+1 yn − xn+1
0
hd − hV,n hV,n − hL,n+1
= (6.4.5)
xd − yn yn − xn+1
This form of equation means that key pairs line on the same straight line, these are:
(yn , hV,n ), (xn+1 , hL,n+1 ), and (xd , h0d ) = PC .
The same approach can also be carried out around the bottom of the column to give,
hV,m − h0b hV,m − hL,m+1
= (6.4.6)
ym − xb ym − xm+1
where h0b = hL,b − Q̇R /B.

(ym , hV,m ), (xm+1 , hL,m+1 ), and (xb , h0b ) = PR .
A mass and energy balance can also be taken over the whole column. For the mass
balance,
F zf = Bxb + Dxd (6.4.7)
T.L.
c Rodgers 2019 159
CHAPTER 6. REVISION
As F = B + D then,
(B + D) zf = Bxb + Dxd
B (zf − xb ) = D (xd − zf )
B xd − zf
= (6.4.8)
D zf − xb
For the energy balance,
F hf + Q̇R = DhL,d + Q̇C + BhL,b

F hf = DhL,d + Q̇C + BhL,b − Q̇R
F hf = Dh0d + Bh0b
(B + D) hf = Dh0d + Bh0b
B (hf − h0b ) = D (h0d − hf )
B h0 − hf
= d (6.4.9)
D hf − h0b
Combining equations 6.4.8 and 6.4.9 gives,
xd − zf h0 − hf
= d
zf − xb hf − h0b
hf − h0b h0 − hf
= d (6.4.10)
zf − xb xd − zf
(xd , h0d ) = PC , (xb , h0b ) = PR , and (zf , hf ) = F .
This means that the operating points can be plotted on the enthalpy data graph for the
system of interest on Figure 6.8. The condenser operating point, PC , in red is above
the hV line by the amount Q̇C /D, this amount is related to the reflux ratio. For a total
condenser,
V =L+D
= RD + D = (R + 1) D
Q̇C = V (hV − hL )
= (R + 1) (hV − hL ) D
Q̇C
= (R + 1) (hV − hL ) (6.4.11)
D
The feed point, F , in green is plotted as the point (zf , hf ) and hf is related to the feed
quality as,
hV − hf
q= (6.4.12)
hV − hL
The reboiler operating point, PR , in blue can then be plotted as it is on a straight line from
PC through F and at the x-coordinate of xb , this position allows the calculation of the
reboiler duty from h0b .
160 T.L.
c Rodgers 2019
6.4. PONCHON-SAVARIT METHOD
h
(xd , h0d ) = PC
•
• hV
(zf , hf ) = F
hL
•
(xb , h0b ) = PR
x,y
Figure 6.8: Graphical Ponchon-Savarit operating points. Feed point in green, condenser
operating point in red, and reboiler operating point in blue.
Now that the operating points are plotted, the number of stages needed for the separation
can be determined as in Figure 6.9. Starting at the top of the column, xd , the liquid
fraction can be determined from the VLE data and then the hL value, red lines. The vapour
composition of the stage below can then be calculated joining the liquid composition to
the condenser operating point, green line. This is the equivalence of the operating line in
the McCabe-Thiele method.
Now the liquid composition on the same stage can be determined from the VLE chart,
blue, and then back to the condenser operating point, purple line. This process is repeated
until the lines pass the line through the feed point, after this the reboiler operating point,
PR is used with the VLE data.
T.L.
c Rodgers 2019 161
CHAPTER 6. REVISION
h
PC
•
• hV
F
hL
•
PR
x,y
y 1
2
Figure 6.9: Graphical Ponchon-Savarit stages drawn from the operating points coupled
with the VLE data.
6.5 Absorption/Desorption
In absorption/desorption there is a gas phase and a liquid phase

and a solute which passes between the two phases. The gas and.
liquid phases are insoluble in each other.
Summary Video
For convenience key variables are used:
• L0 is the solute-free liquid flow rate
• G0 is the solute-free gas flow rate
162 T.L.
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6.5. ABSORPTION/DESORPTION
• X is the mole ratio of solute in the liquid to the solute-free liquid, i.e.
xA
XA = (6.5.1)
1 − xA
• Y is the mole ratio of solute in the gas to the solute-free gas, i.e.
yA
YA = (6.5.2)
1 − yA
The mass balance is shown in Figure 6.10 for the top of the column as the red bor-
der,
G0 Yn + L0 XT +1 = G0 YT + L0 Xn+1
L0 L0
Yn = 0 Xn+1 + YT − 0 XT +1 (6.5.3)
G G
For the bottom of the column as the green border,
G0 Y0 + L0 Xn+1 = G0 Yn + L0 X1
L0 L0
Yn = 0 Xn+1 + Y0 − 0 X1 (6.5.4)
G G
G0 YT L0 XT +1
T −1
L0 Xn+1
n+1
n
G0 Yn
1
G0 Y0 L0 X1
Figure 6.10: Absorption column mass balance.
Equations 6.5.3 and 6.5.4 are the same line with a gradient of L0 /G0 and pass through
points (X1 , Y0 ) and (XT +1 , YT ).
T.L.
c Rodgers 2019 163
CHAPTER 6. REVISION
6.5.1 Scrubbing
For Absorption the liquid gets more concentrated as it goes down the column, i.e. the
solute is absorbed from the gas phase carrier into the liquid solvent.
This means that the operating line, shown in red, is above the solubility line, Figure 6.11.
As with the McCabe-Thiele method the stages, shown in blue, are determined by stepping
between the equilibrium line and the operating line.
(X1 , Y0 )
•
2
(XT +1 , YT )
•
1
Figure 6.11: Graphical scrubbing operating lines. Operating line in red, stages in blue.
6.5.2 Stripping
For Desorption the liquid gets less concentrated as it goes down the column, i.e. the solute
is desorbed from the liquid phase carrier into the gas solvent.
This means that the operating line, shown in red, is below the solubility line, Figure 6.12.
As with the McCabe-Thiele method the stages, shown in blue, are determined by stepping
between the equilibrium line and the operating line.
164 T.L.
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6.6. LIQUID-LIQUID EXTRACTION
1
• (XT +1 , YT )
•
(X1 , Y0 )
X
Figure 6.12: Graphical stripping operating lines. Operating line in red, and stages in blue.
6.6 Liquid-Liquid Extraction

Liquid-liquid extraction uses a solvent, S, to remove a solute, A, from an original carrier,
C. If an assumption is made that the carrier and the solvent do not dissolve in each other
(then their flow rate is constant through the column), and the fraction of the solute is
relatively small then a method similar to absorption can be used to calculate the number
of stages needed for the separation.
As with absorption key variables are used to make the equations easier to solve:
• X is the mass ratio of solute, A, to the carrier, C, in the feed/rafinate phase i.e.
mass of A
XA = (6.6.1)
mass of C
• Y is the mass ratio of solute, A, to the solvent, S, in the solvent/extract phase i.e.
mass of A
YA = (6.6.2)
mass of S
The mass balance is shown in Figure 6.13 for the whole of the column as the red border,
remembering that the carrier flow is C and the solvent flow is S, and don’t change in the
column,
CX0 + SYT +1 = CXT + SY1
C (X0 − XT ) = S (Y1 − YT +1 )
C Y1 − YT +1
= (6.6.3)
S X0 − XT
As in absorption this defines a straight line with a gradient of C/S that passes through
points (X0 , Y1 ) and (XT , YT +1 ).
The operating line, shown in red, is below the solubility line, Figure 6.14. As with the
McCabe-Thiele method the stages, shown in blue, are determined by stepping between
the equilibrium line and the operating line.
T.L.
c Rodgers 2019 165
CHAPTER 6. REVISION
R, XT L, YT +1
T −1
n+1
1
F, X0 E, Y1
Figure 6.13: Liquid-liquid extraction column mass balance.
1
• (X0 , Y1 )
•
(XT , YT +1 )
X
Figure 6.14: Graphical liquid-liquid extraction operating lines. Operating line in red, and
stages in blue.
166 T.L.
c Rodgers 2019

AES Notes

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List of Figures vii

Course Information xiii

5 Azeotropic Distillation 115

1.1 Example of a simple chemical process. . . . . . . . . . . . . . . . . . . . 3

2.1 Common liquid-liquid extraction cascade configurations. . . . . . . . . . 32

3.1 Multi-component distillation. . . . . . . . . . . . . . . . . . . . . . . . . 62

4.1 A simple column. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

5.1 Minimum-boiling-point azeotrope. . . . . . . . . . . . . . . . . . . . . . 117

6.1 Flash Vessel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

1.1 Separation Operations Based on Phase Creation or Addition. . . . . . . . 8

2.1 Example solubility parameters . . . . . . . . . . . . . . . . . . . . . . . 31

3.1 Representative commercial distillation operations. . . . . . . . . . . . . . 81

4.1 Number of sequences changes with the number of components. . . . . . . 94

5.1 Example relative volatilities for a ternary system. . . . . . . . . . . . . . 133

1.1 Chapter 1 ILOs

Figure 1.1: Example of a simple chemical process.

1.3 Basic Separation Techniques

Solid Phase 1 Feed Force Field

2. Thermodynamic and transport properties

1.4 Separations by Phase Addition or Creation

Created or Added Separating Agent /

Flash vaporisation V Liquid Vapour Pressure reduction Recovery of water CHEN10082

Continued on next page

Continued on next page

Coagulation Liquid/solid Polymers and salts (MSA) Removal of small

1.5 Separations by Barriers

Osmosis Liquid Nonporous mem-

Gas permeation Vapour Nonporous mem- Hydrogen enrichment

Pervaporation Liquid Nonporous mem- Separation of

1.6 Separations by Solid Agents

1.7 Separations by External Field or Gradient

Continued on next page

Electrodialysis Liquid Electrical force field Desalinization of sea

Field-flow fractionation Liquid Laminar flow in Separation of cells and

L force field [2] platelets from blood

Magnetic Separation Solids in solids or Magnetic force Ferrous scrap are to

1.8 Component Recoveries

1.8.1 Split Fractions and Split Ratios

Alternatively, a split ratio, SR, between two products, p1 and p2 , is,

SF may be a better degree-of-separation indicator than SR because SF is bounded be-

1.8.2 Separation Factor

where C is some measure of composition. SP is readily converted to the following forms

E4 For the system shown in E3 also calculate the

E5 A feed, F , of 100 kmol h−1 of air containing 21 mol% O2 and 79 mol% N2 is to be

2.1 Chapter 2 ILOs

2.2.1 Partition coefficient

An example of some solubility parameters of commonly used liquid-liquid extraction

2.2.2 Solvent Selection

Table 2.1: Some example solubility parameters of common liquid-liquid extraction

Solvent δ / cal1/2 cm−3/2

3. Minimal solubility in the carrier

2.3 General Design Considerations

Feed Feed Feed

Figure 2.1: Common liquid-liquid extraction cascade configurations: (a) single-section

2.4 Representation of Multi-phase Liquid-Liquid Systems

2.5 Single Stage Liquid-Liquid Extraction

Figure 2.4: Single equilibrium stage liquid-liquid extraction.

(xA )F F + (xA )S S = (xA )M M = (xA )E E + (xA )R R

Feed (F) Solvent (S)

Figure 2.5: Ternary phase diagram for a general solute-carrier-solvent system.

By material balances (equations 2.5.1 and 2.5.2), the composition of M is,

M = F + S = 400 + 100 = 500 kg

Raffinate Product Extract Product

2.6 Lever-Arm Rule

(xA )F F + (xA )S S = (xA )M M .

F (xA )S − (xA )M (xC )S − (xC )M

So in our previous example we could have found the position of M by taking,

and measuring the line lengths.

(xC )S − (xC )F (xC )F (xA )S − (xC )S (xA )F

2.7 Hunter-Nash Graphical Equilibrium-Stage Method

Figure 2.6: Counter-current flow, N -equilibrium-stage liquid-liquid extraction cascade.

2.7.1 Step 1 - Calculation of the Mixing Point

2.7.2 Step 2 - Product Mass Balance

Raffinate Product Extract Product

Figure 2.7: Construction 1: Location of product points.