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DANIEL BENEKE, PhD, is a Process Engineering Consultant for the Centre of Material and Process Synthesis at the University of the Witwatersrand, where he works on process design for liquid fuel processes and separations research.
MARK PETERS, PhD, is a Separations Consultant and Research Engineer for the Centre of Material and Process Synthesis at the University of the Witwatersrand. He is actively involved in separations research as well as innovative waste-to-energy processes.
DAVID GLASSER, PhD, is Professor of Chemical Engineering and Director of the Centre of Material and Process Synthesis at the University of the Witwatersrand.
DIANE HILDEBRANDT, PhD, is the SARChI Professor of Sustainable Process Engineering and a Co-Director of the Centre of Material and Process Synthesis at the University of the Witwatersrand.
NOMENCLATURE AND ABBREVIATIONS xix
ABOUT THE AUTHORS xxiii
1 INTRODUCTION 1
1.1 Context and Significance 1
1.2 Important Distillation Concepts 4
1.2.1 ATypical Column 5
1.2.2 Complex Columns 6
1.2.3 Vapor–Liquid Equilibrium 7
1.3 Summary 12
References 12
2 FUNDAMENTALS OF RESIDUE CURVE MAPS 15
2.1 Introduction 15
2.2 Batch Boiling 16
2.3 The Mass Balance Triangle (MBT) 17
2.4 The Residue Curve Equation 19
2.4.1 Derivation 19
2.4.2 Approximation to Equilibrium 20
2.5 Residue Curve Maps 21
2.5.1 Constant Relative Volatility Systems 21
2.5.2 Nonideal Systems 24
2.5.3 Numerical Integration 24
2.6 Properties of Residue Curve Maps 25
2.6.1 Separation Vector Field 25
2.6.2 Stationary Points 26
2.6.3 Isotherms 29
2.6.4 Other Properties of RCMs 30
2.7 Applicability of RCMs to Continuous Processes 30
2.7.1 Total Reflux Columns 30
2.7.2 Infinite Reflux Columns 33
2.7.3 Bow-Tie Regions 35
2.7.4 Column Sequencing at Infinite Reflux 38
2.8 Limitations of RCMs 39
2.8.1 Applications 39
2.9 Residue Curve Maps: The Bigger Picture 40
2.9.1 Extending the Axes 40
2.9.2 Discontinuity 43
2.9.3 Thermodynamic Models in Negative Space 43
2.9.4 Use of Negative Compositions 44
2.10 Summary 46
References 47
3 DERIVATION AND PROPERTIES OF COLUMN PROFILE MAPS 48
3.1 Introduction 48
3.2 The Column Section (CS) 49
3.3 The Difference Point Equation (DPE) 51
3.3.1 The Generalized CS 51
3.3.2 Constant Molar Overflow 52
3.3.3 Material Balances 52
3.4 Column Profile Maps 54
3.4.1 Constant Relative Volatility Systems 55
3.4.2 Nonideal Systems 59
3.5 The Effect of CPM Parameters 61
3.5.1 The Net Flow (D) 61
3.5.2 The Difference Point (XD) 62
3.5.3 The Reflux Ratio (RD) 66
3.6 Properties of Column Profile Maps 67
3.6.1 The Relationship Between RCMs and CPMs 67
3.6.2 Vector Fields 68
3.6.3 Pinch Points 69
3.6.4 Isotherms 71
3.6.5 Transformed Triangles 72
3.7 Pinch Point Loci 75
3.7.1 Analytical Solutions 75
3.7.2 Graphical Approach 79
3.8 Some Mathematical Aspects of CPMs 80
3.8.1 Eigenvalues and Eigenvectors 80
3.8.2 Nature of Pinch Points 83
3.9 Some Insights and Applications of CPMs 84
3.9.1 Column Stability 85
3.9.2 Node Placement 87
3.9.3 Sharp Splits 88
3.10 Summary 89
References 89
4 EXPERIMENTAL MEASUREMENT OF COLUMN PROFILES 91
4.1 Introduction 91
4.2 The Rectifying Column Section 92
4.2.1 The Batch Analogy 92
4.2.2 Experimental Setup and Procedure 94
4.2.3 Experimental Results 96
4.3 The Stripping Column Section 98
4.4 Validation of Thermodynamic Models 103
4.5 Continuous Column Sections 105
4.5.1 Apparatus 106
4.5.2 Experimental Results 112
4.5.3 Temperature Inversion 113
4.6 Summary 114
References 115
5 DESIGN OF SIMPLE COLUMNS USING COLUMN PROFILE MAPS 116
5.1 Introduction 116
5.2 Absorbers and Strippers 117
5.2.1 Absorption Towers 118
5.2.2 Stripping Towers 124
5.2.3 Discussion 128
5.3 Simple Column Design 128
5.3.1 External Mass Balance 128
5.3.2 Internal Mass Balance: Column Section Interaction 130
5.3.3 Finite Reflux Design 132
5.3.4 Design Offshoots 137
5.4 Azeotropic Systems 141
5.5 Constant Relative Volatility Systems 145
5.5.1 Minimum Reflux Design Using TTs 145
5.5.2 Design Using Eigenvectors 153
5.6 Summary 154
References 155
6 DESIGN OF COMPLEX COLUMNS USING COLUMN PROFILE MAPS 157
6.1 Introduction 157
6.2 Distributed Feed Addition 158
6.2.1 Column Section Breakdown 158
6.2.2 The Effect on the Reflux Ratio (RD) 159
6.2.3 The Effect on the Difference Point (XD) 160
6.2.4 Feasible Designs 162
6.2.5 Potential Benefits and Limitations 166
6.2.6 Discussion 173
6.3 Sidestream Withdrawal 175
6.3.1 Refluxes and Difference Points 176
6.3.2 Preliminary Design Considerations 177
6.3.3 Design Procedure 180
6.4 Thermally Coupled Columns: Side Rectifiers and Strippers 184
6.4.1 Column Section Breakdown 185
6.4.2 Degrees of Freedom 186
6.4.3 Difference Points 186
6.4.4 Refluxes and Net Flow 187
6.4.5 General Design Procedure 190
6.4.6 Design with Transformed Triangles 193
6.5 Summary 205
References 205
7 DESIGN OF FULLY THERMALLY COUPLED COMPLEX COLUMNS USING COLUMN PROFILE MAPS 206
7.1 Introduction 206
7.2 A Simplified Infinite Reflux Case 208
7.2.1 All CSs at Infinite Reflux 208
7.2.2 Overall Infinite Reflux 213
7.3 General Petlyuk Design 216
7.3.1 Degree of Freedom Analysis and Variable Selection 217
7.3.2 Net Flow Patterns 218
7.3.3 Difference Point Behavior and Placement 223
7.3.4 Reflux Ratios 228
7.3.5 Properties of Variables in F-Space 230
7.3.6 Feasibility Conditions 234
7.3.7 Putting it all Together 236
7.4 Sharp Split Petlyuk Design Using TTs 240
7.4.1 Feasibility Criteria Using TTs 240
7.4.2 Design Implications 245
7.5 Insights into Kaibel Column Design 250
7.5.1 Structure and CS Breakdown 252
7.5.2 Similarities to the Petlyuk 252
7.5.3 Net Flow Patterns 253
7.5.4 Sharp Split Constraints 256
7.6 Summary 258
References 259
8 REACTIVE DISTILLATION DESIGN USING COLUMN PROFILE MAPS 261
8.1 Introduction 261
8.2 Simple Reactive Distillation 262
8.2.1 Extending the Residue Curve Map 262
8.2.2 Characteristics of the Reaction Vector Field 265
8.2.3 Overall Reactive Distillation Vector Field 266
8.2.4 Simple Reactive Distillation Design 269
8.2.5 Zero-Order Reactions—An Interesting Analogy 273
8.3 Reactive Column Sections 275
8.3.1 Definition 275
8.3.2 The Reactive Difference Point Equation 276
8.3.3 RCS Transition 281
8.3.4 Conserved Moles and Low Reaction Heat—A Simplified Case 284
8.3.5 Column Design 285
8.3.6 Column Stability 292
8.4 Summary 293
References 294
9 APPLICATION OF COLUMN PROFILE MAPS TO ALTERNATIVE SEPARATION PROCESSES: MEMBRANE PERMEATION 296
9.1 Introduction 296
9.2 Membrane Permeation 297
9.3 Generalized Membrane Column Sections 299
9.4 Theory 299
9.4.1 Membrane Column Sections 299
9.4.2 The Difference Point Equation for an MCS 300
9.4.3 Permeation Modeling 301
9.4.4 Properties of the MDPE 303
9.5 MCS Profiles: Total Reflux 304
9.5.1 Operating Conditions 304
9.5.2 Mathematics 304
9.5.3 Membrane Residue Curve Map 304
9.6 Column Section Profiles: Finite Reflux 306
9.6.1 Operating Conditions 306
9.6.2 Mathematics 307
9.6.3 Membrane Column Profile 308
9.6.4 Pinch Point Loci 308
9.6.5 Analysis of Column Profile 309
9.6.6 Pinch Points 311
9.6.7 Further Column Profiles 312
9.6.8 Variations in XD and rD 312
9.7 Conclusions 314
9.8 Example: Design of Hybrid Systems Using Distillation-Membrane Processes 315
9.8.1 Introduction 315
9.8.2 The Methanol/Butene/MTBE System 316
9.8.3 Design of a Hybrid Configuration 318
9.8.4 Conclusion 325
References 326
10 CONCLUDING REMARKS 328
10.1 Overall Conclusions 328
10.2 Limitations 329
10.3 Extensions and the Way Forward 330
References 330
APPENDIX A: DODS SOFTWARE PACKAGE 331
APPENDIX B: NRTL PARAMETERS AND ANTOINE COEFFICIENTS 345
INDEX 349
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