Table Of Contentcover1.fm Page III Thursday, March 10, 2005 1:47 PM
Integrated Chemical Processes
Synthesis, Operation, Analysis, and Control
Edited by
Kai Sundmacher,
Achim Kienle and
Andreas Seidel-Morgenstern
cover1.fm Page IV Monday, March 21, 2005 9:34 AM
Prof. Dr.-Ing. Kai Sundmacher All books published by Wiley-VCH are carefully
Prof. Dr.-Ing. Achim Kienle produced. Nevertheless, authors, editors, and
Prof. Dr. Andreas Seidel-Morgenstern publisher do not warrant the information contained
Max Planck Institute for Dynamics of Complex in these books, including this book, to be free of errors.
Technical Systems Readers are advised to keep in mind that statements,
Sandtorstr. 1 data, illustrations, procedural details or other items
39106 Magdeburg may inadvertently be inaccurate.
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA,
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All rights reserved (including those of translation into
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duced in any form – by photoprinting, microfilm, or
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ISBN-13: 987-3-527-30831-6
ISBN-10: 3-527-30831-8
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V
Contents
Preface XV
Part I Integration of Heat Transfer and Chemical Reactions 1
1 Enhancing Productivity and Thermal Efficiency of High-Temperature
Endothermic Processes in Heat-Integrated Fixed-Bed Reactors 3
Grigorios Kolios, Achim Gritsch,
Bernd Glöckler and Gerhart Eigenberger
Abstract 3
1.1 Introduction 3
1.2 Heat-Integrated Processes for Endothermic Reactions 4
1.2.1 Optimality Conditions 6
1.2.1.1 Efficiency of Heat Recovery 6
1.2.1.2 Temperature Control 8
1.3 Multifunctional Reactor Concepts 10
1.3.1 Regenerative Processes 12
1.3.1.1 Simultaneous Mode 13
1.3.1.2 Asymmetric Mode 13
1.3.1.3 Symmetric Mode with Side Stream Injection 20
1.3.1.4 Counter-cocurrent Mode 21
1.3.1.5 Overheating During Oxidative Coke Removal 24
1.3.2 Recuperative Processes 27
1.3.2.1 Processes for Large-Scale Applications 29
1.3.2.2 Processes for Small-scale Applications 31
1.4 Conclusions 39
Symbols and Abbreviations 39
References 41
2 Conceptual Design of Internal Reforming in High-Temperature Fuel Cells 45
Peter Heidebrecht and Kai Sundmacher
2.1 Introduction 45
2.2 Technical Background 46
2.3 Modeling 48
2.3.1 Model Derivation 48
2.3.1.1 Anode Channel 49
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2.3.1.2 Mixing Rules 52
2.3.1.3 Cathode Channel 53
2.3.1.4 Reaction Kinetics 54
2.3.1.5 Cell Power 55
2.3.2 Conversion Diagram 56
2.4 Applications 58
2.4.1 Comparison of Reforming Concepts 59
2.4.2 Anode Cascade 59
2.4.3 Anode Exhaust Gas Recycling 63
2.5 Summary and Conclusions 65
Symbols 66
References 67
3 Instabilities in High-Temperature Fuel Cells due to Combined Heat
and Charge Transport 69
Michael Mangold, M Krasnyk, Achim Kienle and Kai Sundmacher
3.1 Introduction 69
3.2 Modeling 70
3.2.1 Model Assumptions 70
3.2.2 Model Equations 70
3.2.3 Simplified Model 72
3.3 Potentiostatic Operation 74
3.3.1 Cell with Infinite Length 74
3.3.2 Cell with Finite Length 76
3.4 Galvanostatic Operation 78
3.5 Conclusions 81
Symbols 82
Appendix: Numerical Methods for the Bifurcation Analysis in
Section 3.0 83
References 84
Part II Integration of Separations and Chemical Reactions 85
4 Thermodynamic and Kinetic Effects on the Feasible Products of Reactive
Distillation: A-zeo-tropes and A-rheo-tropes 87
Kai Sundmacher, Zhiwen Qi, Yuan-Sheng Huang and Ernst-Ulrich Schlünder
4.1 Introduction 87
4.2 Azeotropes 89
4.2.1 Reactive Condenser and Reboiler 89
4.2.2 Conditions for Singular Points 90
4.2.2.1 Potential Singular Point Surface 90
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Contents VII
4.2.2.2 Reaction Kinetic Surface 91
4.2.3 Examples 92
4.2.3.1 Hypothetical Ternary Systems 92
4.2.3.2 Real Ternary System: MTBE-Synthesis 97
4.2.3.3 Real Ternary System with Phase Splitting: Methanol Dehydration 101
4.2.3.4 Real Quaternary System: Isopropyl Acetate Hydrolysis 103
4.2.4 Application of Feasibility Diagram: Column Feasible Split 106
4.2.5 Remarks on Azeotropes 110
4.3 Arheotropes 110
4.3.1 Definition and Conditions 110
4.3.2 Illustrative Examples 111
4.3.2.1 Example 1: Stagnant Sweep Gas 111
4.3.2.2 Example 2: Flowing Sweep Gas 114
4.3.2.3 Example 3: Flowing Sweep Gas with Pervaporation 117
4.3.2.4 Example 4: Reactive Liquid Mixture 119
4.3.3 Remarks on Arheotropes 126
4.4 Kinetic Arheotropes in Reactive Membrane Separation 127
4.4.1 Model Formulation 127
4.4.1.1 Reaction Kinetics and Mass Balances 127
4.4.1.2 Kinetics of Vapor Permeation 129
4.4.2 Residue Curve Maps 130
4.4.2.1 Example 1: Ideal Ternary System 130
4.4.2.2 Example 2: THF Formation 133
4.4.3 Singular Point Analysis 137
4.4.3.1 Approach 137
4.4.3.2 Ideal Ternary System 138
4.4.3.3 THF-System 142
4.4.4 Remarks on Kinetic Arheotropes 144
4.5 Summary and Conclusions 144
Symbols and Abbreviations 145
References 147
5 Equilibrium Theory and Nonlinear Waves for
Reaction Separation Processes 149
Achim Kienle and Stefan Grüner
5.1 Introduction 149
5.2 Theoretical Background 150
5.2.1 Wave Phenomena 150
5.2.2 Mathematical Model 153
5.2.3 Prediction of Wave Patterns 157
5.3 Analysis of Reaction Separation Processes 161
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5.3.1 Reactive Distillation 161
5.3.2 Chromatographic Reactors 163
5.3.2.1 Reactions of Type 164
5.3.2.2 Reactions of type 166
5.3.2.3 Binaphthol Separation Problem 168
5.3.3 Extension to Other Processes 171
5.4 Applications 172
5.4.1 New Modes of Operation 172
5.4.2 New Control Strategies 173
5.5 Conclusion 175
Acknowledgments 177
Symbols 178
References 179
6 Simulated Moving-Bed Reactors 183
Guido Ströhlein, Marco Mazzotti and Massimo Morbidelli
6.1 Introduction 183
6.2 Continuous Reactive Chromatography 185
6.2.1 Annular Reactive Chromatography 185
6.2.2 Simulated Moving-Bed Reactors 185
6.3 Design Parameters for Simulated Moving-bed Reactors 188
6.4 Modeling Simulated Moving-bed Reactors 195
6.5 Influence of the Stationary Phase Properties on SMBR Efficiency 197
6.6 Conclusion 200
References 200
7 The Dos and Don’ts of Adsorptive Reactors 203
David W. Agar
7.1 Introduction 203
7.1.1 Adsorptive Reactors 203
7.1.2 Multifunctional Reactors 204
7.1.3 Preliminary Evaluation 205
7.2 Reaction Systems 206
7.2.1 The Claus Process 207
7.2.2 Direct Hydrogen Cyanide Synthesis 208
7.2.3 Water-gas Shift Reaction 210
7.2.4 The Deacon Process 211
7.3 Catalyst and Adsorbent 212
7.3.1 The Claus Process 212
7.3.2 Direct Hydrogen Cyanide Synthesis and Water-gas Shift Reaction 214
7.3.3 The Deacon Process 217
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Contents IX
7.3.4 Other Adsorptive Catalysts 217
7.4 Reactor and Regeneration 218
7.4.1 Fixed-bed Reactors 218
7.4.2 Fluidized-bed Reactors 219
7.4.3 Pressure Swing Regeneration 220
7.4.4 Temperature Swing Regeneration 221
7.4.5 Reactive Regeneration 221
7.5 Design and Operation 222
7.5.1 Fixed-bed Macrostructuring 222
7.5.2 Pellet Microstructuring 223
7.5.3 Operating Parameter Profiling 224
7.5.4 Heat Effects 227
7.6 Conclusions and Perspectives 228
Acknowledgments 230
References 230
8 Reactive Stripping in Structured Catalytic Reactors: Hydrodynamics
and Reaction Performance 233
Tilman J.Schildhauer, FreekKapteijn, Achim K.Heibel,
Archis A.Yawalkar and Jacob A.Moulijn
8.1 Introduction 233
8.2 Hydrodynamics 236
8.2.1 Flow Patterns 236
8.2.1.1 Monoliths 236
8.2.1.2 Sulzer DX® 240
8.2.1.3 Sulzer katapak-S® 241
8.2.2 Hold-up, Pressure Drop, and Flooding Limits 242
8.2.3 Residence Time Distribution 244
8.2.4 Gas–Liquid Mass Transfer 247
8.2.5 Conclusions 248
8.3 Reactive Experiments 249
8.3.1 Model Reaction 250
8.3.1.1 Kinetics 250
8.3.1.2 Side Reactions 250
8.3.2 Experimental 251
8.3.2.1 Catalysts 251
8.3.2.2 Experimental Set-ups 251
8.3.3 Experimental Results 253
8.3.3.1 Effect of Water Removal 253
8.3.3.2 Co-current versus Countercurrent 254
8.3.3.3 Selectivity 255
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8.3.3.4 Acid Excess 257
8.3.4 Conclusions 258
8.4 Comparison of Different Internals 259
8.4.1 Film-flow Monoliths 259
8.4.2 Monoliths versus DX® and katapak-S® 260
8.4.2.1 Activity 260
8.4.2.2 Selectivity 261
8.5 Conclusions and Future Trends 262
Acknowledgments 263
Symbols 263
References 264
9 Reactive Absorption 265
Eugeny Y. Kenig and Andrzej Górak
9.1 Introduction 265
9.2 Reactive Absorption Equipment 267
9.3 Modeling Concept 270
9.3.1 General Aspects 270
9.3.2 Equilibrium Stage Model 270
9.3.3 HTU/NTU-concept and Enhancement Factors 271
9.3.4 Rate-based Stage Model 272
9.3.4.1 Balance Equations 273
9.3.4.2 Mass Transfer and Reaction Coupling in the Fluid Film 274
9.4 Model Parameters 276
9.4.1 Thermodynamic Equilibrium 276
9.4.2 Chemical Equilibrium 277
9.4.3 Physical Properties 278
9.4.4 Mass Transport and Fluid Dynamics Properties 280
9.4.5 Reaction Kinetics 280
9.5 Case Studies 282
9.5.1 Absorption of NOx 283
9.5.1.1 Chemical System 283
9.5.1.2 Process Set-up 284
9.5.1.3 Modeling Peculiarities 284
9.5.1.4 Model Parameters 285
9.5.1.5 Results 286
9.5.2 Coke Gas Purification 286
9.5.2.1 Chemical System 286
9.5.2.2 Process Set-up 289
9.5.2.3 Modeling Peculiarities 290
9.5.2.4 Model Parameters 290
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Contents XI
9.5.2.5 Results 291
9.5.2.6 Dynamic Issues 292
9.5.3 CO3 Absorption by Aqueous Amine Solutions 295
9.5.3.1 Chemical System 295
9.5.3.2 Process Set-up 296
9.5.3.3 Modeling Peculiarities 296
9.5.3.4 Model Parameters 297
9.5.3.5 Results 298
9.5.4 SO2 Absorption into Aqueous NaHCO3/Na2CO3 Solutions 299
9.5.4.1 Chemical System 299
9.5.4.2 Process Set-up 300
9.5.4.3 Modeling Peculiarities 301
9.5.4.4 Model Parameters 301
9.5.4.5 Results 302
9.6 Conclusions and Outlook 304
Acknowledgments 305
Symbols 305
References 307
10 Reactive Extraction: Principles and Apparatus Concepts 313
Hans-Jörg Bart
10.1 Introduction 313
10.1.1 Physical Extraction 313
10.1.2 Reactive Extraction 314
10.1.3 Additives 319
10.2 Phase Equilibria 321
10.3 Reactive Mass Transfer 323
10.4 Hydrodynamics 328
10.5 Conclusions 332
Acknowledgments 333
References 334
11 Development of Reactive Crystallization Processes 339
Christianto Wibowo, Vaibhav V. Kelkar,
Ketan D. Samant, Joseph W. Schroer and Ka M. Ng
11.1 Introduction 339
11.2 Workflow in Process Development 339
11.3 Process Synthesis 341
11.4 Reactive Phase Diagrams 344
11.4.1 Projections and Canonical Coordinates 344
11.4.2 High-Dimensional Phase Diagrams 346
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11.5 Kinetic Effects 351
11.5.1 Reactive Crystallization with a Solid Reactant 351
11.6 Asymmetric Transformation of Enantiomers 353
11.6.1 Base Case (BC) 353
11.6.2 Seeded Crystallization (SC) 354
11.6.3 Seeded Crystallization with Racemization (SR) 356
11.7 Conclusions 357
Acknowledgments 357
References 357
12 Analysis and Experimental Investigation of Catalytic
Membrane Reactors 359
Andreas Seidel-Morgenstern
12.1 Introduction 359
12.2 Basic Aspects of Chemical Reaction Engineering 359
12.2.1 Reaction Rates 360
12.2.2 Conversion as a Function of Rate Laws and
Feed Composition 361
12.2.3 Selectivity and Yield 364
12.3 Mass Transfer through Membranes 366
12.4 Kinetic Compatibility in Membrane Reactors 368
12.5 Example 1: Product Removal with Membranes
(“Extractor”) 369
12.5.1 Model Reaction, Procedures and Set-up 370
12.5.2 Reaction Rates 370
12.5.3 Fixed-bed Reactor Experiments 372
12.5.4 Mass Transfer through the Membrane 373
12.5.5 Membrane Reactor Experiments and Modeling 374
12.5.6 Evaluation of the Extractor-type of Membrane Reactor 376
12.6 Example 2: Reactant Dosing with Membranes
(“Distributor”) 378
12.6.1 Model Reaction, Set-ups and Procedures 380
12.6.1 Reaction Rates 381
12.6.2 Fixed-bed and Membrane Reactor Experiments 382
12.6.3 Theoretical Analysis 383
12.7 Summary and Conclusions 385
Acknowledgments 386
References 387
