integrated chemical processes synthesis operation analysis and control

Integrated Chemical Processes
Edited by
Kai Sundmacher,
Achim Kienle,
Andreas Seidel-Morgenstern
Integrated Chemical Processes. Edited by K. Sundmacher, A. Kienle and A. Seidel-Morgenstern
Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN 3-527-30831-8
cover1.fm Page I Thursday, March 10, 2005 1:47 PM
Further Titles of Interest
K. Sundmacher, A. Kienle (Eds.)
Reactive Distillation
Status and Future Directions
2003
ISBN 3-527-30579-3
J. G. Sanchez Marcano, T. T. Tsotsis
Catalytic Membranes and Membrane Reactors
2002
ISBN 3-527-30277-8
T. G. Dobre, J. G. Sanchez Marcano
Chemical Engineering
Modelling, Simulation and Similitude
2005
ISBN 3-527-30607-2
S. Pereira Nunes, K V. Peinemann (Eds.)
Membrane Technology
in the Chemical Industry
2001
ISBN 3-527-28458-0
Ullmann’s
Processes and Process Engineering

3 Volumes
2004
ISBN 3-527-31096-7
cover1.fm Page II 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 III Thursday, March 10, 2005 1:47 PM
Prof. Dr Ing. Kai Sundmacher
Prof. Dr Ing. Achim Kienle
Prof. Dr. Andreas Seidel-Morgenstern
Max Planck Institute for Dynamics of Complex
Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
and
Otto-von-Guericke-University
Magdeburg
Universitätsplatz 2
39016 Magdeburg
Germany
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cover1.fm Page IV Monday, March 21, 2005 9:34 AM
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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Contents VI
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
SundmacherTOC-2.fm Page VI Wednesday, February 23, 2005 1:22 PM
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
SundmacherTOC-2.fm Page VII Wednesday, February 23, 2005 1:22 PM
Contents VIII
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, Freek Kapteijn, Achim K. Heibel,
Archis A. Yawalkar and Jacob A. Moulijn
8.1 Introduction 233
8.2 Hydrodynamics 23 6
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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Contents X
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 CO
3
Absorption by Aqueous Amine Solutions 29 5
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 SO

2
Absorption into Aqueous NaHCO
3
/Na
2
CO
3
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 32 8
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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Contents XII
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
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Contents XIII
Part III Integration of Mechanical Operations and Chemical Reactions 391
13 Reactive Extrusion for Solvent-Free Processing: Facts and Fantasies 393
Leon P. B. M. Janssen
Abstract
393
13.1 Introduction 393
13.2 Advantages and Disadvantages 394

13.3 Main Reactions in Extruders 395
13.4 Extruder Types 396
13.5 Kinetic Considerations 398
13.6 Heat Transfer and Thermal Instabilities 401
13.7 Instabilities 402
13.8 Conclusions 405
References 406
14 Reactive Comminution 407
Ulrich Hoffmann, Christian Horst and Ulrich Kunz
14.1 Introduction 407
14.2 Mechanical Comminution of Solids 408
14.2.1 Reactivity of Mechanically Activated Solids 413
14.3 Equipment and Processes 415
14.3.1 Milling Designs 415
14.3.1.1 Crushers 415
14.3.1.2 Cutting Mills 415
14.3.1.3 Roller and Ring-roller Mills 415
14.3.1.4 Disk Attrition Mills 416
14.3.1.5 Grinding Media Mills 416
14.3.1.6 Impact Mills 419
14.3.1.7 Jet Mills 420
14.3.1.8 Pressure and Shear Devices 421
14.3.1.9 Special Milling and Activation Devices 421
14.3.1.10 Dry and Wet Grinding 422
14.3.1.11 Machine Wear 422
14.3.1.12 Energy Efficiency 422
14.3.1.13 Solid Guidance 423
14.4 Applications 423
14.4.1 Surface Area Creation 423
14.4.2 Mechanical Activation 424

14.4.2.1 Phase Transitions 424
14.4.2.2 Enhanced Solubility of Minerals 425
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Contents XIV
14.4.2.3 Surface Cleaning 425
14.4.3 Mechanical Alloying 425
14.4.4 Simultaneous Reaction and Comminution 426
14.4.4.1 Solid–Solid Reactions 426
14.4.4.2 Catalyst Preparation 427
14.4.4.3 Solid–Gas Reactions 428
14.4.4.4 Solid–Liquid Reactions 429
14.4.4.5 Depolymerization Reactions 430
14.5 Conclusions 431
References 431
15 Reactive Filtration 437
Thomas Rieckmann and Susanne Völker
15.1 Introduction 437
15.2 Separation of Particulates and Catalytic Reaction of Volatiles 438
15.2.1 Flue-gas Treatment 438
15.2.2 Biomass Gasification 440
15.3 Separation of Particulates and Reaction of Solids 441
15.3.1 Diesel Soot Abatement 441
15.3.1.1 Filter Types and Catalyst Performance 443
15.3.1.2 Formal Kinetics and Modeling 445
15.3.2 Filtration Combustion of Solid Fuels 447
15.3.3 Reaction Cyclone 448
15.4 Conclusions 449
References 450
16 Reaction-Assisted Granulation in Fluidized Beds 453
Matthias Ihlow, Jörg Drechsler, Markus Henneberg,

Mirko Peglow, Stefan Heinrich and Lothar Mörl
16.1 Introduction 453
16.1.1 Gas Cleaning 453
16.1.2 Application of the Gas-solid Fluidized Bed 455
16.1.3 Modeling and Experimental Set-up 456
16.2 Modeling 460
16.2.1 Model Assumptions 461
16.2.2 Phase and Reaction Equilibrium 462
16.2.3 Mass and Energy Flows 463
16.2.3.1 Gas Balance 463
16.2.3.2 Suspension Balance 467
16.2.3.3 Gas–Liquid Phase Boundary 471
16.2.3.4 Particle Balance 474
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Contents XV
16.2.3.5 Apparatus Wall Balance 477
16.2.3.6 Solution of the Equations 477
16.3 Experiments 479
16.3.1 Fluidized-bed Plant 479
16.3.2 Experiments of Absorption without Granulation of Solid
(Reactive Absorption)
481
16.3.2.1 Experimental Realization 481
16.3.2.2 Influence of the Liquid Injection Rate 481
16.3.2.3 Influence of Ca/S Ratio 488
16.3.2.4 Influence of the Gas Inlet Temperature 493
16.3.2.5 Influence of Gas Mass Flow 495
16.3.2.6 Influence of the Particle Diameter 497
16.3.3 Experiments for Reactive Absorption with Overlapped
Granulation of Solid

502
16.3.3.4 Experimental Realization 502
16.3.3.2 Batch Experiments 503
16.3.3.3 Continuous Experiments 510
16.3.4 Comparison between Measurement and Simulation 519
16.3.5 Simplified Stationary Balancing 519
16.4 Conclusions 523
Symbols and Abbreviations 526
References 529
Index 543
SundmacherTOC-2.fm Page XV Wednesday, February 23, 2005 1:22 PM
XVII
Preface
In the chemical industries, the pretreatment of educts, their chemical conversion
into valuable products, and the purification of resulting product mixtures in down-
stream processes are carried out traditionally in sequentially structured trains of unit
operations. In many cases, the performance of this classical chemical process struc-
ture can be significantly improved by an integrative coupling of different process
units.
The integration of unit operations to form multifunctional processes very often
gives rise to synergetic effects which can be technically exploited. By suitable process
design, an efficient and environmentally benign process operation can be achieved.
Possible advantages of process integration include:
• higher productivity;
• higher selectivity;
• reduced energy consumption;
• improved operational safety; and
• improved ecological harmlessness by avoidance of auxiliary agents and
chemical wastes.
Due to the interaction of several process steps in one apparatus, the steady-state

and the dynamic operating behavior of an integrated process unit is often much
more complex than the behavior of single, non-integrated units. Therefore, suitable
methods for the design and control must be developed and applied, ensuring opti-
mal and safe operation of the considered integrated process.
The major objectives of current research activities in this highly interesting
domain of chemical engineering are to develop new concepts for process integration,
to investigate their efficiency, and to make them available for technical application.
The importance of this field is reflected by the increasing number of articles in jour-
nals and book contributions that have been published during the past three decades
(Fig. 1).
Among these published articles and books, some excellent reviews have appeared
which focused on specific aspects of the process integration. Agar and Ruppel [1]
were among the first to investigate the whole area of integration of heat-exchanging
functions in chemical reactors, whilst Agar [2] later also surveyed other innovative
integration concepts in chemical reactor engineering. According to the present
editors’ knowledge, the first review which covered a broader range of integration
concepts including heat exchange, separation and also mechanical unit operations,
was published in 1997 by Hoffmann and Sundmacher [3]. The cited works refer to
integrated chemical processes as “multifunctional reactors”, which is often used as a
Integrated Chemical Processes. Edited by K. Sundmacher, A. Kienle and A. Seidel-Morgenstern
Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN 3-527-30831-8
PrefaceNew.fm Page XVII Wednesday, February 23, 2005 1:21 PM
Preface XVIII
synonym. Multifunctional reactors can be seen as a very important sub-class of the
area of “process intensification” which was summarized by Stankiewicz and
Moulin [4].
A comprehensive volume covering all aspects of integrated chemical processes
including heat exchange, separations and mechanical unit operations is still miss-
ing, however, and as a consequence the present book was prepared to fill this gap.

The book’s chapters have been authored by leading international experts, and pro-
vide overviews on the present state of knowledge and on challenging future issues.
The book is divided into three parts. Part I surveys concepts for heat-integrated
chemical reactors, with special focus on coupling reactions and heat transfer in fixed
beds and in fuel cells. Part II is dedicated to the conceptual design, control and analysis
of chemical processes with integrated separation steps, whilst Part III focuses on how
mechanical unit operations can be integrated into chemical reactors.
Part I:
Integration of Heat Transfer and Chemical Reactions
Chapters 1 to 3 discuss two recent and important applications of heat-integrated
chemical reactions. Chapter 1, by Kolios et al., is concerned with high-temperature
endothermic processes in heat integrated fixed-bed reactors. Emphasis is placed on
reforming processes, which are widely used for the production of basic chemicals
and fuels from fossil feed stocks. These processes require large amounts of heat at
temperatures up to 1000 °C. In conventional solutions, only about half of the heat
supplied at high temperatures is transferred into the endothermic reaction. Emerg-
ing applications such as decentralized hydrogen production for residential and
mobile power generation require considerable improvement in specific productivity
and thermal efficiency. Therefore, this topic is currently the subject of vivid research
activities in industry and academia alike. Chapter 1 also includes an introduction to
Fig. 1. Journal publications on integrated chemical
processes according to the Science Citation Index.
PrefaceNew.fm Page XVIII Wednesday, February 23, 2005 1:21 PM
Part II: Integration of Separation Processes and Chemical Reactions XIX
the fundamentals of heat-integrated processes, an overview on recent trends in pro-
cess and apparatus design, and an analysis of the state of the art, with special
emphasis on the steam reforming of methane.
The focus in Chapters 2 and 3 is on high-temperature fuel cells with internal reform-
ing. In particular, special attention is given to the Molten Carbonate Fuel Cell
(MCFC) which is increasingly used for decentralized power generation. In Chapter

2, Heidebrecht and Sundmacher use a simple model of an MCFC to discuss the pros
and cons of alternative reforming concepts in high-temperature fuel cells.
The temperature management in a fuel cell stack is a key issue in the operation of
high-temperature fuel cells. In Chapter 3, prepared by Mangold and colleagues, it is
shown that the temperature-dependence of the electrolyte’s electrical conductivity is
a potential source of instabilities, hot spots, and spatial temperature patterns.
Part II:
Integration of Separation Processes and
Chemical Reactions
Due to fact that chemical reactions typically do not deliver the desired product alone
and that separation processes are always required, a wide range of efforts have long
been undertaken to combine these two processes into a single apparatus. Although a
comprehensive overview was published recently [5], nine chapters of the present
book describe and discuss the possibilities of integrating separation processes and
chemical reactions.
In Chapter 4, Sundmacher et al. – in the first contribution – analyze in detail the
thermodynamic and kinetic effects relevant to an understanding of reactive distilla-
tion processes. Although a comprehensive volume on this type of process integration
was published in 2003 [6], Chapter 4 focuses on the a priori determination of prod-
ucts that can be obtained using such processes.
In exploiting the equilibrium theory, Kienle and Grüner present in Chapter 5 a
general analysis of the development and propagation of nonlinear waves in reaction
separation processes. Besides considering reactive distillation as one example, these
authors also analyze reactive chromatography.
In Chapter 6, Morbidelli et al. describe chromatographic separations combined with
chemical reactions, the focus of their contribution being to present possibilities of
performing such processes in a continuous manner.
An analysis of reactors where adsorbents are used as a regenerative source or sink for
one or several of the reactants is discussed systematically by Agar, in Chapter 7.
In cases where reactive distillation cannot be applied because some of the reac-

tants are temperature-sensitive, reactive stripping might be an efficient alternative,
and the current state of the application of this technology is reviewed by Kapteijn
and colleagues in Chapter 8.
Another powerful concept is to combine absorption processes with chemical reac-
tions, and a large number of possible concepts for this approach is presented in
Chapter 9 by Kenig and Górak.
PrefaceNew.fm Page XIX Wednesday, February 23, 2005 1:21 PM
Part III: Integration of Mechanical Unit Operations and Chemical Reactions XX
In addition, extraction processes can be performed with reacting species, and
several advantages of this technique may be realized compared to conventional
consecutive processes, as discussed by Bart in Chapter 10.
Based on a thorough analysis of reactive crystallization, Ng and colleagues,
in Chapter 11, demonstrate that such integrated processes can also be performed
efficiently with solid phases involved.
In the final chapter of Part II, Seidel-Morgenstern presents two examples of how
membrane reactors might become an alternative to conventional technology.
Part III:
Integration of Mechanical Unit Operations and
Chemical Reactions
The last four chapters of the book are dedicated to the successful combination of
chemical reactions and mechanical process operations. In Chapter 13, Janssen eluci-
dates that reactive extrusion has emerged from a scientific curiosity to an industrial
process. Nonlinear effects in this process can give rise to instabilities that are of
thermal, hydrodynamic, or chemical origin.
In Chapter 14, Hoffmann and colleagues provide a survey on the status and direc-
tions of reactive comminution. In this type of process integration, mechanical stress
exerted in mills is used to enhance the chemical reactions of solids with fluids.
Simultaneously, chemical reactions can generate cracks in solid particles and
thereby enhance their comminution.
Filtration and chemical reactions can be usefully integrated in order to separate

diesel soot particles efficiently from motor exhaust gases, and this is illustrated by
Rieckmann and Völker in Chapter 15, together with a series of other examples of
reactive filtration processes which are realized in the chemical industries.
In the final chapter, Mörl and coworkers analyze the complex interaction of
particle granulation and/or agglomeration with chemical reactions in fluidized beds.
For the description of the particle property distribution, a population balance
approach is recommended which is mathematically challenging but which provides
valuable insight into the steady-state and dynamic process operating behavior.
The Book’s History, and the Editors’ Acknowledgments
The present book is the outcome of the International Max Planck Symposium on
Integrated Chemical Processes held in Magdeburg, Germany, on 22–24 March,
2004. At this symposium, renowned scientists met to discuss the current state and
future trends in the field of integrated chemical processes. The conference was
organized by this book’s editors and their colleagues at the Max Planck Institute
for Dynamics of Complex Technical Systems, with financial support from the
Kompetenznetz Verfahrenstechnik Pro3 e.V. in Germany, which is gratefully
acknowledged.
The present editors wish to thank their colleagues Kristin Czyborra, Anett Raasch,
and Carolin Apelt for their excellent support in organizing the symposium, and in
PrefaceNew.fm Page XX Wednesday, February 23, 2005 1:21 PM
The Book’s History, and the Editors’ Acknowledgments XXI
collecting the manuscripts which form the basis of this book. Last – but not least –
we are thankful to Dr. Hubert Pelc and Rainer Münz from Wiley-VCH for their
helpful assistance during the book’s preparation.
Magdeburg, Germany Kai Sundmacher, Achim Kienle,
February 2005 Andreas Seidel-Morgenstern
References
1. D. W. Agar, W. Ruppel,
Multifunktionelle Reaktoren
für die heterogene Katalyse,

Chem. Ing. Tech.
1988, 60, 731–741.
2. D. W. Agar, Multifunctional Reactors:
Old Preconceptions and New
Dimensions, Chem. Eng. Sci.
1999, 54, 1299–1305.
3. U. Hoffmann, K. Sundmacher,
Multifunktionale Reaktoren,
Chem Ing Tech. 1997,
69, 613–622.
4. A. I. Stankiewicz, J. A. Moulin,
Process Intensification, Chem.
Eng. Progress, 2000, Jan., 22–34.
5. S. Kulprathipanja, (Ed.) Reactive
Separation Processes, Taylor & Francis,
New York, 2002.
6. K. Sundmacher, A. Kienle, (Eds.),
Reactive Distillation, Status and
Future Directions, Wiley-VCH,
Weinheim, 2003.
PrefaceNew.fm Page XXI Wednesday, February 23, 2005 1:21 PM
XXIII
List of Contributors
Editors
Prof. Dr Ing. Achim Kienle
Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany

and
Otto-von-Guericke-University Magdeburg
Chair for Automation/Modeling
Universitätsplatz 2
39016 Magdeburg
Germany
Prof. Dr Ing. Andreas Seidel-Morgenstern
Max Planck Institute for Dynamics of Complex
Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
and
Otto-von-Guericke-University Magdeburg
Chair of Chemical Process Engineering
Universitätsplatz 2
39016 Magdeburg
Germany
Prof. Dr Ing. Kai Sundmacher
Max Planck Institute for Dynamics of Complex
Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
and
Otto-von-Guericke-University Magdeburg
Process Systems Engineering
Universitätsplatz 2
39106 Magdeburg
Germany

Authors
Prof. Dr. David W. Agar
University of Dortmund
Institute of Chemical Reaction Engineering
Department of Biochemical and
Chemical Engineering
Emil-Figge-Str. 70
44227 Dortmund
Germany
Prof. Dr. Hans-Jörg Bart
Technische Universität Kaiserslautern
Lehrstuhl für Thermische
Verfahrenstechnik
Gottlieb-Daimler-Str.
67663 Kaiserslautern
Germany
Jörg Drechsler
AVA – Anhaltinische Verfahrens- und
Anlagentechnik Ingenieurgesellschaft
Henneberg & Partner
Steinfeldstr. 5
39176 Barleben
Germany
Prof. Dr Ing. Gerhart Eigenberger
University of Stuttgart
Institute for Chemical Process Engineering
Böblinger Str. 72
70199 Stuttgart
Germany
PrefaceNew.fm Page XXIII Wednesday, February 23, 2005 1:21 PM

List of Contributors XXIV
Bernd Glöckler
University of Stuttgart
Institute for Chemical Process Engineering
Böblinger Str. 72
70199 Stuttgart
Germany
Prof. Dr. Andrzej Górak
University of Dortmund
Department of Biochemical and
Chemical Engineering
Emil-Figge-Str. 70
44227 Dortmund
Germany
Achim Gritsch
University of Stuttgart
Institute for Chemical Process Engineering
Böblinger Str. 72
70199 Stuttgart
Germany
Stefan Grüner
University of Stuttgart
Institute for System Dynamics and
Control Engineering
Pfaffenwaldring 9
70569 Stuttgart
Germany
Achim K. Heibel
Delft University of Technology
Reactor and Catalysis Engineering

Julianalaan 136
2628 BL Delft
The Netherlands
Dr Ing. Peter Heidebrecht
Otto-von-Guericke-University Magdeburg
Process Systems Engineering
Universitätsplatz 2
39106 Magdeburg
Germany
Jun Prof. Dr Ing. Stefan Heinrich
Otto-von-Guericke-University Magdeburg
Institute of Process Equipment and
Environmental Technology
Universitätsplatz 2
39106 Magdeburg
Germany
Dr Ing. Markus Henneberg
AVA – Anhaltinische Verfahrens- und Anlagentechnik
Ingenieurgesellschaft Henneberg & Partner
Steinfeldstr. 5
39176 Barleben
Germany
Prof. Dr. Ulrich Hoffmann
Technische Universität Clausthal
Institut für Chemische
Verfahrenstechnik
Leibnizstr. 17
38678 Clausthal-Zellerfeld
Germany
Dr. Christian Horst

Technische Universität Clausthal
Institut für Chemische Verfahrenstechnik
Leibnizstr. 17
38678 Clausthal-Zellerfeld
Germany
Yuan-Sheng Huang
Max Planck Institute for Dynamics of Complex
Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
Dr Ing. Matthias Ihlow
AVA – Anhaltinische Verfahrens- und
Anlagentechnik
Ingenieurgesellschaft Henneberg & Partner
Steinfeldstr. 5
39176 Barleben
Germany
Prof. Dr. Leon P.B.M. Janssen
University of Groningen
Department of Chemical Engineering
Nijenborgh 4
9747 AG Groningen
The Netherlands
Prof. Dr. Freek Kapteijn
Delft University of Technology
Reactor and Catalysis Engineering
Julianalaan 136
2628 BL Delft
The Netherlands

Vaibhav V. Kelkar
ClearWaterBay Technologies Inc.
20311 Valley Blvd., Suite C
Walnut, CA 91789
USA
Dr. Eugeny Y. Kenig
University of Dortmund
Department of Biochemical and
Chemical Engineering
Emil-Figge-Str. 70
44227 Dortmund
Germany
PrefaceNew.fm Page XXIV Wednesday, February 23, 2005 1:21 PM
List of Contributors XXV
Prof. Dr Ing. Achim Kienle
Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
and
Otto-von-Guericke-University Magdeburg
Chair for Automation/Modeling
Universitätsplatz 2
39016 Magdeburg
Germany
Dr Ing. Grigorios Kolios
Christ Pharma & Life Science AG
Hauptstr. 192
4147 Aesch

Switzerland
Mykhaylo Krasnyk
Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
Prof. Dr. Ulrich Kunz
Technische Universität Clausthal
Institut für Chemische Verfahrenstechnik
Leibnizstr. 17
38678 Clausthal-Zellerfeld
Germany
Dr Ing. Michael Mangold
Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
Prof. Dr. Marco Mazzotti
Swiss Federal Institute of Technology Zürich
Institut für Verfahrenstechnik
Sonneggstr. 3
8092 Zürich
Switzerland
Prof. Dr. Massimo Morbidelli
Swiss Federal Institute of Technology Zürich
Institut für Chemie- und
Bioingenieurwissenschaften
ETH-Hönggerberg, HCI-F

8093 Zürich
Switzerland
Prof. Dr Ing. habil. Dr. h. c. Lothar Mörl
Otto-von-Guericke-University Magdeburg
Faculty of Process and Systems Engineering
Institute of Process Equipment and Environmental
Technology
Universitätsplatz 2
39106 Magdeburg
Germany
Prof. Dr. Jacob A. Moulijn
Delft University of Technology
Reactor and Catalysis Engineering
Julianalaan 136
2628 BL Delft
The Netherlands
Prof. Dr. Ka M. Ng
Hong Kong University of Science and Technology
Department of Chemical Engineering
Clear Water Bay
Kowloon, Hong Kong
China
Mirko Peglow
Fraunhofer Institute for Factory Operation and
Automation IFF Magdeburg
Product Design and Modelling Group
Sandtorstr. 22
39106 Magdeburg
Germany
Dr. Zhiwen Qi

Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
Prof. Dr Ing. Thomas Rieckmann
University of Applied Sciences Cologne
Institute of Chemical Engineering and
Plant Design
Betzdorfer Str. 2
50679 Köln
Germany
Dr. Ketan D. Samant
ClearWaterBay Technology Inc.
20311 Valley Blvd., Suite C
Walnut, CA 91789
USA
Dr. Tilman J. Schildhauer
Delft University of Technology
Reactor and Catalysis Engineering
Julianalaan 136
2628 BL Delft
The Netherlands
PrefaceNew.fm Page XXV Wednesday, February 23, 2005 1:21 PM
List of Contributors XXVI
Prof. Dr Ing. Dr. h. c. mult. Ernst-Ulrich
Schlünder (emeritus)
University of Karlsruhe
Institute of Thermal Process Engineering
Kaiserstr. 12

76128 Karlsruhe
Germany
Dr. Joseph W. Schroer
ClearWaterBay Technology Inc.
20311 Valley Blvd., Suite C
Walnut, CA 91789
USA
Prof. Dr Ing. Andreas Seidel-Morgenstern
Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1
39106 Magdeburg
Germany
and
Otto-von-Guericke-University Magdeburg
Chair of Chemical Process Engineering
Universitätsplatz 2
39016 Magdeburg
Germany
Guido Ströhlein
Swiss Federal Institute of Technology Zürich
Institut für Chemie- und
Bioingenieurwissenschaften
ETH-Hönggerberg, HCI-F
8093 Zürich
Switzerland
Prof. Dr Ing. Kai Sundmacher
Max Planck Institute for Dynamics of
Complex Technical Systems
Sandtorstr. 1

39106 Magdeburg
Germany
and
Otto-von-Guericke-University Magdeburg
Process Systems Engineering
Universitätsplatz 2
39106 Magdeburg
Germany
Dr Ing. Susanne Völker
42 Engineering – Chemical Engineering
Consulting Services
von-Behring-Str. 9
34260 Kaufungen
Germany
Dr. Christianto Wibowo
ClearWaterBay Technology Inc.
20311 Valley Blvd., Suite C
Walnut, CA 91789
USA
Dr. Archis A. Yawalkar
Delft University of Technology
Reactor and Catalysis Engineering
Julianalaan 136
2628 BL Delft
The Netherlands
PrefaceNew.fm Page XXVI Wednesday, February 23, 2005 1:21 PM
Part I
Integration of Heat Transfer and Chemical Reactions
Ch01.fm Page 1 Friday, February 25, 2005 7:01 PM
Integrated Chemical Processes. Edited by K. Sundmacher, A. Kienle and A. Seidel-Morgenstern

Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN 3-527-30831-8