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 All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for. British Library Cataloguing-in-Publication Data: A catalogue record for this book is available from the British Library Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at http://dnb.ddb.de © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be repro- duced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. 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Bangalore, India Printing betz-druck GmbH, Darmstadt Bookbinding Schäffer GmbH i.G., Grünstadt ISBN-13: 987-3-527-30831-6 ISBN-10: 3-527-30831-8 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 SundmacherTOC-2.fm Page V Wednesday, February 23, 2005 1:22 PM 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 SundmacherTOC-2.fm Page VIII Wednesday, February 23, 2005 1:22 PM 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 SundmacherTOC-2.fm Page IX Wednesday, February 23, 2005 1:22 PM 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 SundmacherTOC-2.fm Page X Wednesday, February 23, 2005 1:22 PM [...]... 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. .. 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. .. Stankiewicz and Moulin [4] A comprehensive volume covering all aspects of integrated chemical processes including heat exchange, separations and mechanical unit operations is still missing, 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 provide overviews on the present state of knowledge and on challenging... 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... 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... by Kapteijn and colleagues in Chapter 8 Another powerful concept is to combine absorption processes with chemical reactions, and a large number of possible concepts for this approach is presented in Chapter 9 by Kenig and Górak XIX PrefaceNew.fm Page XX Wednesday, February 23, 2005 1:21 PM Part III: Integration of Mechanical Unit Operations and Chemical Reactions In addition, extraction processes can... 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... high-temperature processes 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 Ch01.fm Page 4 Friday, February 25, 2005 7:01 PM 4 1 Enhancing Productivity and Thermal Efficiency of High-Temperature Endothermic Processes Two emerging trends endorse the concept of heat -integrated processes: first,... 1.3.1 Regenerative Processes Surprisingly, the majority of advanced heat -integrated reactor concepts employ a cyclic mode of operation with regenerative heat exchange They have been proposed mainly for syngas and olefin production Their potential field of application is in large chemical and petrochemical processes, where a compact reactor could replace a complex network of reactors and heat exchangers... 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 Authors Prof Dr David W Agar University of Dortmund Institute of Chemical Reaction Engineering Department of Biochemical and Chemical Engineering . 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. 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. 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,