Reactive Separation Processes

268 Pages·2002·2.613 MB·\268

by  Kulprathipanja (Author)

REACTIVE
SEPARATION
PROCESSES

REACTIVE
SEPARATION
PROCESSES
Edited by
Santi Kulprathipanja
UOP LLC, Research Center, Des Plaines, Illinois
CRC Press
Taylor & Francis Group
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CONTENTS
Preface xi
Acknowledgments xiii
Contributors xv
1 Reactive Separation Processes 1
William A. Leet and Santi Kulprathipanja
1.1 Introduction 1
1.2 Advantages and Disadvantages 6
1.2.1 Advantages 7
1.2.2 Disadvantages 10
1.3 Applications Topics 12
1.4 Conclusions 16
References 16
2 Reactive Distillation 18
Gavin P. Towler and Stanley J. Frey
2.1 Introduction 18
2.2 Industrial Applications 20
2.2.1 Esterification 20
2.2.2 Etherification 22
2.3 Theory 25
2.3.1 Equilibrium Behavior 25
2.3.2 Kinetically Limited Behavior 28
2.4 Modeling and Design 33
2.4.1 Equilibrium Modeling 33
2.4.2 Rate-Limited Modeling 35
2.5 Practical Design Considerations 36
2.5.1 Installation, Containment, and Removal of the
Catalyst 37
v
vi Contents
2.5.2 Design for Good Reactive Phase Contact with the
Catalyst 38
2.5.3 Design for Liquid–Vapor Contacting Through
the Reactive Zone 39
2.5.4 Design for Proper Pressure Drop Through the
Reactive Zone 39
2.5.5 Design for Proper Liquid Hold-Up 40
2.5.6 Design for Catalyst Deactivation 40
2.6 Commercially Proven Equipment Technology 41
2.6.1 Chemical Research & Licensing (CR&L) Catalyst
Bales 41
2.6.2 Koch-Glitsch, Inc. Catalyst-Containing Structured
Packing 42
2.6.3 Eastman Chemical High Liquid Hold-up Trays 45
2.6.4 Other Leading Reactive Distillation Equipment
Concepts 45
2.7 Conclusions 47
Symbols 48
References 48
3 Extraction with Reaction 51
Vincent Van Brunt and Jeffrey S. Kanel
3.1 Introduction 51
3.2 Hydrometallurgical Separations 52
3.3 Homogeneous Reactions: Organic Separations 57
3.3.1 Introduction 57
3.3.2 Hydrolysis 58
3.3.3 Saponification 62
3.3.4 Esterification 64
3.3.5 Transesterification 66
3.3.6 Polycarbonates 67
3.3.7 Nitration 68
3.3.8 UOP HF Alkylation Technology 70
3.3.9 UOP HF Detergent Alkylate Process 72
3.3.10 Oxidation 74
3.3.11 Oximation 75
3.3.12 Shell Higher Olefin Process (SHOP) 77
3.3.13 Hydroformylation 78
3.3.14 Modifiers, Phase Transfer Catalysts, and Surfactants 80
3.3.15 Dense Gas and Ionic Fluid Applications 86
3.4 Conclusions 87
References 87
Contents vii
4 Absorption with Reaction 93
Jerry H. Meldon
4.1 Introduction 93
4.2 Local Mass Transfer Models 94
4.3 Mass Transfer with Chemical Reaction 97
4.3.1 Irreversible Reaction 97
4.3.2 Reversible Reaction 103
4.3.3 Perturbation Methods 104
4.4 Simultaneous Absorption of Carbon Dioxide and
Hydrogen Sulfide in Alkaline Solutions 107
4.5 Conclusions 111
Symbols 111
References 112
5 Adsorption with Reaction 115
Robert W. Carr and Hemant W. Dandekar
5.1 Introduction 115
5.1.1 Applicability 116
5.1.2 Attributes 116
5.2 Reactor Types 117
5.2.1 Rotating Cylindrical Annulus Chromatographic
Reactors 118
5.2.2 Countercurrent Moving-Bed Chromatographic
Reactors 120
5.2.3 Simulated Countercurrent Moving-Bed
Chromatographic Reactors 121
5.2.4 Pressure-Swing Adsorption Reactors 128
5.2.5 The Trickle-Bed Reactor 130
5.3 Issues in Adsorbent/Catalyst and Reactor Design 131
5.3.1 Adsorption Issues 131
5.3.2 Reaction Issues 132
5.3.3 Particle Design 132
5.4 Applications 133
5.4.1 Equilibrium-Limited Reactions 133
5.4.2 Selectivity-Limited Reactions 144
5.5 Process Evaluation 150
5.5.1 Impact on Process Flowsheet 150
5.5.2 Economic Impact 151
5.6 Conclusions 152
Symbols 152
References 153
viii Contents
6 Reactive Membrane Separation 155
Jose´ G. Sanchez Marcano and Theodore T. Tsotsis
6.1 Introduction 155
6.2 Catalytic Reactive Separation Processes 161
6.2.1 Dehydrogenation Reactions 161
6.2.2 Hydrogenation Reactions 164
6.2.3 Oxidation Reactions 165
6.2.4 Other High-Temperature Applications 172
6.2.5 Economic Considerations 176
6.2.6 Emerging Applications 178
6.3 Pervaporation Membrane Reactors 181
6.4 Membrane-Based Reactive Separations for Biological
Processes 183
6.5 Environmental Applications of Membrane Bioreactors 189
6.6 Modeling of Membrane-Based Reactive Separation
Processes 191
6.7 Conclusions 195
Symbols 196
References 196
7 Reactive Crystallization 209
Vaibhav V. Kelkar, Ketan D. Samant, and Ka M. Ng
7.1 Introduction 209
7.2 Solid–Liquid Phase Diagrams with Reactions 210
7.2.1 Generation of Phase Diagrams 210
7.2.2 Example Phase Diagrams 211
7.2.3 Representation of High-Dimensional Phase
Diagrams 212
7.2.4 Process Synthesis Based on Phase Diagrams 216
7.3 Crystallization Kinetics 218
7.3.1 Kinetics of Nucleation 219
7.3.2 Kinetics of Crystal Growth 221
7.4 The Population Balance 224
7.5 Generic Model for a Reactive Crystallizer 226
7.6 Mixing in Reactive Crystallizers 229
7.6.1 Experimental Studies 231
7.6.2 Modeling of Turbulent Mixing in Reactive
Crystallizers 234
7.6.3 Operating Regimes 237
7.6.4 Effect of Operating Conditions on Crystal
Attributes 239
Contents ix
7.6.5 Choice of Operating Regimes 241
7.7 Conclusions 242
Symbols 242
References 245
Index 249