Fundamentals of Chemical Reactor Engineering
A Multi-Scale Approach
1. Edition October 2021
352 Pages, Hardcover
Wiley & Sons Ltd
FUNDAMENTALS OF CHEMICAL REACTOR ENGINEERING
A comprehensive introduction to chemical reactor engineering from an industrial perspective
In Fundamentals of Chemical Reactor Engineering: A Multi-Scale Approach, a distinguished team of academics delivers a thorough introduction to foundational concepts in chemical reactor engineering. It offers readers the tools they need to develop a firm grasp of the kinetics and thermodynamics of reactions, hydrodynamics, transport processes, and heat and mass transfer resistances in a chemical reactor.
This textbook describes the interaction of reacting molecules on the molecular scale and uses real-world examples to illustrate the principles of chemical reactor analysis and heterogeneous catalysis at every scale. It includes a strong focus on new approaches to process intensification, the modeling of multifunctional reactors, structured reactor types, and the importance of hydrodynamics and transport processes in a chemical reactor.
With end-of-chapter problem sets and multiple open-ended case studies to promote critical thinking, this book also offers supplementary online materials and an included instructor's manual. Readers will also find:
* A thorough introduction to the rate concept and species conservation equations in reactors, including chemical and flow reactors and the stoichiometric relations between reacting species
* A comprehensive exploration of reversible reactions and chemical equilibrium, including the thermodynamics of chemical reactions and different forms of the equilibrium constant
* Practical discussions of chemical kinetics and analysis of batch reactors, including batch reactor data analysis
* In-depth examinations of ideal flow reactors, CSTR, and plug flow reactor models
Ideal for undergraduate and graduate chemical engineering students studying chemical reactor engineering, chemical engineering kinetics, heterogeneous catalysis, and reactor design, Fundamentals of Chemical Reactor Engineering is also an indispensable resource for professionals and students in food, environmental, and materials engineering.
Foreword by Marc-Olivier Coppens xv
Foreword by Umit S. Ozkan xvii
About the Authors and Acknowledgments xix
List of Symbols xxi
About the Companion Website xxvii
1 Rate Concept and Species Conservation Equations in Reactors 1
1.1 Reaction Rates of Species in Chemical Conversions 1
1.2 Rate of a Chemical Change 3
1.3 Chemical Reactors and Conservation of Species 6
1.4 Flow Reactors and the Reaction Rate Relations 8
1.5 Comparison of Perfectly Mixed Flow and Batch Reactors 9
1.6 Ideal Tubular Flow Reactor 10
1.7 Stoichiometric Relations Between Reacting Species 13
1.7.1 Batch Reactor Analysis 13
1.7.2 Steady-Flow Analysis for a CSTR 13
1.7.3 Unsteady Perfectly Mixed-Flow Reactor Analysis 14
Problems and Questions 15
References 18
2 Reversible Reactions and Chemical Equilibrium 19
2.1 Equilibrium and Reaction Rate Relations 19
2.2 Thermodynamics of Chemical Reactions 21
2.3 Different Forms of Equilibrium Constant 23
2.4 Temperature Dependence of Equilibrium Constant and Equilibrium Calculations 25
Problems and Questions 33
References 34
3 Chemical Kinetics and Analysis of Batch Reactors 35
3.1 Kinetics and Mechanisms of Homogeneous Reactions 35
3.2 Batch Reactor Data Analysis 39
3.2.1 Integral Method of Analysis 41
3.2.1.1 First-Order Reaction 41
3.2.1.2 nth-Order Reaction and Method of Half-Lives 43
3.2.1.3 Overall Second-Order Reaction Between Reactants A and B 44
3.2.1.4 Second-Order Autocatalytic Reactions 48
3.2.1.5 Zeroth-Order Dependence of Reaction Rate on Concentrations 50
3.2.1.6 Data Analysis for a Reversible Reaction 51
3.2.2 Differential Method of Data Analysis 52
3.3 Changes in Total Pressure or Volume in Gas-Phase Reactions 54
Problems and Questions 56
References 61
4 Ideal-Flow Reactors: CSTR and Plug-Flow Reactor Models 63
4.1 CSTR Model 63
4.1.1 CSTR Data Analysis 67
4.2 Analysis of Ideal Plug-Flow Reactor 69
4.3 Comparison of Performances of CSTR and Ideal Plug-Flow Reactors 71
4.4 Equilibrium and Rate Limitations in Ideal-Flow Reactors 72
4.5 Unsteady Operation of Reactors 76
4.5.1 Unsteady Operation of a Constant Volume Stirred-Tank Reactor 76
4.5.2 Semi-batch Reactors 77
4.6 Analysis of a CSTR with a Complex Rate Expression 79
Problems and Questions 81
References 85
5 Multiple Reactor Systems 87
5.1 Multiple CSTRs Operating in Series 87
5.1.1 Graphical Method for Multiple CSTRs 91
5.2 Multiple Plug-Flow Reactors Operating in Series 93
5.3 CSTR and Plug-Flow Reactor Combinations 94
Problems and Questions 96
References 98
6 Multiple Reaction Systems 99
6.1 Selectivity and Yield Definitions 100
6.2 Selectivity Relations for Ideal Flow Reactors 101
6.3 Design of Ideal Reactors and Product Distributions for Multiple Reaction Systems 104
6.3.1 Parallel Reactions 104
6.3.2 Consecutive Reactions 110
Problems and Questions 113
References 116
7 Heat Effects and Non-isothermal Reactor Design 117
7.1 Heat Effects in a Stirred-Tank Reactor 118
7.2 Steady-State Multiplicity in a CSTR 121
7.3 One-Dimensional Energy Balance for a Tubular Reactor 126
7.4 Heat Effects in Multiple Reaction Systems 131
7.4.1 Heat Effects in a CSTR with Parallel Reactions 131
7.4.2 Heat Effects in a CSTR with Consecutive Reactions 132
7.4.3 Energy Balance for a Plug-Flow Reactor with Multiple Reactions 133
7.5 Heat Effects in Multiple Reactors and Reversible Reactions 133
7.5.1 Temperature Selection and Multiple Reactor Combinations 133
7.5.1.1 Endothermic-Reversible Reactions in a Multi-stage Reactor System 141
7.5.2 Cold Injection Between Reactors 147
7.5.3 Heat-Exchanger Reactors 149
Problems and Questions 150
Case Studies 154
References 160
8 Deviations from Ideal Reactor Performance 161
8.1 Residence Time Distributions in Flow Reactors 161
8.2 General Species Conservation Equation in a Reactor 163
8.3 Laminar Flow Reactor Model 166
8.4 Dispersion Model for a Tubular Reactor 168
8.5 Prediction of Axial Dispersion Coefficient 172
8.6 Evaluation of Dispersion Coefficient by Moment Analysis 174
8.7 Radial Temperature Variations in Tubular Reactors 175
8.8 A Criterion for the Negligible Effect of Radial Temperature Variations on the Reaction Rate 177
8.9 Effect of L/dt Ratio on the Performance of a Tubular Reactor and Pressure Drop 179
Problems and Questions 180
Exercises 181
References 182
9 Fixed-Bed Reactors and Interphase Transport Effects 185
9.1 Solid-Catalyzed Reactions and Transport Effects within Reactors 185
9.2 Observed Reaction Rate and Fixed-Bed Reactors 187
9.3 Significance of Film Mass Transfer Resistance in Catalytic Reactions 189
9.4 Tubular Reactors with Catalytic Walls 191
9.4.1 One-Dimensional Model 192
9.4.2 Two-Dimensional Model 193
9.5 Modeling of a Non-isothermal Fixed-Bed Reactor 194
9.6 Steady-State Multiplicity on the Surface of a Catalyst Pellet 196
Exercises 197
References 198
10 Transport Effects and Effectiveness Factor for Reactions in Porous Catalysts 199
10.1 Effectiveness Factor Expressions in an Isothermal Catalyst Pellet 199
10.2 Observed Activation Energy and Observed Reaction Order 205
10.3 Effectiveness Factor in the Presence of Pore-Diffusion and Film Mass Transfer Resistances 208
10.4 Thermal Effects in Porous Catalyst Pellets 210
10.5 Interphase and Intrapellet Temperature Gradients for Catalyst Pellets 215
10.6 Pore Structure Optimization and Effectiveness Factor Analysis for Catalysts with Bi-modal Pore-Size Distributions 217
10.7 Criteria for Negligible Transport Effects in Catalytic Reactions 221
10.7.1 Criteria for Negligible Diffusion and Heat Effects on the Observed Rate of Solid-Catalyzed Reactions 221
10.7.2 Relative Importance of Concentration and Temperature Gradients in Catalyst Pellets 222
10.7.3 Intrapellet and External Film Transport Limitations 225
10.7.4 A Criterion for Negligible Diffusion Resistance in Bidisperse Catalyst Pellets 225
10.8 Transport Effects on Product Selectivities in Catalytic Reactions 226
10.8.1 Film Mass Transfer Effect 226
10.8.2 Pore-Diffusion Effect 227
Problems and Questions 228
Exercises 229
References 233
11 Introduction to Catalysis and Catalytic Reaction Mechanisms 235
11.1 Basic Concepts in Heterogeneous Catalysis 235
11.2 Surface Reaction Mechanisms 237
11.3 Adsorption Isotherms 241
11.4 Deactivation of Solid Catalysts 244
Exercises 246
References 246
12 Diffusion in Porous Catalysts 247
12.1 Diffusion in a Capillary 247
12.2 Effective Diffusivities in Porous Solids 251
12.3 Surface Diffusion 252
12.4 Models for the Prediction of Effective Diffusivities 253
12.4.1 Random Pore Model 253
12.4.2 Grain Model 254
12.5 Diffusion and Flow in Porous Solids 254
12.6 Experimental Methods for the Evaluation of Effective Diffusion Coefficients 255
12.6.1 Steady-State Methods 255
12.6.2 Dynamic Methods 256
12.6.3 Single-Pellet Moment Method 257
Exercises 259
References 259
13 Process Intensification and Multifunctional Reactors 261
13.1 Membrane Reactors 262
13.1.1 Modeling of a Membrane Reactor 263
13.1.2 General Conservation Equations and Heat Effects in a Membrane Reactor 265
13.2 Reactive Distillation 266
13.2.1 Equilibrium-Stage Model 267
13.2.2 A Rate-Based Model for a Continuous Reactive Distillation Column 269
13.3 Sorption-Enhanced Reaction Process 270
13.4 Monolithic and Microchannel Reactors 275
13.4.1 Microchannel Reactors 278
13.5 Chromatographic Reactors 279
13.6 Alternative Energy Sources for Chemical Processing 279
13.6.1 Microwave-Assisted Chemical Conversions 280
13.6.2 Ultrasound Reactors 282
13.6.3 Solar Energy for Chemical Conversion 282
References 283
14 Multiphase Reactors 285
14.1 Slurry Reactors 285
14.2 Trickle-Bed Reactors 289
14.3 Fluidized-Bed Reactors 290
References 294
15 Kinetics and Modeling of Non-catalytic Gas-Solid Reactions 295
15.1 Unreacted-Core Model 296
15.2 Deactivation and Structural Models for Gas-Solid Reactions 299
15.3 Chemical Vapor Deposition Reactors 302
Exercises 305
References 307
Appendix A Some Constants of Nature 309
Appendix B Conversion Factors 311
Appendix C Dimensionless Groups and Parameters 313
Index 315
Güls¸en DogØu, PhD, is a Professor at Gazi University. She received her doctorate from the University of California at Davis. Her research focuses on environmentally clean processes, diffusion and reaction in porous media, catalyst development and alternative fuels.
