Description
Professor Timur Dogu received his bachelor degree in chemical engineering from the Middle East Technical University in Turkey, his MSc degree from Stanford University and his PhD from the University of California at Davis. He developed most of his academic career at the Middle East Technical University. Professor T. Dogu has considerably contributed to advancements in reaction engineering, heterogeneous catalysis, environmental catalysis, synthesis of nanostructured mesoporous materials, transport phenomena effects on reaction rates, and process intensification. Professor T. Dogu is the author of 140 refereed publications in high impact international journals. He has successfully supervised more than 60 Masters and PhDs. His citations in the Web of Science are more than 2,700. Since 2016, he has been the Chair of the Label Committee of the European Network for Accreditation of Engineering Education. Professor T. Dogu is also an elected member of the Turkish Academy of Sciences. Professor Glsen Dogu received her bachelor degree in chemical engineering from the Middle East Technical University in Turkey, her MSc degree from Stanford University and her PhD from the University of California at Davis. She progressed through the academic ranks in Turkey with a first appointment at the Middle East Technical University, followed by a 1985 Full Professorship at Gazi University. She has been a research advisor to more than 50 Master and PhD graduate students. Professor G. Dogu’s most valuable contribution to chemical reaction engineering has been in the areas of environmentally clean processes, diffusion and reaction in porous media, catalyst development and alternative fuels. Professor G. Dogu is the author of more than 90 refereed publications in high impact chemical engineering journals, with more than 1,800 citations in the Web of Science. Preface xiii 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
