CONTENTS

Preface to the Second Edition xiii Preface to the First Edition xv PART I: FUNDAMENTALS 1 INTRODUCTION
1.1 1.2 1.3 1.4 1.5 1.6 1.7

1 3
4 5

Chemical Reactors 3 Chemical Reaction Engineering What Do We Need To Know? Industrial Processes 7 Modeling 10 Sources 11 References 14 Problems 16

2

REACTION RATES, THE BATCH REACTOR, AND THE REAL WORLD
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 Chemical Reactions 21 Multiple Reactions 25 Reaction Rates 26 Approximate Reactions 29 Rate Coefficients 30 Elementary Reactions 32 Stoichiometry 32 Reaction Rates Near Equilibrium

21

34

v

11 2.15 2.7 3.9 2. and PFTR 98 The 1/r Plot 100 Semibatch Reactors 101 Variable-Density Reactors 102 Space Velocity and Space Time 108 Chemical Reactors in Series 109 Autocatalytic Reactions 113 Reversible Reactions 115 Transients in Continuous Reactors 116 Some Important Single-Reaction Processes: Alkane Activation Synthesis Gas Reactions 119 Staged Reactors 125 The Major Chemical Companies 127 Reactor Design for a Single Reaction 133 Notation 134 References 136 Problems 136 87 118 4 MULTIPLE REACTIONS IN CONTINUOUS REACTORS 4.8 3.21 Continuous Reactors 87 The Continuous Stirred Tank Reactor 87 Conversion in a Constant-Density CSTR 90 The Plug-Flow Tubular Reactor 93 Conversion in a Constant-Density PFTR 95 Comparison Between Batch.3 3.16 3.18 3.17 2.9 3. CSTR.14 3.10 2.20 3.16 2.18 2.vi Contents 2.19 3.4 3.5 3.6 3.19 2.21 Reactor Mass Balances 37 The Batch Reactor 38 Variable Density 47 Chemical Reactors 51 Thermodynamics and Reactors 53 Adiabatic Reactor Temperature 54 Chemical Equilibrium 57 Petroleum Refining 59 Polyester from Refinery Products and Natural Gas 68 “What Should I Do When I Don’t Have Reaction Rates?” Reaction-Rate Data 74 Summary 80 References 80 Problems 80 73 3 SINGLE REACTIONS IN CONTINUOUS ISOTHERMAL REACTORS 3.17 3.4 Some Important Industrial Chemical Processes The Petrochemical Industry 149 Olefins 152 Mass Balances 153 148 148 .3 4.20 2.11 3.14 2.12 3.12 2.2 3.13 3.1 3.1 4.15 3.13 2.2 4.10 3.

7 6.10 Other Tubular Reactor Configurations 236 5.Contents 4. and Yield 155 Complex Reaction Networks 159 Series Reactions 160 Parallel Reactions 171 Multiple Reactions with Variable Density 180 Real Reaction Systems and Modeling 183 Approximate Rate Expressions for Multiple-Reaction Systems Simplified Reactions 185 Reaction Mechanisms 192 Collision Theory of Bimolecular Reactions 195 Activated Complex Theory 196 Designing Reactors for Multiple Reactions 198 Problems 199 vii 184 5 NONISOTHERMAL REACTORS 210 5.4 6.8 Trajectories of Wall-Cooled Reactors 233 5.2 Energy Balance in a CSTR 214 5.5 4.16 Conversion.1 Heat Generation and Removal 211 5.4 Equations to be Solved 217 5.10 4.9 4.5 6.15 4.11 4.8 4.5 Heat Removal or Addition to Maintain a Reactor Isothermal 5.12 4.8 Heat Generation and Removal in a CSTR 247 Adiabatic CSTR 251 Stability of Steady States in a CSTR 252 Observation of Multiple Steady States 254 Transients in the CSTR with Multiple Steady States Other Reactions in a CSTR 259 Variable Coolant Temperature in a CSTR 261 Designing Reactors for Energy Management 262 Problems 264 247 258 7 CATALYTIC REACTORS AND MASS TRANSFER 7.7 4.6 Adiabatic Reactors 221 5.3 6.11 Temperature Profile in a Packed Bed 240 Problems 242 219 6 MULTIPLE STEADY STATES AND TRANSIENTS 6.2 7.6 6.14 4.4 Catalytic Reactions 269 Catalytic Reactors 271 Surface and Enzyme Reaction Rates Porous Catalysts 275 274 269 .3 7.1 6.13 4.3 Energy Balance in a PFTR 215 5.7 Trajectories and Phase-Plane Plots 232 5. Selectivity.9 Exothermic Versus Endothermic Reactions 236 5.2 6.6 4.1 7.

1 9.9 7.10 7.11 9.3 9.3 8. Spheres.6 8.9 9.18 7.5 7.6 7.17 7.14 7.7 9.9 327 332 NONIDEAL CHEMICAL REACTORS The “Complete” Equations 332 Reactor Mass and Energy Balances 335 Residence Time Distribution 337 Laminar Flow Tubular Reactors 341 Dispersion in a Tubular Reactor 344 Recycle Reactors 345 CSTRs in Series 348 Diagnosing Reactors 349 Summary 349 Problems 350 9 REACTIONS OF SOLIDS 9.10 9.viii Contents 7.16 7.5 8.8 9.8 8. and Cylinders 359 Macroscopic and Microscopic Solids 362 Dissolving and Growing Films 364 Dissolving and Growing Spheres 368 Diffusion Through Solid Films 371 Transformation of Spheres 375 Mass Balances in Solid and Continuous Phases 377 Electrical Analogy 380 .7 7.12 353 Reactions Involving Solids 353 Chemical Vapor Deposition and Reactive Etching 354 Solids Reactors 357 Reaction Rates of Solids 358 Films.19 Transport and Reaction 277 Mass Transfer Coefficients 280 External Mass Transfer 283 Pore Diffusion 285 Temperature Dependence of Catalytic Reaction Rates The Automotive Catalytic Converter 291 The Catalytic Wall Reactor 295 Langmuir–Hinshelwood Kinetics 298 Summary of Surface Reaction Kinetics 309 Designing Catalytic Reactors 310 Electrochemical Reactors 312 Real Catalytic Reactions 313 Bioreactors 314 The Human Reactor 315 References 317 Problems 318 290 PART II: APPLICATIONS 8 8.1 8.11 7.12 7.6 9.2 8.13 7.15 7.5 9.8 7.2 9.4 9.7 8.4 8.

1 11.13 10.3 10.6 10.4 10.3 Introduction 465 Biological Molecules Cells 476 470 465 .17 10.15 10.4 11.8 10.18 10. COMBUSTION REACTORS.9 10. AND SAFETY 10.13 9.19 Chain Reactions 388 Characteristics of Chain Reactions 395 Autooxidation and Lab Safety 397 Chemical Synthesis by Autooxidation 400 Combustion 403 Hydrogen Oxidation 403 Chain Branching Reactions 406 Alkane Oxidation 408 Thermal Ignition 409 Thermal and Chemical Autocatalysis 411 Premixed Flames 411 Diffusion Flames 413 Energy Generation 414 Combustion of Liquids and Solids 415 Solid and Liquid Explosives 421 Explosions and Detonations 422 Reactor Safety 423 Summary 425 References 425 Problems 426 388 11 POLYMERIZATION REACTIONS AND REACTORS 11.14 10.9 11.7 11.6 11.Contents 9.2 10.3 11.14 Summary References Problems 381 382 382 ix 10 CHAIN REACTIONS.10 10.16 10.11 10.2 12.12 10.10 11.2 11.1 12.8 11.7 10.11 Ideal Addition Polymerization 434 Polyolefins 441 Free-Radical Polymerization 443 Catalytic Polymerization 446 Condensation Polymerization 449 Fisher–Tropsch Polymerization 454 Polymerization Reactors 455 Forming Polymers 457 Integrated Polymer Processing 457 Crystallization 458 References 459 Problems 459 432 12 BIOLOGICAL REACTION ENGINEERING 12.5 11.1 10.5 10.

5 14.9 14.4 Origins and Changes in Living Systems 480 12.1 14.3 13.10 Economics of Bioprocesses 518 12.9 Chemically Synthesized Biological Molecules 515 12.5 13.18 14.8 Biochemical Engineering 510 12.8 13.7 13.3 14.6 13.14 14.7 14.12 Summary 521 12.9 526 526 Only Chemical Engineers Can Solve Environmental Problems Green Chemistry 527 Renewable Chemical Resources 530 Regulations 534 Accidents 535 Waste Treatment 537 Modeling the Environment 537 Ecological Modeling 544 Summary 549 Problems 549 14 MULTIPHASE REACTORS 14.13 References 521 Problems 522 13 ENVIRONMENTAL REACTION ENGINEERING 13.19 555 Types of Multiphase Reactors 555 Mass Transfer Reactors 556 Mass Balance Equations 557 Interfacial Surface Area 560 Mass Transfer Between Phases 560 Multiphase Reactor Equations 562 Equilibrium Between Phases 563 Membrane Reactors 564 Falling Film Reactor 567 Bubble Column Reactors 572 Falling Film Catalytic Wall Reactor 578 Trickle Bed Reactor 580 Multiphase Reactors with Catalysts 581 Other Multiphase Reactors 582 Analysis of Multiphase Reactors 585 Reactor–Separation Integration 586 Catalytic Distillation 587 Chromatographic Reactors 588 Iron Ore Refining 591 .13 14.5 Bioenergy and Metabolic Pathways 484 12.7 Rates and Kinetics of Biological Processes 491 12.1 13.8 14.11 14.x Contents 12.4 13.17 14.15 14.16 14.2 13.12 14.4 14.2 14.6 14.11 Biological Reactors 519 12.6 Measurements in Biological Systems 489 12.10 14.

21 The Petroleum Refinery Summary 594 Problems 594 592 xi Appendix A: Integrating Differential Equations Appendix B: Notation 607 611 Appendix C: Conversion Factors Index 613 603 .Contents 14.20 14.

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