目录 List of Contributors xiii Preface xv 1. Introduction 1 1.1 Chemical Reaction Engineering 1 1.2 Conversion and Yield of Chemical Reactions 4 1.2.1 Extent of Reaction 4 1.2.2 Conversion 5 1.2.3 Yield and Selectivity 7 1.3 Classifications of Chemical Reactors 10 1.4 Operation Modes of Chemical Reactors 13 1.5 Models in Reactor Design 16 1.6 Scale-Up of Industrial Reactors 19 Further Reading 22 Problems 22 2. Fundamentals of Reaction Kinetics 25 2.1 Reaction Rate 26 2.2 Reaction Rate Equations 30 2.3 Effect of Temperature on Reaction Rate 37 2.4 Multiple Reactions 44 2.4.1 Consumption Rate and Formation Rate 44 2.4.2 Basic Types of Multiple Reactions 45 2.4.3 Reaction Network 50 2.5 Transformation and Integration of Reaction Rate Equations 52 2.5.1 Single Reaction 52 2.5.2 Multiple Reactions 57 2.6 Heterogeneous Catalysis and Adsorption 60 2.6.1 Heterogeneous Catalysis 61 2.6.2 Adsorption and Desorption 62 2.7 Kinetics of Heterogeneous Catalytic Reactions 67 2.7.1 Steady-State Approximation and Rate-Determining Step 68 2.7.2 Rate Equations of Heterogeneous Catalytic Reactions 70 2.8 Determination of Kinetic Parameters 77 2.8.1 Integration Method 77 2.8.2 Differential Method 79 2.9 Procedure for Developing Reaction Rate Equation 86 Further Reading 87 Problems 88 3. Tank Reactor 95 3.1 Mass Balance for Tank Reactor 96 3.2 Design of Isothermal Batch Tank Reactor(Single Reaction) 97 3.2.1 Calculation of Reaction Time and Reaction Volume 98 3.2.2 Optimal Reaction Time 102 3.3 Design of Isothermal Batch Tank Reactor (Multiple Reactions) 103 3.3.1 Parallel Reactions 103 3.3.2 Consecutive Reactions 107 3.4 Reactor Volume for Continuous Tank Reactor (CSTR) 111 3.5 CSTR in Series and Parallel 115 3.5.1 Overview 115 3.5.2 Calculations for Multiple Reactors in Series 117 3.5.3 Optimal Reaction Volume Ratio for CSTR in Series 122 3.6 Yield and Selectivity for Multiple Reactions in a Tank Reactor 123 3.6.1 Overall Yield and Overall Selectivity 124 3.6.2 Parallel Reactions 125 3.6.3 Consecutive Reactions 129 3.7 Semibatch Tank Reactor 133 3.8 Nonisothermal Batch Reactor 138 3.9 Steady-State Operation of CSTR 145 3.9.1 Heat Balance for CSTR 145 3.9.2 Steady-States of CSTR 147 Summary 151 Further Reading 152 Problems 153 4. Tubular Reactor 161 4.1 Plug Flow 161 4.2 Design of Isothermal Tubular Reactor 163 4.2.1 Single Reaction 164 4.2.2 Multiple Reactions 168 4.2.3 Pseudo Homogeneous Model 176 4.3 Comparison of Reactor Volumes of Tubular and Tank Reactors 178 4.4 Recycle Reactor 184 4.5 Nonisothermal Tubular Reactor 185 4.5.1 Heat Balance Equation for Tubular Reactor 186 4.5.2 Adiabatic Tubular Reactor 188 4.5.3 Nonadiabatic Nonisothermal Tubular Reactor 193 4.6 Optimal Temperature Sequence for Tubular Reactors 197 4.6.1 Single Reaction 198 4.6.2 Multiple Reactions 200 Further Reading 203 Problems 203 5. Residence Time Distribution and Flow Models for Reactors 213 5.1 Residence Time Distribution 214 5.1.1 Overview 214 5.1.2 Quantitative Delineation of RTD 215 5.2 Experimental Determination of RTD 218 5.2.1 Pulse Experiments 219 5.2.2 Step Experiments 221 5.3 Statistical Eigenvalues of RTD 224 5.4 RTD of Ideal Reactors 228 5.4.1 Plug-Flow Model 228 5.4.2 Perfectly-Mixed Flow Model 230 5.5 Nonideal Flow Phenomenon 234 5.6 Nonideal Flow Models 238 5.6.1 Segregation Model 238 5.6.2 Tanks-in-Series Model 242 5.6.3 Axial Dispersion Model 247 5.7 Design of Nonideal Reactors 251 5.8 Mixing of Fluids in Flow Reactors 256 Further Reading 260 Problems 261 6. Chemical Reaction and Transport Phenomena in Heterogeneous System 265 6.1 Steps in Heterogeneous Reactions 266 6.1.1 Macroscopic Structures and Properties of Solid Catalyst Particles 266 6.1.2 Steps in a Catalytic Reaction 269 6.2 Heat and Mass Transfer Between Bulk Fluid and the Catalyst External Surface 270 6.2.1 Transport Coefficient 270 6.2.2 Concentration and Temperature Difference Between the External Surface of Catalyst and Bulk Fluid 272 6.2.3 Effect of External Diffusion on Heterogeneous Catalytic Reactions 275 6.3 Gas Diffusion in Porous Media 279 6.3.1 Diffusion in Pores 279 6.3.2 Diffusion in Porous Particles 280 6.4 Diffusion and Reaction in Porous Catalysts 281 6.4.1 Reactant Concentration Profile in Porous Catalysts 282 6.4.2 Internal Effectiveness Factor 285 6.4.3 Internal Effectiveness Factor for Non-first Order Reactions 290 6.4.4 Effectiveness Factor Under the Influences of Both Internal and External Diffusions 292 6.5 Effect of Internal Diffusion on Selectivity of Multiple Reactions 294 6.6 Determination of Diffusion Impact on Heterogeneous Reactions 297 6.6.1 Determination of the Effects of External Diffusion 297 6.6.2 Determining the Effects of Internal Diffusion 299 6.7 Effects of Diffusion on Experimental Measurement of Reaction Rate 301 Further Reading 305 Problems 306 7. Analysis and Design of Heterogeneous Catalytic Reactors 311 7.1 Transport Phenomena Inside Fixed Bed Reactors 312 7.1.1 Fluid Flow Inside a Fixed Bed 312 7.1.2 Mass and Heat Dispersion Along Axial Direction 316 7.1.3 Mass and Heat Transfer in Radial Direction 317 7.2 Mathematical Model for Fixed Bed Reactor 320 7.3 Adiabatic Fixed Bed Reactor 325 7.3.1 Adiabatic Reactors 325 7.3.2 Catalyst Volume for Adiabatic Fixed Bed Reactor 327 7.3.3 Multistage Adiabatic Reactors 331 7.4 Fixed Bed Reactor With Internal Heat Exchanger 337 7.4.1 Overview 337 7.4.2 Analysis for Single Reaction 339 7.4.3 Analysis of Multiple Reaction Systems 342 7.5 Autothermal Fixed Bed Reactors 347 7.5.1 Feed Flow Direction 348 7.5.2 Mathematical Model 349 7.6 Parameter Sensitivity 351 7.7 Laboratory Catalytic Reactor 355 7.7.1 Basic Requirements 355 7.7.2 Main Types of Experimental Reactor 357 Further Reading 361 Problems 361 8. Fluidized Bed Reactor 369 8.1 Introduction 369 8.2 Fluidization 369 8.2.1 Fluidization Phenomenon 369 8.2.2 Particle Classifications 370 8.2.3 Fluidization Parameters 371 8.2.4 Fluidization Regimes 375 8.3 Bubbling Fluidized Bed 376 8.3.1 Bubble Behaviors 377 8.3.2 Mathematical Model of Bubbling Fluidized Bed 380 8.4 Turbulent Fluidized Bed 388 8.4.1 Regime Transition 388 8.4.2 Hydrodynamic Characteristics 389 8.5 Circulating Fluidized Bed 389 8.5.1 Introduction 389 8.5.2 Configuration of CFB 391 8.5.3 Mathematical Models of CFB 392 8.6 Downer Reactor 398 Further Reading 401 Problems 402 9. Multiple-Phase Reactors 405 9.1 Gas-Liquid Reactions 405 9.1.1 Pseudo First Order Reaction 408 9.2 Gas-Liquid Reactors 412 9.2.1 Main Types of Reactors 412 9.2.2 Design of Bubble Column Reactor 414 9.2.3 Design of Stirred Tank Reactor 419 9.3 Gas-Liquid-Solid Reactions 421 9.3.1 Introduction 421 9.3.2 Mass Transfer Steps and Rates in Gas-Solid-Liquid Catalytic Reactions 422 9.4 Trickle Bed Reactors 425 9.4.1 Introduction 425 9.4.2 Mathematical Model 427 9.5 Slurry Reactor 431 9.5.1 Types of Reactors 431 9.5.2 Mass Transfer and Reaction 432 9.5.3 Design of Mechanically Stirred Slurry Tank Reactor 437 Further Reading 441 Problems 441 10. Fluid-Solid Noncatalytic Reaction Kinetics and Reactors 445 10.1 Fluid-Solid Noncatalytic Reactions and Their Applications 446 10.2 Reaction Rate of Particles in Different Shapes 448 10.3 Theoretical Models of Solid Reactions 451 10.4 Kinetic Analysis of Continuous Model 452 10.5 Kinetic Analysis at Constant Particle Size Using the Shrinking Core Model 454 10.5.1 Overall Macroreaction Rate 456 10.5.2 Macroreaction Rate Under Internal Diffusion Control 459 10.5.3 Macroreaction Rate Under External Diffusion Control 460 10.5.4 Intrinsic Reaction Rate Under Surface Reaction Control 461 10.5.5 Comparison and Differentiation of Rate-Controlling Steps at Constant Particle Size 463 10.6 Kinetic Analysis With Changing Particle Diameter Using the Shrinking Core Model 466 10.6.1 Internal Diffusion Control 469 10.6.2 External Diffusion Control 470 10.6.3 Chemical Reaction Control 471 10.6.4 Overall Reaction Time 473 10.7 Microparticle Model 473 10.8 Chemical Vapor Deposition 477 10.9 Design of Fluid-Solid Noncatalytic Reactor 479 10.9.1 Reactor Types 480 10.9.2 Flowing and Mixing of Reaction Components 480 10.9.3 Reactor Design When Fluid Is a Complete Mixing Flow and Solid Phase Is a Plug Flow 483 10.9.4 Reactor Design When Fluid and Solid Phases Can Be Treated as Complete Mixing Flow 484 Further Reading 487 Problems 487 11. Fundamentals of Biochemical Reaction Engineering 491 11.1 Introduction 491 11.2 Fundamentals of Biochemical Reaction Kinetics 494 11.2.1 Enzyme-Catalyzed Reactions and Its Kinetics 494 11.2.2 Kinetics of Microbial Reactions 507 11.3 Immobilized Biocatalysts 513 11.3.1 Introduction 513 11.3.2 Enzyme and Cel
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