●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 Cell Immobilization 514
11.3.3 Catalytic Kinetics of Immobilized Biocatalyst 517
11.4 Bioreactors 521
11.4.1 Types of Bioreactors 522
11.4.2 Bioreactor Calculations 527
Reference 536
Further Reading 536
Problems 536
12. Fundamentals of Polymerization Reaction Engineering 541
12.1 Overview 542
12.2 Kinetic Analysis 544
12.2.1 Types of Polymerization Reaction 544
12.2.2 Degree of Polymerization and Distribution 545
12.2.3 Homogeneous Free Radical Polymerization Reaction 553
12.2.4 Polycondensation Reaction 576
12.2.5 Factors That Influence Polymerization Rate 582
12.3 Analysis of Heat and Mass Transfers in the Polymerization Process 585
12.3.1 Thermal Effect in Polymerization Process 585
12.3.2 Heat Transfer and Fluid Flow in Polymerization Process 587
12.3.3 Heat and Mass Transfer Coefficients 589
12.4 Design and Analysis of Polymerization Reactor 589
12.4.1 Polymerization Reactor and Agitator 589
12.4.2 Mathematical Model 590
12.4.3 Calculation and Analysis of Polymerization Reactors 591
References 596
Further Reading 596
Problems 597
13. Introduction to Electrochemical Reaction Engineering 599
13.1 Introduction 599
13.1.1 Characters of Electrochemical Reactions 599
13.1.2 Performance Parameters for Electrochemical Reaction Engineering 601
13.2 Spe Issues in Electrochemical Reaction Engineering 608
13.2.1 Electrical Potential and Current Distribution on Electrode Surface 608
13.2.2 Effects of Gassing 618
13.2.3 Mass Transfer in Electrochemical Engineering 622
13.2.4 Heat Transfer and Balance in Electrochemical Engineering 625
13.3 Electrochemical Reactors 629
13.3.1 Types of Electrochemical Reactors 630
13.3.2 Operation Characters of Electrochemical Reactors 633
13.3.3 Connections and Combination of Electrochemical Reactors 645
References 651
Further Reading 651
Problems 651
Index 653
內容簡介
本書立足於傳授反應工程基本原理,並與工程實踐相結合;服務於高等院校化工類專業的廣大師生,工程公司的設計人員以及生產企業的工程技術人員。
內容編排采用了循序漸進的方式。首先,分別介紹氣固相催化反應的本征和宏觀動力學,推導了間歇反應器、全混流反應器和活塞流反應器三種理想反應器的設計方程;在連續反應器流動模型的基礎之上,建立起固定床、流化床和流固相非催化反應動力學及真實反應器的模型;同時,將反應器的間歇與連續、恆容與變容、絕熱與換熱的各種操作方式貫穿其中,並簡要介紹了操作過程的多定態和定態穩定性;很後,針對生化、聚合及電化學反應工程的特點,分章加以介紹。全書共計13章,前7章可用作本科生教材,後6章可作為研究生的學習內容。
全書文字敘述精煉、模型推導詳盡、知識內容完整,並結合大量的例題和習題,深入淺出地傳授反應工程知識,培養讀者建立反應器模型和與之相關的工程設計能力。