Table of Contents
Preface to the first edition vii
Preface to the second edition ix
About the author xi
1 The basics 1
1.1 Catalytic concepts 1
1.1.1 Definitions 1
1.1.2 Length and time scales in catalysis 5
1.1.3 Catalytic trinity: activity, selectivity, stability 7
1.1.4 Composition of catalysts 13
1.2 Reactivity of solids 16
1.2.1 Physisorption and chemisorption 17
1.2.2 Basics of chemisorption theory 20
1.2.3 Surface crystallography 21
1.2.4 Mechanisms of some catalytic reactions 24
1.3 Catalysis in industry and for environmental protection 30
1.4 Fuel cells and electrocatalysis 45
References 47
2 Engineering catalysts 49
2.1 Catalyst design 49
2.1.1 Being in shape 50
2.1.2 Catalysis informatics and high-throughput experimentation 57
2.2 Toolbox in catalysis 59
2.2.1 General overview of the characterization methods 59
2.2.2 Adsorption methods 62
2.2.3 Physisorption methods 63
2.2.4 Chemisorption 74
2.2.5 Temperature-programmed methods 77
2.2.6 Calorimetry 82
2.2.7 X-ray diffraction 83
2.2.8 X-ray photoelectron spectroscopy and X-ray fluorescence 84
2.2.9 Infrared and Raman spectroscopies 87
2.2.10 Catalyst particle size measurements 93
2.2.11 Electron paramagnetic/spin resonance 94
2.2.12 Mossbauer spectroscopy 96
2.2.13 X-ray absorption spectroscopy 98
2.2.14 Nuclear magnetic resonance 99
2.2.15 Imaging of catalysts 101
2.2.16 Catalytic reactions: product analysis 110
2.2.17 Theory as a part of a toolbox 114
2.3 Preparation of catalytic materials 117
2.3.1 General overview 117
2.3.2 Unsupported metals 132
2.3.3 Preparation of bulk oxides by precipitation 135
2.3.4 Heteropoly acids 145
2.3.5 Catalyst supports 146
2.3.6 Supported catalysts 180
2.3.7 Catalyst forming operations 202
References 224
3 Engineering reactions 229
3.1 Introduction 229
3.2 Thermodynamics 229
3.3 Kinetics 232
3.3.1 Definitions 232
3.3.2 Reaction mechanism 237
3.4 Kinetics of complex reactions 247
3.4.1 Theory of complex reactions kinetics 247
3.4.2 Relationship between thermodynamics and kinetics 256
3.4.3 Non-ideal surfaces 257
3.4.4 Kinetic aspects of selectivity 261
3.4.5 Structure sensitivity 266
3.4.6 Mechanism-free kinetics - kinetic polynomial 268
3.4.7 What is behind a rate constant? 269
3.4.8 Apparent activation energy of complex reactions 272
3.4.9 Dynamic catalysis and deactivation 274
3.4.10 Mathematical treatment of experimental data 280
3.5 Mass transfer 284
3.5.1 Diffusion effects in heterogeneous catalysis 284
3.5.2 Reactor dependent external diffusion (interphase mass transfer, film diffusion) 286
3.5.3 Calculation of diffusion coefficients 295
3.5.4 Size dependent internal (pore) diffusion 298
3.5.5 Non-isothermal conditions 307
3.5.6 Multiple reactions and diffusional limitations 311
3.5.7 Diffusion in micropores 314
3.5.8 Criteria for the absence of diffusional limitations 315
3.6 Catalytic reactors 320
3.6.1 Laboratory reactors 320
3.6.2 Industrial reactors 328
3.6.3 Two-phase reactors 328
3.6.4 Three-phase catalytic reactors 336
3.6.5 Reactor modeling 365
3.6.6 Catalyst handing in a plant 377
References 386
4 Engineering technology 391
4.1 General structures of chemical processes 391
4.1.1 Safety in design 393
4.1.2 Conceptual process design: examples 394
4.1.3 Conceptual process design: general comments 404
4.1.4 Reactor selection 406
4.2 (Petro)chemical industry 423
4.3 Fluid catalytic cracking 423
4.3.1 Feedstock 424
4.3.2 Reactions/mechanism 426
4.3.3 Kinetics/process variables 431
4.3.4 Catalysts 433
4.3.5 Technology 437
4.4 Hydrocracking 441
4.4.1 Overview of hydrocracking 441
4.4.2 Hydrocracking catalysts 444
4.4.3 Hydrocracking technology 448
4.5 Steam reforming of natural gas 454
4.5.1 General 454
4.5.2 Process conditions for sulfur removal and primary reforming 457
4.5.3 Kinetics and mechanism 459
4.5.4 Technology 463
4.5.5 Catalysts 465
4.6 Ammonia synthesis 468
4.6.1 General 468
4.6.2 Thermodynamics 469
4.6.3 Kinetics 471
4.6.4 Catalysts 474
4.6.5 Reactors and process design 480
4.7 Oxidation 483
4.7.1 General 483
4.7.2 Epoxidation of olefins 485
4.7.3 Oxidation of alkanes to anhydrides 491
4.7.4 From alcohols to aldehydes: oxidative dehydrogenation of methanol to formaldehyde 507
4.7.5 Ammoxidation 512
4.8 Oxychlorination 518
4.8.1 Overview 518
4.8.2 Catalysts and reactors 520
4.8.3 Reaction network and kinetics 524
4.8.4 Technology 525
References 527
Acknowledgments 533
Recommended reading 535
Index 539
