List of Contributors XVII
Preface XXI
Part I Basic Concepts 1
1 Catalysis in Perspective: Historic Review 3
Rutger van Santen
1.1 History of Catalysis Science 3
1.2 The Development of Catalytic Processes: History and Future 11
1.3 Fundamental Catalysis in Practice 13
1.4 Catalyst Selection 13
1.5 Reactor Choice 16
1.6 Process Choice 17
References 19
Further Reading 19
2 Kinetics of Heterogeneous Catalytic Reactions 20
Rutger van Santen
2.1 Physical chemical principles 20
2.2 The Lock and Key Model, the Role of Adsorption Entropy 27
2.3 Equivalence of Electrocatalysis and Chemocatalysis 30
2.4 Microkinetics; the Rate-Determining Step 32
2.5 Elementary Rate Constant Expressions for Surface Reactions 34
2.6 The Pressure Gap 36
2.7 The Materials Gap 39
2.8 Coupling of Catalytic Reaction and Inorganic Solid Chemistry 42
2.9 In situ Generation of Organo-Catalyst 42
2.10 The Compensation Effect 44
References 46
3 Kinetics in Homogeneous Catalysis 48
Detlef Heller
3.1 Principles of a Catalyst and Kinetic Description 48
3.2 Catalyst Activity 54
3.3 Catalyst Activation and Deactivation 58
References 64
4 Catalytic Reaction Engineering Principles 67
Albert Renken and Lioubov Kiwi-Minsker
4.1 Preface 67
4.2 Formal Kinetics of Catalytic Reactions 68
4.3 Mass and Heat Transfer Effects 77
4.4 Homogenous Catalysis in Biphasic Fluid/Fluid Systems 103
References 108
Part II The Chemistry of Catalytic Reactivity 111
5 Heterogeneous Catalysis 113
Rutger van Santen
5.1 General Introduction 113
5.2 Transition Metal Catalysis 114
5.3 Solid Acids and Bases 132
5.4 Reducible Oxides 143
References 150
6 Homogeneous Catalysis 152
Matthias Beller, Serafino Gladiali, and Detlef Heller
6.1 General Features 152
References 169
7 Biocatalysis 171
Uwe Bornscheuer
7.1 Introduction 171
7.2 Examples 176
7.3 Summary/Conclusions 194
References 194
8 Electrocatalysis 201
Timo Jacob
8.1 Introduction 201
8.2 Theory 203
8.3 Application to the Oxygen Reduction Reaction (ORR) on Pt(111) 207
8.4 Summary 212
References 213
9 Heterogeneous Photocatalysis 216
Guido Mul
9.1 Introduction 216
9.2 Applications of Photocatalysis 219
9.3 Case Studies 220
9.4 Concluding Remarks 228
References 228
Part III Industrial Catalytic Conversions 231
10 Carbonylation Reactions 233
Matthias Beller
10.1 General Aspects 233
10.2 Hydroformylation 234
10.3 Other Carbonylations of Olefins and Alkynes 238
10.4 Carbonylations of Alcohols and Aryl Halides 244
References 246
11 Biocatalytic Processes 250
Uwe Bornscheuer
11.1 Introduction 250
11.2 Examples 253
11.2.1 General Applications 253
11.3 Case Study: Synthesis of Lipitor Building Blocks 257
11.4 Conclusions 259
References 259
12 Polymerization 261
Vincenzo Busico
12.1 Introduction 261
12.2 Polyolefins in Brief 262
12.3 Olefin Polymerization Catalysts 264
12.4 Olefin Polymerization Process Technology 273
12.5 The Latest Breakthroughs 280
References 285
13 Ammonia Synthesis 289
Jens Rostrup-Nielsen
13.1 Ammonia Plant 289
13.2 Synthesis 291
13.3 Steam Reforming 295
13.4 Conclusions 299
Abbreviations 299
References 299
14 Fischer–Tropsch Synthesis in a Modern Perspective 301
Hans Schulz
14.1 Introduction 301
14.2 Stoichiometry and Thermodynamic Aspects 304
14.3 Processes and Product Composition 308
14.4 Catalysts, General 311
14.5 Reaction Fundamentals 313
14.6 Concluding Remarks 323
References 323
15 Zeolite Catalysis 325
Rutger van Santen
15.1 Introduction 325
15.2 The Hydrocracking Reaction; Acid Catalysis 325
15.3 Lewis Acid–Lewis Base Catalysis; Hydrocarbon Activation 332
15.4 Selective Oxidation; Redox Catalysis 333
15.5 Framework-Substituted Redox Ions 335
References 339
16 Catalytic Selective Oxidation –Fundamentals, Consolidated Technologies, and Directions for Innovation 341
Fabrizio Cavani
16.1 Catalytic Selective Oxidation: Main Features 341
16.2 Catalytic Selective Oxidation: What Makes the Development of an Industrial Process More Challenging (and Troublesome) than Other Reactions 353
16.3 Catalytic Selective Oxidation: the Forefront in the Continuous Development of More-Sustainable Industrial Technologies 355
16.4 The Main Issue in Catalytic Oxidation: the Control of Selectivity 356
16.5 Dream Reactions in Catalytic Selective Oxidation: a Few Examples (Some Sustainable, Some Not Sustainable) 359
16.6 A New Golden Age for Catalytic Selective Oxidation? 361
16.7 Conclusions: Several Opportunities for More Sustainable Oxidation
Processes 363
References 363
17 High-Temperature Catalysis: Role of Heterogeneous, Homogeneous, and Radical Chemistry 365
Olaf Deutschmann
17.1 Introduction 365
17.2 Fundamentals 366
17.3 Applications 372
17.4 Hydrogen Production from Logistic Fuels by High-Temperature Catalysis 378
17.5 High-Temperature Catalysis in Solid Oxide Fuel Cells 380
References 385
18 Hydrodesulfurization 390
Roel Prins
18.1 Introduction 390
18.2 Hydrodesulfurization 391
18.3 The C-X Bond-Breaking Mechanism 393
18.4 Structure of the Sulfidic Catalyst 393
18.5 Hydrodenitrogenation 397
18.6 Determination of Surface Sites 398
References 398
Part IV Catalyst Synthesis and Materials 399
19 Molecularly Defined Systems in Heterogeneous Catalysis 401
Fernando Rasc´on and Christophe Cop´eret
19.1 Introduction 401
19.2 Single Sites: On the Border between Homogeneous and Heterogeneous Catalysis 402
19.3 Conclusion and Perspectives 415
References 415
20 Preparation of Supported Catalysts 420
Krijn P. de Jong
20.1 Introduction 420
20.2 Support Surface Chemistry 422
20.3 Ion Adsorption 423
20.4 Impregnation and Drying 425
20.5 Deposition Precipitation 427
20.6 Thermal Treatment 428
References 429
21 Porous Materials as Catalysts and Catalyst Supports 431
Petra de Jongh
21.1 General Characteristics 431
21.2 Sol-gel and Fumed Silica 433
21.3 Alumina and Other Oxides 436
21.4 Carbon Materials 438
21.5 Zeolites 440
21.6 Ordered Mesoporous Materials 442
21.7 Metal-Organic Frameworks 442
21.8 Shaping 443
References 444
22 Development of Catalytic Materials 445
Manfred Baerns
22.1 Introduction 445
22.2 Fundamental Aspects 446
22.3 Micro-Kinetics and Solid-State Properties as a Knowledge Source in Catalyst Development 448
22.4 Combinatorial Approaches and High-Throughput Technologies in the Development of Solid Catalysts 453
References 459
Part V Characterization Methods 463
23 In-situ Techniques for Homogeneous Catalysis 465
Detlef Selent and Detlef Heller
23.1 Introduction 465
23.2 In-situ Techniques for Homogeneous Catalysis 466
23.3 Gas Consumption and Gas Formation 467
23.4 NMR Spectroscopy 470
23.5 IR-Spectroscopy 481
23.6 UV/Vis Spectroscopy 486
23.7 Summary 490
References 490
24 In-situ Characterization of Heterogeneous Catalysts 493
Bert Weckhuysen
24.1 Introduction 493
24.2 Some History, Recent Developments, and Applications 495
24.3 In situ Characterization of a Reactor Loaded with a Catalytic Solid 497
24.4 In situ Characterization at a Single Catalyst Particle Level 501
24.5 Concluding Remarks 511
Acknowledgments 511
References 511
25 Adsorption Methods for Characterization of Porous Materials 514
Evgeny Pidko and Emiel Hensen
25.1 Introduction 514
25.2 Physical Adsorption 514
25.3 Classification of Porous Materials 517
25.4 Adsorption Isotherms 517
25.5 The Application of Adsorption Methods 518
25.6 Theoretical Description of Adsorption 519
25.7 Characterization of Microporous Materials 524
25.8 Characterization of Mesoporous Materials 527
25.9 Mercury Porosimetry 533
25.10 Xenon Porosimetry 533
References 534
26 A Critical Review of Some ‘‘Classical’’ Guidelines for Catalyst Testing 536
Frits Dautzenberg
26.1 Introduction 536
26.2 Encouraging Effectiveness 536
26.3 Ensuring Efficiency 537
26.4 Concluding Remarks 552
Appendix A: Three-Phase Trickle-Bed Reactors 552
List of Symbols and Abbreviations 558
References 559
Part VI Catalytic Reactor Engineering 561
27 Catalytic Reactor Engineering 563
Albert Renken and Madhvanand N. Kashid
27.1 Introduction 563
27.2 Types of Catalytic Reactors 564
27.3 Ideal Reactor Modeling/Heat Management 575
27.4 Residence Time Distribution 587
27.5 Microreaction Engineering 602
References 625
Index 629