Catalysis (eBook)
462 Seiten
Elsevier Science (Verlag)
978-0-08-088698-5 (ISBN)
In the introductory section Chapter 1 presents a brief survey of the history of industrial heterogeneous and homogeneous catalysis. Subsequently, a selection of current industrial catalytic processes is described (Chapter 2). A broad spectrum of important catalytic applications is presented, including the basic chemistry, some engineering aspects, feedstock sources and product utilisation. In Chapter 3, kinetic principles are treated.
The section on fundamental catalysis begins with a description of the bonding in complexes and to surfaces (Chapter 4). The elementary steps on complexes and surfaces are described. The chapter on heterogeneous catalysis (5) deals with the mechanistic aspects of three groups of important reactions: syn-gas conversion, hydrogenation, and oxidation. The main principles of metal and metal oxide catalysis are presented. Likewise, the chapter on homogeneous catalysis (6) concentrates on three reactions representing examples from three areas: carbonylation, polymerization, and asymmetric catalysis. Identification by in situ techniques has been included. Many constraints to the industrial use of a catalyst have a macroscopic origin. In applied catalysis it is shown how catalytic reaction engineering deals with such macroscopic considerations in heterogeneous as well as homogeneous catalysis (Chapter 7). The transport and kinetic phenomena in both model reactors and industrial reactors are outlined.
The section on catalyst preparation (Chapters 8 and 9) is concerned with the preparation of catalyst supports, zeolites, and supported catalysts, with an emphasis on general principles and mechanistic aspects. For the supported catalysts the relation between the preparative method and the surface chemistry of the support is highlighted. The molecular approach is maintained throughout. The first chapter (10) in the section on catalyst characterization summarizes the most common spectroscopic techniques used for the characterisation of heterogeneous catalysts such as XPS, Auger, EXAFS, etc. Temperature programmed techniques, which have found widespread application in heterogeneous catalysis both in catalyst characterization and simulation of pretreatment procedures, are discussed in Chapter 11. A discussion of texture measurement, theory and application, concludes this section (12). The final chapter (13) gives an outline of current trends in catalysis. Two points of view are adopted: the first one focusses on developments in process engineering. Most often these have their origin in demands by society for better processes. The second point of view draws attention to the autonomous developments in catalysis, which is becoming one of the frontier sciences of physics and chemistry. In this book emphasis is on those reactions catalyzed by heterogeneous and homogeneous catalysts of industrial relevance. The integrative treatment of the subject matter involves many disciplines, consequently, the writing of the book has been a multi-author task. The editors have carefully planned and harmonized the contents of the chapters.
Catalysis is a multidisciplinary activity which is reflected in this book. The editors have chosen a novel combination of basic disciplines - homogeneous catalysis by metal complexes is treated jointly with heterogeneous catalysis with metallic and non-metallic solids. The main theme of the book is the molecular approach to industrial catalysis.In the introductory section Chapter 1 presents a brief survey of the history of industrial heterogeneous and homogeneous catalysis. Subsequently, a selection of current industrial catalytic processes is described (Chapter 2). A broad spectrum of important catalytic applications is presented, including the basic chemistry, some engineering aspects, feedstock sources and product utilisation. In Chapter 3, kinetic principles are treated.The section on fundamental catalysis begins with a description of the bonding in complexes and to surfaces (Chapter 4). The elementary steps on complexes and surfaces are described. The chapter on heterogeneous catalysis (5) deals with the mechanistic aspects of three groups of important reactions: syn-gas conversion, hydrogenation, and oxidation. The main principles of metal and metal oxide catalysis are presented. Likewise, the chapter on homogeneous catalysis (6) concentrates on three reactions representing examples from three areas: carbonylation, polymerization, and asymmetric catalysis. Identification by in situ techniques has been included. Many constraints to the industrial use of a catalyst have a macroscopic origin. In applied catalysis it is shown how catalytic reaction engineering deals with such macroscopic considerations in heterogeneous as well as homogeneous catalysis (Chapter 7). The transport and kinetic phenomena in both model reactors and industrial reactors are outlined.The section on catalyst preparation (Chapters 8 and 9) is concerned with the preparation of catalyst supports, zeolites, and supported catalysts, with an emphasis on general principles and mechanistic aspects. For the supported catalysts the relation between the preparative method and the surface chemistry of the support is highlighted. The molecular approach is maintained throughout. The first chapter (10) in the section on catalyst characterization summarizes the most common spectroscopic techniques used for the characterisation of heterogeneous catalysts such as XPS, Auger, EXAFS, etc. Temperature programmed techniques, which have found widespread application in heterogeneous catalysis both in catalyst characterization and simulation of pretreatment procedures, are discussed in Chapter 11. A discussion of texture measurement, theory and application, concludes this section (12). The final chapter (13) gives an outline of current trends in catalysis. Two points of view are adopted: the first one focusses on developments in process engineering. Most often these have their origin in demands by society for better processes. The second point of view draws attention to the autonomous developments in catalysis, which is becoming one of the frontier sciences of physics and chemistry. In this book emphasis is on those reactions catalyzed by heterogeneous and homogeneous catalysts of industrial relevance. The integrative treatment of the subject matter involves many disciplines, consequently, the writing of the book has been a multi-author task. The editors have carefully planned and harmonized the contents of the chapters.
Front Cover 1
Catalysis: An Integrated Approach to Homogeneous, Heterogeneous and Industrial Catalysis 4
Copyright Page 5
Contents 10
Preface 6
List of Contributors 18
Part I: Introductory Section 20
Chapter 1. History of Catalysis 22
1.1 Introduction 22
1.2 Industrial Catalysis 23
1.3 Summary 37
References 40
Chapter 2. Catalytic Processes in Industry 42
2.1 Introduction 42
2.2 Catalytic Processes in the Oil Refinery 42
2.3 Total Isomerization Process of Paraffins 52
2.4 Isotactic Polypropylene 55
2.5 Catalysts for Automotive Pollution Control 58
2.6 Ethene Oxide 60
2.7 Styrene and Propylene Oxide (SMPO Process) 62
2.8 Higher Olefins 64
2.9 Rhodium Catalyzed Hydroformylation of Propene 67
2.10 Methanol Synthesis 70
2.11 Maleic Anhydride 74
2.12 Methyl t-Butyl Ether (MTBE) 77
2.13 Caprolactam 80
2.14 Vitamin A Intermediates 82
2.15 Ibuprofen 85
References 86
Chapter 3. Chemical Kinetics of Catalysed Reactions 88
3.1 Introduction 88
3.2 Rate Expression (Single Site Model) 89
3.3 Rate Determining Step — Quasi-Equilibrium 91
3.3 Adsorption Isotherms 92
3.4 Rate Expression (Other Models) 95
3.5 Initial Rate Expressions 96
3.6 Temperature Dependency — Limiting Cases 97
3.7 Sabatier Principle — Volcano Plot 102
3.8 Concluding Remarks 104
References 104
Part II: Fundamental Catalysis 106
Chapter 4. Bonding and elementary Steps in Catalysis 108
4.1 Introduction 108
4.2 Bonding 108
4.3 Elementary Steps in Organometallic Complexes 125
4.4 Elementary Reaction Steps on Surfaces 142
References 174
Chapter 5. Heterogeneous Catalysis 178
5.1 Introduction 178
5.2 Synthesis Gas Reactions 178
5.3 Hydro-Dehydrogenation Reactions on Metals 195
5.4 Catalytic Oxidation 205
References 213
Chapter 6. Homogeneous Catalysis with Transition Metal Complexes 218
6.1 Introduction 218
6.2 Rhodium Catalyzed Hydroformylation 220
6.3 Zirconium Catalyzed Polymerization of Alkenes 241
6.4 Asymmetric Hydrogenation 256
References 265
Part III: Applied Catalysis 268
Chapter 7. Catalytic Reaction Engineering 270
7.1 Introduction 270
7.2 Major Reactor Categories 271
7.3 Reaction Combined with Transport 281
7.4 Experimental Determination of Reaction Kinetics 307
Appendix 7.A: Multicomponent Diffusion in the Presence of Reaction 318
References 325
Part IV: Catalyst Preparation 326
Chapter 8. Preparation of Catalyst Supports and Zeolites 328
8.1 Introduction 328
8.2 Preparation of Silica Gel Catalyst Supports 329
8.3 Preparation of Alumina Catalyst Supports 333
8.4 Zeolite Synthesis 337
8.5 Catalyst Shaping 341
References 351
Chapter 9. Preparation of Supported Catalysts 354
9.1 Introduction 354
9.2 Selective Removal 356
9.3 Application on a Separately Produced Support 357
Further Reading 379
Part V: Catalyst Characterization 380
Chapter 10. Catalyst Characterization with Spectroscopic Techniques 382
10.1 Introduction 382
10.2 Techniques 383
10.3 Concluding Remarks 416
References 418
Chapter 11. Temperature Programmed Reduction and Sulphiding 420
11.1 Introduction 420
11.2 Application of TPR 421
11.3 Thermodynamics 422
11.4 Apparatus 422
11.5 Example 1: Temperature-Programmed Study of CoO/Al2O3 424
11.6 Example 2: Temperature-Programmed Sulphiding of MoO3/Al2O3 425
11.7 Modelling 428
11.8 Example 3: Modelling of TPR of Fe2O3 432
References 436
Chapter 12. The use of Adsorption Methods for the Assessment of the Surface Area and Pore Size Distribution of Heterogeneous Catalysts 438
12.1 Introduction 438
12.2 Physical Adsorption 439
12.3 Adsorption Isotherms 441
12.4 Classification of Pore Sizes 442
12.5 Porosity of Porous Substances 442
12.6 The Yardstick in the Determination of Surface Areas 443
12.7 The Langmuir Adsorption Isotherm (Monolayer Adsorption) and the BET Equation (Multilayer Adsorption) 444
12.8 The Concept of a Standard Isotherm the t Method
12.9 Microporosity 451
12.10 Pore Radii and Pore Volume Distributions 452
12.11 Hysteresis Loops 454
12.12 The Corrected Kelvin Equation 455
12.13 Conclusions 456
References 456
Part VI: Future Trends 458
Chapter 13. Future Trends 460
13.1 Environmental Demands 461
13.2 Autonomous Developments: Chemistry 461
13.3 Autonomous Developments: Catalytic Reaction Engineering 463
Subject Index 466
| Erscheint lt. Verlag | 9.9.1993 |
|---|---|
| Sprache | englisch |
| Themenwelt | Naturwissenschaften ► Chemie ► Anorganische Chemie |
| Naturwissenschaften ► Chemie ► Organische Chemie | |
| Naturwissenschaften ► Chemie ► Physikalische Chemie | |
| Naturwissenschaften ► Chemie ► Technische Chemie | |
| Technik ► Umwelttechnik / Biotechnologie | |
| ISBN-10 | 0-08-088698-1 / 0080886981 |
| ISBN-13 | 978-0-08-088698-5 / 9780080886985 |
| Haben Sie eine Frage zum Produkt? |
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