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Industrial Catalysis: A Practical Approach Vital Source e-bog
Jens Hagen
(2015)
Industrial Catalysis
A Practical Approach
Jens Hagen
(2015)
Sprog: Engelsk
om ca. 10 hverdage
Detaljer om varen
- 3. Udgave
- Vital Source searchable e-book (Reflowable pages)
- Udgiver: John Wiley & Sons (September 2015)
- ISBN: 9783527684649
The updated edition covers the full range of industrial aspects, from catalyst development and testing to process examples and catalyst recycling. The book is characterized by its practical relevance, expressed by a selection of over 40 examples of catalytic processes in industry. In addition, new chapters on catalytic processes with renewable materials and polymerization catalysis have been included. Existing chapters have been carefully revised and supported by new subchapters, for example, on metathesis reactions, refinery processes, petrochemistry and new reactor concepts.
"I found the book accesible, readable and interesting - both as a refresher and as an introduction to new topics - and a convenient first reference on current industrial catalytic practise and processes."
Excerpt from a book review for the second edition by P. C. H. Mitchell, Applied Organometallic Chemistry (2007)
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Detaljer om varen
- 3. Udgave
- Hardback: 544 sider
- Udgiver: John Wiley & Sons, Incorporated (November 2015)
- ISBN: 9783527331659
The updated edition covers the full range of industrial aspects, from catalyst development and testing to process examples and catalyst recycling. The book is characterized by its practical relevance, expressed by a selection of over 40 examples of catalytic processes in industry. In addition, new chapters on catalytic processes with renewable materials and polymerization catalysis have been included. Existing chapters have been carefully revised and supported by new subchapters, for example, on metathesis reactions, refinery processes, petrochemistry and new reactor concepts.
"I found the book accesible, readable and interesting - both as a refresher and as an introduction to new topics - and a convenient first reference on current industrial catalytic practise and processes."
Excerpt from a book review for the second edition by P. C. H. Mitchell, Applied Organometallic Chemistry (2007)
1.1 The Phenomenon Catalysis 1
1.2 Mode of Action of Catalysts 2
1.2.1 Activity 4
1.2.1.1 Turnover Frequency TOF 6
1.2.1.2 Turnover Number TON 7
1.2.2 Selectivity 7
1.2.3 Stability 8
1.2.4 Mole Balance and Conversion 8
1.3 Classification of Catalysts 10
1.4 Comparison of Homogeneous and Heterogeneous Catalysis 11 Exercises 14 References 15 2 Homogeneous Catalysis with Transition Metal Catalysts 17
2.1 Key Reactions in Homogeneous Catalysis 18
2.1.1 Coordination and Exchange of Ligands 18
2.1.2 Complex Formation 20
2.1.3 Acid-Base Reactions 22
2.1.4 Redox Reactions: Oxidative Addition and Reductive Elimination 23
2.1.4.1 Oxidative Coupling and Reductive Cleavage 27
2.1.5 Insertion and Elimination Reactions 28
2.1.5.1 β-Elimination 30
2.1.5.2 α-Elimination 30
2.1.6 Reactions at Coordinated Ligands 31
2.2 Catalyst Concepts in Homogeneous Catalysis 32
2.2.1 The 16/18-Electron Rule 32
2.2.2 Catalytic Cycles 34
2.3 Characterization of Homogeneous Catalysts 35
2.3.1 Infrared Spectroscopy 38
2.3.2 NMR Spectroscopy 40 Exercises 42 References 45 3 Homogeneously Catalyzed Industrial Processes 47
3.1 Overview 47
3.2 Examples of Industrial Processes 48
3.2.1 Oxo Synthesis 50
3.2.2 Production of Acetic Acid by Carbonylation of Methanol 52
3.2.3 Selective Ethylene Oxidation by theWacker Process 55
3.2.4 Oxidation of Cyclohexane 57
3.2.5 Suzuki Coupling 58
3.2.6 Oligomerization of Ethylene (SHOP Process) 59
3.2.7 Telomerization of Butadiene 61
3.2.8 Adipodinitrile 63
3.3 Asymmetric Catalysis 63
3.3.1 Introduction 63
3.3.2 Catalysts 64
3.3.3 Commercial Applications 65
3.3.3.1 Asymmetric Hydrogenation 65
3.3.3.2 Enantioselective Isomerization: L-Menthol 67
3.3.3.3 Asymmetric Epoxidation 68
3.4 Alkene Metathesis 69
3.4.1 Examples of Heterogeneous Catalysis 72
3.5 Recycling of Homogeneous Catalysts 73
3.5.1 Overview 73
3.5.1.1 Precipitation of the Catalyst or of the Product(s) 73
3.5.1.2 Thermal Separation 73
3.5.1.3 Membrane Separation 73
3.5.1.4 Adsorption 74
3.5.1.5 Phase Separation/Extraction 74
3.5.2 Reactions in Two-Phase Liquid-Liquid Systems 74 Exercises 76 References 78 4 Biocatalysis 81
4.1 Introduction 81
4.1.1 Active Sites 83
4.1.2 Coenzymes 84
4.2 Kinetics of Enzyme-Catalyzed Reactions 84
4.3 Industrial Processes with Biocatalysts 90
4.3.1 Acrylamide from Acrylonitrile 90
4.3.2 Aspartame Through Enzymatic Peptide Synthesis 91
4.3.3 L-Amino Acids by Aminoacylase Process 92
4.3.4 Pharmaceuticals 93
4.3.5 Herbicides 95
4.3.5.1 4-Hydroxyphenoxypropionic Acid as Herbicide Intermediate 96 Exercises 97 References 97 5 Heterogeneous Catalysis: Fundamentals 99
5.1 Individual Steps in Heterogeneous Catalysis 99
5.2 Kinetics and Mechanisms of Heterogeneously Catalyzed Reactions 101
5.2.1 The Importance of Adsorption in Heterogeneous Catalysis 102
5.2.2 Kinetic Treatment 106
5.2.3 Mechanisms of Heterogeneously Catalyzed Gas-Phase Reactions 108
5.2.3.1 Langmuir-Hinshelwood Mechanism (1921) 109
5.2.3.2 Eley-Rideal Mechanism (1943) 111
5.3 Catalyst Concepts in Heterogeneous Catalysis 113
5.3.1 Energetic Aspects of Catalytic Activity 113
5.3.2 Steric Effects 124
5.3.3 Electronic Factors 134
5.3.3.1 Redox Catalysts 134
5.3.3.2 Acid/Base Catalysts (Ionic Catalysts) 135
5.3.3.3 Metals 136
5.3.3.4 Bimetallic Catalysts 140
5.3.3.5 Semiconductors 144
5.3.3.6 Insulators: Acidic and Basic Catalysts 157
5.4 Catalyst Performance 164
5.4.1 FactorsWhich Affect the Catalyst Performance 164
5.4.2 Supported Catalysts 166
5.4.3 Promoters 172
5.4.4 Inhibitors 176
5.5 Catalyst Deactivation 177
5.5.1 Catalyst Poisoning 179
5.5.2 Poisoning of Metals 179
5.5.3 Poisoning of Semiconductor Oxides 182
5.5.4 Poisoning of Solid Acids 182
5.5.5 Deposits on the Catalyst Surface 183
5.5.6 Thermal Processes and Sintering 185
5.5.7 Catalyst Losses via the Gas Phase 186
5.6 Regeneration and Recycling of Heterogeneous Catalysts 186
5.7 Characterization of Heterogeneous Catalysts 189
5.7.1 Physical Characterization 190
5.7.1.1 Temperature-Programmed Desorption 195
5.7.2 Chemical Characterization and Surface Analysis 195
5.7.2.1 Temperature-Programmed Reaction Methods 196
5.7.2.2 Transmission Electron Microscopy 197
5.7.2.3 Low-Energy Electron Diffraction (LEED) 198
5.7.2.4 IR Spectroscopy 199
5.7.2.5 Electron Spectroscopy for Chemical Analysis (ESCA) 199
5.7.2.6 Auger Electron Spectroscopy (AES) 201
5.7.2.7 Ion Scattering Spectroscopy (ISS) 201
5.7.2.8 Secondary Ion Mass Spectrometry (SIMS) 202 Exercises 203 References 209 6 Catalyst Shapes and Production of Heterogeneous Catalysts 211
6.1 Introduction 211
6.2 Bulk Catalysts 212
6.2.1 Precipitation 212
6.2.2 Fusion and Alloy Leaching 214
6.2.3 Sol-Gel Synthesis 215
6.2.4 Flame Hydrolysis 217
6.2.5 Hydrothermal Synthesis 217
6.2.6 Heteropolyacids 219
6.3 Supported Catalysts 219
6.3.1 Impregnation 220
6.3.2 Coprecipitation 225
6.3.3 Adsorption/Ion-Exchange 226
6.3.3.1 Ion-Exchange Resins 227
6.3.4 Anchoring/Grafting 228
6.3.5 Monolithic Catalysts 229
6.4 Shaping of Catalysts and Catalyst Supports 230
6.5 Immobilization of Homogeneous Catalysts 232
6.5.1 Supported Solid-Phase Catalysts (SSPC) 234
6.5.2 Supported Liquid-Phase Catalysts (SLPC) 236
6.5.3 Encapsulation 236 Exercises 237 References 238 7 Shape-Selective Catalysis: Zeolites 239
7.1 Composition and Structure of Zeolites 239
7.2 Catalytic Properties of the Zeolites 242
7.2.1 Shape Selectivity 243
7.2.1.1 Reactant Selectivity 243
7.2.1.2 Product Selectivity 246
7.2.1.3 Restricted Transition State Selectivity 246
7.2.2 Acidity of Zeolites 247
7.3 Isomorphic Substitution of Zeolites 251
7.4 Metal-Doped Zeolites 252
7.5 Applications of Zeolites 255 Exercises 258 References 259 8 Heterogeneously Catalyzed Processes in Industry 261
8.1 Overview 261
8.1.1 Production of Inorganic Chemicals 261
8.1.2 Production of Organic Chemicals 261
8.1.3 Refinery Processes 262
8.1.4 Catalysts in Environmental Protection 264
8.2 Examples of Industrial Processes - Bulk Chemicals 266
8.2.1 Ammonia Synthesis 266
8.2.2 Hydrogenation 268
8.2.3 Methanol Synthesis 270
8.2.4 Selective Oxidation of Propene 272
8.2.4.1 Oxidation of Propene with H2O2 to Propylene Oxide 277
8.2.5 Selective Oxidation of Hydrocarbons 277
8.2.5.1 n-Butane to Maleic Anhydride 278
8.2.5.2 o-Xylene to Phthalic Anhydride 280
8.3 Fine Chemicals Manufacture 281
8.3.1 Fine Chemicals andTheir Synthesis 281
8.3.2 Selected Examples of Industrial Processes 285
8.3.2.1 Hydrogenation 286
8.3.2.2 Oxidation 288
8.3.2.3 Catalytic C-C Linkage 290
8.3.2.4 Acid/Base Catalysis 292 Exercises 294 References 297 9 Refinery Processes and Petrochemistry 299
9.1 Hydrotreating 300
9.2 Catalytic Cracking 302
9.3 Hydrocracking 304
9.4 Catalytic Reforming 306
9.5 Alkylation 307
9.6 Hydroisomerization 308
9.7 Synthesis Gas and Hydrogen by Steam Reforming 310
9.8 Natural Gas Conversion to Fuels and Chemicals 312
9.9 Fischer-Tropsch Synthesis 313
9.10 Etherification Reactions 315 Exercises 316 References 317 10 Electrocatalytic Processes 319
10.1 Comparison Between Electrocatalysis and Heterogeneous Catalysis 319
10.2 Electroorganic Syntheses 319
10.2.1 Electrocatalytic Hydrogenation 320
10.2.2 Electrocatalytic Oxidation 322
10.2.3 Electrochemical Addition 323
10.3 Electrocatalysis in Fuel Cells 324
10.3.1 Basic Principles 324
10.3.2 Types of Fuel Cell and Catalyst 325
10.3.3 Important Reactions in Fuel Cell Technology 328
10.3.3.1 The Anodic Reaction 328
10.3.3.2 The Cathodic Reaction 329
10.3.3.3 Methanol Oxidation 331 Exercises 332 References 333 11 Environmental Catalysis and Green Chemistry 335
11.1 Automotive Exhaust Catalysis 335
11.2 NOx Removal Systems 338
11.2.1 Selective Catalytic Reduction of Nitrogen Oxides 338
11.2.2 NOx Storage-Reduction Catalyst for Lean-Burning Engines 340
11.3 Catalytic Afterburning 341
11.4 Green Chemistry and Catalysis 344
11.4.1 Examples of Catalytical Processes 345
11.4.1.1 Aldol Condensation 345
11.4.1.2 Diels-Alder Reaction 346
11.4.1.3 Hydrogenation 347
11.4.1.4 Cyclization inWater 347
11.4.1.5 Use of Ionic Liquids 347
11.4.1.6 Green Solvents 349 Exercises 350 References 351 12 Phase-Transfer Catalysis 353
12.1 Definition 353
12.2 Catalysts for PTC 353
12.3 Mechanism and Benefits of PTC 354
12.4 PTC Reactions 355
12.5 Selected Industrial Proc