Table of Contents
Preface v
1 Introduction 1
1.1 Catalysis and Catalysts 1
1.2 Heterogeneous and Homogeneous Catalysis 3
1.3 Production of Ammouia 7
1.3.1 Kinetics and Thermodynamics 8
1.3.2 Activity, Selectivity and Stability 11
1.3.3 H2 Synthesis 14
1.3.4 Ammonia Synthesis 18
1.4 Relevance of Catalysis 22
References 22
Questions 23
2 Adsorption 25
2.1 Physisorption 25
2.1.1 Adsorption on Surfaces 28
2.1.2 Adsorption Isotherms 30
2.1.3 Multilayer Adsorption, BET 33
2.2 Surface Diffusion 39
2.3 Chemisorption 42
2.3.1 Chemical Bonding 42
2.3.2 Dissociative Chemisorption 50
References 53
Questions 54
3 Catalyst Characterisation 55
3.1 Crystal Structures 55
3.2 X-Hay Diffraction 62
3.3 Electron Microscopy 66
3.4 Scanning Tunnelling Microscopy and Atomic Force Microscopy 71
3.5 Infrared and Raman Spectroscopy 73
3.6 Nuclear Magnetic Resonance 81
3.7 Thermal Techniques 85
References 88
Questions 90
4 Catalyst Preparation 91
4.1 Heterogeneous Catalysts 91
4.2 Aluminas 94
4.2.1 Aluminium Hydroxides, Oxyhydroxides and Oxides 95
4.2.2 α-Al2O3 100
4.2.3 γ-Al2O3, η-Al2O3 and x-Al2O3 101
4.2.4 θ-Al2O3 and κ-Al2O3 105
4.3 Surface of γ-Al2O3 106
4.4 Silica 111
4.5 Zeolites 113
4.6 Preparation of Supported Catalysts 122
References 127
Questions 129
5 Kinetics 131
5.1 Langmuir Hinshelwood Model 131
5.2 Monomolecular Reaction 133
5.2.1 Surface Reaction is Rate-Determining 134
5.2.2 Adsorption of the React ant or Product is Rate-Determining 137
5.3 Rimolecnlar Reaction 137
5.4 Influence of Diffusion 139
Questions 148
6 Metal Surfaces 149
6.1 Surface Structures 149
6.2 Surface Analysis 152
6.2.1 X-ray Photoelectron Spectroscopy 153
6.2.2 Auger Electron Spectroscopy 156
6.2.3 Surface Sensitivity 157
6.3 Surface Enrichment 159
6.4 Metal Binding 164
References 169
Questions 171
7 Metal Catalysis 173
7.1 Dissociation of H2 174
7.2 Hydrogenation of Ethene 177
7.3 Synthesis of CO and H2 181
7.3.1 Bergius, Fischer-Tropsch and Methanation Reactions 181
7.3.2 Production of CO and H2 183
7.4 Hydrogenation of CO 185
7.4.1 Fischer Tropsch and Methanation 185
7.4.1.1 CO dissociation 185
7.4.1.2 Methanation 190
7.4.1.3 Fischer-Tropsch reaction 193
7.4.2 Methanol Synthesis 197
7.5 Hydrogenation of N2 to Ammonia 201
7.5.1 Fe Catalyst 201
7.5.2 Ru Catalyst 203
7.6 Volcano Curves 207
References 211
Questions 214
8 Catalysis by Acids 215
5.1 Reactions Catalysed by Solid Acids 215
8.1 Reactions of Carbenium Ions 217
8.2 Isomerisation of C5, C6 and C4 224
8.3 Alcohols from Alkenes 231
8.5 Alkylation of Aromaties 233
8.5.1 Ethylation and Propylation of Benzene 233
8.5.2 Methylation of Toluene 238
8.5.3 Isomerisation, Disproportionation, Transalkylation 242
8.6 Methanol to Hydrocarbons 247
8.7 Bifunctional Catalysis 253
8.7.1 Principles 253
8.7.2 Industrially Relevant Bifunctional Catalysis 262
References 264
Questions 267
9 Oxidation Catalysis 269
9.1 CO Oxidation 269
9.1.1 Mechanism 269
9.1.2 Three-Way Catalysis 276
9.2 Production of Sulphuric and Nitric Acid 279
9.2.1 Sulphuric Acid 279
9.2.2 Nitric Acid 281
9.3 Oxidation of Hydrocarbons 284
9.3.1 Oxidation by Oxygen 287
9.3.2 Oxidation by Hydroperoxide 291
9.3.3 Selective Partial Oxidation of Hydrocarbons 295
9.3.3.1 Oxidation of propene to acrylic acid and acrylonitrile 295
9.3.3.2 Oxidation of C4 and C6 molecules 299
References 300
Questions 303
Answers 305
Index 321
