Description
Book SynopsisIntroduces major catalytic processes including products from the petroleum, chemical, environmental and alternative energy industries. This book provides a description of the fundamentals of catalysis and some of the major catalytic industrial processes used today. It offers a rationale for process designs based on kinetics and thermodynamics.
Trade Review"In less than 300 pages it serves as an excellent introduction to these subjects whether for advanced students or those seeking to learn more about these subjects on their own time...Particularly useful are the succinct summaries throughout the book...excellent detail in the table of contents, a detailed index, key references at the end of each chapter, and challenging classroom questions..." (GlobalCatalysis.com, May 2016)
Table of ContentsPreface xv
Acknowledgments xvii
List of Figures xix
Nomenclature xxvii
Chapter 1 Catalyst Fundamentals of Industrial Catalysis 1
1.1 Introduction 1
1.2 Catalyzed versus Noncatalyzed Reactions 1
1.2.1 Example Reaction: Liquid-Phase Redox Reaction 2
1.2.2 Example Reaction: Gas-Phase Oxidation Reaction 4
1.3 Physical Structure of a Heterogeneous Catalyst 6
1.3.1 Active Catalytic Species 7
1.3.2 Chemical and Textural Promoters 7
1.3.3 Carrier Materials 8
1.3.4 Structure of the Catalyst and Catalytic Reactor 8
1.4 Adsorption and Kinetically Controlled Models for Heterogeneous Catalysis 10
1.4.1 Langmuir Isotherm 11
1.4.2 Reaction Kinetic Models 13
1.4.2.1 Langmuir–Hinshelwood Kinetics for CO Oxidation on Pt 14
1.4.2.2 Mars–van Krevelen Kinetic Mechanism 17
1.4.2.3 Eley–Rideal (E–R) Kinetic Mechanism 18
1.4.2.4 Kinetic versus Empirical Rate Models 18
1.5 Supported Catalysts: Dispersed Model 19
1.5.1 Chemical and Physical Steps Occurring during Heterogeneous Catalysis 19
1.5.2 Reactant Concentration Gradients within the Catalyzed Material 22
1.5.3 The Rate-Limiting Step 22
1.6 Selectivity 24
1.6.1 Examples of Selectivity Calculations for Reactions with Multiple Products 25
1.6.2 Carbon Balance 26
1.6.3 Experimental Methods for Measuring Carbon Balance 27
Questions 27
Bibliography 29
Chapter 2 The Preparation of Catalytic Materials 31
2.1 Introduction 31
2.2 Carrier Materials 32
2.2.1 Al2O3 32
2.2.2 SiO2 34
2.2.3 TiO2 34
2.2.4 Zeolites 35
2.2.5 Carbons 37
2.3 Incorporating the Active Material into the Carrier 37
2.3.1 Impregnation 37
2.3.2 Incipient Wetness or Capillary Impregnation 38
2.3.3 Electrostatic Adsorption 38
2.3.4 Ion Exchange 38
2.3.5 Fixing the Catalytic Species 39
2.3.6 Drying and Calcination 39
2.4 Forming the Final Shape of the Catalyst 40
2.4.1 Powders 40
2.4.1.1 Milling and Sieving 41
2.4.1.2 Spray Drying 42
2.4.2 Pellets, Pills, and Rings 43
2.4.3 Extrudates 43
2.4.4 Granules 44
2.4.5 Monoliths 44
2.5 Catalyst Physical Structure and Its Relationship to Performance 45
2.6 Nomenclature for Dispersed Catalysts 45
Questions 46
Bibliography 46
Chapter 3 Catalyst Characterization 48
3.1 Introduction 48
3.2 Physical Properties of Catalysts 49
3.2.1 Surface Area and Pore Size 49
3.2.1.1 Nitrogen Porosimetry 49
3.2.1.2 Pore Size by Mercury Intrusion 51
3.2.2 Particle Size Distribution of Particulate Catalyst 51
3.2.2.1 Particle Size Distribution 51
3.2.2.2 Mechanical Strength 53
3.2.3 Physical Properties of Environmental Washcoated Monolith Catalysts 54
3.2.3.1 Washcoat Thickness 54
3.2.3.2 Washcoat Adhesion 54
3.3 Chemical and Physical Morphology Structures of Catalytic Materials 54
3.3.1 Elemental Analysis 54
3.3.2 Thermal Gravimetric Analysis and Differential Thermal Analysis 55
3.3.3 The Morphology of Catalytic Materials by Scanning Electron Microscopy 56
3.3.4 Structural Analysis by X-Ray Diffraction 57
3.3.5 Structure and Morphology of Al2O3 Carriers 58
3.3.6 Dispersion or Crystallite Size of Catalytic Species 58
3.3.6.1 Chemisorption 58
3.3.6.2 Transmission Electron Microscopy 61
3.3.7 X-Ray Diffraction 62
3.3.8 Surface Composition of Catalysts by X-Ray Photoelectron Spectroscopy 62
3.3.9 The Bonding Environment of Metal Oxides by Nuclear Magnetic Resonance 64
3.4 Spectroscopy 65
Questions 66
Bibliography 67
Chapter 4 Reaction Rate in Catalytic Reactors 69
4.1 Introduction 69
4.2 Space Velocity, Space Time, and Residence Time 69
4.3 Definition of Reaction Rate 71
4.4 Rate of Surface Kinetics 72
4.4.1 Empirical Power Rate Expressions 72
4.4.2 Experimental Measurement of Empirical Kinetic Parameters 73
4.4.3 Accounting for Chemical Equilibrium in Empirical Rate Expression 77
4.4.4 Special Case for First-Order Isothermal Reaction 77
4.5 Rate of Bulk Mass Transfer 78
4.5.1 Overview of Bulk Mass Transfer Rate 78
4.5.2 Origin of Bulk Mass Transfer Rate Expression 79
4.6 Rate of Pore Diffusion 80
4.6.1 Overview of Pore Diffusion 80
4.6.2 Pore Diffusion Theory 81
4.7 Apparent Activation Energy and the Rate-Limiting Process 82
4.8 Reactor Bed Pressure Drop 83
4.9 Summary 84
Questions 84
Bibliography 87
Chapter 5 Catalyst Deactivation 88
5.1 Introduction 88
5.2 Thermally Induced Deactivation 88
5.2.1 Sintering of the Catalytic Species 89
5.2.2 Sintering of Carrier 92
5.2.3 Catalytic Species–Carrier Interactions 95
5.3 Poisoning 96
5.3.1 Selective Poisoning 96
5.3.2 Nonselective Poisoning or Masking 97
5.4 Coke Formation and Catalyst Regeneration 99
Questions 101
Bibliography 103
Chapter 6 Generating Hydrogen and Synthesis Gas by Catalytic Hydrocarbon Steam Reforming 104
6.1 Introduction 104
6.1.1 Why Steam Reforming with Hydrocarbons? 104
6.2 Large-Scale Industrial Process for Hydrogen Generation 105
6.2.1 General Overview 105
6.2.2 Hydrodesulfurization 106
6.2.3 Hydrogen via Steam Reforming and Partial Oxidation 106
6.2.3.1 Steam Reforming 106
6.2.3.2 Deactivation of Steam Reforming Catalyst 110
6.2.3.3 Pre-reforming 111
6.2.3.4 Partial Oxidation and Autothermal Reforming 111
6.2.4 Water Gas Shift 112
6.2.4.1 Deactivation of Water Gas Shift Catalyst 116
6.2.5 Safety Considerations During Catalyst Removal 116
6.2.6 Other CO Removal Methods 116
6.2.6.1 Pressure Swing Absorption 116
6.2.6.2 Methanation 117
6.2.6.3 Preferential Oxidation of CO 117
6.2.7 Hydrogen Generation for Ammonia Synthesis 119
6.2.8 Hydrogen Generation for Methanol Synthesis 120
6.2.9 Synthesis Gas for Fischer–Tropsch Synthesis 120
6.3 Hydrogen Generation for Fuel Cells 121
6.3.1 New Catalyst and Reactor Designs for the Hydrogen Economy 122
6.3.2 Steam Reforming 123
6.3.3 Water Gas Shift 124
6.3.4 Preferential Oxidation 125
6.3.5 Combustion 125
6.3.6 Autothermal Reforming for Complicated Fuels 126
6.3.7 Steam Reforming of Methanol: Portable Power Applications 126
6.4 Summary 126
Questions 127
Bibliography 128
Chapter 7 Ammonia, Methanol, Fischer–Tropsch Production 129
7.1 Ammonia Synthesis 129
7.1.1 Thermodynamics 129
7.1.2 Reaction Chemistry and Catalyst Design 130
7.1.3 Process Design 132
7.1.4 Catalyst Deactivation 134
7.2 Methanol Synthesis 134
7.2.1 Process Design 136
7.2.1.1 Quench Reactor 136
7.2.1.2 Staged Cooling Reactor 137
7.2.1.3 Tube-Cooled Reactor 137
7.2.1.4 Shell-Cooled Reactor 138
7.2.2 Catalyst Deactivation 139
7.3 Fischer–Tropsch Synthesis 140
7.3.1 Process Design 142
7.3.1.1 Bubble/Slurry-Phase Process 142
7.3.1.2 Packed Bed Process 143
7.3.1.3 Slurry/Loop Reactor (Synthol Process) 143
7.3.2 Catalyst Deactivation 143
Questions 144
Bibliography 145
Chapter 8 Selective Oxidations 146
8.1 Nitric Acid 146
8.1.1 Reaction Chemistry and Catalyst Design 146
8.1.1.1 The Importance of Catalyst Selectivity 147
8.1.1.2 The PtRh Alloy Catalyst 147
8.1.2 Nitric Acid Production Process 148
8.1.3 Catalyst Deactivation 150
8.2 Hydrogen Cyanide 151
8.2.1 HCN Production Process 152
8.2.2 Deactivation 152
8.3 The Claus Process: Oxidation of H2S 154
8.3.1 Clause Process Description 154
8.3.2 Catalyst Deactivation 155
8.4 Sulfuric Acid 155
8.4.1 Sulfuric Acid Production Process 155
8.4.2 Catalyst Deactivation 158
8.5 Ethylene Oxide 159
8.5.1 Catalyst 159
8.5.2 Catalyst Deactivation 160
8.5.3 Ethylene Oxide Production Process 160
8.6 Formaldehyde 160
8.6.1 Low-Methanol Production Process 162
8.6.1.1 Fe+Mo Catalyst 162
8.6.2 High-Methanol Production Process 163
8.6.2.1 Ag Catalyst 164
8.7 Acrylic Acid 164
8.7.1 Acrylic Acid Production Process 164
8.7.2 Acrylic Acid Catalyst 165
8.7.3 Catalyst Deactivation 166
8.8 Maleic Anhydride 166
8.8.1 Catalyst Deactivation 166
8.9 Acrylonitrile 166
8.9.1 Acrylonitrile Production Process 167
8.9.2 Catalyst 168
8.9.3 Deactivation 168
Questions 168
Bibliography 169
Chapter 9 Hydrogenation, Dehydrogenation, and Alkylation 171
9.1 Introduction 171
9.2 Hydrogenation 171
9.2.1 Hydrogenation in Stirred Tank Reactors 171
9.2.2 Kinetics of a Slurry-Phase Hydrogenation Reaction 174
9.2.3 Design Equation for the Continuous Stirred Tank Reactor 176
9.3 Hydrogenation Reactions and Catalysts 177
9.3.1 Hydrogenation of Vegetable Oils for Edible Food Products 177
9.3.2 Hydrogenation of Functional Groups 180
9.3.3 Biomass (Corn Husks) to a Polymer 183
9.3.4 Comparing Base Metal and Precious Metal Catalysts 183
9.4 Dehydrogenation 185
9.5 Alkylation 187
Questions 188
Bibliography 189
Chapter 10 Petroleum Processing 190
10.1 Crude Oil 190
10.2 Distillation 191
10.3 Hydrodemetalization and Hydrodesulfurization 193
10.4 Hydrocarbon Cracking 197
10.4.1 Fluid Catalytic Cracking 197
10.4.2 Hydrocracking 200
10.5 Naphtha Reforming 200
Questions 202
Bibliography 203
Chapter 11 Homogeneous Catalysis and Polymerization Catalysts 205
11.1 Introduction to Homogeneous Catalysis 205
11.2 Hydroformylation: Aldehydes from Olefins 206
11.3 Carboxylation: Acetic Acid Production 208
11.4 Enzymatic Catalysis 209
11.5 Polyolefins 210
11.5.1 Polyethylene 210
11.5.2 Polypropylene 212
Questions 213
Bibliography 213
Chapter 12 Catalytic Treatment from Stationary Sources: Hc, Co, Nox, and O3 215
12.1 Introduction 215
12.2 Catalytic Incineration of Hydrocarbons and Carbon Monoxide 216
12.2.1 Monolith (Honeycomb) Reactors 218
12.2.2 Catalyzed Monolith (Honeycomb) Structures 219
12.2.3 Reactor Sizing 220
12.2.4 Catalyst Deactivation 222
12.2.5 Regeneration of Deactivated Catalysts 224
12.3 Food Processing 225
12.3.1 Catalyst Deactivation 226
12.4 Nitrogen Oxide (NOx) Reduction from Stationary Sources 226
12.4.1 SCR Technology 227
12.4.2 Ozone Abatement in Aircraft Cabin Air 229
12.4.3 Deactivation 229
12.5 CO2 Reduction 230
Questions 231
Bibliography 233
Chapter 13 Catalytic Abatement of Gasoline Engine Emissions 235
13.1 Emissions and Regulations 235
13.1.1 Origins of Emissions 235
13.1.2 Regulations in the United States 236
13.1.3 The Federal Test Procedure for the United States 238
13.2 Catalytic Reactions Occurring During Catalytic Abatement 238
13.3 First-Generation Converters: Oxidation Catalyst 239
13.4 The Failure of Nonprecious Metals: A Summary of Catalyst History 240
13.4.1 Deactivation and Stabilization of Precious Metal Oxidation Catalysts 241
13.5 Supporting the Catalyst in the Exhaust 242
13.5.1 Ceramic Monoliths 242
13.5.2 Metal Monoliths 245
13.6 Preparing the Monolith Catalyst 246
13.7 Rate Control Regimes in Automotive Catalysts 247
13.8 Catalyzed Monolith Nomenclature 248
13.9 Precious Metal Recovery from Catalytic Converters 248
13.10 Monitoring Catalytic Activity in a Monolith 248
13.11 The Failure of the Traditional Beaded (Particulate) Catalysts for Automotive Applications 250
13.12 NOx, CO and HC Reduction: The Three-Way Catalyst 251
13.13 Simulated Aging Methods 255
13.14 Close-Coupled Catalyst 256
13.15 Final Comments 258
Questions 259
Bibliography 261
Chapter 14 Diesel Engine Emission Abatement 262
14.1 Introduction 262
14.1.1 Emissions from Diesel Engines 262
14.1.2 Analytical Procedures for Particulates 264
14.2 Catalytic Technology for Reducing Emissions from Diesel Engines 265
14.2.1 Diesel Oxidation Catalyst 265
14.2.2 Diesel Soot Abatement 266
14.2.3 Controlling NOx in Diesel Engine Exhaust 267
Questions 272
Bibliography 273
Chapter 15 Alternative Energy Sources Using Catalysis: Bioethanol by Fermentation, Biodiesel by Transesterification, and H2-Based Fuel Cells 274
15.1 Introduction: Sources of Non-Fossil Fuel Energy 274
15.2 Sources of Non-Fossil Fuels 276
15.2.1 Biodiesel 276
15.2.1.1 Production Process 276
15.2.2 Bioethanol 277
15.2.2.1 Process for Bioethanol from Corn 278
15.2.3 Lignocellulose Biomass 278
15.2.4 New Sources of Natural Gas and Oil Sands 279
15.3 Fuel Cells 279
15.3.1 Markets for Fuel Cells 281
15.3.1.1 Transportation Applications 281
15.3.1.2 Stationary Applications 282
15.3.1.3 Portable Power Applications 282
15.4 Types of Fuel Cells 283
15.4.1 Low-Temperature PEM Fuel Cell 284
15.4.1.1 Electrochemical Reactions for H2-Fueled Systems 284
15.4.1.2 Mechanistic Principles of the PEM Fuel Cell 286
15.4.1.3 Membrane Electrode Assembly 287
15.4.2 Solid Polymer Membrane 288
15.4.3 PEM Fuel Cells Based on Direct Methanol 289
15.4.4 Alkaline Fuel Cell 290
15.4.5 Phosphoric Acid Fuel Cell 290
15.4.6 Molten Carbonate Fuel Cell 291
15.4.7 Solid Oxide Fuel Cell 293
15.5 The Ideal Hydrogen Economy 293
Questions 294
Bibliography 295
Index 297
