CONTENTS 12
Preface 19
Acknowledgments 21
Nomenclature 22
Part One: Introduction and Fundamentals 29
1 Catalysis: Introduction and Fundamental Catalytic Phenomena 31
1.1 Emergence of Catalyst Technology, A Brief History 32
1.1.1 Basic Variables for Control of Chemical Reactions 32
1.1.2 A Brief History of Catalyst Technology Development 32
1.2 Importance of Catalysis and Catalyst Technology 34
1.2.1 Impact on Society and Life Forms 34
1.2.2 Economic Importance of Catalyst Technology 36
1.2.3 Catalyst Technology of the Present 36
1.2.4 Catalysis in Your Future 38
1.3 Fundamental Catalytic Phenomena and Principles 40
1.3.1 Definitions 40
1.3.2 The Structure of a Supported Catalyst: Model and Reality 44
1.3.3 Steps in a Heterogeneous Catalytic Reaction 45
1.3.4 Adsorption and Desorption 46
1.3.5 Reaction and Diffusional Resistances for a Catalytic Reaction 52
1.3.6 Kinetics of Catalytic Surface Reactions 61
1.3.7 Effects of Surface Structure and Support on Catalytic Activity 69
1.4 Summary of Important Principles 79
1.5 Recommended Sources for Further Study 82
1.6 Exercises 82
1.7 References 85
2 Catalyst Materials, Properties and Preparation 88
2.1 Introduction 89
2.2 Catalyst Materials 89
2.2.1 Make-up of a Typical Heterogeneous Catalyst 90
2.2.2 Active Phases, Carriers, Promoters 90
2.2.3 Molecular Sieves and Zeolites 96
2.3 Catalyst Properties 106
2.3.1 Catalyst Engineering 106
2.3.2 Physical, Mechanical, and Chemical Properties 108
2.3.3 Dynamic (Catalytic) Properties of Catalysts 117
2.4 Catalyst Preparation and Forming 118
2.4.1 Making the Finished Catalyst 119
2.4.2 Catalyst Forming 130
2.5 The Future 135
2.5.1 Multidisciplinary, Mission-Oriented, Fundamental Research Aimed at Development of New Concepts of Catalysis Design 135
2.5.2 Design of New Molecular Sieves 135
2.5.3 Design of Sophisticated Composite Catalysts Based on Nanostructures 136
2.5.4 Biocatalysts: The Development of Stabilized and/or Supported Enzymes and Organometallic Enzyme Mimics 137
2.5.5 Novel Catalyst Preparation Methods: The Preparation of Amorphous Metal Powders, Supported Catalysts and Nanocolloids by a Sonochemical Technique 137
2.5.6 Combinatorial Design of Catalysts 138
2.5.7 Computational Methods for Design of Catalysts 139
2.6 Summary 139
2.7 Recommended Sources for Further Study 140
2.8 Exercises 141
2.9 References 142
3 Catalyst Characterization and Selection 146
3.1 Principles and Objectives of Catalyst Characterization 147
3.1.1 Definition of Catalyst Characterization 147
3.1.2 Objectives of Catalyst Characterization 149
3.1.3 Some Perspectives and Principles of Characterization 151
3.2 Determining Physical Properties of Catalysts 152
3.2.1 Surface Area, Pore Size, and Pore Volume 152
3.2.2 Particle Size and Size Distribution 163
3.2.3 Mechanical Strength 164
3.2.4 Density 165
3.3 Determining Chemical Properties of Catalysts 166
3.3.1 Chemical Composition 167
3.3.2 Chemical Structure and Morphology 167
3.3.3 Dispersion or Crystallite Size of Catalytic Species 173
3.3.4 Surface Acidity 180
3.3.5 Surface Reactivity 181
3.3.6 Surface Chemistry, Structure, and Composition 188
3.4 Catalyst Selection 207
3.5 The Future 209
3.5.1 Future Directions 209
3.5.2 Future Needs for Catalyst Characterization 212
3.6 Summary 212
3.7 Recommended Sources for Further Study 214
3.8 Exercises 215
3.9 References 219
4 Reactors, Reactor Design, and Activity Testing 225
4.1 Introduction 226
4.2 Definition and Classification of Reactors 226
4.2.1 Definition 226
4.2.2 Classification 227
4.3 Fundamentals of Reactor Design 228
4.3.1 Basic Approach to Reactor Design 228
4.3.2 Material Balances for Ideal Reactors 230
4.3.3 Temperature Effects and Energy Balances 236
4.3.4 Examples of Reactor Design 244
4.4 Collecting, Analyzing and Reporting Data from Laboratory Reactors 252
4.4.1 Collection of Data: Integral and Differential Reactors 252
4.4.2 Analyzing and Reporting Data from Laboratory Reactors 255
4.4.3 Examples of Rate Data Analysis 258
4.5 Choosing Reactors in the Laboratory and Plant 265
4.5.1 Choosing Reactors for the Laboratory 265
4.5.2 Selection of Plant Reactors 270
4.6 The Future 275
4.6.1 Future Trends in Reactor Design and Kinetics 275
4.6.2 Kinetic Models for Reactor and Process Design 276
4.6.3 Process Plant Simulation and Corporate Modeling: A New Paradigm 277
4.7 Summary 278
4.8 Recommended Sources for Further Study 279
4.9 Exercises 280
4.10 References 286
5 Catalyst Deactivation: Causes, Mechanisms, and Treatment 288
5.1 Introduction 289
5.2 Causes and Mechanisms of Deactivation 289
5.2.1 Poisoning 290
5.2.2 Fouling, Coking, and Carbon Deposition 295
5.2.3 Thermal Degradation and Sintering 302
5.2.4 Loss of Catalytic Phases by Vapor Transport 307
5.2.5 Mechanical Failure: Attrition and Crushing of Catalysts 309
5.3 Prevention and Regenerative Treatment of Catalyst Decay 311
5.3.1 Prevention of Catalyst Decay 311
5.3.2 Regeneration of Deactivated Catalysts 315
5.4 Treatment of Catalyst Decay in Reactor and Process Design and Operation 321
5.4.1 Modeling and Design of Deactivation Processes 321
5.4.2 Experimental Assessment of Deactivation Kinetics 328
5.4.3 Reactor and Process Design and Operation with Deactivating Catalyst 340
5.5 The Future 349
5.5.1 Projected Trends 349
5.5.2 Future Needs 350
5.6 Summary 350
5.7 Recommended Sources for Further Study 351
5.8 Exercises 352
5.9 References 359
Part Two: Industrial Practice 365
6 Hydrogen Production and Synthesis Gas Reactions 367
6.1 Introduction 368
6.2 Production of Hydrogen and Synthesis Gas via Steam Reforming 370
6.2.1 Overall Process 370
6.2.2 Purification of Hydrocarbons 372
6.2.3 Primary Steam Reforming 373
6.2.4 Secondary Steam Reforming 395
6.2.5 High-Temperature Water-Gas-Shift 395
6.2.6 Low-Temperature Water-Gas-Shift 397
6.2.7 Final CO/CO2 Removal/Methanation 398
6.3 Ammonia Synthesis 399
6.3.1 Introduction and Background 399
6.3.2 Reaction Chemistry, Thermodynamics, Kinetics, and Mechanism 400
6.3.3 Catalyst Design 404
6.3.4 Catalyst Deactivation 407
6.3.5 Reactor and Process Design 408
6.4 Methanol Synthesis 410
6.4.1 Introduction 410
6.4.2 Reaction Chemistry and Equilibrium Thermodynamics 410
6.4.3 Reaction Mechanism, Active Sites, and Kinetics 413
6.4.4 Methanol Synthesis Catalysts 418
6.4.5 Catalyst Deactivation 420
6.4.6 Methanol Synthesis Process 421
6.4.7 Methanol Synthesis Literature 425
6.4.8 Higher Alcohol Synthesis 426
6.5 Fischer-Tropsch Synthesis 426
6.5.1 Introduction 426
6.5.2 History 426
6.5.3 Chemistry and Thermodynamics 430
6.5.4 Mechanisms, Kinetics, and Models 433
6.5.5 Co Product Distributions in and Selectivity Models of FTS 445
6.5.6 Co Product Distributions in and Selectivity Models of FTS 457
6.5.7 Catalyst Deactivation and Regeneration 478
6.5.8 Reactor Design 489
6.5.9 Process Technology 493
6.6 The Future 496
6.6.1 General Trends 496
6.6.2 Hydrogen and Synthesis Gas Production 497
6.6.3 Ammonia Synthesis 497
6.6.4 Methanol Synthesis 497
6.6.5 Fischer-Tropsch Synthesis 498
6.7 Summary 498
6.8 Recommended Readings for Further Study 499
6.9 Exercises 502
6.10 References 504
7 Hydrogenation and Dehydrogenation of Organic Compounds 519
7.1 Introduction 520
7.2 Hydrogenation Catalyst and Reactor Technologies 520
7.2.1 Hydrogenation Catalysts 520
7.2.2 Hydrogenation Reactor Design, Reactor Technology, and Process Conditions 528
7.3 Hydrogenation Reactions and Processes 545
7.3.1 Hydrogenation of Alkenes to Alkanes and Alkadienes or Alkynes to Alkenes 545
7.3.2 Hydrogenation of Aromatics and Nitroaromatics 550
7.3.3 Hydrogenation of Nitriles to Amines 555
7.3.4 Hydrogenation of Fats and Oils 556
7.3.5 Hydrogenation of Carbonyl Groups 563
7.3.6 Miscellaneous Hydrogenation Reactions 564
7.4 Dehydrogenation: Reaction Chemistry; Catalyst and Reactor Technologies 565
7.4.1 Dehydrogenation Reaction Chemistry 566
7.4.2 Dehydrogenation Catalysts 567
7.4.3 Dehydrogenation Reactor Technology 568
7.5 Important Dehydrogenation Reactions and Processes 568
7.5.1 Alkanes to Alkenes 568
7.5.2 Dehydrogenation of Ethylbenzene to Styrene 575
7.6 The Future 577
7.6.1 Hydrogenation Catalysis 577
7.6.2 Dehydrogenation Catalysis 580
7.7 Summary 581
7.8 Recommended Sources for Further Study 582
7.9 Exercises 583
7.10 References 586
8 Catalytic Oxidations of Inorganic and Organic Compounds 592
8.1 Catalytic Oxidation Reactions 593
8.1.1 Introduction, Background, and Perspective 593
8.1.2 Classification of Oxidation Reactions 593
8.2 Oxidation of Inorganic Compounds 594
8.2.1 Introduction 594
8.2.2 Sulfuric Acid Production 594
8.2.3 Nitric Acid Production 602
8.3 Hydrogen Cyanide Production (Ammoxidation of Methane) 607
8.3.1 Reaction Chemistry 607
8.3.2 Catalyst 608
8.3.3 Processes 608
8.3.4 Catalyst Deactivation 610
8.4 Selective (Partial) Oxidation of Organic Compounds 610
8.4.1 Introduction, Background and Chemistry 610
8.4.2 Methanol to Formaldehyde 616
8.4.3 Ethylene to Ethylene Oxide 629
8.4.4 Ammoxidation of Propylene to Acrylonitrile and Related Processes 636
8.4.5 n-Butane to Maleic Anhydride 642
8.5 Future of Catalytic Oxidation 650
8.5.1 Short-Term Trends 651
8.5.2 Long-Term Future 653
8.6 Summary 656
8.7 Recommended Sources for Further Study 658
8.8 Exercises 659
8.9 References 661
9 Petroleum Refining and Processing 667
9.1 Petroleum Refining 668
9.1.1 Introduction 668
9.1.2 Fractionation of Petroleum 669
9.1.3 Major Catalytic Applications for Upgrading Distilled Crude Oil 671
9.2 Hydrotreating 671
9.2.1 Reaction Chemistry and Kinetics 671
9.2.2 Hydrotreating Catalyst Design 677
9.2.3 Reactor Design 679
9.2.4 Hydrotreating Process 680
9.2.5 Catalyst Deactivation and Regeneration 681
9.2.6 Ultra Low Sulfur Diesel 684
9.3 Catalytic Cracking 685
9.3.1 Reaction Chemistry of Fluidized Catalytic Cracking 685
9.3.2 Mechanisms and Kinetics 687
9.3.3 Cracking Catalysts 694
9.3.4 Catalytic Cracking Process 701
9.3.5 Deactivation 702
9.4 Hydrocracking 703
9.4.1 Chemistry 703
9.4.2 Catalysts 704
9.4.3 Process 705
9.4.4 Catalyst Deactivation 705
9.5 Naphtha Reforming 706
9.5.1 Chemistry 707
9.5.2 Catalysts 710
9.5.3 Process 711
9.5.4 Catalyst Deactivation and Regeneration 713
9.6 Isomerization 714
9.6.1 Hydroisomerization of Normal Butane, Pentane and Hexane 714
9.6.2 Isomerization of Xylenes 716
9.7 Alkylation 717
9.7.1 Catalysts 717
9.7.2 Liquid Acid Process 718
9.7.3 Ethylbenzene Synthesis 719
9.8 Reformulated Gasoline and Methyl-t-Butyl Ether 719
9.8.1 Reformulated Gasoline (RFG) 719
9.8.2 MTBE Production 720
9.9 The Future 721
9.9.1 Near-Term and Process-Specific Trends 721
9.9.2 The Long Term Future of Refining (the next 10\u201325 years) 724
9.10 Summary 727
9.11 Recommended Sources for Further Study 728
9.12 Exercises 728
9.13 References 731
10 Environmental Catalysis: Mobile Sources 737
10.1 Introduction 738
10.2 Automotive Gasoline Catalytic Converters 739
10.2.1 Introduction and Background 739
10.2.2 Early Oxidation Converters (1976\u20131979) 740
10.2.3 Three-way Catalysts (1979\u20132000) 745
10.2.4 Modern Three Way Catalytic Converters (Post\u20132000) 749
10.2.5 Lean Burn Engines and Emissions Abatement Catalysts 756
10.2.6 Converter Design 757
10.3 Catalytic Abatement of Emissions from Diesel Engines 763
10.3.1 Diesel Emissions 763
10.3.2 Diesel Oxidation Catalyst 765
10.3.3 Engine Testing of Catalysts 768
10.3.4 Catalyst Deactivation 768
10.3.5 Catalytic Treatment of Soot from Diesel Emission 769
10.3.6 Future of Diesel Emission Abatement 770
10.4 Ozone Abatement in High-Flying Commercial Aircraft 774
10.5 Summary 775
10.5.1 Development, Technological Significance and Status of Catalytic Emissions Controls for Gasoline-Powered Vehicles 775
10.5.2 Development and Status of Catalytic Emissions Control Technology for Diesel-Powered Vehicles 776
10.5.3 Future Trends in Catalytic Emissions Control for Mobile Sources 777
10.6 Recommended Sources for Further Study 777
10.7 Exercises 778
10.8 References 779
11 Environmental Catalysis: Stationary Sources 785
11.1 Introduction 786
11.2 Catalytic Reduction of NOx 787
11.2.1 Non-Selective Catalytic Reduction of NOx 787
11.2.2 Selective Catalytic Reduction of NOx 788
11.2.3 N2O Decomposition 809
11.3 Catalytic Oxidation of Hydrocarbon (VOC) Emissions 810
11.4 Catalytic Oxidation of CO Emissions 815
11.5 Kinetics of and Reactor Design for CO and VOC Oxidations 816
11.5.1 Kinetics and Reactor Design for Oxidation of CO 817
11.5.2 Kinetics and Reactor Design for Oxidation of Hydrocarbons 821
11.5.3 Representative, Relevant Modeling Studies 826
11.6 Catalytic Abatement of Emissions from Wood Stoves 827
11.7 The Future 828
11.7.1 Introduction 828
11.7.2 Advanced/Novel Catalytic Materials 828
11.7.3 Catalytically Supported Thermal Combustion 829
11.7.4 Management of Hazardous and Toxic Materials, Wastes and CFCs 832
11.7.5 Catalytic Clean-up for Specialty Applications 832
11.7.6 Green Engineering/Chemistry and Renewable Processes 834
11.7.7 Future Needs 837
11.8 Summary 837
11.9 Recommendations for Further Study 838
11.10 Exercises 839
11.11 References 842
12 Homogeneous, Enzyme, And Polymerization Catalysis 852
12.1 Homogeneous Catalysis 853
12.1.1 Introduction and Definitions 853
12.1.2 Fundamentals of Homogeneous Catalysis 854
12.1.3 Industrial Homogeneous Catalytic Processes 869
12.1.4 Examples of Important Processes 872
12.1.5 The Future of Homogeneous Catalysis 876
12.2 Enzyme Catalysis 878
12.2.1 Introduction 878
12.2.2 Chemistry, Kinetics, and Mechanisms 879
12.2.3 Industrial Enzymatic Processes and Biotechnology 884
12.2.4 Examples of Important Processes 891
12.2.5 The Future of Enzyme Catalysis 894
12.3 Polymerization Catalysis 896
12.3.1 Introduction and Definitions 896
12.3.2 Fundamentals of Polymerization Synthesis/Catalysis 902
12.3.3 Industrial Polymerization Catalysts and Catalytic Processes 911
12.3.4 Examples of Important Polymerization Processes 919
12.3.5 The Future of Polymerization Catalysis 927
12.4 Summary 929
12.5 Recommended Sources for Further Study 931
12.6 Exercises 933
12.7 References 935
13 Hydrogen Production and Fuel Cells: Catalyst Technology 941
13.1 Introduction, Perspective, and Objectives 942
13.2 Production of Hydrogen for Fuel cells 944
13.2.1 Traditional catalytic steps in the production of Hydrogen for Chemical Applications 944
13.2.2 Alternative Approaches to Generating Hydrogen for the Fuel Cell 946
13.3 The Proton Exchange Membrane (PEM) Fuel Cell 953
13.3.1 PEM Fuel Cell 953
13.3.2 Electrochemical Reactions 954
13.3.3 The Membrane Electrode Assembly (MEA) 955
13.3.4 The Solid Polymer Membrane 956
13.3.5 Potential Applications of PEM Fuel Cells 957
13.3.6 Operational Factors in a PEM Fuel Processor/Fuel Cell 958
13.4 Other Fuel Cells 959
13.4.1 Alkaline Electrolyte Fuel Cell 959
13.4.2 Phophoric Acid Fuel Cell 959
13.4.3 Molten Carbonate Fuel Cell 960
13.4.4 Solid Oxide Fuel Cell 962
13.4.5 Direct Methanol Fuel Cell 963
13.5 Summary and Concluding Remarks 963
13.6 Recommended Sources for Further Study 964
13.7 Exercises 965
13.8 References 965
Glossary 971
Index 986