Preface xiii
1 Introduction 1
References 6
General Literature 6
2 The Chemical Industry 7
2.1 A Brief History 7
2.1.1 Inorganic Chemicals 7
2.1.2 Organic Chemicals 10
2.1.3 The Oil Era 11
2.1.4 The Age of Sustainability 12
2.2 Structure of the Chemical Industry 13
2.3 Raw Materials and Energy 16
2.3.1 Fossil Fuel Consumption and Reserves 16
2.3.2 Biomass as an Alternative for Fossil Fuels 19
2.3.3 Energy and the Chemical Industry 21
2.3.4 Composition of Fossil Fuels and Biomass 23
2.4 Base Chemicals 35
2.5 Global Trends in the Chemical Industry 37
References 39
General Literature 40
3 Processes in the Oil Refinery 41
3.1 The Oil Refinery An Overview 41
3.2 Physical Processes 42
3.2.1 Desalting and Dehydration 42
3.2.2 Crude Distillation 43
3.2.3 Propane Deasphalting 45
3.3 Thermal Processes 46
3.3.1 Visbreaking 46
3.3.2 Delayed Coking 47
3.3.3 Flexicoking 48
3.4 Catalytic Processes 49
3.4.1 Octane and Cetane Numbers 49
3.4.2 Catalytic Cracking 51
3.4.3 Catalytic Reforming 63
3.4.4 Alkylation 69
3.4.5 Hydroprocessing 76
3.5 Current and Future Trends in Oil Refining 91
3.5.1 Stricter Environmental Regulations 92
3.5.2 Refinery Configurations 94
References 96
4 Production of Light Alkenes 99
4.1 Introduction 99
4.2 Cracking Reactions 100
4.2.1 Thermodynamics 100
4.2.2 Mechanism 101
4.2.3 Kinetics 102
4.3 The Industrial Process 103
4.3.1 Influence of Feedstock on Steam Cracker Operation and Products 103
4.3.2 Cracking Furnace 106
4.3.3 Heat Exchanger 109
4.3.4 Coke Formation 110
4.4 Product Processing 111
4.5 Novel Developments 113
4.5.1 Selective Dehydrogenation of Light Alkanes 114
4.5.2 Metathesis of Alkenes 116
4.5.3 Production of Light Alkenes from Synthesis Gas 118
4.5.4 Dehydration of Bioethanol 121
4.5.5 Direct Conversion of Methane 122
References 123
5 Production of Synthesis Gas 127
5.1 Introduction 127
5.2 Synthesis Gas from Natural Gas 129
5.2.1 Reactions and Thermodynamics 129
5.2.2 Steam Reforming Process 131
5.2.3 Autothermal Reforming Process 137
5.2.4 Novel Developments 139
5.3 Coal Gasification 142
5.3.1 Gasification Reactions 142
5.3.2 Thermodynamics 143
5.3.3 Gasification Technologies 146
5.3.4 Recent Developments in Gasification Technology 151
5.3.5 Applications of Coal Gasification 154
5.3.6 Integrated Gasification Combined Cycle 156
5.3.7 Why Gasify, Not Burn for Electricity Generation? 158
5.3.8 Carbon Capture and Storage (CCS) 159
5.4 Cleaning and Conditioning of Synthesis Gas 161
5.4.1 Acid Gas Removal 161
5.4.2 Water-Gas Shift Reaction 163
5.4.3 Methanation 166
References 168
6 Bulk Chemicals and Synthetic Fuels Derived from Synthesis Gas 171
6.1 Ammonia 171
6.1.1 Background Information 171
6.1.2 Thermodynamics 173
6.1.3 Commercial Ammonia Synthesis Reactors 175
6.1.4 Ammonia Synthesis Loop 178
6.1.5 Integrated Ammonia Plant 180
6.1.6 Hydrogen Recovery 182
6.1.7 Production of Urea 185
6.2 Methanol 191
6.2.1 Background Information 191
6.2.2 Reactions, Thermodynamics, and Catalysts 192
6.2.3 Synthesis Gas for Methanol Production 195
6.2.4 Methanol Synthesis 196
6.2.5 Production of Formaldehyde 199
6.3 Synthetic Fuels and Fuel Additives 201
6.3.1 Fischer-Tropsch Process 202
6.3.2 Methanol-to-Gasoline (MTG) Process 212
6.3.3 Recent Developments in the Production of Synthetic Fuels 214
6.3.4 Fuel Additives Methyl Tert-Butyl Ether 215
References 218
7 Processes for the Conversion of Biomass 221
7.1 Introduction 221
7.2 Production of Biofuels 223
7.2.1 Bioethanol and Biobutanol 224
7.2.2 Diesel-Type Biofuels 226
7.3 Production of Bio-based Chemicals 231
7.3.1 Ethanol 232
7.3.2 Glycerol 233
7.3.3 Succinic Acid 234
7.3.4 Hydroxymethylfurfural (HMF) 236
7.4 The Biorefinery 236
7.4.1 Biorefinery Design Criteria and Products 236
7.4.2 Biorefinery Concepts 238
7.4.3 Core Technologies of a Thermochemical Biorefinery 239
7.4.4 Existing and Projected Biorefineries 243
7.4.5 Possibility of Integrating a Biorefinery with Existing Plants 243
7.4.6 Biorefinery versus Oil Refinery 245
7.5 Conclusions 246
References 246
8 Inorganic Bulk Chemicals 249
8.1 The Inorganic Chemicals Industry 249
8.2 Sulfuric Acid 250
8.2.1 Reactions and Thermodynamics 252
8.2.2 SO 2 Conversion Reactor 252
8.2.3 Modern Sulfuric Acid Production Process 254
8.2.4 Catalyst Deactivation 256
8.3 Sulfur Production 256
8.4 Nitric Acid 260
8.4.1 Reactions and Thermodynamics 260
8.4.2 Processes 262
8.4.3 No X Abatement 266
8.5 Chlorine 268
8.5.1 Reactions for the Electrolysis of NaCl 269
8.5.2 Technologies for the Electrolysis of NaCl 270
References 274
9 Homogeneous Transition Metal Catalysis in the Production of Bulk Chemicals 275
9.1 Introduction 275
9.2 Acetic Acid Production 278
9.2.1 Background Information 278
9.2.2 Methanol Carbonylation - Reactions, Thermodynamics, and Catalysis 281
9.2.3 Methanol Carbonylation - Processes 284
9.3 Hydroformylation 286
9.3.1 Background Information 286
9.3.2 Thermodynamics 288
9.3.3 Catalyst Development 289
9.3.4 Processes for the Hydroformylation of Propene 292
9.3.5 Processes for the Hydroformylation of Higher Alkenes 294
9.3.6 Comparison of Hydroformylation Processes 296
9.4 Ethene Oligomerization and More 297
9.4.1 Background Information 297
9.4.2 Reactions of the SHOP Process 298
9.4.3 The SHOP Process 299
9.5 Oxidation of p-Xylene: Dimethyl Terephthalate and Terephthalic Acid Production 301
9.5.1 Background Information 301
9.5.2 Conversion of p-Toluic Acid Intermediate 302
9.5.3 Processes 303
9.5.4 Process Comparison 305
9.6 Review of Reactors Used in Homogeneous Catalysis 305
9.6.1 Choice of Reactor 306
9.6.2 Exchanging Heat 308
9.7 Approaches for Catalyst/Product Separation 308
9.7.1 Biphasic Catalyst Systems 309
9.7.2 Immobilized Catalyst Systems 309
References 311
10 Heterogeneous Catalysis - Concepts and Examples 313
10.1 Introduction 313
10.2 Catalyst Design 314
10.2.1 Catalyst Size and Shape 314
10.2.2 Mechanical Properties of Catalyst Particles 316
10.3 Reactor Types and Their Characteristics 316
10.3.1 Reactor Types 316
10.3.2 Exchanging Heat 319
10.3.3 Role of Catalyst Deactivation 321
10.3.4 Other Issues 322
10.4 Shape Selectivity Zeolites 323
10.4.1 Production of Isobutene 325
10.4.2 Isomerization of Pentanes and Hexanes 328
10.4.3 Production of Ethylbenzene 330
10.5 Some Challenges and (Unconventional) Solutions 334
10.5.1 Adiabatic Reactor with Periodic Flow Reversal 334
10.5.2 Highly Exothermic Reactions with a Selectivity Challenge Selective Oxidations 338
10.6 Monolith Reactors Automotive Emission Control 344
10.6.1 Exhaust Gas Composition 346
10.6.2 Reduction of Exhaust Gas Emissions 347
References 354
General Literature 355
11 Production of Polymers Polyethene 357
11.1 Introduction 357
11.2 Polymerization Reactions 357
11.2.1 Step growth Polymerization 358
11.2.2 Chain growth Polymerization Radical and Coordination Pathways 360
11.3 Polyethenes - Background Information 363
11.3.1 Catalyst Development 363
11.3.2 Classification and Properties 364
11.3.3 Applications 365
11.4 Processes for the Production of Polyethenes 366
11.4.1 Monomer Production and Purification 366
11.4.2 Polymerization - Exothermicity 367
11.4.3 Production of Polyethenes 367
References 375
12 Production of Fine Chemicals 377
12.1 Introduction 377
12.2 Role of Catalysis 380
12.2.1 Atom Economy 380
12.2.2 Alternative Reagents and Catalysts 381
12.2.3 Novel Reaction Routes 384
12.2.4 Selectivity 384
12.2.5 Biocatalysis 392
12.3 Solvents 394
12.3.1 Conventional Solvents 394
12.3.2 Alternative Solvents 395
12.4 Production Plants 398
12.4.1 Multiproduct and Multipurpose Plants (MMPs) 398
12.4.2 Dedicated Continuous Plants 406
12.5 Batch Reactor Selection 407
12.5.1 Reactors for Liquid and Gas-Liquid Systems 408
12.5.2 Reactors for Gas-Liquid-Solid Systems 409
12.6 Batch Reactor Scale-up Effects 411
12.6.1 Temperature Control 411
12.6.2 Heat Transfer 411
12.6.3 Example of the Scale-up of a Batch and Semi-Batch Reactor 412
12.6.4 Summary of the Scale-up of Batch Reactors 416
12.7 Safety Aspects of Fine Chemicals 416
12.7.1 Thermal Risks 416
12.7.2 Safety and Process Development 417
References 419
13 Biotechnology 423
13.1 Introduction 423
13.2 Principles of Fermentation Technology 424
13.2.1 Mode of Operation 425
13.2.2 Reactor Types 426
13.2.3 Sterilization 432
13.3 Cell Biomass Bakers' Yeast Production 433
13.3.1 Process Layout 433
13.3.2 Cultivation Equipment 434
13.3.3 Downstream Processing 434
13.4 Metabolic Products Biomass as Source of Renewable Energy 435
13.4.1 Bioethanol and Biobutanol 435
13.4.2 Biogas 438
13.5 Environmental Application - Wastewater Treatment 438
13.5.1 Introduction 438
13.5.2 Process Layout 438
13.5.3 Aerobic Treatment Processes 440
13.5.4 Anaerobic Treatment Processes 443
13.6 Enzyme Technology - Biocatalysts for Transformations 445
13.6.1 General Aspects 445
13.6.2 Immobilization of Enzymes 446
13.6.3 Production of L-Amino Acids 447
13.6.4 Production of Artificial Sweeteners 448
References 452
General Literature 453
14 Process Intensification 455
14.1 Introduction 455
14.1.1 What is Process Intensification 455
14.1.2 How to Intensify Processes 457
14.2 Structured Catalytic Reactors 459
14.2.1 Types of Structured Catalysts and Reactors 460
14.2.2 Monoliths 462
14.2.3 Microreactors 468
14.3 Multifunctional Reactors/Reactive Separation 472
14.3.1 Reactive Distillation 473
14.3.2 Coupling Reaction and Membrane Separation 477
14.3.3 Coupling Reaction and Adsorption 481
References 482
15 Process Development 485
15.1 Dependence of Strategy on Product Type and Raw Materials 485
15.2 The Course of Process Development 487
15.3 Development of Individual Steps 489
15.3.1 Exploratory Phase 489
15.3.2 From Process Concept to Preliminary Flow Sheet 489
15.3.3 Pilot Plants/Miniplants 494
15.4 Scale-up 499
15.4.1 Reactors with a Single Fluid Phase 499
15.4.2 Fixed Bed Catalytic Reactors with One or More Fluid Phases 501
15.5 Safety and Loss Prevention 505
15.5.1 Safety Issues 505
15.5.2 Reactivity Hazards 511
15.5.3 Design Approaches to Safety 513
15.6 Process Evaluation 514
15.6.1 Capital Cost Estimation 515
15.6.2 Operating Costs and Earnings 523
15.6.3 Profitability Measures 524
15.7 Current and Future Trends 526
References 528
General Literature 529
Magazines 529
Appendix A Chemical Industry Figures 531
Appendix B Main Symbols Used in Flow Schemes 535
Index 539
