A comprehensive textbook on petrochemical conversion processes for petroleum and natural gas fractions as produced by refinery operations
This innovative textbook provides essential links between the chemical sciences and chemical technology, between petrochemistry and hydrocarbon technology. The book brings alive key concepts forming the basis of chemical technology and presents a solid background for innovative process development. In all chapters, the processes described are accompanied by simplified flow schemes, encouraging students to think in terms of conceptual process designs.
Petrochemistry: Petrochemical Processing, Hydrocarbon Technology and Green Engineering introduces students to a variety of topics related to the petrochemical industry, hydrocarbon processing, fossil fuel resources, as well as fuels and chemicals conversion. The first chapter covers the fundamentals and principals for designing several of the processes in the book, including discussions on thermodynamics, chemical kinetics, reactor calculations, and industrial catalysts. The following chapters address recent advances in hydrocarbon technology, energy technology, and sources of hydrocarbons. The book then goes on to discuss the petrochemical industry based on four basic pillars, all derived from petroleum and natural gas:
- Production of lower alkenes; other sources of lower alkenes; petrochemicals from C2-C3 alkenes
- Production of BTX aromatics; chemicals from BTX aromatics
- C1 technology
- Diversification of petrochemicals
The growing importance of sustainable technology, process intensification and addressing greenhouse gas emissions is reflected throughout the book.
Written for advanced students working in the areas of petrochemistry, hydrocarbon technology, natural gas, energy materials and technologies, alternative fuels, and recycling technologies the book is also a valuable reference for industrial practitioners in the oil and gas industry.
Table of Contents
About the Book xv
Preface xvii
Acknowledgments xix
General Literature xxi
Nomenclature xxv
Abbreviations and Acronyms xxvii
1 Chemical Technology 1
1.1 Introduction 2
1.2 Chemical Engineering 5
1.2.1 Conservation of Mass 7
1.2.2 Conservation of Energy 7
1.2.3 Conservation of Momentum 8
1.2.4 Thermodynamics of Chemical Reactions 8
1.2.5 Chemical Kinetics 11
1.2.5.1 Reaction Rate: Activation Energy 11
1.2.6 Reactors 12
1.2.6.1 Conversion, Selectivity, and Yields 12
1.2.6.2 Continuous Tubular Reactor 13
1.2.6.3 The Reaction Order 15
1.2.6.4 Rate Constant 15
1.2.7 Industrial Catalysts 16
1.2.7.1 The Place of Catalytic Processes in Hydrocarbon Technology 16
1.2.7.2 Homogeneous Catalysts 16
1.2.7.3 Heterogeneous Catalysts 18
1.2.7.4 Classifying Catalysts 19
1.2.8 Conversion of Hydrocarbons: Active Intermediate Forms 21
1.2.8.1 Carbocations 21
1.2.8.2 Radicals 23
1.2.8.3 Initiated Decomposition 26
1.3 Potential Steps Toward Greener Chemical Technology 28
1.3.1 Maturity 29
1.3.2 Participation in International Trade 29
1.3.3 Competition from Developing Countries 30
1.3.4 Capital Intensity and Economies of Scale 31
1.3.5 Criticality and Pervasiveness 32
1.3.6 Freedom of Market Entry 33
1.3.7 Stringent Requirements of the Clean Air Act (CAA) 34
1.3.8 High R&D for Ecologically Oriented Projects 34
1.3.9 Dislocations and Environmental Impacts 38
1.3.10 Feedstock Recycling 40
1.4 The Top Chemical Companies 41
1.5 The Top Chemicals 43
Further Reading 45
2 Current Trends in Green Hydrocarbon Technology 47
2.1 Introduction 47
2.2 Eco-Friendly Catalysts 48
2.3 Hydrogen 50
2.4 Alternative Feedstocks 51
2.5 Alternative Technologies 53
2.6 Feedstock Recycling 54
2.7 Functionalization of Hydrocarbons 55
2.7.1 Partial Oxidation of Methane 55
2.8 Biorefining 56
Further Reading 56
3 Clean Energy Technology 59
3.1 Rational Use of Energy 59
3.2 The Problem of Energy in Chemical Technology 62
3.2.1 The Basics of Energy Management to Improve Economic Budgeting 63
3.2.2 Types of Energy and Energy Sources for Chemical Technology 63
3.3 Waste Fuel Utilization 65
3.3.1 Electricity 65
3.3.2 Energy Efficiency Improvements 65
3.3.3 Energy and the Environment 66
3.3.3.1 Carbon and Greenhouse Emissions 66
3.3.3.2 Formation of Particulate Matter 67
3.3.3.3 CO2 Emissions 68
3.4 Energy Technology 70
3.4.1 Thermodynamics 70
3.4.2 Power Recovery in Other Systems 71
3.4.3 Heat Recovery, Energy Balances, and Heat-Exchange Networks 71
3.4.4 Waste-Heat Boilers 72
3.4.5 Product-to-Feed Heat Interchange 73
3.4.6 Combustion Air Preheat 73
3.4.7 Heat Pumps 74
3.5 Energy Accounting 75
Further Reading 77
4 Sources of Hydrocarbons 79
4.1 Introduction 80
4.2 Natural Gas 81
4.2.1 Definitions and Terminology 82
4.2.2 Origin 83
4.2.3 Occurrence 84
4.2.4 Reserves 84
4.2.5 Recovery 84
4.2.6 Storage 85
4.3 Petroleum or Crude Oil 85
4.4 Coal and Its Liquefaction 88
4.5 Shale Gas and Tight Oil: Unconventional Fossil Fuels 89
4.5.1 Introduction 90
4.5.2 Glossary and Terminology 91
4.5.3 Energy in 2018 93
4.5.4 Energy Outlook 2035 94
4.6 Shale Gas 96
4.6.1 Geology 98
4.6.2 Formation of Natural Gas Reservoirs 99
4.6.2.1 General 99
4.6.2.2 Unconventional Reservoir 99
4.6.2.3 Low-Permeability Gas Reservoirs 101
4.6.2.4 Fractured Shales 102
4.7 Tight Oil 102
4.7.1 Types of Tight Oil Plays 103
4.7.1.1 Geo-Stratigraphic Play 104
4.7.1.2 Shale Oil Play 104
4.7.2 Technologies Used to Recover Tight Oil 104
4.7.2.1 Horizontal Drilling 105
4.7.2.2 Hydraulic Fracturing 105
4.7.2.3 Microseismic Events 106
4.7.3 Initial Production 106
4.7.3.1 Infill Drilling 106
4.7.3.2 Wellbore Construction and Groundwater Protection 107
4.7.3.3 Minimizing Footprint 107
4.7.4 Environmental Impacts of Natural Gas 107
4.7.4.1 Water and Air Quality, Methane, and Other Important Greenhouse Gases 108
4.7.4.2 Earthquakes 108
4.7.5 Conclusion 108
4.8 Heavy Oils, Shale, and Tar Sand 109
Further Reading 110
5 Links with Natural Gas, Crude Oil, and Petroleum Refineries 113
5.1 Links with Natural Gas 113
5.1.1 Introduction 113
5.1.2 Processing 114
5.1.3 Water Removal 114
5.1.4 Acid Gas Removal: Environmentally Friendly Solvents 115
5.1.5 Fractionation 115
5.1.6 Turboexpander Process 116
5.1.7 Solvent Recovery 116
5.1.8 Chemicals From Natural Gas 117
5.2 LPG as an Ethylene Feedstock 117
5.3 Heavy Condensates 117
5.4 Links with Crude Oil 118
5.4.1 Naphtha 119
5.4.2 Middle Distillates 122
5.4.3 Heavy Condensates Recovery 123
5.5 Links with Petroleum Refineries 124
5.5.1 Fluid Catalytic Cracking 124
5.5.2 Catalytic Reforming 128
5.5.2.1 Maximum Aromatic Production 131
5.5.2.2 Aromatics Complex 131
6 Hydrocarbon Technology, Trends, and Outlook in Petrochemistry 133
6.1 Definition 133
6.2 Petrochemistry and Its Products 140
Further Reading 142
7 Pillar A of Petrochemistry 143
Production of Lower Alkenes
7.1 Steam Cracking (Pyrolysis) 143
7.1.1 Reaction in Steam Cracking 145
7.1.2 Thermodynamics 145
7.1.3 Mechanism 145
7.1.4 Kinetics 145
7.2 Industrial Process 145
7.2.1 Composition of Feedstock 146
7.2.2 Pyrolysis Temperature and Residence Time 146
7.2.3 Partial Pressure of Hydrocarbon and Steam-to-Naphtha Ratio 147
7.2.4 Severity and Selectivity 147
7.2.5 Furnace Run Length 148
7.3 Ethylene Furnace Design 148
7.3.1 Heat Exchanger 149
7.4 Coke Formation During Pyrolysis and Decoking Measures 150
7.4.1 Catalytic Gasification of Coke During Production 150
7.4.2 Sulfur Addition to Ethane Feedstocks 153
7.5 Product Processing 153
7.5.1 Hot Section 155
7.5.2 Quench Section 155
7.6 Typical Naphtha Cracker Plant 155
7.6.1 Hot Section 155
7.6.2 Cold Section 156
7.7 Gas-Feed Cracker Process Design 156
7.8 Trends in Technological Development of Steam Crackers for Production of Ethylene 159
7.8.1 Direct Involvement in Petrochemical Production 161
7.8.2 Integrating SC Operations 162
Further Reading 164
8 Pillar A of Petrochemistry 165
Other Sources of Lower Alkenes
8.1 Catalytic Dehydrogenation of Light Alkanes 165
8.2 Methanol to Alkenes 169
8.2.1 MTO Catalyst 169
8.3 Metathesis 171
8.3.1 Process Chemistry 171
8.4 Oxidative Coupling of Methane 172
8.5 Current and Future Developments 174
Further Reading 175
9 Pillar A of Petrochemistry 177
Petrochemicals from C2 - C3 Alkenes
9.1 Introduction 177
9.2 Chemicals from Ethylene 178
9.3 Chemicals from Propylene 178
9.4 Polymerization 179
10 Pillar B of Petrochemistry 181
Production of BTX Aromatics
10.1 Introduction 181
10.2 Alkylation 183
10.2.1 Ethylbenzene 183
10.2.1.1 Process Chemistry 183
10.2.1.2 New Eco-Friendly Catalyst 184
10.2.1.3 Environmental Protection of the Described Process 185
10.2.1.4 CDTECH EB Process 185
10.2.1.5 EBMAX Process 187
10.2.2 Cumene 188
10.2.2.1 Process Chemistry 188
10.2.2.2 Environmental Protection of the Process Description 189
Further Reading 190
11 Pillar B of Petrochemistry 191
Chemicals from BTX Aromatics
11.1 Chemicals from Aromatic Hydrocarbons 191
11.2 Styrene 192
11.2.1 Process Chemistry 193
11.2.2 Process Descriptions 193
11.3 Hydrogenation 194
11.3.1 Partial Hydrogenation of Benzene to Cyclohexene 195
11.4 Hydrodealkylation of Toluene 196
11.5 Isomerization 197
11.6 Disproportionation of Toluene 198
11.7 Oxidation Processes 199
11.7.1 Cumene → Phenol + Acetone 199
11.7.2 Process Chemistry 200
11.7.2.1 Cumene Oxidation to Cumene Hydroperoxide 200
11.7.2.2 Cumene Hydroperoxide Cleavage to Phenol and Acetone 200
11.7.2.3 Distillation Section 200
11.7.3 Process Description 201
11.7.4 Benzene → Maleic Anhydride 202
11.7.5 Cyclohexane → Cyclohexanol + Cyclohexanone → Adipic Acid 202
11.7.6 P-Xylene → Terephthalic Acid / Dimethyl Terephthalate 203
11.8 Condensation Processes 204
11.8.1 Aniline 204
11.8.2 4,4′-Diphenylmethane Diisocyanate 204
11.8.3 Toluene → Dinitrotoluene and Toluene Diisocyanate 205
11.8.4 Bisphenol A 206
11.8.4.1 Bisphenol Reaction 208
11.8.4.2 Process Description 208
12 Pillar C of Petrochemistry 209
C1 Technologies
12.1 Introduction 210
12.2 Synthesis Gas 211
12.2.1 Steam Reforming of Methane - Stringent Greenhouse Gas 212
12.2.1.1 Reactions and Thermodynamics 213
12.2.2 Steam Reforming Process 214
12.2.3 Hydrogen 215
12.2.4 MegaMethanol Technology 215
12.2.4.1 Process Description 216
12.2.5 Autothermal Reforming 218
12.2.6 Combined Reforming 219
12.2.7 Methanol Synthesis 220
12.2.7.1 Methanol Synthesis Loop 222
12.2.7.2 Methanol Distillation 222
12.2.8 MTBE 223
12.2.8.1 Environmentally Friendly Process of Catalytic Distillation 224
12.2.9 Etherification of Glycerol by Isobutylene 225
12.2.10 Fisher-Tropsch Synthesis 228
12.2.11 Acetic Acid 229
12.2.11.1 Background Information 229
12.2.11.2 Principal Reaction 230
12.2.11.3 Catalyst Preparation Reactions 230
12.2.11.4 Process Description 231
12.2.12 Hydroformylation 231
12.2.12.1 Thermodynamics 232
12.2.12.2 Catalyst Development 233
12.2.12.3 Catalytic Cycle 233
12.2.12.4 Kinetics 234
12.2.12.5 Process Flowsheet 234
12.2.12.6 Comparison of the Hydroformylation Process 235
Further Reading 236
13 Hydrogen Technologies 237
13.1 Introduction 237
13.2 Hydrogen as an Alternative Fuel 239
13.2.1 Production of Hydrogen 240
13.2.1.1 Dry Reforming, Methane, and CO2 Chemical Transformation 241
13.3 Vehicle On-Board Fuel Reforming 243
13.3.1 Steam Reforming of Naphtha (Gasoline) 245
13.3.2 On-Board Diesel Fuel Processing 246
13.3.3 Direct and Gradual Internal Reforming of Methane 248
13.3.4 Methanol-to-Hydrogen Production 249
13.3.5 Steam Reforming of Ethanol 252
13.4 Vehicular Hydrogen Storage Approaches 254
13.4.1 Reversible On-Board Approaches 255
13.4.1.1 Compressed Hydrogen Gas 255
13.4.1.2 Liquid Hydrogen Tanks 256
13.4.1.3 Metal Hydrides 256
13.4.1.4 High-Surface-Area Sorbents and Carbon-Based Materials 256
13.4.2 Chemical Hydrogen Storage: Regenerable Off-Board 257
13.4.2.1 Hydrolysis Reactions 257
13.4.2.2 Hydrogenation/Dehydrogenation Reactions 257
13.4.2.3 Ammonia Borane and Other Boron Hydrides 258
13.4.2.4 Ammonia 258
13.4.2.5 Alane 258
13.5 Gas Conversion Technologies/Natural Gas Upgrading 258
13.5.1 GTL Conversion of Syngas to Fuel 259
Further Reading 259
14 Biorefineries 263
14.1 Introduction 263
14.2 Petrochemistry 264
14.3 Carbonization of Coal 264
14.4 Manufacturing of Activated Carbon 265
14.5 Chemicals and Fuels from Biomass 266
14.5.1 Degasification 266
14.5.2 Oxygenation 268
14.5.3 Levoglucosan 270
Further Reading 272
15 Recycling Technologies 273
15.1 Feedstock Recycling of Plastic Wastes 273
15.2 Fuels and Chemicals from Polymer Waste 275
15.3 Fuels and Chemicals from Used Tires 277
Further Reading 281
16 Microchannel Technologies and Nanotechnology 283
16.1 Introduction 283
16.2 Fluid Flow in Microchannels 285
16.3 Intensified Superheated Processing 286
16.3.1 Oxidative Dehydrogenation of Hydrocarbons 287
16.3.2 Steam Reforming of Ethanol 287
16.3.3 Fischer-Tropsch Synthesis and GTL 288
16.4 Steam Cracking of Hydrocarbons 289
16.5 Nanotechnology 292
16.5.1 Definition 292
16.5.2 Fundamental Concepts 294
16.5.3 Nanomaterials 295
16.5.4 Applications 295
Further Reading 296
Index 297
