Petrochemistry

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.

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