Introduces the reader to the various petrochemical intermediates are generally produced by chemical conversion of primary pe
Table of Contents
Contents
Preface..............................................................................................................................................xv
About the Author............................................................................................................................xvii
Chapter 1 The Petrochemical Industry..........................................................................................1
1.1 Introduction........................................................................................................1
1.2 Historical Aspects and Overview..................................................................... 10
1.3 The Petrochemical Industry............................................................................. 11
1.4 Petrochemicals.................................................................................................. 17
1.4.1 Primary Petrochemicals...................................................................... 19
1.4.2 Products and End Use......................................................................... 19
1.5 Production of Petrochemicals...........................................................................20
1.6 The Future........................................................................................................24
References...................................................................................................................29
Chapter 2 Feedstock Composition and Properties....................................................................... 31
2.1 Introduction...................................................................................................... 31
2.2 Natural Gas....................................................................................................... 31
2.2.1 Composition and Properties................................................................ 33
2.2.2 Natural Gas Liquids............................................................................ 42
2.2.3 Gas Condensate................................................................................... 43
2.2.4 Gas Hydrates.......................................................................................44
2.2.5 Other Types of Gases..........................................................................46
2.2.5.1 Biogas.................................................................................. 47
2.2.5.2 Coalbed Methane.................................................................48
2.2.5.3 Coal Gas..............................................................................49
2.2.5.4 Geopressurized Gas............................................................. 51
2.2.5.5 Landfill Gas......................................................................... 51
2.2.5.6 Refinery Gas........................................................................ 53
2.2.5.7 Synthesis Gas....................................................................... 57
2.2.5.8 Tight Gas............................................................................. 58
2.3 Petroleum.......................................................................................................... 59
2.3.1 Composition and Properties................................................................ 59
2.3.1.1 Opportunity Crude Oil........................................................ 61
2.3.1.2 High Acid Crude Oil........................................................... 61
2.3.1.3 Foamy Oil............................................................................ 62
2.3.1.4 Tight Oil............................................................................... 62
2.3.2 Other Petroleum-Derived Feedstocks.................................................63
2.3.2.1 Naphtha................................................................................63
2.3.2.2 Kerosene..............................................................................64
2.3.2.3 Fuel Oil................................................................................65
2.3.2.4 Gas Oil................................................................................. 67
2.3.2.5 Residua................................................................................. 67
2.3.2.6 Used Lubricating Oil...........................................................68
2.4 Heavy Oil, Extra Heavy Oil, and Tar Sand Bitumen.......................................68
2.4.1 Heavy Oil............................................................................................69
2.4.2 Extra Heavy Oil...................................................................................69
2.4.3 Tar sand Bitumen................................................................................ 71
References................................................................................................................... 74
Chapter 3 Other Feedstocks—Coal, Oil Shale, and Biomass..................................................... 79
3.1 Introduction...................................................................................................... 79
3.2 Coal.................................................................................................................. 81
3.2.1 Coal Feedstocks..................................................................................82
3.2.2 Properties and Composition................................................................83
3.2.3 Conversion...........................................................................................83
3.2.4 Coal Tar Chemicals.............................................................................85
3.3 Oil Shale...........................................................................................................90
3.3.1 Shale Oil Production...........................................................................90
3.3.2 Shale Oil Properties............................................................................ 91
3.3.2.1 Hydrocarbon Products.........................................................92
3.3.2.2 Nitrogen-Containing Compounds.......................................93
3.3.2.3 Oxygen-Containing Compounds.........................................94
3.3.2.4 Sulfur-Containing Compounds...........................................94
3.4 Biomass............................................................................................................94
3.4.1 Biomass Feedstocks............................................................................97
3.4.1.1 Carbohydrates......................................................................99
3.4.1.2 Vegetable Oils......................................................................99
3.4.1.3 Plant Fibers..........................................................................99
3.4.2 Biorefining......................................................................................... 100
3.4.2.1 Pyrolysis............................................................................ 103
3.4.2.2 Gasification........................................................................ 103
3.4.2.3 Anaerobic Digestion.......................................................... 107
3.4.2.4 Fermentation...................................................................... 110
3.4.3 Chemicals from Biomass.................................................................. 111
3.4.3.1 Gaseous Products............................................................... 111
3.4.3.2 Liquid Products.................................................................. 112
3.4.3.3 Solid Products.................................................................... 114
3.5 Waste.............................................................................................................. 114
References................................................................................................................. 115
Chapter 4 Feedstock Preparation............................................................................................... 119
4.1 Introduction.................................................................................................... 119
4.2 Gas Streams.................................................................................................... 120
4.2.1 Sources.............................................................................................. 121
4.2.1.1 Gas Streams from Natural Gas.......................................... 121
4.2.1.2 Natural Gas Liquids and Liquefied Petroleum Gas........... 123
4.2.1.3 Gas Streams from Crude Oil.............................................124
4.2.2 Gas Processing.................................................................................. 127
4.2.2.1 Acid Gas Removal............................................................. 128
4.2.2.2 Recovery of Condensable Hydrocarbon Derivatives......... 137
4.2.2.3 Water Removal.................................................................. 142
4.2.2.4 Nitrogen Removal.............................................................. 145
4.2.2.5 The Claus Process.............................................................. 145
4.3 Petroleum Streams.......................................................................................... 147
4.3.1 Refinery Configuration...................................................................... 149
4.3.2 Cracking Processes........................................................................... 150
4.3.2.1 Thermal Cracking Processes............................................. 150
4.3.2.2 Catalytic Cracking Processes............................................ 153
4.3.3 Dehydrogenation Processes............................................................... 155
4.3.4 Dehydrocyclization Processes........................................................... 157
4.4 Streams from Coal, Oil Shale, and Biomass.................................................. 158
4.4.1 Coal................................................................................................... 158
4.4.1.1 Coal Gas............................................................................ 158
4.4.1.2 Coal Liquids...................................................................... 158
4.4.2 Oil Shale............................................................................................ 159
4.4.2.1 Oil Shale Gas..................................................................... 159
4.4.2.2 Shale Oil............................................................................ 160
4.4.3 Biomass............................................................................................. 161
4.4.3.1 Biogas................................................................................ 161
4.4.3.2 Bio-liquids......................................................................... 161
References................................................................................................................. 162
Chapter 5 Feedstock Preparation by Gasification...................................................................... 165
5.1 Introduction.................................................................................................... 165
5.2 Gasification Chemistry................................................................................... 168
5.2.1 General Aspects................................................................................ 169
5.2.2 Pretreatment...................................................................................... 170
5.2.3 Reactions........................................................................................... 171
5.2.3.1 Primary Gasification.......................................................... 174
5.2.3.2 Secondary Gasification...................................................... 174
5.2.3.3 Water-Gas Shift Reaction.................................................. 176
5.2.3.4 Carbon Dioxide Gasification............................................. 177
5.2.3.5 Hydrogasification............................................................... 178
5.2.3.6 Methanation....................................................................... 178
5.3 Gasification Processes.................................................................................... 179
5.3.1 Gasifiers............................................................................................. 180
5.3.2 FT Synthesis...................................................................................... 181
5.3.3 Feedstocks......................................................................................... 183
5.3.3.1 Heavy Feedstocks.............................................................. 183
5.3.3.2 Solvent Deasphalter Bottoms............................................. 184
5.3.3.3 Asphalt, Tar, and Pitch...................................................... 184
5.3.3.4 Petroleum Coke.................................................................. 186
5.3.3.5 Coal.................................................................................... 188
5.3.3.6 Biomass.............................................................................. 189
5.3.3.7 Solid Waste........................................................................ 191
5.3.3.8 Black Liquor...................................................................... 193
5.4 Gasification in a Refinery............................................................................... 193
5.4.1 Gasification of Heavy Feedstocks..................................................... 195
5.4.2 Gasification of Heavy Feedstocks with Coal.................................... 195
5.4.3 Gasification of Heavy Feedstocks with Biomass.............................. 196
5.4.4 Gasification of Heavy Feedstocks with Waste.................................. 198
5.5 Gas Production and Other Products............................................................... 198
5.5.1 Gaseous Products.............................................................................. 199
5.5.1.1 Synthesis Gas..................................................................... 199
5.5.1.2 Low Btu Gas......................................................................200
5.5.1.3 Medium Btu Gas................................................................200
5.5.1.4 High Btu Gas..................................................................... 201
5.5.2 Liquid Products................................................................................. 201
5.5.3 Solid Products...................................................................................202
5.6 The Future......................................................................................................202
References.................................................................................................................204
Chapter 6 Chemicals from Paraffin Hydrocarbons...................................................................209
6.1 Introduction....................................................................................................209
6.2 Methane.......................................................................................................... 211
6.2.1 Physical Properties............................................................................ 212
6.2.2 Chemical Properties.......................................................................... 213
6.2.3 Chemicals from Methane.................................................................. 215
6.2.3.1 Carbon Disulfide................................................................ 216
6.2.3.2 Ethylene............................................................................. 217
6.2.3.3 Hydrogen Cyanide............................................................. 218
6.2.3.4 Chloromethane Derivatives............................................... 218
6.2.3.5 Synthesis Gas.....................................................................220
6.2.3.6 Urea....................................................................................223
6.2.3.7 Methyl Alcohol..................................................................223
6.2.3.8 Formaldehyde....................................................................226
6.2.3.9 Aldehyde Derivatives.........................................................229
6.2.3.10 Ethylene Glycol..................................................................229
6.2.3.11 Nitration.............................................................................230
6.2.3.12 Oxidation...........................................................................230
6.2.3.13 Carboxylic Acids............................................................... 231
6.2.3.14 Alkylation.......................................................................... 231
6.2.3.15 Thermolysis....................................................................... 232
6.2.4 Oxidative Coupling........................................................................... 233
6.3 Ethane............................................................................................................. 235
6.3.1 Physical Properties............................................................................ 235
6.3.2 Chemical Properties..........................................................................236
6.3.3 Chemicals from Ethane..................................................................... 237
6.4 Propane...........................................................................................................238
6.4.1 Physical Properties............................................................................238
6.4.2 Chemical Properties.......................................................................... 239
6.4.3 Chemicals from Propane...................................................................240
6.4.3.1 Oxidation...........................................................................240
6.4.3.2 Chlorination.......................................................................240
6.4.3.3 Dehydrogenation................................................................ 241
6.4.3.4 Nitration............................................................................. 247
6.5 Butane Isomers............................................................................................... 247
6.5.1 Physical Properties............................................................................249
6.5.2 Chemical Properties..........................................................................249
6.5.3 Chemicals from Butane.....................................................................250
6.5.3.1 Oxidation...........................................................................250
6.5.3.2 Production of Aromatics.................................................... 252
6.5.3.3 Isomerization..................................................................... 252
6.5.4 Chemicals from Isobutane................................................................ 252
6.6 Liquid Petroleum Fractions and Residues...................................................... 252
6.6.1 Naphtha.............................................................................................254
6.6.1.1 Physical Properties............................................................254
6.6.1.2 Chemical Properties.......................................................... 255
6.6.1.3 Chemicals from Naphtha...................................................256
6.6.2 Kerosene............................................................................................ 257
6.6.2.1 Physical Properties............................................................ 257
6.6.2.2 Chemical Properties.......................................................... 257
6.6.2.3 Chemicals from Kerosene................................................. 258
6.6.3 Gas Oil.............................................................................................. 258
6.6.3.1 Physical Properties............................................................ 258
6.6.3.2 Chemical Properties.......................................................... 259
6.6.3.3 Chemicals from Gas Oil.................................................... 259
6.6.4 Fuel Oil..............................................................................................260
6.6.4.1 Physical Properties............................................................ 261
6.6.4.2 Chemical Properties.......................................................... 261
6.6.4.3 Chemicals from Fuel Oil................................................... 262
6.6.5 Resids................................................................................................ 262
6.6.5.1 Physical Properties............................................................263
6.6.6 Used Lubricating Oil.........................................................................263
6.6.7 Naphthenic Acids..............................................................................263
6.6.8 Chemicals from Liquid Petroleum Fractions and Residues..............264
6.6.8.1 Oxidation...........................................................................265
6.6.8.2 Chlorination.......................................................................265
6.6.8.3 Sulfonation.........................................................................265
6.6.8.4 Other Products...................................................................266
References.................................................................................................................266
Chapter 7 Chemicals from Olefin Hydrocarbons......................................................................269
7.1 Introduction....................................................................................................269
7.2 Chemicals from Ethylene............................................................................... 271
7.2.1 Alcohols............................................................................................ 273
7.2.2 Alkylation.......................................................................................... 275
7.2.3 Halogen Derivatives.......................................................................... 276
7.2.4 Oxygen Derivatives...........................................................................277
7.2.4.1 Ethylene Glycol.................................................................. 279
7.2.4.2 Ethoxylates......................................................................... 281
7.2.4.3 Ethanolamines...................................................................282
7.2.4.4 1,3-Propanediol..................................................................282
7.2.4.5 Acetaldehyde.....................................................................283
7.2.5 Carbonylation....................................................................................285
7.2.6 Chlorination......................................................................................286
7.2.6.1 Vinyl Chloride...................................................................286
7.2.6.2 Perchloroethylene and Trichloroethylene..........................287
7.2.7 Hydration...........................................................................................287
7.2.8 Oligomerization.................................................................................288
7.2.9 Polymerization..................................................................................289
7.2.10 1 -Butylene..........................................................................................290
7.2.11 Polymerization..................................................................................290
7.3 Chemicals from Propylene............................................................................. 291
7.3.1 Oxidation...........................................................................................294
7.3.2 Ammoxidation...................................................................................296
7.3.3 Oxyacylation......................................................................................299
7.3.4 Chlorination......................................................................................300
7.3.5 Hydration...........................................................................................300
7.3.6 Addition of Organic Acids................................................................302
7.3.7 Hydroformylation..............................................................................302
7.3.8 Disproportionation............................................................................303
7.3.9 Alkylation..........................................................................................303
7.4 Chemicals from C4 Olefins.............................................................................303
7.4.1 Butylene.............................................................................................304
7.4.1.1 Oxidation...........................................................................306
7.4.1.2 Hydration...........................................................................308
7.4.1.3 Isomerization.....................................................................309
7.4.1.4 Metathesis..........................................................................309
7.4.1.5 Oligomerization................................................................. 310
7.4.2 Isobutylene........................................................................................ 310
7.4.2.1 Oxidation........................................................................... 311
7.4.2.2 Epoxidation........................................................................ 311
7.4.2.3 Addition of Alcohols......................................................... 312
7.4.2.4 Hydration........................................................................... 312
7.4.2.5 Carbonylation.................................................................... 312
7.4.2.6 Dimerization...................................................................... 312
7.5 Chemicals from Diolefins............................................................................... 313
7.5.1 Chemicals from Butadiene................................................................ 313
7.5.1.1 Adiponitrile........................................................................ 314
7.5.1.2 Hexamethylenediamine..................................................... 314
7.5.1.3 Adipic Acid........................................................................ 314
7.5.1.4 Butanediol.......................................................................... 315
7.5.1.5 Chloroprene....................................................................... 315
7.5.1.6 Cyclic Oligomers............................................................... 316
7.5.2 Isoprene............................................................................................. 316
7.6 Chemicals from Acetylene............................................................................. 316
References................................................................................................................. 321
Chapter 8 Chemicals from Aromatic Hydrocarbons................................................................. 323
8.1 Introduction.................................................................................................... 323
8.2 Chemicals from Benzene............................................................................... 331
8.2.1 Alkylation.......................................................................................... 334
8.2.2 Chlorination...................................................................................... 339
8.2.3 Hydrogenation...................................................................................340
8.2.4 Nitration............................................................................................ 342
8.2.5 Oxidation........................................................................................... 343
8.3 Chemicals from Toluene................................................................................. 343
8.3.1 Carbonylation.................................................................................... 345
8.3.2 Chlorination...................................................................................... 345
8.3.3 Dealkylation...................................................................................... 347
8.3.4 Disproportionation............................................................................348
8.3.5 Nitration............................................................................................348
8.3.6 Oxidation........................................................................................... 350
8.4 Chemicals from Xylene Isomers.................................................................... 352
8.5 Chemicals from Ethylbenzene....................................................................... 355
References................................................................................................................. 357
Chapter 9 Chemicals from Non-hydrocarbons.......................................................................... 359
9.1 Introduction.................................................................................................... 359
9.2 Ammonia........................................................................................................360
9.2.1 Production......................................................................................... 361
9.2.2 Properties and Uses........................................................................... 362
9.3 Carbon Black.................................................................................................. 363
