Handbook of Petrochemical Processes
Chemical Industries Series

The petrochemical industry is a scientific and engineering field that encompasses the production of a wide range of chemicals and polymers. The purpose of this book is not only to provide a follow-on to form the later chapters of the highly successful Chemistry and Technology of Petroleum 5th Edition but also provides a simplified approach to a very diverse chemical subject dealing with the chemistry and technology of various petroleum and petrochemical process. Following from the introductory chapters, this book provides the readers with a valuable source of information containing insights into petrochemical reactions and products, process technology, and polymer synthesis.

• Provides readers with a valuable source of information containing insights into petrochemical reactions and products, process technology, and polymer synthesis
• Introduces the reader to the various petrochemical intermediates are generally produced by chemical conversion of primary petrochemicals to form more complicated derivative products
• The reactions and processes involved in transforming petroleum-based hydrocarbons into the chemicals that form the basis of the multi-billion dollar petrochemical industry are reviewed and described
• The book includes information on new process developments for the production of raw materials and intermediates for petrochemicals
• Includes a description of the origin of the raw materials for the petrochemicals industry ? including an overview of the coal chemicals industry

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

Dr. James G. Speight has doctorate degrees in Chemistry, Geological Sciences, and Petroleum Engineering and is the author of more than 75 books in petroleum science, petroleum engineering, and environmental sciences.

Dr. Speight has fifty years of experience in areas associated with (i) the properties, recovery, and refining of reservoir fluids, conventional petroleum, heavy oil, and tar sand bitumen, (ii) the properties and refining of natural gas, gaseous fuels, (iii) the production and properties of petrochemicals, (iv) the properties and refining of biomass, biofuels, biogas, and the generation of bioenergy, and (v) the environmental and toxicological effects of fuels. His work has also focused on safety issues, environmental effects, remediation, and safety issues as well as reactors associated with the production and use of fuels and biofuels. He is the author of more than 70 books in petroleum science, petroleum engineering, biomass and biofuels, environmental sciences.

Although he has always worked in private industry which focused on contract-based work, he has served as Adjunct Professor in the Department of Chemical and Fuels Engineering at the University of Utah and in the Departments of Chemistry and Chemical and Petroleum Engineering at the University of Wyoming. In addition, he was a Visiting Professor in the College of Science, University of Mosul, Iraq and has also been a Visiting Professor in Chemical Engineering at the following universities: University of Missouri-Columbia, the Technical University of Denmark, and the University of Trinidad and Tobago.

In 1996, Dr. Speight was elected to the Russian Academy of Sciences and awarded the Gold Medal of Honor that same year for outstanding contributions to the field of petroleum sciences. In 2001, he received the Scientists without Borders Medal of Honor of the Russian Academy of Sciences and was also awarded Dr. Speight the Einstein Medal for outstanding contributions and ser