Environmental Analysis and Technology for the Refining Industry

Preface xi

Part I Petroleum Technology 1

Chapter 1 Definitions and Terminology 3

1.1 The Environment 4

1.2 Petroleum 9

1.3 Classification 11

1.3.1 Chemical Composition 12

1.3.2 Correlation Index 13

1.3.3 Density 14

1.3.4 Carbon Distribution 15

1.3.5 Viscosity–Gravity Constant 15

1.3.6 UOP Characterization Factor 16

1.4 Petroleum Products 16

1.4.1 Boiling Range 19

1.4.2 Environmental Behavior 19

1.5 Refinery Waste 20

1.5.1 Chemical Characteristics 21

1.5.2 Environmental Behavior 25

References 27

Chapter 2 Composition and Properties 31

2.1 Composition 32

2.1.1 Elemental Composition 32

2.1.2 Chemical Composition 33

2.1.3 Composition by Volatility 35

2.1.4 Composition by Fractionation 37

2.2 Properties 40

2.2.1 Density and Specific Gravity 40

2.2.2 Elemental (Ultimate) Analysis 41

2.2.3 Fractionation by Chromatography 42

2.2.4 Liquefaction and Solidification 44

2.2.5 Metals Content 44

2.2.6 Spectroscopic Properties 45

2.2.7 Surface and Interfacial Tension 47

2.2.8 Viscosity 49

2.2.9 Volatility 51

References 53

Chapter 3 Refinery Products and By-Products 57

3.1 Refinery Products 60

3.1.1 Liquefied Petroleum Gas 64

3.1.2 Naphtha, Gasoline, and Solvents 68

3.1.3 Kerosene and Diesel Fuel 71

3.1.4 Fuel Oil 71

3.1.5 Lubricating Oil 74

3.1.6 White Oil, Insulating Oil, and Insecticides 75

3.1.7 Grease 75

3.1.8 Wax 76

3.1.9 Asphalt 77

3.1.10 Coke 77

3.2 Petrochemicals 78

3.3 Refinery Chemicals 80

3.3.1 Alkalis 80

3.3.2 Acids 81

3.3.3 Catalysts 83

References 86

Chapter 4 Refinery Wastes 87

4.1 Process Wastes 90

4.1.1 Desalting 92

4.1.2 Distillation 93

4.1.3 Visbreaking and Coking 96

4.1.4 Fluid Catalytic Cracking 98

4.1.5 Hydrocracking and Hydrotreating 99

4.1.6 Alkylation and Polymerization 101

4.1.7 Catalytic Reforming 105

4.1.8 Isomerization 105

4.1.9 Deasphalting and Dewaxing 106

4.2 Entry into the Environment 108

4.2.1 Storage and Handling of Petroleum Products 108

4.2.2 Release into the Environment 110

4.3 Toxicity 113

4.3.1 Lower-Boiling Constituents 114

4.3.2 Higher-Boiling Constituents 117

4.3.3 Total Petroleum Hydrocarbons 119

4.3.4 Wastewater 120

References 121

Part II Environmental Technology and Analysis 123

Chapter 5 Environmental Regulations 125

5.1 Environmental Impact of Refining 131

5.1.1 Air Pollution 131

5.1.2 Water Pollution 132

5.1.3 Soil Pollution 132

5.2 Environmental Regulations in the United States 132

5.2.1 Clean Air Act 133

5.2.2 Resource Conservation and Recovery Act 137

5.2.3 Clean Water Act 140

5.2.4 Safe Drinking Water Act 141

5.2.5 Comprehensive Environmental Response, Compensation, and Liability Act 142

5.2.6 Oil Pollution Act 143

5.2.7 Occupational Safety and Health Act 144

5.2.8 Toxic Substances Control Act 144

5.2.9 Hazardous Materials Transportation Act 146

5.3 Refinery Outlook 146

5.3.1 Hazardous Waste Regulations 146

5.3.2 Regulatory Background 147

5.3.3 Requirements 147

5.4 Management of Refinery Waste 148

References 149

Chapter 6 Sample Collection and Preparation 151

6.1 Petroleum Chemicals 151

6.2 Sample Collection and Preparation 153

6.2.1 Sample Collection 154

6.2.2 Extract Concentration 168

6.2.3 Sample Cleanup 170

6.3 Measurement 170

6.4 Accuracy 172

6.5 Precision 173

6.6 Method Validation 174

6.7 Quality Control and Quality Assurance 179

6.7.1 Quality Control 179

6.7.2 Quality Assurance 181

6.8 Method Detection Limit 182

References 183

Chapter 7 Analytical Methods 185

7.1 Leachability and Toxicity 186

7.2 Total Petroleum Hydrocarbons 186

7.2.1 Gas Chromatographic Methods 191

7.2.2 Infrared Spectroscopy Methods 195

7.2.3 Gravimetric Methods 196

7.2.4 Immunoassay Methods 198

7.3 Petroleum Group Analysis 198

7.3.1 Thin-Layer Chromatography 200

7.3.2 Immunoassay 201

7.3.3 Gas Chromatography 201

7.3.4 High-Performance Liquid Chromatography 203

7.3.5 Gas Chromatography–Mass Spectrometry 204

7.4 Petroleum Fractions 205

References 206

Chapter 8 Total Petroleum Hydrocarbons 207

8.1 Petroleum Constituents 209

8.2 Analytical Methods 210

8.2.1 Environmental Samples 210

8.2.2 Biological Samples 217

8.2.3 Semivolatile and Nonvolatile Hydrocarbons 228

8.3 Assessment of the Methods 230

References 234

Chapter 9 Analysis of Gaseous Effluents 237

9.1 Gaseous Products 239

9.1.1 Liquefied Petroleum Gas 239

9.1.2 Natural Gas 240

9.1.3 Refinery Gas 241

9.1.4 Sulfur Oxides, Nitrogen Oxides, Hydrogen Sulfide, and Carbon Dioxide 244

9.1.5 Particulate Matter 244

9.2 Environmental Effects 245

9.3 Sampling 247

9.4 Analysis 247

9.4.1 Calorific Value (Heat of Combustion) 248

9.4.2 Composition 249

9.4.3 Density 252

9.4.4 Sulfur 253

9.4.5 Volatility and Vapor Pressure 253

References 254

Chapter 10 Analysis of Liquid Effluents 257

10.1 Naphtha 258

10.1.1 Composition 261

10.1.2 Density (Specific Gravity) 266

10.1.3 Evaporation Rate 266

10.1.4 Flash Point 266

10.1.5 Odor and Color 267

10.1.6 Volatility 267

10.2 Fuel Oil 268

10.2.1 Asphaltene Content 269

10.2.2 Composition 270

10.2.3 Density (Specific Gravity) 271

10.2.4 Elemental Analysis 272

10.2.5 Flash Point 276

10.2.6 Metals Content 276

10.2.7 Pour Point and Viscosity 277

10.2.8 Stability 278

10.3 Wastewaters 279

References 280

Chapter 11 Analysis of Solid Effluents 283

11.1 Residua and Asphalt 283

11.1.1 Acid Number 286

11.1.2 Asphaltene Content 287

11.1.3 Carbon Disulfide Insoluble Constituents 288

11.1.4 Composition 289

11.1.5 Density (Specific Gravity) 290

11.1.6 Elemental Analysis 292

11.1.7 Float Test 293

11.1.8 Softening Point 293

11.1.9 Viscosity 294

11.1.10 Weathering 294

11.2 Coke 294

11.2.1 Ash 296

11.2.2 Composition 297

11.2.3 Density 299

11.2.4 Dust Control Material 300

11.2.5 Hardness 300

11.2.6 Metals 300

11.2.7 Sulfur 301

References 302

Chapter 12 Pollution Prevention 305

12.1 Refinery Wastes and Treatment 306

12.1.1 Air Emissions 306

12.1.2 Wastewater and Treatment 309

12.1.3 Other Waste and Treatment 311

12.2 Pollution Prevention 311

12.2.1 Pollution Prevention Options 312

12.2.2 Recycling 315

12.2.3 Treatment Options 316

12.3 Adoption of Pollution Reduction Options 317

References 319

Glossary 321

Index 343