Part I. History, Occurrence, and Recovery ....................... 1
Chapter 1. History and Terminology .............................. 3
1.1. Historical Perspectives .................................... 3
1.2. Modern Perspectives ....................................... 10
1.3. Definitions and Terminology ............................... 12
1.4. Native Materials .......................................... 14
1.4.1. Petroleum .......................................... 14
1.4.2. Heavy Oil .......................................... 16
1.4.3. Bitumen ............................................ 16
1.4.4. Wax ................................................ 17
1.4.5. Asphaltite ......................................... 18
1.4.6. Asphaltoid ......................................... 18
1.4.7. Bituminous Rock and Bituminous Sand ................ 19
1.4.8. Kerogen ............................................ 19
1.4.9. Natural Gas ........................................ 20
1.5. Manufactured Materials .................................... 22
1.5.1. Wax ................................................ 22
1.5.2. Residuum (Residua) ................................. 22
1.5.3. Asphalt ............................................ 22
1.5.4. Tar and Pitch ...................................... 23
1.5.5. Coke ............................................... 24
1.5.6. Synthetic Crude Oil ................................ 24
1.6. Derived Materials ......................................... 24
1.6.1. Asphaltenes, Carbenes, and Carboids ................ 24
1.6.2. Resins and Oils .................................... 25
1.7. Oil Prices ................................................ 26
1.7.1. Pricing Strategies ................................. 27
1.7.2. Oil Price History .................................. 27
1.7.3. Future of Oil ...................................... 28
1.7.4. Epilog ............................................. 28
References ..................................................... 28
Chapter 2. Classification ...................................... 31
2.1. Introduction .............................................. 31
2.2. Classification Systems .................................... 33
2.2.1. Classification as a Hydrocarbon Resource ........... 33
2.2.2. Classification by Chemical Composition ............. 34
2.2.3. Correlation Index .................................. 36
2.2.4. Density ............................................ 37
2.2.1. API Gravity ........................................ 38
2.2.6. Viscosity .......................................... 38
2.2.7. Carbon Distribution ................................ 39
2.2.8. Viscosity-Gravity Constant ......................... 39
2.2.9. UOP Characterization Factor ........................ 40
2.2.10.Recovery Method .................................... 40
2.2.11.Pour Point ......................................... 41
2.3. Miscellaneous Systems ..................................... 41
2.4. Reservoir Classification .................................. 43
2.4.1. Identification and Quantification .................. 43
2.4.2. Future ............................................. 44
References ..................................................... 45
Chapter 3. Origin and Occurrence ............................... 47
3.1. Introduction .............................................. 47
3.2. Origin .................................................... 48
3.2.1. Abiogenic Origin ................................... 48
3.2.2. Biogenic Origin .................................... 50
3.2.2.1. Deposition of Organic Matter .............. 52
3.2.2.2. Establishment of Source Beds .............. 52
3.2.2.3. Nature of the Source Material ............. 54
3.2.2.4. Transformation of Organic Matter into
Petroleum ................................. 57
3.2.2.5. Accumulation in Reservoir Sediments ....... 58
3.2.2.6. In Situ Transformation of Petroleum ....... 63
3.2.3. Differences between the Abiogenic Theory and the
Biogenic Theory .................................... 66
3.2.4. Relationship of Petroleum Composition and
Properties ......................................... 67
3.3. Occurrence ................................................ 69
3.3.1. Reserves ........................................... 70
3.3.2. Conventional Petroleum ............................. 73
3.3.3. Natural Gas ........................................ 74
3.3.4. Heavy Oil .......................................... 76
3.3.5. Bitumen (Extra Heavy Oil) .......................... 76
References ..................................................... 79
Chapter 4. Kerogen ............................................. 83
4.1. Introduction .............................................. 83
4.2. Properties ................................................ 83
4.3. Composition ............................................... 87
4.4. Classification ............................................ 87
4.5. Isolation ................................................. 88
4.6. Methods for Probing Kerogen Structure ..................... 89
4.6.1. Ultimate (Elemental) Analysis ...................... 89
4.6.2. Functional Group Analysis .......................... 90
4.6.3. Oxidation .......................................... 90
4.6.4. Thermal Methods .................................... 91
4.6.5. Acid-Catalyzed Hydrogenolysis ...................... 92
4.7. Structural Models ......................................... 92
4.8. Kerogen Maturation ........................................ 94
References ..................................................... 96
Chapter 5. Exploration, Recovery, and Transportation ........... 99
5.1. Introduction .............................................. 99
5.2. Exploration .............................................. 100
5.2.1. Gravity Methods ................................... 101
5.2.2. Magnetic Methods .................................. 102
5.2.3. Seismic Methods ................................... 103
5.2.4. Electrical Methods ................................ 104
5.2.5. Electromagnetic Methods ........................... 104
5.2.6. Radioactive Methods ............................... 105
5.2.7. Borehole Logging .................................. 105
5.3. Drilling Operations ...................................... 106
5.3.1. Preparing to Drill ................................ 106
5.3.2. Drilling Rig ...................................... 107
5.3.3. Drilling Rig Components ........................... 109
5.3.4. Drilling .......................................... 109
5.4. Well Completion .......................................... 110
5.5. Recovery ................................................. 1ll
5.5.1. Primary Recovery (Natural Methods) ................ 114
5.5.2. Secondary Recovery ................................ 117
5.5.3. Enhanced Oil Recovery ............................. 119
5.6. Products and Product Quality ............................. 133
5.7. Transportation ........................................... 135
References .................................................... 140
Chapter 6. Recovery of Heavy Oil and Tar Sand Bitumen ......... 143
6.1. Introduction ............................................. 143
6.2. Oil Mining ............................................... 150
6.2.1. Tar Sand Mining ................................... 150
6.2.2. Hot-Water Process ................................. 152
6.2.3. Other Processes ................................... 155
6.3. Nonmining Methods ........................................ 157
6.3.1. Steam-Based Processes ............................. 159
6.3.2. Combustion Processes .............................. 160
6.3.3. Other Processes ................................... 163
References .................................................... 173
Part II. Composition and Properties ........................... 175
Chapter 7. Chemical Composition ............................... 177
7.1. Introduction ............................................. 177
7.2. Ultimate (Elemental) Composition ......................... 178
7.3. Chemical Components ...................................... 179
7.3.1. Hydrocarbon Constituents .......................... 181
7.3.1.1. Paraffin Hydrocarbons .................... 182
7.3.1.2. Cycloparaffin Hydrocarbons
(Naphthenes) ............................. 184
7.3.1.3. Aromatic Hydrocarbons .................... 185
7.3.1.4. Unsaturated Hydrocarbons ................. 187
7.3.2. Nonhydrocarbon Constituents ....................... 187
7.3.2.1. Sulfur Compounds ......................... 188
7.3.2.2. Oxygen Compounds ......................... 190
7.3.2.3. Nitrogen Compounds ....................... 190
7.3.2.4. Metallic Constituents .................... 192
7.3.2.5. Porphyrins ............................... 193
7.4. Chemical Composition by Distillation ..................... 195
7.4.1. Gases and Naphtha ................................. 197
7.4.2. Middle Distillates ................................ 198
7.4.3. Vacuum Residua (1050°F+) .......................... 200
References .................................................... 201
Chapter 8. Fractional Composition ............................. 205
8.1. Introduction ............................................. 205
8.2. Distillation ............................................. 207
8.2.1. Atmospheric Pressure .............................. 210
8.2.2. Reduced Pressures ................................. 211
8.2.3. Azeotropic and Extractive Distillation ............ 213
8.3. Solvent Treatment ........................................ 214
8.3.1. Asphaltene Separation ............................. 216
8.3.1.1. Influence of Solvent Type ................ 216
8.3.1.2. Influence of the Degree of Dilution ...... 219
8.3.1.3. Influence of Temperature ................. 219
8.3.1.4. Influence of Contact Time ................ 220
8.3.2. Fractionation ..................................... 220
8.4. Adsorption ............................................... 222
8.4.1. Chemical Factors .................................. 222
8.4.2. Fractionation Methods ............................. 223
8.4.2.1. General Methods .......................... 223
8.4.2.2. ASTM Methods ............................. 227
8.5. Chemical Methods ......................................... 229
8.5.1. Acid Treatment .................................... 229
8.5.2. Molecular Complex Formation ....................... 231
8.5.2.1. Urea Adduction ........................... 231
8.5.2.2. Thiourea Adduction ....................... 232
8.5.2.3. Adduct Composition ....................... 232
8.5.2.4. Adduct Structure ......................... 233
8.5.2.5. Adduct Properties ........................ 234
8.6. Use of the Data ..................................... 235
References .................................................... 237
Chapter 9. Petroleum Analysis ................................. 239
9.1. Introduction ............................................. 239
9.2. Petroleum Assay .......................................... 240
9.3. Physical Properties ...................................... 243
9.3.1. Elemental (Ultimate) Analysis ..................... 243
9.3.2. Density and Specific Gravity ...................... 244
9.3.3. Viscosity ......................................... 246
9.3.4. Surface and Interfacial Tension ................... 249
9.3.5. Metals Content .................................... 251
9.4. Thermal Properties ....................................... 252
9.4.1. Volatility ........................................ 252
9.4.2. Liquefaction and Solidification ................... 255
9.4.3. Carbon Residue .................................... 257
9.4.4. Aniline Point ..................................... 258
9.4.5. Specific Heat ..................................... 259
9.4.6. Latent Heat ....................................... 259
9.4.7. Enthalpy or Heat Content .......................... 259
9.4.8. Thermal Conductivity .............................. 259
9.4.9. Pressure-Volume-Temperature Relationships ......... 260
9.4.10.Heat of Combustion ................................ 260
9.4.11.Critical Properties ............................... 260
9.5. Electrical Properties .................................... 261
9.5.1. Conductivity ...................................... 261
9.5.2. Dielectric Constant ............................... 261
9.5.3. Dielectric Strength ............................... 261
9.5.4. Dielectric Loss and Power Factor .................. 262
9.5.5. Static Electrification ............................ 262
9.6. Optical Properties ....................................... 263
9.6.1. Refractive Index .................................. 263
9.6.2. Optical Activity .................................. 264
9.7. Spectroscopic Methods .................................... 264
9.7.1. Infrared Spectroscopy ............................. 265
9.7.2. Nuclear Magnetic Resonance ........................ 265
9.7.3. Mass Spectrometry ................................. 266
9.8. Chromatographic Methods .................................. 266
9.8.1. Gas Chromatography ................................ 266
9.8.2. Simulated Distillation ............................ 269
9.8.3. Adsorption Chromatography ......................... 270
9.8.4. Gel Permeation Chromatography ..................... 271
9.8.5. Ion-Exchange Chromatography ....................... 273
9.8.6. High-Performance Liquid Chromatography ............ 274
9.8.7. Supercritical Fluid Chromatography ................ 275
9.9. Molecular Weight ......................................... 275
9.10.Use of the Data .......................................... 276
References .................................................... 277
Chapter 10.Structural Group Analysis .......................... 281
10.1.Introduction ............................................. 281
10.2.Methods for Structural Group Analysis .................... 283
10.2.1.Physical Property Methods ......................... 286
10.2.1.1.Direct Method ............................ 286
10.2.1.2.Waterman Ring Analysis ................... 288
10.2.1.3.Density Method ........................... 289
10.2.1.4.n.d.M.Method ............................. 289
10.2.1.5.Dispersion-Refraction Method ............. 290
10.2.1.6.Density-Temperature Coefficient
Method ................................... 290
10.2.1.7.Molecular Weight-Refractive Index
Method ................................... 291
10.2.1.8.Miscellaneous Methods ........................... 292
10.2.2.Spectroscopic Methods ............................. 293
10.2.2.1.Infrared Spectroscopy .................... 294
10.2.2.2.Nuclear Magnetic Resonance
Spectroscopy ............................. 297
10.2.2.3.Mass Spectrometry ........................ 301
10.2.2.4.Electron Spin Resonance .................. 303
10.2.2.5.Ultraviolet Spectroscopy ................. 304
10.2.2.6.X-Ray Diffraction ........................ 305
10.2.3.Heteroatom Systems ................................ 307
10.2.3.1.Nitrogen ................................. 307
10.2.3.2.Oxygen ................................... 308
10.2.3.3.Sulfur ................................... 308
10.2.3.4.Metals ................................... 309
10.3.Miscellaneous Methods ............................... 309
References .................................................... 310
Chapter 11.Asphaltene Constituents ............................ 315
11.1.Introduction ............................................. 315
11.2.Separation ............................................... 316
11.3.Composition .............................................. 319
11.4.Molecular Weight ......................................... 324
11.5.Reactions ................................................ 328
11.6.Solubility Parameter ..................................... 333
11.7.Structural Aspects ....................................... 335
References .................................................... 341
Chapter 12.Structure of Petroleum ............................. 345
12.1.Introduction ............................................. 345
12.2.Molecular Species in Petroleum ........................... 346
12.2.1.Volatile Fractions ................................ 346
12.2.2.Resin Constituents ................................ 347
12.2.2.1.Composition .............................. 347
12.2.2.2.Resins (Structure) ....................... 347
12.2.2.3.Molecular Weight ......................... 349
12.2.3.Nonvolatile Oils .................................. 349
12.2.3.1.Composition .............................. 349
12.2.3.2.Structure ................................ 349
12.2.3.3.Molecular Weight ......................... 350
12.3.Chemical and Physical Structure of Petroleum ............. 350
12.4.Stability or Instability of the Crude Oil System ......... 355
12.5.Effects on Recovery and Refining ......................... 364
12.5.1.Effects on Recovery Operations .................... 365
12.5.2.Effects on Refining Operations .................... 368
References .................................................... 370
Chapter 13. Instability and Incompatibility ................... 373
13.1.Introduction ............................................. 373
13.2.Instability and Incompatibility in Petroleum ............. 377
13.3.Factors Influencing Instability and Incompatibility ...... 378
13.3.1.Elemental Analysis ................................ 378
13.3.2.Density and Specific Gravity ...................... 379
13.3.3.Volatility ........................................ 379
13.3.4.Viscosity ......................................... 380
13.3.5.Asphaltene Content ................................ 380
13.3.6.Pour Point ........................................ 381
13.3.7.Acidity ........................................... 382
13.3.8.Metals (Ash) Content .............................. 382
13.3.9.Water Content, Salt Content, and Bottom Sediment
and Water (BS&W) .................................. 383
13.4.Methods for Determining Instability and
Incompatibility .......................................... 383
13.5.Effect of Asphaltene Constituents ................... 388
References .................................................... 391
Part III. Refining ............................................ 393
Chapter 14.Introduction to Refining Processes ................. 395
14.1.Introduction ............................................. 395
14.2.Dewatering and Desalting ................................. 398
14.3.Early Processes .......................................... 399
14.4.Distillation ............................................. 400
14.4.1.Historical Development ............................ 401
14.4.2.Modern Processes .................................. 402
14.4.2.1.Atmospheric Distillation ................. 402
14.4.2.2.Vacuum Distillation ...................... 403
14.4.2.3.Azeotropic and Extractive Distillation ... 405
14.5.Thermal Methods .......................................... 405
14.5.1.Historical Development ............................ 405
14.5.2.Modern Processes .................................. 408
14.5.1.Thermal Cracking .................................. 408
14.5.2.2.Visbreaking .............................. 408
14.5.2.3.Coking ................................... 409
14.6.Catalytic Methods ........................................ 411
14.6.1.Historical Development ............................ 411
14.6.2.Modern Processes .................................. 413
14.6.3.Catalysts ......................................... 414
14.7.Hydroprocesses ........................................... 415
14.7.1.Historical Development ............................ 415
14.7.2.Modern Processes .................................. 415
14.7.2.1.Hydrofining .............................. 418
14.8.Reforming ................................................ 418
14.8.1.Historical Development ............................ 418
14.8.2.Modern Processes .................................. 419
14.8.2.1.Thermal Reforming ........................ 419
14.8.2.2.Catalytic Reforming ...................... 419
14.8.2.3.Catalysts ................................ 420
14.9.Isomerization ............................................ 421
14.9.1.Historical Development ............................ 421
14.9.2.Modern Processes .................................. 421
14.9.3.Catalysts ......................................... 422
14.10.Alkylation Processes .................................... 423
14.10.1.Historical Development ........................... 423
14.10.2.Modern Processes ................................. 423
14.10.3.Catalysts ........................................ 424
14.11.Polymerization Processes ................................ 424
14.11.1.Historical Development ........................... 424
14.11.2.Modern Processes ................................. 424
14.11.3.Catalysts ........................................ 425
14.12.Solvent Process ......................................... 425
14.12.1.Deasphalting ..................................... 425
14.12.2.Dewaxing ......................................... 426
14.13.Refining Heavy Feedstocks ............................... 427
14.14.Petroleum Products ...................................... 431
14.15.Petrochemicals .......................................... 433
References .................................................... 434
Chapter 15.Refining Chemistry ................................. 437
15.1.Introduction ............................................. 437
15.2.Cracking ................................................. 439
15.2.1.Thermal Cracking .................................. 439
15.2.2.Catalytic Cracking ................................ 440
15.2.3.Dehydrogenation ................................... 443
15.2.4.Dehydrocyclization ................................ 443
15.3.Hydrogenation ....................................... 443
15.3.1.Hydrocracking ..................................... 444
15.3.2.Hydrotreating ..................................... 444
15.4.Isomerization ............................................ 445
15.5.Alkylation ............................................... 446
15.4.Polymerization ........................................... 446
15.7.Process Chemistry ........................................ 447
15.7.1.Thermal Chemistry ................................. 447
15.7.2.Hydroconversion Chemistry ......................... 456
15.7.3.Chemistry in the Refinery ......................... 457
15.7.3.1.Visbreaking .............................. 457
15.7.3.2.Hydroprocessing .......................... 460
References .................................................... 462
Chapter 16. Distillation ...................................... 465
16.1.Introduction ............................................. 465
16.2.Pretreatment ............................................. 467
16.3.Atmospheric and Vacuum Distillation ...................... 468
16.3.1.Atmospheric Distillation .......................... 470
16.3.2.Vacuum Distillation ............................... 473
16.4.Equipment ................................................ 475
16.4.1.Columns ........................................... 475
16.4.2.Packings .......................................... 477
16.4.3.Trays ............................................. 477
16.5.Other Processes .......................................... 478
16.5.1.Stripping ......................................... 478
16.5.2.Rerunning ......................................... 479
16.5.3.Stabilization and Light End Removal ............... 479
16.5.4.Superfractionation ................................ 480
16.5.5.Azeotropic Distillation ........................... 481
16.5.6.Extractive Distillation ........................... 483
16.5.7.Process Options for Heavy Feedstocks .............. 484
References .................................................... 485
Chapter 17.Thermal Cracking ................................... 487
17.1.Introduction ............................................. 487
17.2.Early Processes .......................................... 492
17.3.Commercial Processes ..................................... 493
17.3.1.Visbreaking ....................................... 494
17.3.2.Coking Processes .................................. 499
17.3.2.1.Delayed Coking ........................... 500
17.3.2.2.Fluid Coking ............................. 503
17.3.2.3.Flexicoking .............................. 505
17.3.3.Process Options for Heavy Feedstocks .............. 507
17.3.3.1.Aquaconversion ........................... 507
17.3.3.2.Asphalt Coking Technology (ASCOT)
Process .................................. 507
17.3.3.3.Comprehensive Heavy Ends Reforming
Refinery (Cherry-P) Process .............. 508
17.3.3.4.Decarbonizing ............................ 509
17.3.3.5.ET-II Process ............................ 510
17.3.3.6.Eureka Process ........................... 510
17.3.3.7.Fluid Thermal Cracking (FTC) Process ..... 511
17.3.3.8.High Conversion Soaker Cracking (HSC)
Process .................................. 512
17.3.3.4.Mixed-Phase Cracking ..................... 515
17.3.3.10.Naphtha Cracking ........................ 515
17.3.3.11.Selective Cracking ...................... 515
17.3.3.12.Shell Thermal Cracking .................. 515
17.3.3.13.Tervahl T Process ....................... 517
17.3.3.14.Vapor-Phase Cracking .................... 518
References .................................................... 518
Chapter 18.Catalytic Cracking ................................. 521
18.1.Introduction ............................................. 521
18.2.Early Processes .......................................... 525
18.3.Commercial Processes ..................................... 525
18.3.1.Fixed-Bed Processes ............................... 526
18.3.2.Fluid-Bed Processes ............................... 526
18.3.2.1.Fluid-Bed Catalytic Cracking ............. 526
18.3.2.2.Model IV Fluid-Bed Catalytic Cracking
Unit ..................................... 528
18.3.2.3.Orthoflow Fluid-Bed Catalytic Cracking ... 528
18.3.2.4.Shell Two-Stage Fluid-Bed Catalytic
Cracking ................................. 528
18.3.2.5.Universal Oil Products (UOP) Fluid-Bed
Catalytic Cracking ....................... 528
18.3.3.Moving-Bed Processes .............................. 529
18.3.3.1.Airlift Thermofor Catalytic Cracking
(Socony Airlift TCC Process) ............. 529
18.3.3.2.Houdresid Catalytic Cracking ............. 529
18.3.3.3.Houdriflow Catalytic Cracking ............ 529
18.3.3.4.Suspensoid Catalytic Cracking ............ 529
18.3.4.Process Options for Heavy Feedstocks .............. 530
18.3.4.1.Asphalt Residual Treating (ART)
Process .................................. 530
18.3.4.2.Residue Fluid Catalytic Cracking (HOC)
Process .................................. 531
18.3.4.3.Heavy Oil Treating (HOT) Process ......... 532
18.3.4.4.R2R Process .............................. 533
18.3.4.5.Reduced Crude Oil Conversion (RCC)
Process .................................. 533
18.3.4.6.Shell FCC Process ........................ 534
18.3.4.7.S&W Fluid Catalytic Cracking Process ..... 536
18.4.Catalysts ................................................ 537
18.4.1.Catalyst Treatment ................................ 538
18.4.1.1.Demet .................................... 538
18.4.1.2.Met-X .................................... 538
18.5.Process Parameters ....................................... 538
18.5.1.Reactor ........................................... 539
18.5.2.Coking ............................................ 540
18.5.3.Catalyst Variables ................................ 542
18.5.4.Process Variables ................................. 543
18.5.5.Additives ......................................... 544
References .................................................... 544
Chapter 19.Deasphalting and Dewaxing Processes ................ 547
19.1.Introduction ............................................. 547
19.2.Commercial Processes ..................................... 547
19.2.1.Deasphalting Process .............................. 548
19.2.2.Process Options for Heavy Feedstocks .............. 554
19.2.2.1.Deep Solvent Deasphalting Process ........ 555
19.2.2.2.Demex Process ............................ 558
19.2.2.3.MDS Process .............................. 559
19.2.2.4.Residuum Oil Supercritical Extraction
(ROSE) Process ........................... 560
19.2.2.5.Solvahl Process .......................... 561
19.2.2.6.Lube Deasphalting ........................ 561
19.3.Dewaxing Processes ....................................... 562
References .................................................... 567
Chapter 20.Hydrotreating and Desulfurization .................. 569
20.1.Introduction ............................................. 569
20.2.Process Parameters and Reactors .......................... 577
20.2.1.Hydrogen Partial Pressure ......................... 578
20.2.2.Space Velocity .................................... 578
20.2.3.Reaction Temperature .............................. 578
20.2.4.Catalyst Life ..................................... 578
20.2.5.Feedstock Effects ................................. 579
20.2.6.Reactors .......................................... 581
20.2.6.1.Downflow Fixed-Bed Reactor ............... 581
20.2.6.2.Upflow Expanded-Bed Reactor .............. 582
20.2.6.3.Demetallization Reactor (Guard Bed
Reactor) ................................. 583
20.3.Commercial Processes ..................................... 583
20.3.1.Autofining ........................................ 584
20.3.2.Ferrofining ....................................... 584
20.3.3.Gulf-HDS .......................................... 584
20.3.4.Hydrofming ........................................ 585
20.3.5.Isomax ............................................ 587
20.3.6.Ultrafining ....................................... 587
20.3.7.Unifining ......................................... 587
20.3.8.Unionfming ........................................ 587
20.3.9.Process Options for Heavy Feedstocks .............. 587
20.3.9.1.Residuum Desulfurization and Vacuum
Residuum Desulfurization Process ......... 588
20.3.9.2.Residfining Process ...................... 589
20.4.Catalysts ........................................... 590
20.5.Biodesulfurization .................................. 594
20.6.Gasoline and Diesel Fuel Polishing .................. 595
References .................................................... 597
Chapter 21.Hydrocracking ...................................... 599
21.1.Introduction ............................................. 599
21.2.Commercial Processes ..................................... 605
21.2.1.Process Design .................................... 606
21.2.1.1.Single-Stage and Two-Stage Options ....... 606
21.2.2.Process Options for Heavy Feedstocks .............. 610
21.2.2.1.Asphaltenic Bottom Cracking (ABC)
Process .................................. 610
21.2.2.2.CANMET Hydrocracking Process ............. 610
21.2.2.3.H-Oil Process ............................ 612
21.2.2.4.Hydrovisbreaking (HYCAR) Process ......... 614
21.2.2.5.Hyvahl F Process ......................... 614
21.2.2.6.IFP Hydrocracking Process ................ 615
21.2.2.7.Isocracking Process ...................... 616
21.2.2.8.LC-Fining Process ........................ 617
21.2.2.9.MAKfining Process ........................ 619
21.2.2.10.Microcat-RC Process ..................... 619
21.2.2.11.Mild Hydrocracking Process .............. 621
21.2.2.12.MRH Process ............................. 622
21.2.2.13.RCD Unibon (BOC) Process ................ 623
21.2.2.14.Residfining Process ..................... 623
21.2.2.15.Residue Hydroconversion (RHC) Process ... 624
21.2.2.16.Tervahl-H Process ....................... 624
21.2.2.17.Unicracking Process ..................... 625
21.2.2.18.Veba Combi Cracking Process ............. 627
21.3.Catalysts ................................................ 628
References .................................................... 635
Chapter 22.Hydrogen Production ................................ 637
22.1.Introduction ............................................. 637
22.2.Processes Requiring Hydrogen ............................. 640
22.2.1.Hydrotreating ..................................... 640
22.2.2.Hydrocracking ..................................... 641
22.3.Feedstocks ............................................... 642
22.4.Process Chemistry ........................................ 643
22.5.Commercial Processes ..................................... 645
22.5.1.Heavy Residue Gasification and Combined
Cycle Power Generation ............................ 646
22.5.2.Hybrid Gasification Process ....................... 647
22.5.3.Hydrocarbon Gasification .......................... 647
22.5.4.Hypro Process ..................................... 647
22.5.5.Pyrolysis Processes ............................... 648
22.5.6.Shell Gasification (Partial Oxidation) Process .... 649
22.5.7.Steam-Methane Reforming ........................... 649
22.5.8.Steam-Naphtha Reforming ........................... 651
22.5.9.Synthesis Gas Generation .......................... 651
22.5.10.Texaco Gasification (Partial Oxidation)
Process ........................................... 652
22.6.Catalysts ................................................ 653
22.6.1.Reforming Catalysts ............................... 653
22.6.2.Shift Conversion Catalysts ........................ 654
22.6.3.Methanation Catalysts ............................. 655
22.7.Hydrogen Purification .................................... 655
22.7.1.Wet Scrubbing ..................................... 656
22.7.2.Pressure-Swing Adsorption Units ................... 656
22.7.3.Membrane Systems .................................. 658
22.7.4.Cryogenic Separation .............................. 658
22.8.Hydrogen Management ...................................... 658
References .................................................... 659
Chapter 23.Product Improvement ................................ 661
23.1.Introduction ............................................. 661
23.2.Reforming ................................................ 662
23.2.1.Thermal Reforming ................................. 664
23.2.2.Catalytic Reforming ............................... 665
23.2.2.1.Fixed-Bed Processes ...................... 668
23.2.2.2.Moving-Bed Processes ..................... 672
23.2.2.3.Fluid-Bed Processes ...................... 672
23.3.Isomerization ............................................ 673
23.3.1.Butamer Process ................................... 675
23.3.2.Butomerate Process ................................ 675
23.3.3.Hysomer Process ................................... 676
23.3.4.Iso-Kel Process ................................... 676
23.3.5.Isomate Process ................................... 676
23.3.6.Isomerate Process ................................. 676
23.3.7.Penex Process ..................................... 676
23.3.8.Pentafining Process ............................... 677
23.4.Alkylation ............................................... 677
23.4.1.Cascade Sulfuric Acid Alkylation .................. 678
23.4.2.Hydrogen Fluoride Alkylation ...................... 679
23.5.Polymerization ........................................... 680
23.5.1.Thermal Polymerization ............................ 680
23.5.2.Solid Phosphoric Acid Condensation ................ 681
23.5.3.Bulk Acid Polymerization .......................... 681
23.6.Catalysts ................................................ 682
23.6.1.Reforming Processes ............................... 682
23.6.2.Isomerization Processes ........................... 683
23.6.3.Alkylation Processes .............................. 683
23.6.4.Polymerization Processes .......................... 683
References .................................................... 684
Chapter 24.Product Treating ................................... 685
24.1.Introduction ............................................. 685
24.2.Commercial Processes ..................................... 688
24.2.1.Caustic Processes ................................. 688
24.2.1.1.Dualayer Distillate Process .............. 689
24.2.1.2.Dualayer Gasoline Process ................ 689
24.2.1.3.Electrolytic Mercaptan Process ........... 689
24.2.1.4.Ferrocyanide Process ..................... 689
24.2.1.5.Lye Treatment ............................ 689
24.2.1.6.Mercapsol Process ........................ 690
24.2.1.7.Polysulfide Treatment .................... 690
24.2.1.8.Sodasol Process .......................... 690
24.2.1.9.Solutizer Process ........................ 691
24.2.1.10.Steam Regenerative Caustic Treatment .... 691
24.2.1.11.Unisol Process .......................... 691
24.2.2.Acid Processes .................................... 691
24.2.2.1.Nalfining Process ........................ 693
24.2.2.2.Sulfuric Acid Treatment .................. 693
24.2.3.Clay Processes ............................. 694
24.2.3.1.Alkylation Effluent Treatment ............ 694
24.2.3.2.Arosorb Process .......................... 694
24.2.3.3.Bauxite Treatment ........................ 694
24.2.3.4.Continuous Contact Filtration Process .... 695
24.2.3.5.Cyclic Adsorption Process ................ 695
24.2.3.6.Gray Clay Treatment ...................... 695
24.2.3.7.Percolation Filtration Process ........... 695
24.2.3.8.Thermofor Continuous Percolation
Process .................................. 695
24.2.4.Oxidative Processes ............................... 696
24.2.4.1.Bender Process ........................... 696
24.2.4.2.Copper Sweetening Process ................ 696
24.2.4.3.Doctor Process ........................... 697
24.2.4.4.Hypochlorite Sweetening Process .......... 697
24.2.4.5.Inhibitor Sweetening Process ............. 698
24.2.4.6.Merox Process ............................ 698
24.2.5.Solvent Processes ................................. 698
24.2.5.1.Deasphalting ............................. 699
24.2.5.2.Solvent Refining ......................... 700
24.2.5.3.Dewaxing ................................. 703
References .................................................... 706
Chapter 25.Gas Processing ..................................... 707
25.1.Introduction ............................................. 707
25.1.1.Gas Streams from Crude Oil ........................ 708
25.1.2.Gas Streams from Natural Gas ...................... 711
25.2.Gas Cleaning ............................................. 712
25.3.Water Removal ............................................ 719
25.3.1.Absorption ........................................ 720
25.3.2.Solid Adsorbents .................................. 720
25.3.3.Use of Membranes .................................. 721
25.4.Liquids Removal .......................................... 722
25.4.1.Extraction ........................................ 722
25.4.2.Absorption ........................................ 723
25.4.3.Fractionation of Natural Gas Liquids .............. 723
25.5.Nitrogen Removal ......................................... 724
25.6.Acid Gas Removal ......................................... 724
25.7.Enrichment ............................................... 728
25.8.Fractionation ............................................ 728
25.9.Claus Process ............................................ 729
References .................................................... 731
Chapter 26.Products ........................................... 733
26.1.Introduction ............................................. 733
26.2.Gaseous Fuels ............................................ 738
26.2.1.Composition ....................................... 738
26.2.2.Manufacture ....................................... 739
26.2.3.Properties and Uses ............................... 739
26.3.Gasoline ................................................. 742
26.3.1.Composition ....................................... 742
26.3.2.Manufacture ....................................... 743
26.3.3.Properties and Uses ............................... 746
26.3.4.Octane Numbers .................................... 746
26.3.5.Additives ......................................... 748
26.4.Solvents (Naphtha) ....................................... 750
26.4.1.Composition ....................................... 750
26.4.2.Manufacture ....................................... 751
26.4.3.Properties and Uses ............................... 753
26.5.Kerosene ................................................. 754
26.5.1.Composition ....................................... 755
26.5.2.Manufacture ....................................... 755
26.5.3.Properties and Uses ............................... 756
26.6.Fuel Oil ................................................. 756
26.7.Lubricating Oil .......................................... 758
26.7.1.Composition ....................................... 759
26.7.2.Manufacture ....................................... 759
26.7.2.1.Chemical Refining Processes .............. 760
26.7.2.2.Hydroprocessing .......................... 760
26.7.2.3.Solvent Refining Processes ............... 760
26.7.2.4.Catalytic Dewaxing ....................... 761
26.7.2.5.Solvent Dewaxing ......................... 761
26.7.2.6.Finishing Processes ...................... 761
26.7.2.7.Older Processes .......................... 762
26.7.3.Properties and Uses ............................... 763
26.8.Other Oil Products ....................................... 764
26.8.1.White Oil ......................................... 764
26.8.2.Insulating Oil .................................... 765
26.8.3.Insecticides ...................................... 766
26.9.Grease ................................................... 766
26.9.1.Lime Soap ......................................... 767
26.9.2.Soda Soap ......................................... 768
26.9.3.Lithium and Barium Soap ........................... 768
26.9.4.Aluminum Soap ..................................... 768
26.9.5.Cold Sett Grease .................................. 768
26.10.Wax ..................................................... 769
26.10.1.Composition ...................................... 769
26.10.2.Manufacture ...................................... 769
26.10.3.Properties and Uses .............................. 771
26.11.Asphalt ................................................. 771
26.11.1.Composition ...................................... 771
26.11.2.Manufacture ...................................... 772
26.11.3.Properties and Uses .............................. 774
26.12.Coke .................................................... 774
26.13.Sulfonic Acids .......................................... 776
26.14.Acid Sludge ............................................. 777
26.15.Product Blending ........................................ 777
References .................................................... 778
Chapter 27.Petrochemicals ..................................... 781
27.1.Introduction ............................................. 781
27.2.Chemicals from Paraffins ................................. 789
27.2.1.Halogenation ...................................... 789
27.2.2.Nitration ......................................... 790
27.2.3.Oxidation ......................................... 791
27.2.4.Alkylation ........................................ 792
27.2.5.Thermolysis ....................................... 793
27.3.Chemicals from Olefins ................................... 793
27.3.1.Hydroxylation ..................................... 794
27.3.2.Halogenation ...................................... 796
27.3.3.Polymerization .................................... 796
27.3.4.Oxidation ......................................... 797
27.3.5.Miscellaneous ..................................... 797
27.4.Chemicals from Aromatics ................................. 797
27.5.Chemicals from Acetylene ................................. 799
27.6.Chemicals from Natural Gas ............................... 799
27.7.Inorganic Petrochemicals ................................. 801
27.8.Synthesis Gas ............................................ 802
References .................................................... 803
Part IV. Environmental Issues ................................. 805
Chapter 28.Environmental Aspects of Refining .................. 807
28.1.Introduction ............................................. 807
28.2.Definitions .............................................. 809
28.3.Environmental Regulations ................................ 811
28.3.1.Clean Air Act Amendments .......................... 812
28.3.2.Water Pollution Control Act (The Clean Water
Act) .............................................. 812
28.3.3.Safe Drinking Water Act ........................... 812
28.3.4.Resource Conservation and Recovery Act ............ 813
28.3.5.Toxic Substances Control Act ...................... 813
28.3.6.Comprehensive Environmental Response,
Compensation, and Liability Act ................... 814
28.3.7.Occupational Safety and Health Act ................ 814
28.3.8.Oil Pollution Act ................................. 814
28.3.9.Hazardous Materials Transportation Act ............ 815
28.4.Process Analysis ......................................... 815
28.4.1.Gaseous Emissions ................................. 818
28.4.2.Liquid Effluents .................................. 822
28.4.3.Solid Effluents ................................... 823
28.5.Epilog ................................................... 824
References .................................................... 824
Chapter 29.Refinery Wastes .................................... 827
29.1.Introduction ............................................. 827
29.2.Process Wastes ........................................... 830
29.2.1.Desalting ......................................... 831
29.2.2.Distillation ...................................... 832
29.2.3.Thermal Cracking and Visbreaking .................. 835
29.2.4.Coking Processes .................................. 836
29.2.5.Fluid Catalytic Cracking .......................... 838
29.2.6.Hydrocracking and Hydrotreating ................... 839
29.2.7.Catalytic Reforming ............................... 842
29.2.8.Alkylation ........................................ 843
29.2.9.Isomerization ..................................... 845
29.2.10.Polymerization ................................... 846
29.2.11.Deasphalting ..................................... 847
29.2.12.Dewaxing ......................................... 848
29.2.13.Gas Processing ................................... 849
29.3.Types of Waste ........................................... 850
29.3.1.Gases and Lower Boiling Constituents .............. 852
29.3.2.Higher Boiling Constituents ....................... 854
29.3.3.Wastewater ........................................ 855
29.3.4.Solid Waste ....................................... 857
29.4.Waste Toxicity ........................................... 857
29.5.Refinery Outlook ......................................... 858
29.5.1.Hazardous Waste Regulations ....................... 858
29.5.2.Regulatory Background ............................. 858
29.5.3.Requirements ...................................... 858
29.6.Management of Refinery Waste ............................. 859
References .................................................... 860
Chapter 30.Environmental Analysis ............................. 861
30.1.Introduction ............................................. 861
30.2.Petroleum and Petroleum Products ......................... 862
30.3.Leachability and Toxicity ................................ 864
30.4.Total Petroleum Hydrocarbons ............................. 864
30.4.1.Gas Chromatographic Methods ....................... 866
30.4.2.Infrared Spectroscopy Methods ..................... 869
30.4.1.Gravimetric Methods ............................... 870
30.4.4.Immunoassay Methods ............................... 871
30.5.Petroleum Group Analysis ................................. 872
30.5.1.Thin Layer Chromatography ......................... 873
30.5.2.Immunoassay ....................................... 873
30.5.3.Gas Chromatography ................................ 874
30.5.4.High-Performance Liquid Chromatography ............ 875
30.5.5.Gas Chromatography-Mass Spectrometry .............. 876
30.6.Petroleum Fractions ...................................... 877
30.7.Assessment of the Methods ................................ 877
References .................................................... 880
Conversion Factors ............................................ 883
Glossary ...................................................... 885
Index ......................................................... 921
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