Handbook of Petroleum Refining

Handbook of Petroleum Refining
اسم المؤلف
James G. Speight
التاريخ
15 فبراير 2021
المشاهدات
التقييم
(لا توجد تقييمات)
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Handbook of Petroleum Refining
James G. Speight
Contents
Preface xvii
Author .xix
Section i Feedstock: Availability and evaluation
Chapter 1 Crude Oil, Heavy Oil, and Tar Sand Bitumen .3
1.1 Introduction .3
1.2 Native Materials 4
1.2.1 Petroleum 4
1.2.1.1 Crude Oil from Tight Formations . 10
1.2.1.2 Opportunity Crudes 11
1.2.1.3 High-Acid Crude Oil 12
1.2.1.4 Foamy Oil . 13
1.2.2 Heavy Oil . 14
1.2.3 Tar Sand Bitumen . 19
1.2.4 Kerogen 24
1.2.5 Biomass 25
1.3 Natural Gas 27
1.3.1 Petroleum-Related Gas .28
1.3.2 Gas Hydrates 32
1.3.3 Coalbed Methane . 32
1.3.4 Biogenic Gas 33
1.4 Manufactured Materials 33
1.4.1 Residuum 33
1.4.2 Asphalt .34
1.4.3 Synthetic Crude Oil 35
1.4.4 Shale Oil .36
1.5 Derived Materials 36
1.5.1 Asphaltene Constituents .37
1.5.2 Nonasphaltene Constituents .37
1.6 Resources and Reserves 37
1.6.1 Conventional Crude Oil and Heavy Oil .40
1.6.2 Tar Sand Bitumen .40
1.6.3 Natural Gas 41
References 42
Chapter 2 Feedstock Evaluation 45
2.1 Introduction . 45
2.2 Petroleum Assay 47
2.3 Physical Properties 52
2.3.1 Acid Number 54
2.3.1.1 Potentiometric Titration 55
2.3.1.2 Color-Indicating Titration . 55vi Contents
2.3.2 Elemental Analysis .56
2.3.3 Density and Specific Gravity . 57
2.3.4 Metal Content . 59
2.3.5 Surface and Interfacial Tension 60
2.3.6 Viscosity . 62
2.4 Thermal Properties 64
2.4.1 Aniline Point 65
2.4.2 Carbon Residue 65
2.4.3 Critical Properties 67
2.4.4 Enthalpy .69
2.4.5 Heat of Combustion 69
2.4.6 Latent Heat .70
2.4.7 Liquefaction and Solidification 70
2.4.8 Pressure–Volume–Temperature Relationships .72
2.4.9 Specific Heat 72
2.4.10 Thermal Conductivity 73
2.4.11 Volatility .73
2.5 Electrical Properties 76
2.5.1 Conductivity . 76
2.5.2 Dielectric Constant .77
2.5.3 Dielectric Strength . 78
2.5.4 Dielectric Loss and Power Factors . 78
2.5.5 Static Electrification .79
2.6 Optical Properties 79
2.6.1 Optical Activity 79
2.6.2 Refractive Index .80
2.7 Spectroscopic Properties . 81
2.7.1 Infrared Spectroscopy 82
2.7.2 Mass Spectrometry .82
2.7.3 Nuclear Magnetic Resonance Spectroscopy 83
2.8 Chromatographic Properties .83
2.8.1 Adsorption Chromatography 83
2.8.2 Gas Chromatography .85
2.8.3 Gel Permeation Chromatography .87
2.8.4 High-Performance Liquid Chromatography 88
2.8.5 Ion-Exchange Chromatography .89
2.8.6 Simulated Distillation .90
2.8.7 Supercritical Fluid Chromatography 91
2.9 Molecular Weight 91
2.10 Use of the Data 92
References 94
Chapter 3 Feedstock Composition 101
3.1 Introduction . 101
3.2 Elemental Composition . 102
3.3 Chemical Composition 104
3.3.1 Hydrocarbon Constituents 107
3.3.1.1 Paraffin Hydrocarbons 108
3.3.1.2 Cycloparaffin Hydrocarbons . 109Contents vii
3.3.1.3 Aromatic Hydrocarbons . 110
3.3.1.4 Unsaturated Hydrocarbons . 113
3.3.2 Nonhydrocarbon Constituents 113
3.3.2.1 Sulfur Compounds 114
3.3.2.2 Nitrogen Compounds 116
3.3.2.3 Oxygen Compounds . 118
3.3.2.4 Metallic Constituents 118
3.3.2.5 Porphyrins . 119
3.4 Chemical Composition by Distillation 121
3.4.1 Gases and Naphtha . 123
3.4.2 Middle Distillates .124
3.4.3 Vacuum Residua .126
3.5 Fractional Composition . 127
3.5.1 Solvent Methods . 128
3.5.2 Adsorption Methods . 133
3.5.3 Chemical Methods . 135
3.6 Use of the Data 135
References 139
Chapter 4 Introduction to Refining Processes 143
4.1 Introduction . 143
4.2 Dewatering and Desalting . 147
4.3 Distillation . 148
4.3.1 Distillation at Atmospheric Pressure 149
4.3.2 Distillation under Reduced Pressure 150
4.3.3 Azeotropic and Extractive Distillation . 151
4.4 Thermal Processes . 152
4.4.1 Thermal Cracking 154
4.4.2 Visbreaking 155
4.4.3 Coking 155
4.4.3.1 Delayed Coking 157
4.4.3.2 Fluid Coking . 157
4.5 Catalytic Processes 159
4.5.1 Catalytic Cracking 159
4.5.2 Catalysts . 160
4.6 Hydroprocesses 162
4.6.1 Hydrotreating . 163
4.6.1.1 Hydrofining . 163
4.6.2 Hydrocracking 163
4.7 Reforming Processes . 165
4.7.1 Thermal Reforming 165
4.7.2 Catalytic Reforming . 166
4.7.3 Catalysts . 167
4.8 Isomerization Processes 167
4.8.1 Processes 168
4.8.2 Catalysts . 168
4.9 Alkylation Processes . 169
4.9.1 Processes 170
4.9.2 Catalysts . 170viii Contents
4.10 Polymerization Processes 170
4.10.1 Processes 171
4.10.2 Catalysts . 171
4.11 Solvent Processes . 171
4.11.1 Deasphalting . 172
4.11.2 Dewaxing . 173
4.12 Petroleum Products 174
4.13 Petrochemicals . 175
4.14 Ancillary Operations . 177
References 178
Chapter 5 Refining Chemistry 181
5.1 Introduction . 181
5.2 Cracking Chemistry 183
5.2.1 Thermal Cracking 183
5.2.1.1 General Chemistry 183
5.2.1.2 Asphaltene Chemistry 186
5.2.1.3 Biomass Chemistry . 188
5.2.2 Catalytic Cracking 188
5.2.3 Dehydrogenation 190
5.2.4 Dehydrocyclization . 193
5.3 Hydrogenation . 193
5.3.1 Hydrotreating . 194
5.3.1.1 General Chemistry 194
5.3.1.2 Asphaltene Chemistry 194
5.3.1.3 Catalysts 196
5.3.2 Hydrocracking 196
5.3.2.1 General Chemistry 197
5.3.2.2 Asphaltene Chemistry 198
5.3.2.3 Catalysts 198
5.3.3 Solvent Deasphalting 199
5.3.3.1 Effects of Temperature and Pressure 199
5.3.3.2 Effects of the Solvent-to-Oil Ratio .200
5.3.3.3 Effects of Solvent Types .200
5.4 Isomerization . 201
5.5 Alkylation 202
5.6 Polymerization .202
5.7 Process Chemistry .202
5.7.1 Thermal Chemistry 203
5.7.2 Hydroconversion Chemistry . 211
5.7.3 Chemistry in the Refinery 212
5.7.3.1 Visbreaking . 212
5.7.3.2 Hydroprocessing . 215
References 216
Chapter 6 Refinery Reactors . 221
6.1 Introduction . 221
6.2 Reactor Types 226
6.2.1 Batch Reactors 227
6.2.1.1 Heating and Cooling Systems .228Contents ix
6.2.2 Semibatch Reactors 230
6.2.3 Continuous Reactors 230
6.2.4 Plug Flow Reactors . 232
6.2.5 Flash Reactors 232
6.2.6 Slurry Reactors . 233
6.3 Bed Types 234
6.3.1 Packed Beds .234
6.3.2 Plug Flow Reactors .238
6.3.3 Fluidized-Bed Reactors 238
6.3.4 Downflow Fixed-Bed Reactors 240
6.3.5 Upflow Expanded-Bed Reactors 241
6.3.6 Ebullating Bed Reactors . 241
6.3.7 Demetallization Reactors .242
6.4 Process Parameters 243
6.4.1 Partial Pressure 244
6.4.2 Space Velocity 244
6.4.3 Temperature 244
6.4.4 Catalyst Life .245
6.4.5 Feedstock 245
References 247
Section ii Refining
Chapter 7 Pretreatment and Distillation . 251
7.1 Introduction . 251
7.2 Dewatering and Desalting . 253
7.3 Distillation .259
7.3.1 Distillation at Atmospheric Pressure 264
7.3.2 Distillation at a Reduced Pressure .268
7.3.3 Distillation Towers . 272
7.3.3.1 Tray Towers . 273
7.3.3.2 Packed Towers 275
7.4 Other Distillation Processes 277
7.4.1 Stripping .277
7.4.2 Rerunning . 278
7.4.3 Stabilization 278
7.4.4 Superfractionation 281
7.4.5 Azeotropic Distillation . 281
7.4.6 Extractive Distillation 282
7.5 Options for Heavy Feedstocks .285
7.5.1 Distillation Operations .285
7.5.2 Corrosion 287
References 288
Chapter 8 Thermal Cracking Processes 291
8.1 Introduction . 291
8.2 Thermal Cracking .296
8.3 Visbreaking .299x Contents
8.4 Coking . 315
8.4.1 Delayed Coking 316
8.4.2 Fluid Coking . 321
8.4.3 Flexicoking . 329
8.5 Other Processes . 330
8.6 Options for Heavy Feedstocks . 332
8.6.1 Aquaconversion Process . 332
8.6.2 Asphalt Coking Technology (ASCOT) Process . 332
8.6.3 Cherry-P Process 333
8.6.4 Continuous Coking Process . 333
8.6.5 Decarbonizing Process . 334
8.6.6 ET-II Process 334
8.6.7 Eureka Process . 335
8.6.8 FTC Process . 336
8.6.9 HSC Process . 336
8.6.10 Mixed-Phase Cracking Process 336
8.6.11 Selective Cracking Process 337
8.6.12 Shell Thermal Cracking Process 337
8.6.13 Tervahl-T Process . 338
References 339
Chapter 9 Catalytic Cracking Processes . 341
9.1 Introduction . 341
9.2 Fixed-Bed Processes 349
9.3 Moving-Bed Processes 350
9.4 Fluid-Bed Processes 354
9.5 Coke Formation and Additives 361
9.5.1 Coke Formation 361
9.5.2 Additives . 363
9.6 Process Variables . 363
9.6.1 Feedstock Quality 363
9.6.2 Feedstock Preheating . 367
9.6.3 Feedstock Pressure .368
9.6.4 Feedstock Conversion .368
9.6.5 Reactor Temperature 369
9.6.6 Recycle Rate . 370
9.6.7 Space Velocity 370
9.6.8 Catalyst Activity . 371
9.6.9 Catalyst/Oil Ratio . 371
9.6.10 Regenerator Temperature . 373
9.6.11 Regenerator Air Rate 373
9.6.12 Process Design . 373
9.6.12.1 Modifications for Existing Units 373
9.6.12.2 Commercial Technology Changes 374
9.6.12.3 New Directions . 376
9.7 Catalysts 376
9.7.1 Catalyst Types 377
9.7.2 Catalyst Manufacture . 379
9.7.3 Catalyst Selectivity .380
9.7.4 Catalyst Deactivation . 381Contents xi
9.7.5 Catalyst Stripping . 381
9.7.6 Catalyst Treatment 382
9.7.6.1 Demet 392
9.7.6.2 Met-X 392
9.7.7 Recent Advances 393
9.7.7.1 Matrix, Binder, and Zeolite 393
9.7.7.2 Additives . 393
9.7.7.3 Metal Traps .394
9.7.7.4 Low Rare Earths .394
9.7.7.5 Catalysts for Olefin Production .394
9.7.7.6 Catalysts for Jet and Diesel Production 395
9.7.7.7 New Directions . 395
9.8 Options for Heavy Feedstocks .396
9.8.1 Asphalt Residual Treating (ART) Process .397
9.8.2 Residue Fluid Catalytic Cracking Process . 398
9.8.3 Heavy Oil Treating Process .399
9.8.4 R2R Process .399
9.8.5 Reduced Crude Oil Conversion Process 400
9.8.6 Shell FCC Process 400
9.8.7 S&W Fluid Catalytic Cracking Process . 401
9.9 Other Options 401
References 404
Chapter 10 Hydrotreating Processes .409
10.1 Introduction .409
10.1.1 Benzene Cyclohexane 411
10.2 Hydrodesulfurization . 418
10.2.1 Process Configuration 420
10.2.2 Downflow Fixed-Bed Reactors 420
10.2.3 Upflow Expanded-Bed Reactors 421
10.2.4 Demetallization Reactors . 422
10.2.5 Catalysts . 423
10.3 Distillate Hydrodesulfurization .424
10.3.1 Processes 424
10.3.2 Process Parameters . 429
10.3.2.1 Hydrogen Partial Pressure 429
10.3.2.2 Space Velocity 429
10.3.2.3 Reaction Temperature . 430
10.3.2.4 Catalyst Life 430
10.3.2.5 Feedstock Effects 430
10.4 Heavy Feedstock Hydrodesulfurization 435
10.4.1 Processes 435
10.4.1.1 Resid Desulfurization and Vacuum Resid
Desulfurization Process 435
10.4.1.2 Residfining Process 438
10.4.1.3 Other Options . 438
10.4.2 Process Parameters . 441
10.4.2.1 Catalyst Types . 441
10.4.2.2 Metals Accumulation 441
10.4.2.3 Catalyst Activity .442xii Contents
10.4.2.4 Temperature and Space Velocity .442
10.4.2.5 Feedstock Effects .442
10.5 Other Options 449
10.5.1 Catalyst Technology 450
10.5.2 Gasoline and Diesel Fuel Polishing 452
10.5.3 Biodesulfurization . 453
10.5.4 Bio-Feedstocks 455
References 455
Chapter 11 Hydrocracking 457
11.1 Introduction . 457
11.2 Processes and Process Design .466
11.2.1 Process Design 467
11.2.2 Feedstocks and Hydrogen Requirements 470
11.2.3 Design Improvements . 471
11.3 Catalysts 475
11.4 Options for Heavy Feedstocks .484
11.4.1 Aquaconversion .484
11.4.2 Asphaltenic Bottom Cracking Process .485
11.4.3 CANMET Process 486
11.4.4 Chevron RDS Isomax and VRDS Process .488
11.4.5 ENI Slurry-Phase Technology 489
11.4.6 Gulf Resid Hydrodesulfurization Process 489
11.4.7 H-G Hydrocracking Process . 491
11.4.8 H-Oil Process 492
11.4.9 HYCAR Process . 495
11.4.10 Hyvahl-F Process 495
11.4.11 IFP Hydrocracking Process 496
11.4.12 Isocracking Process .496
11.4.13 LC-Fining Process 499
11.4.14 MAKfining Process 501
11.4.15 Microcat-RC Process 502
11.4.16 Mild Hydrocracking Process 503
11.4.17 MRH Process 505
11.4.18 RCD Unibon Process 505
11.4.19 Residfining Process .507
11.4.20 Residue Hydroconversion Process 508
11.4.21 Shell Residual Oil Process 508
11.4.22 Tervahl-H Process .509
11.4.23 Unicracking Process . 511
11.4.24 Uniflex Process . 514
11.4.25 Veba Combi Cracking Process 516
11.5 Other Options 517
References 520
Chapter 12 Solvent Processes . 525
12.1 Introduction . 525
12.2 Deasphalting Processes . 526
12.2.1 Deasphalting Process 527Contents xiii
12.2.2 Deep Solvent Deasphalting Process . 534
12.2.3 Demex Process . 538
12.2.4 MDS Process 539
12.2.5 Residuum Oil Supercritical Extraction Process .540
12.2.6 Solvahl Process 541
12.2.7 Lube Deasphalting . 542
12.3 Dewaxing Processes 542
12.3.1 Cold Press Process .544
12.3.2 Solvent Dewaxing Process .544
12.3.3 Urea Dewaxing Process . 547
12.3.4 Centrifuge Dewaxing Process 548
12.3.5 Catalytic Dewaxing Process 548
12.3.6 Dewaxing Heavy Feedstocks . 550
References 551
Chapter 13 Product Improvement . 553
13.1 Introduction . 553
13.2 Reforming 554
13.2.1 Thermal Reforming 556
13.2.2 Catalytic Reforming . 557
13.2.2.1 Fixed-Bed Processes .560
13.2.2.2 Moving-Bed Processes . 563
13.2.3 Fluid-Bed Processes .564
13.3 Isomerization .565
13.3.1 Butamer Process . 567
13.3.2 Butomerate Process 567
13.3.3 Hysomer Process 568
13.3.4 Iso-Kel Process .568
13.3.5 Isomate Process 568
13.3.6 Isomerate Process .568
13.3.7 Penex Process .568
13.3.8 Pentafining Process 569
13.4 Hydroisomerization .569
13.5 Alkylation 570
13.5.1 Sulfuric Acid Alkylation 571
13.5.2 Hydrogen Fluoride Alkylation . 572
13.6 Polymerization . 573
13.6.1 Thermal Polymerization . 574
13.6.2 Solid Phosphoric Acid Polymerization 574
13.6.3 Bulk Acid Polymerization 574
13.7 Catalysts 575
13.7.1 Reforming Processes 575
13.7.2 Isomerization Processes . 575
13.7.3 Alkylation Processes 576
13.7.4 Polymerization Processes . 577
13.8 Treating Processes . 577
13.8.1 Caustic Processes . 577
13.8.1.1 Dualayer Distillate Process . 578
13.8.1.2 Dualayer Gasoline Process . 578
13.8.1.3 Electrolytic Mercaptan Process 578xiv Contents
13.8.1.4 Ferrocyanide Process . 578
13.8.1.5 Lye Treatment 579
13.8.1.6 Mercapsol Process . 579
13.8.1.7 Polysulfide Treatment 579
13.8.1.8 Sodasol Process . 579
13.8.1.9 Solutizer Process .580
13.8.1.10 Steam-Regenerative Caustic Treatment .580
13.8.1.11 Unisol Process .580
13.8.2 Acid Processes 580
13.8.2.1 Nalfining Process 582
13.8.2.2 Sulfuric Acid Treatment 582
13.8.3 Clay Processes 582
13.8.3.1 Alkylation Effluent Treatment . 583
13.8.3.2 Arosorb Process . 583
13.8.3.3 Bauxite Treatment . 583
13.8.3.4 Continuous Contact Filtration Process 583
13.8.3.5 Cyclic Adsorption Process 584
13.8.3.6 Gray Clay Treatment .584
13.8.3.7 Percolation Filtration Process 584
13.8.3.8 Thermofor Continuous Percolation Process 584
13.8.4 Oxidative Processes .584
13.8.4.1 Bender Process 584
13.8.4.2 Copper Sweetening Process 585
13.8.4.3 Doctor Process . 585
13.8.4.4 Hypochlorite Sweetening Process . 586
13.8.4.5 Inhibitor Sweetening Process 586
13.8.4.6 Merox Process . 586
13.8.5 Solvent Processes . 586
References 589
Chapter 14 Gasification Processes 591
14.1 Introduction . 591
14.2 Gasification Chemistry 593
14.2.1 General Aspects .594
14.2.2 Pretreatment . 595
14.2.3 Reactions 596
14.2.3.1 Primary Gasification . 598
14.2.3.2 Secondary Gasification 598
14.2.3.3 Water-Gas Shift Reaction 600
14.2.3.4 Carbon Dioxide Gasification . 601
14.2.3.5 Hydrogasification .602
14.2.3.6 Methanation .603
14.3 Processes and Feedstocks 603
14.3.1 Gasifiers 604
14.3.2 Fischer–Tropsch Synthesis .606
14.3.3 Feedstocks 607
14.3.3.1 Residua 607
14.3.3.2 Petroleum Coke .608
14.3.3.3 Asphalt, Tar, and Pitch 611Contents xv
14.3.3.4 Tar Sand Bitumen . 612
14.3.3.5 Coal . 613
14.3.3.6 Biomass . 615
14.3.3.7 Solid Waste . 616
14.3.3.8 Black Liquor . 619
14.4 Gasification in a Refinery 620
14.4.1 Gasification of Residua and Residua—Coal Mixtures 621
14.4.2 Cogasification of Residua with Biomass 622
14.4.3 Cogasification of Residua with Waste 623
14.5 Synthetic Fuel Production . 625
14.5.1 Gaseous Products . 625
14.5.1.1 Synthesis Gas 625
14.5.1.2 Low-Btu Gas .626
14.5.1.3 Medium-Btu Gas 626
14.5.1.4 High-Heat-Content (High-Btu) Gas 627
14.5.2 Liquid Products 627
14.5.3 Solid Products 628
14.6 The Future . 629
References 630
Chapter 15 Hydrogen Production 635
15.1 Introduction . 635
15.2 Processes Requiring Hydrogen . 638
15.2.1 Hydrotreating . 638
15.2.2 Hydrocracking 639
15.3 Hydrogen Production . 641
15.3.1 Feedstocks 641
15.3.2 Chemistry . 641
15.3.3 Catalysts .643
15.3.3.1 Reforming Catalysts .643
15.3.3.2 Shift Conversion Catalysts 644
15.3.3.3 Methanation Catalysts 645
15.4 Hydrogen Purification .645
15.4.1 Wet Scrubbing 646
15.4.2 Pressure Swing Adsorption Units 646
15.4.3 Membrane Systems 647
15.4.4 Cryogenic Separation .648
15.5 Hydrogen Management 648
15.6 Commercial Processes 649
15.6.1 Heavy Residue Gasification and Combined
Cycle Power Generation .650
15.6.2 Hybrid Gasification Process . 651
15.6.3 Hydrocarbon Gasification 651
15.6.4 Hypro Process 651
15.6.5 Pyrolysis Processes 651
15.6.6 Shell Gasification Process 652
15.6.7 Steam–Methane Reforming . 653
15.6.8 Steam–Naphtha Reforming 655
15.6.9 Synthesis Gas Generation . 655xvi Contents
15.6.10 Texaco Gasification Process .656
15.6.11 Recovery from Process Gas .656
15.7 Refining Heavy Feedstocks . 657
References 657
Chapter 16 Gas Cleaning 661
16.1 Introduction . 661
16.2 Gas Streams .667
16.2.1 Gas Streams from Crude Oil 667
16.2.2 Gas Streams from Natural Gas 671
16.3 Enrichment 672
16.4 Water Removal 673
16.4.1 Absorption 674
16.4.2 Solid Adsorbents 674
16.4.3 Membranes . 676
16.5 Liquid Removal . 676
16.5.1 Extraction . 677
16.5.2 Absorption 677
16.5.3 Fractionation of Natural Gas Liquids . 678
16.6 Nitrogen Removal 679
16.7 Acid Gas Removal . 679
16.8 Fractionation 684
16.9 Claus Process .684
References 687
Chapter 17 Refining in the Future 689
17.1 Introduction .689
17.2 History .689
17.3 Refinery Configurations 692
17.3.1 Petroleum Refinery .692
17.3.2 Biorefinery 696
17.3.3 Coal Liquids Refinery 698
17.3.4 Shale Oil Refinery 699
17.3.5 Gasification Refinery 701
17.4 The Future Refinery 701
References 703
Glossary 707
Index
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