Fischer-Tropsch Refining

The Fischer-Tropsch process is gaining recognition again due to the world-wide increase in energy needs and decrease in oil availability. The increasing interest in utilizing biomass as a potential renewable feedstock in energy generation is further supporting this development. The book covers the production and refining of Fischer-Tropsch syncrude to fuels and chemicals systematically and comprehensively, presenting a wealth of new knowledge and material. As such, it deals extensively with aspects of engineering, chemistry and catalysis. This handbook and ready reference adopts a fundamental approach, looking at the molecules and their transformation from feed to product. Numerous examples illustrate the possibilities and limitations of Fischer-Tropsch syncrude as feesdstock. Of great interest to everyone interested in refining - not just Fischer-Tropsch specialists. From the Contents: Fischer-Tropsch Facilities and Refineries at a Glance Production of Fischer-Tropsch Syncrude Industrial Fischer-Tropsch Facilities Synthetic Transportation Fuels Refining Technology Refinery Design

Table of Contents:
Preface xix Part I Introduction 1 1 Fischer–Tropsch Facilities at a Glance 3 1.1 Introduction 3 1.2 Feed-to-Syngas Conversion 4 1.2.1 Feed Logistics and Feed Preparation 5 1.2.2 Syngas Production 5 1.2.3 Syngas Cleaning and Conditioning 7 1.3 Syngas-to-Syncrude Conversion 8 1.4 Syncrude-to-Product Conversion 10 1.4.1 Upgrading versus Refining 10 1.4.2 Fuels versus Chemicals 11 1.4.3 Crude Oil Compared to Syncrude 12 1.5 Indirect Liquefaction Economics 14 1.5.1 Feed Cost 14 1.5.2 Product Pricing 15 1.5.3 Capital Cost 17 References 19 2 Refining and Refineries at a Glance 21 2.1 Introduction 21 2.2 Conventional Crude Oil 22 2.2.1 Hydrocarbons in Crude Oil 23 2.2.2 Sulfur Compounds in Crude Oil 23 2.2.3 Nitrogen Compounds in Crude Oil 25 2.2.4 Oxygenates in Crude Oil 25 2.2.5 Metals in Crude Oil 26 2.2.6 Physical Properties 27 2.3 Products from Crude Oil 28 2.3.1 Boiling Range and Product Quality 29 2.4 Evolution of Crude Oil Refineries 31 2.4.1 First-Generation Crude Oil Refineries 32 2.4.2 Second-Generation Crude Oil Refineries 33 2.4.3 Third-Generation Crude Oil Refineries 36 2.4.4 Fourth-Generation Crude Oil Refineries 39 2.4.5 Petrochemical Refineries 43 2.4.6 Lubricant Base Oil Refineries 44 References 46 Part II Production of Fischer–Tropsch Syncrude 49 3 Synthesis Gas Production, Cleaning, and Conditioning 51 3.1 Introduction 51 3.2 Raw Materials 51 3.2.1 Natural Gas 51 3.2.2 Solid Carbon Sources 52 3.3 Syngas from Natural Gas 53 3.3.1 Natural Gas Cleaning 55 3.3.2 Adiabatic Prereforming 55 3.3.3 Steam Reforming 56 3.3.4 Adiabatic Oxidative Reforming 56 3.3.5 Gas Reforming Comparison 57 3.4 Syngas from Solid Carbon Sources 58 3.4.1 Gasification of Heteroatoms 59 3.4.2 Low-Temperature Moving Bed Gasification 60 3.4.3 Medium-Temperature Fluidized Bed Gasification 62 3.4.4 High-Temperature Entrained Flow Gasification 64 3.4.5 Gasification Comparison 66 3.5 Syngas Cleaning 66 3.5.1 Acid Gas Removal 67 3.6 Syngas Conditioning 69 3.6.1 Water Gas Shift Conversion 69 3.7 Air Separation Unit 70 References 71 4 Fischer–Tropsch Synthesis 73 4.1 Introduction 73 4.2 Fischer–Tropsch Mechanism 74 4.3 Fischer–Tropsch Product Selectivity 77 4.3.1 Probability of Chain Growth 78 4.3.2 Hydrogenation versus Desorption 80 4.3.3 Readsorption Chemistry 81 4.4 Selectivity Manipulation in Fischer–Tropsch Synthesis 81 4.4.1 Fischer–Tropsch Catalyst Formulation 81 4.4.2 Fischer–Tropsch Operating Conditions 83 4.4.3 Fischer–Tropsch Reaction Engineering 84 4.5 Fischer–Tropsch Catalyst Deactivation 88 4.5.1 Poisoning by Syngas Contaminants 89 4.5.2 Volatile Metal Carbonyl Formation 90 4.5.3 Metal Carboxylate Formation 91 4.5.4 Mechanical Catalyst Degradation 92 4.5.5 Deactivation of Fe-HTFT Catalysts 93 4.5.6 Deactivation of Fe-LTFT Catalysts 93 4.5.7 Deactivation of Co-LTFT Catalysts 95 References 99 5 Fischer–Tropsch Gas Loop 105 5.1 Introduction 105 5.2 Gas Loop Configurations 107 5.2.1 Open Gas Loop Design 107 5.2.2 Closed Gas Loop Design 108 5.3 Syncrude Cooling and Separation 109 5.3.1 Pressure Separation 110 5.3.2 Cryogenic Separation 110 5.3.3 Oxygenate Partitioning 111 5.3.4 HTFT Syncrude Recovery 113 5.3.5 LTFT Syncrude Recovery 114 References 116 Part III Industrial Fischer–Tropsch Facilities 117 6 German Fischer–Tropsch Facilities 119 6.1 Introduction 119 6.2 Synthesis Gas Production 119 6.3 Fischer–Tropsch Synthesis 121 6.3.1 Normal-Pressure Synthesis 122 6.3.2 Medium-Pressure Synthesis 125 6.3.3 Gas Loop Design 127 6.3.4 Carbon Efficiency 128 6.4 Fischer–Tropsch Refining 128 6.4.1 Refining C 3 –C 4 Crude LPG 129 6.4.2 Refining Carbon Gasoline 130 6.4.3 Refining of Condensate Oil 132 6.4.4 Refining of Waxes 135 6.4.5 Aqueous Product Refining 136 6.5 Discussion of the Refinery Design 137 References 138 7 American Hydrocol Facility 141 7.1 Introduction 141 7.2 Synthesis Gas Production 142 7.3 Fischer–Tropsch Synthesis 143 7.4 Fischer–Tropsch Refining 145 7.4.1 Oil Product Refining 146 7.4.2 Refining Aqueous Product 149 7.5 Discussion of the Refinery Design 150 References 151 8 Sasol 1 Facility 153 8.1 Introduction 153 8.2 Synthesis Gas Production 154 8.2.1 Lurgi Dry Ash Coal Gasification 154 8.2.2 Rectisol Synthesis Gas Cleaning 155 8.3 Fischer–Tropsch synthesis 157 8.3.1 Kellogg HTFT synthesis 157 8.3.2 Arge LTFT Synthesis 159 8.3.3 Gas Loop Design 162 8.4 Fischer–Tropsch Refining 163 8.4.1 Kellogg HTFT Oil Refining 163 8.4.2 Arge LTFT Oil Refining 165 8.4.3 Aqueous Product Refining 166 8.4.4 Coal Pyrolysis Product Refining 169 8.4.5 Synthetic Fuel Properties 170 8.5 Evolution of the Sasol 1 Facility 172 8.5.1 Changes in Synthesis Gas Production 172 8.5.2 Changes in Fischer–Tropsch Synthesis 173 8.5.3 Changes in Fischer–Tropsch Refining 174 8.5.4 Changes in Coal Pyrolysis Product Refining 177 8.6 Discussion of the Refinery Design 177 References 179 9 Sasol 2 and 3 Facilities 181 9.1 Introduction 181 9.2 Synthesis Gas Production 182 9.2.1 Lurgi Dry Ash Coal Gasification 182 9.2.2 Synthesis Gas Cleaning 182 9.3 Fischer–Tropsch Synthesis 183 9.3.1 Gas Loop Design 184 9.4 Fischer–Tropsch Refining 186 9.4.1 Synthol HTFT Condensate Refining 188 9.4.2 Synthol HTFT Oil Refining 192 9.4.3 Aqueous Product Refining 194 9.4.4 Coal Pyrolysis Product Refining 196 9.4.5 Synthetic Fuel Properties 198 9.5 Evolution of Sasol Synfuels 199 9.5.1 Changes in Synthesis Gas Production 201 9.5.2 Changes in Fischer–Tropsch Synthesis 201 9.5.3 Changes in Fischer–Tropsch Condensate Refining 202 9.5.4 Extraction of Linear 1-Alkenes 204 9.5.5 Changes in Fischer–Tropsch Oil Refining 205 9.5.6 Changes in Fischer–Tropsch Aqueous Product Refining 210 9.5.7 Changes in Coal Pyrolysis Product Refining 211 9.5.8 Synthetic Jet Fuel 212 9.6 Discussion of the Refinery Design 212 References 214 10 Mossgas Facility 217 10.1 Introduction 217 10.2 Synthesis Gas Production 218 10.2.1 Natural Gas Liquid Recovery 218 10.2.2 Gas Reforming 218 10.3 Fischer–Tropsch Synthesis 220 10.3.1 Gas Loop Design 221 10.4 Fischer–Tropsch Refining 222 10.4.1 Oil Refining 222 10.4.2 Aqueous Product Refining 225 10.4.3 Synthetic Fuel Properties 227 10.5 Evolution of the PetroSA Facility 227 10.5.1 Addition of Low-Temperature Fischer–Tropsch Synthesis 227 10.5.2 Changes in the Fischer–Tropsch Refinery 227 10.6 Discussion of the Refinery Design 228 References 229 11 Shell Middle Distillate Synthesis (SMDS) Facilities 231 11.1 Introduction 231 11.2 Synthesis Gas Production in Bintulu GTL 232 11.3 Fischer–Tropsch Synthesis in Bintulu GTL 233 11.4 Fischer–Tropsch Refining in Bintulu GTL 235 11.4.1 Oil Refining 235 11.4.2 Aqueous Product Treatment 238 11.5 Pearl GTL Facility 238 11.6 Discussion of the Refinery Design 239 References 239 12 Oryx and Escravos Gas-to-Liquids Facilities 241 12.1 Introduction 241 12.2 Synthesis Gas Production in Oryx GTL 242 12.3 Fischer–Tropsch Synthesis in Oryx GTL 243 12.4 Fischer–Tropsch Refining in Oryx GTL 244 12.4.1 Oil Refining 244 12.4.2 Aqueous Product Treatment 247 12.5 Discussion of the Refinery Design 247 References 248 Part IV Synthetic Transportation Fuels 249 13 Motor-Gasoline 251 13.1 Introduction 251 13.2 Motor-Gasoline Specifications 252 13.3 Motor-Gasoline Properties 253 13.3.1 Octane Number 253 13.3.2 Density 259 13.3.3 Volatility 259 13.3.4 Fuel Stability 261 13.3.5 Alkene Content 261 13.3.6 Aromatic Content 262 13.3.7 Sulfur Content 262 13.3.8 Oxygenate Content 262 13.3.9 Metal Content 263 13.4 Aviation-Gasoline 264 13.5 Future Motor-Gasoline Specification Changes 265 References 266 14 Jet Fuel 269 14.1 Introduction 269 14.2 Jet Fuel Specifications 270 14.2.1 Synthetic Jet Fuel 271 14.2.2 Fuel for Military Use 272 14.3 Jet Fuel Properties 273 14.3.1 Net Heat of Combustion 274 14.3.2 Density and Viscosity 275 14.3.3 Freezing Point Temperature 276 14.3.4 Aromatic Content and Smoke Point 276 14.3.5 Sulfur and Acid Content 278 14.3.6 Volatility 278 14.3.7 Stability 278 14.3.8 Elastomer Compatibility and Lubricity 279 14.4 Future Jet Fuel Specification Changes 280 References 280 15 Diesel Fuel 283 15.1 Introduction 283 15.2 DieselFuelSpecifications 284 15.3 DieselFuelProperties 286 15.3.1 Cetane Number 286 15.3.2 Density and Viscosity 290 15.3.3 Flash Point 290 15.3.4 Lubricity 290 15.3.5 Aromatic Content 292 15.3.6 Sulfur Content 292 15.3.7 Cold-Flow Properties 293 15.3.8 Stability 294 15.3.9 Elastomer Compatibility 294 15.4 Diesel Fuel Additives That Affect Refinery Design 295 15.5 Future Diesel Fuel Specification Changes 296 References 297 Part V Refining Technology 301 16 Refining Technology Selection 303 16.1 Introduction 303 16.2 Hydrotreating 305 16.2.1 Hydrogenation of Alkenes 306 16.2.2 Hydrodeoxygenation 307 16.3 Addition and Removal of Oxygen 308 16.3.1 Dehydration 308 16.3.2 Etherification 309 16.3.3 Hydration 309 16.3.4 Esterification 310 16.3.5 Carbonyl Aromatization 310 16.3.6 Hydroformylation 311 16.3.7 Autoxidation 311 16.4 Alkene Conversion 312 16.4.1 Double Bond Isomerization 312 16.4.2 Metathesis 314 16.4.3 Skeletal Isomerization 314 16.4.4 Oligomerization 315 16.4.5 Aliphatic Alkylation 316 16.4.6 Aromatic Alkylation 317 16.5 Alkane Conversion 319 16.5.1 Hydroisomerization 319 16.5.2 Hydrocracking 320 16.5.3 Naphtha Reforming and Aromatization 321 16.5.4 Dehydrogenation 322 16.6 Residue Conversion 323 16.6.1 Catalytic Cracking 323 16.6.2 Visbreaking 324 16.6.3 Thermal Cracking 324 16.6.4 Coking 326 16.7 Fischer–Tropsch Refining Technology Selection 326 References 328 17 Dehydration, Etherification, and Hydration 335 17.1 Introduction 335 17.2 Dehydration 336 17.2.1 Reaction Chemistry 339 17.2.2 Catalysis 340 17.2.3 Syncrude Process Technology 341 17.3 Etherification 343 17.3.1 Reaction Chemistry 345 17.3.2 Catalysis 346 17.3.3 Syncrude Process Technology 347 17.4 Hydration 347 17.4.1 Reaction Chemistry 349 17.4.2 Catalysis 349 17.4.3 Syncrude Process Technology 350 References 350 18 Isomerization 353 18.1 Introduction 353 18.2 Reaction Chemistry 354 18.2.1 Alkene Skeletal Isomerization 354 18.2.2 Alkane Hydroisomerization 356 18.3 Skeletal Isomerization 357 18.3.1 Butene Isomerization Catalysis 358 18.3.2 Pentene Isomerization Catalysis 359 18.3.3 Syncrude Process Technology 360 18.4 Hydroisomerization 360 18.4.1 Butane Hydroisomerization Catalysis 362 18.4.2 C5 –C6 Naphtha Hydroisomerization catalysis 362 18.4.3 Heavy Alkane and Wax Hydroisomerization Catalysis 364 18.4.4 Syncrude Process Technology 364 References 366 19 Oligomerization 369 19.1 Introduction 369 19.2 Reaction Chemistry 372 19.3 Catalysis 374 19.3.1 Solid Phosphoric Acid 375 19.3.2 H-ZSM-5 Zeolite 378 19.3.3 Amorphous Silica–Alumina 380 19.3.4 Acidic Resin 381 19.3.5 Homogeneous Nickel 383 19.3.6 Thermal Oligomerization 384 19.4 Syncrude Process Technology 385 References 388 20 Aromatic Alkylation 393 20.1 Introduction 393 20.2 Reaction Chemistry 395 20.3 Catalysis 396 20.3.1 Aromatic Alkylation with Ethene 397 20.3.2 Aromatic Alkylation with Propene 399 20.3.3 Aromatic Alkylation with C 4 and Heavier Alkenes 401 20.4 Syncrude Process Technology 403 References 405 21 Cracking 407 21.1 Introduction 407 21.2 Reaction Chemistry 410 21.2.1 Thermal Cracking 410 21.2.2 Catalytic Cracking 414 21.2.3 Hydrocracking 416 21.3 Thermal Cracking 419 21.3.1 Syncrude Processing Technology 421 21.4 Catalytic Cracking 421 21.4.1 Catalysis 423 21.4.2 Syncrude Processing Technology 425 21.5 Hydrocracking 427 21.5.1 Catalysis 430 21.5.2 Syncrude Processing Technology 434 References 436 22 Reforming and Aromatization 441 22.1 Introduction 441 22.2 Thermal Naphtha Reforming 443 22.3 Conventional Catalytic Naphtha Reforming 444 22.3.1 Reaction Chemistry 444 22.3.2 Catalysis 447 22.3.3 Syncrude Processing Technology 449 22.4 Monofunctional Nonacidic Pt/L-Zeolite Naphtha Reforming 450 22.4.1 Reaction Chemistry 451 22.4.2 Catalysis 452 22.4.3 Syncrude Processing Technology 453 22.5 Aromatization 454 22.5.1 Reaction Chemistry 456 22.5.2 Catalysis 457 22.5.3 Syncrude Processing Technology 460 References 461 23 Chemical Technologies 465 23.1 Introduction 465 23.2 Production of n-1-Alkenes (Linear α-Olefins) 466 23.2.1 Extraction of 1-Pentene and 1-Hexene 467 23.2.2 Extraction of 1-Octene 470 23.2.3 Production of 1-Octene from 1-Heptene 473 23.2.4 Distillate-Range n-1-Alkene Extraction 474 23.3 Autoxidation 474 23.3.1 Autoxidation Regimes 477 23.3.2 Reaction Chemistry 478 23.3.3 Fischer–Tropsch Wax Oxidation 480 23.3.4 Syncrude Process Technology 484 References 485 Part VI Refinery Design 489 24 Principles of Refinery Design 491 24.1 Introduction 491 24.2 Refinery Design Concepts 491 24.2.1 Characteristic of the Refining Business 491 24.2.2 Complex Systems and Design Rules 493 24.2.3 Refining Complexity 495 24.2.4 Refining Efficiency 496 24.3 Conceptual Refinery Design 497 24.3.1 Linear Programming 497 24.3.2 Hierarchical Design 498 24.3.3 Technology Preselection 498 24.3.4 Carbon-Number-Based Design 499 24.4 Real-World Refinery Design 500 24.4.1 Refinery Type 501 24.4.2 Refinery Products and Markets 501 24.4.3 Refinery Feed Selection 502 24.4.4 Refinery Location 503 24.4.5 Secondary Design Objectives 506 References 508 25 Motor-Gasoline Refining 509 25.1 Introduction 509 25.2 Gap Analysis for Syncrude to Motor-Gasoline 510 25.2.1 Motor-Gasoline Specifications 510 25.2.2 Carbon Number Distribution 511 25.2.3 Composition and Quality 512 25.3 Decisions Affecting Motor-Gasoline Refining 514 25.3.1 Chemicals Coproduction 514 25.3.2 Fate of C 2 –C 4 Hydrocarbons 515 25.3.3 Fate of the Residue and Wax 516 25.3.4 Fate of the Aqueous Product 517 25.3.5 Alkane-Based Naphtha Refining 518 25.3.6 Technology Selection 519 25.3.7 Co-refining 521 25.4 Motor-Gasoline Refining from HTFT Syncrude 522 25.4.1 HTFT Motor-Gasoline Design Case I 522 25.4.2 HTFT Motor-gasoline Design Case II 526 25.5 Motor-Gasoline Refining from LTFT Syncrude 529 25.5.1 LTFT Motor-Gasoline Design Case I 529 25.5.2 LTFT Motor-gasoline Design Case II 534 25.5.3 LTFT Motor-gasoline Design Case III 537 References 539 26 Jet Fuel Refining 541 26.1 Introduction 541 26.2 Gap Analysis for Syncrude to Jet Fuel 541 26.2.1 Jet Fuel Specifications 541 26.2.2 Carbon Number Distribution 542 26.2.3 Composition and Quality 542 26.3 Decisions Affecting Jet Fuel Refining 544 26.3.1 Fate of C 2 –C 4 Hydrocarbons 544 26.3.2 Fate of the Residue and Wax 545 26.3.3 Technology Selection 546 26.3.4 Co-refining 547 26.4 Jet Fuel Refining from HTFT Syncrude 548 26.4.1 HTFT Jet Fuel Design Case I 549 26.4.2 HTFT Jet Fuel Design Case II 552 26.5 Jet Fuel Refining from LTFT Syncrude 553 26.5.1 LTFT Jet Fuel Design Case I 555 References 558 27 Diesel Fuel Refining 559 27.1 Introduction 559 27.2 Gap Analysis for Syncrude to Diesel Fuel 560 References 578 28 Chemicals and Lubricant Refining 581 28.1 Introduction 581 28.2 Petrochemical and Lubricant Markets 582 References 601 Index 603

About the Author :
Arno de Klerk has been active in the field of Fischer-Tropsch refining for more than 15 years. Most of his industrial career was spent at Sasol, where he headed the Fischer-Tropsch Refinery Catalysis group from 2001-2008. Presently, he is the Nexen Professor of Catalytic Reaction Engineering in the Department of Chemical and Materials Engineering at the University of Alberta. He is registered as professional engineer in both South Africa and Canada (Alberta), holding a PhD in Chemical Engineering and an MSc in Chemistry. Professor de Klerk received the Innovation Award from the South African Institution of Chemical Engineers for his work on refining and refining catalysis on three occasions.

Review :
“I would strongly recommend this book to all who wish to become informed about the FT industry and its technology. It may well be the case that FT processes will play a dominant role in tomorrow's energy sources.”  (Chemistry World, 2012)