Hydrotreating and XTL by Hydrocarbon Publishing Company

WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in a Single Source

Second Quarter 2011 Hydrotreating and XTL Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

P.O. Box 661 Southeastern, PA 19399 (U.S.A.)

Phone: (610) 408-0117/ Fax: (610) 408-0118

Review@Hydrocarbonpublishing.com

TABLE OF CONTENTS 2Q 2011 Review Hydrotreating and XTL 1. Introduction.....................................................................................................................................1 2. Hydrotreating..................................................................................................................................5 2.1

2.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 5 2.1.1 Introduction .............................................................................................................................................. 5 2.1.2 Market Conditions and Outlook................................................................................................................ 5 2.1.2.1 Refined Products Legislation...................................................................................................... 5 2.1.2.1.1 Gasoline and Diesel................................................................................................... 5 2.1.2.1.2 Bunker Fuels.............................................................................................................. 7 2.1.2.2 Refined Products Supply and Demand ....................................................................................... 8 2.1.2.3 Increasing Middle Distillate Production ................................................................................... 10 2.1.2.4 Capacity Expansion .................................................................................................................. 11 2.1.2.5 Shifting Crude Slate.................................................................................................................. 12 2.1.2.6 Heavy Crude Oil Upgrading..................................................................................................... 15 2.1.2.7 Hydrogen Demand.................................................................................................................... 16 2.1.2.8 Construction Projects and Unit Revamps ................................................................................. 16 2.1.2.9 Hydrotreating Catalysts Market................................................................................................ 17 2.1.3 Technology Competition, Directions, and Future Prospects.................................................................. 18 2.1.3.1 Conventional Hydrotreating ..................................................................................................... 20 2.1.3.2 Resid Hydrotreating.................................................................................................................. 28 2.1.3.3 Renewable Feed Hydrotreating ................................................................................................ 29 2.1.4 Conclusion .............................................................................................................................................. 32 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 33 2.2.1 Introduction ............................................................................................................................................ 33 2.2.2 Commercial Catalysts and Guard Materials .......................................................................................... 33 2.2.2.1 Advanced Refining Technologies............................................................................................. 35 2.2.2.1.1 SmART.................................................................................................................... 35 2.2.2.1.2 ApART .................................................................................................................... 37 2.2.2.2 Albemarle ................................................................................................................................. 39 2.2.2.2.1 STARS Series.......................................................................................................... 40 2.2.2.2.2 NEBULA Series ...................................................................................................... 45 2.2.2.2.3 Combined Implementation ...................................................................................... 47 2.2.2.2.4 KF 901, KF 902, KF 905, KF 859........................................................................... 49 2.2.2.2.5 KF 200..................................................................................................................... 49 2.2.2.2.6 Guard Catalysts ....................................................................................................... 50 2.2.2.3 Axens........................................................................................................................................ 51 2.2.2.3.1 HR 400 Series.......................................................................................................... 51 2.2.2.3.2 HR 500 Series.......................................................................................................... 52 2.2.2.3.3 HR 600 Series.......................................................................................................... 53 2.2.2.3.4 AX 740 Hydrogenation Catalysts............................................................................ 54 2.2.2.3.5 ACT Grading Materials ........................................................................................... 54 2.2.2.4 BASF ........................................................................................................................................ 54 2.2.2.5 Chevron Lummus Global ......................................................................................................... 55 2.2.2.6 Cosmo Oil................................................................................................................................. 55 2.2.2.7 Criterion Catalysts & Technologies.......................................................................................... 55 2.2.2.7.1 CENTINEL ............................................................................................................. 56 2.2.2.7.2 CENTINEL GOLD ................................................................................................. 58 2.2.2.7.3 ASCENT ................................................................................................................. 60

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TABLE OF CONTENTS 2.2.2.7.4 CENTERA ............................................................................................................... 65 2.2.2.7.5 SDD-800/SDD-821.................................................................................................. 68 2.2.2.7.6 Selective Hydrogenation Catalysts .......................................................................... 69 2.2.2.7.7 Guard Catalysts........................................................................................................ 69 2.2.2.8 Crystaphase Products ................................................................................................................ 70 2.2.2.9 ExxonMobil .............................................................................................................................. 70 2.2.2.9.1 RT-225 ..................................................................................................................... 70 2.2.2.9.2 OCTGAIN Catalysts ................................................................................................ 71 2.2.2.10 Haldor Topsøe........................................................................................................................... 71 2.2.2.10.1 Coker Naphtha Hydrotreating.................................................................................. 72 2.2.2.10.2 FCC Feed Pretreat.................................................................................................... 73 2.2.2.10.3 ULSD Production .................................................................................................... 74 2.2.2.10.4 Reduction of Diesel Density and Aromatics............................................................ 77 2.2.2.10.5 Hydrocracker Pretreating ......................................................................................... 77 2.2.2.10.6 Graded Bed Products for Pressure Drop Control..................................................... 78 2.2.2.11 JGC Catalysts & Chemicals Industries ..................................................................................... 79 2.2.2.12 Johnson Matthey Catalysts........................................................................................................ 80 2.2.2.13 Nippon Oil ................................................................................................................................ 81 2.2.2.14 Sinopec...................................................................................................................................... 81 2.2.2.15 Süd-Chemie............................................................................................................................... 82 2.2.2.16 TRICAT Inc. ............................................................................................................................. 83 2.2.2.17 UOP........................................................................................................................................... 84 2.2.3 Summary of Commercially Available Hydrotreating Catalysts .............................................................. 84 2.2.4 Auxiliary Catalyst Technology ................................................................................................................ 87 2.2.4.1 Advanced Refining Technologies ............................................................................................. 88 2.2.4.1.1 Phoenix .................................................................................................................... 88 2.2.4.2 Albemarle.................................................................................................................................. 88 2.2.4.2.1 EasyActive ............................................................................................................... 88 2.2.4.2.2 REACT .................................................................................................................... 88 2.2.4.2.3 STAX ....................................................................................................................... 89 2.2.4.3 Axens ........................................................................................................................................ 90 2.2.4.4 Criterion Catalysts & Technologies .......................................................................................... 90 2.2.4.5 Eurecat ...................................................................................................................................... 90 2.2.4.5.1 Sulficat ..................................................................................................................... 91 2.2.4.5.2 Totsucat.................................................................................................................... 91 2.2.4.6 Haldor Topsøe........................................................................................................................... 92 2.2.4.7 Orient Catalyst/Advanced Refining Technologies.................................................................... 92 2.2.4.8 Oxford Catalysts ....................................................................................................................... 92 2.2.4.9 TRICAT Inc. ............................................................................................................................. 93 2.2.4.9.1 TRICAT Regeneration Process................................................................................ 93 2.2.4.9.2 XpresS...................................................................................................................... 93 2.2.5 Commercial Process Technology ............................................................................................................ 93 2.2.5.1 Albemarle.................................................................................................................................. 94 2.2.5.1.1 UD-HDS .................................................................................................................. 94 2.2.5.1.2 HDAr ....................................................................................................................... 95 2.2.5.1.3 Cold Flow Improvement .......................................................................................... 97 2.2.5.1.4 PLEX Reactor Internals ........................................................................................... 97 2.2.5.2 Axens ........................................................................................................................................ 98 2.2.5.2.1 Prime-G+ ................................................................................................................. 98 2.2.5.2.2 Prime-D.................................................................................................................. 100 2.2.5.2.3 Benzene Saturation ................................................................................................ 102 2.2.5.2.4 EquiFlow Reactor Internals ................................................................................... 104

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TABLE OF CONTENTS 2.2.5.3 Catalytic Distillation Technologies ........................................................................................ 105 2.2.5.3.1 Benzene CDHydro................................................................................................. 105 2.2.5.3.2 LCN CDHydro/CDHDS and CDHDS+................................................................. 106 2.2.5.4 CB&I Howe-Baker ................................................................................................................. 110 2.2.5.5 Chevron Lummus Global ....................................................................................................... 111 2.2.5.6 DuPont Clean Technologies ................................................................................................... 113 2.2.5.7 ExxonMobil Research & Engineering/KBR........................................................................... 115 2.2.5.7.1 GO-Fining ............................................................................................................. 115 2.2.5.7.2 HYDROFINING ................................................................................................... 116 2.2.5.7.3 SCANfining........................................................................................................... 117 2.2.5.7.4 EXOMER .............................................................................................................. 119 2.2.5.7.5 OCTGAIN ............................................................................................................. 119 2.2.5.7.6 MIDW ................................................................................................................... 120 2.2.5.8 Fushun Research Institute of Petroleum and Petrochemicals (Sinopec)................................. 123 2.2.5.8.1 FHI Diesel Hydro-upgrading/Isodewaxing Process .............................................. 123 2.2.5.8.2 FRS........................................................................................................................ 124 2.2.5.8.3 OTA....................................................................................................................... 124 2.2.5.8.4 OCT-M .................................................................................................................. 125 2.2.5.9 Haldor Tops酶e ........................................................................................................................ 125 2.2.5.9.1 Conventional Hydrotreating .................................................................................. 125 2.2.5.9.2 Coker Naphtha Hydrotreating ............................................................................... 127 2.2.5.9.3 Distillate HDS/HDA.............................................................................................. 128 2.2.5.9.4 Diesel Dewaxing ................................................................................................... 129 2.2.5.9.5 Aroshift.................................................................................................................. 130 2.2.5.9.6 Reactor Internals.................................................................................................... 132 2.2.5.10 Instituto Mexicano del Petr贸leo.............................................................................................. 134 2.2.5.11 JGC Catalysts & Chemicals.................................................................................................... 134 2.2.5.11.1 JUST Refinery ....................................................................................................... 134 2.2.5.11.2 Gas Oil Ultra Deep Desulfurization ...................................................................... 135 2.2.5.11.3 GEFINERY ........................................................................................................... 135 2.2.5.11.4 LCO Upgrading ..................................................................................................... 136 2.2.5.12 MOL ....................................................................................................................................... 136 2.2.5.13 Neste Oil ................................................................................................................................. 137 2.2.5.14 Nippon Oil .............................................................................................................................. 138 2.2.5.15 RIPP........................................................................................................................................ 138 2.2.5.16 SK Corp. ................................................................................................................................. 140 2.2.5.17 Shaw Group/BASF ................................................................................................................. 141 2.2.5.18 Shell Global Solutions ............................................................................................................ 143 2.2.5.18.1 SMDH ................................................................................................................... 143 2.2.5.18.2 Reactor Internals.................................................................................................... 144 2.2.5.19 UOP ........................................................................................................................................ 147 2.2.5.19.1 MQD Unionfining ................................................................................................. 148 2.2.5.19.2 VGO Unionfining.................................................................................................. 150 2.2.5.19.3 ISAL ...................................................................................................................... 151 2.2.5.19.4 SelectFining........................................................................................................... 152 2.2.5.19.5 BenSat ................................................................................................................... 154 2.2.5.19.6 Unisar .................................................................................................................... 155 2.2.5.19.7 Unicracking/DW ................................................................................................... 156 2.2.5.19.8 UltraMix Reactor Internals.................................................................................... 157 2.2.6 Summary of Hydrotreating Process Technologies................................................................................ 158 2.2.7 Commercially Available Advanced Control and Optimization Systems ............................................... 168 2.2.7.1 Aspen Technology.................................................................................................................. 168 2.2.7.2 Axens...................................................................................................................................... 169

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2.2.7.3 KBC Advanced Technologies................................................................................................. 171 2.2.7.4 Repsol YPF ............................................................................................................................. 172 2.2.8 Resid Hydrotreating .............................................................................................................................. 172 2.2.9 Coprocessing of Renewable Feed with Conventional Petroleum Feed................................................. 175 2.2.9.1 Albemarle................................................................................................................................ 177 2.2.9.2 BP............................................................................................................................................ 179 2.2.9.3 ConocoPhillips ........................................................................................................................ 179 2.2.9.4 Haldor TopsĂ¸e......................................................................................................................... 180 2.2.9.4.1 Green Diesel Coprocessing Unit............................................................................ 180 2.2.9.4.2 Standalone Renewable Diesel Hydrotreater........................................................... 183 2.2.9.5 Neste Oil ................................................................................................................................. 184 2.2.9.6 Petrobras ................................................................................................................................. 187 2.2.9.7 Repsol YPF ............................................................................................................................. 189 2.2.9.8 UOP/Eni.................................................................................................................................. 189 2.2.10 Summary of Renewable Feed Hydrotreating ........................................................................................ 193 PLANT OPERATIONS AND PRACTICES................................................................................................................. 194 2.3.1 General Hydrotreating Operations ....................................................................................................... 194 2.3.1.1 Feed Considerations, Process Configuration, and Hardware.................................................. 195 2.3.1.1.1 Feedstock Characterization .................................................................................... 195 2.3.1.1.2 Feed Drum Blanketing Gas.................................................................................... 196 2.3.1.1.3 Reactor Configuration............................................................................................ 196 2.3.1.1.4 Limitations of Single Bed or Undersized ULSD Reactors .................................... 197 2.3.1.1.5 Minimize Fouling of Reactor Internals .................................................................. 197 2.3.1.1.6 Twisted Tube Exchanger Bundles for Preheat Service.......................................... 197 2.3.1.2 Catalyst Management.............................................................................................................. 198 2.3.1.2.1 In-situ Catalyst Sulfiding vs. Ex-situ Presulfiding................................................. 198 2.3.1.2.2 Comparison of Various Sulfiding Agents.............................................................. 199 2.3.1.2.3 Measuring Hydrotreating Catalyst Activity ........................................................... 201 2.3.1.2.4 Using Regenerated Catalyst ................................................................................... 201 2.3.1.2.5 Catalyst Dense Loading ......................................................................................... 202 2.3.1.2.6 Protecting HT Catalysts from Contamination........................................................ 203 2.3.1.2.7 Catalyst Deactivation by Carbon Monoxide in Selective HDS Units.................... 205 2.3.1.2.8 Dry Dump vs. Wet Dump Catalyst Change-out Procedures.................................. 205 2.3.1.3 Operating Conditions and Hydrogen Consumption ................................................................ 206 2.3.1.3.1 Effect of Process Severity/Variables on Hydrotreater Performance ...................... 206 2.3.1.3.2 Using High-purity Hydrogen and/or Adjusting Hydrogen Partial Pressure .......... 208 2.3.1.3.3 Optimizing the Hydrogen-to-oil Ratio ................................................................... 209 2.3.1.3.4 Accurately Measuring Hydrogen Consumption in Hydrotreaters.......................... 209 2.3.1.4 Operational Monitoring and Upset Detection ......................................................................... 211 2.3.1.4.1 Process Analyzer Placement .................................................................................. 211 2.3.1.4.2 Reactor Effluent Sampling..................................................................................... 211 2.3.1.4.3 Accurate Level Measurements in a Cold High Pressure Separator ....................... 212 2.3.1.4.4 Maldistribution in Hydrotreaters............................................................................ 212 2.3.1.4.5 Reactor Pressure Drop Buildup: Causes and Remedies......................................... 214 2.3.1.4.6 Detecting and Mitigating Leaks in Equipment ...................................................... 219 2.3.1.4.7 Ammonium Chloride Fouling in Effluent Exchangers and H2 Gas Compressors . 220 2.3.1.5 Best Practices and Troubleshooting ........................................................................................ 222 2.3.1.5.1 Reviewing and Updating Unit Operating Procedures............................................ 222 2.3.1.5.2 Criteria for Selecting Remote Manual and/or Auto Depressuring Equipment and Instrumentation ...................................................................................................... 223 2.3.1.5.3 Interruption of Operations (Emergency or Planned) and Recommended Actions. 223

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2.3.1.5.4 Minimizing Exposure Risks during Reactor Shutdowns....................................... 224 2.3.1.5.5 Preventing Flaring during Unit Startup or Shutdown Procedures ......................... 225 2.3.2 Distillate Hydrotreating........................................................................................................................ 225 2.3.2.1 Diesel Quality Requirements .................................................................................................. 227 2.3.2.1.1 Cetane .................................................................................................................... 227 2.3.2.1.2 ULSD Cold Flow Properties ................................................................................. 229 2.3.2.1.3 ULSD Haze Point .................................................................................................. 230 2.3.2.1.4 Logistics ................................................................................................................ 230 2.3.2.2 Hardware Considerations ....................................................................................................... 230 2.3.2.2.1 Adjusting Hydrotreater Internals to Improve Diesel Production........................... 230 2.3.2.2.2 Using Advanced-phase Separation Techniques .................................................... 231 2.3.2.2.3 Determining Sufficient Reserve Quench in ULSD Hydrotreaters......................... 231 2.3.2.2.4 Fouling on Disposable Feed Filters ....................................................................... 232 2.3.2.2.5 Improving Energy Efficiency ................................................................................ 232 2.3.2.3 Catalyst Management ............................................................................................................. 233 2.3.2.4 Feed Considerations ............................................................................................................... 237 2.3.2.4.1 Options for Converting FCC LCO to ULSD......................................................... 237 2.3.2.4.2 Processing Distillate and Naphtha Blends in a Diesel Hydrotreater...................... 238 2.3.2.4.3 Coprocessing Renewable Feedstocks.................................................................... 239 2.3.2.5 Process Monitoring................................................................................................................. 239 2.3.2.5.1 Calculating Diesel Cetane Number from a Diesel Hydrotreater ........................... 239 2.3.2.6 Revamps for ULSD Production.............................................................................................. 240 2.3.2.6.1 Case Study 1 .......................................................................................................... 241 2.3.2.6.2 Case Study 2 .......................................................................................................... 242 2.3.2.6.3 Case Study 3 .......................................................................................................... 242 2.3.2.6.4 Case Study 4 .......................................................................................................... 243 2.3.2.6.5 Case Study 5 .......................................................................................................... 244 2.3.2.6.6 Case Study 6 .......................................................................................................... 246 2.3.2.6.7 Case Study 7 .......................................................................................................... 247 2.3.2.7 Ultra Low Sulfur Kerosene Production .................................................................................. 248 2.3.3 Naphtha Hydrotreating......................................................................................................................... 249 2.3.3.1 Processing Coker and Visbreaker Naphtha ............................................................................ 249 2.3.3.2 Hydrotreating FCC Naphthaâ&#x20AC;&#x201D;Octane Loss and Other Problems .......................................... 252 2.3.3.3 Minimizing Fouling to Increase Catalyst Run Length............................................................ 254 2.3.4 Gas Oil Hydrotreating .......................................................................................................................... 255 2.3.4.1 Modifying a FCC Feed Pretreater to Increase Yield of Diesel ............................................... 255 2.3.4.2 Impact of Feed Hydrotreatment on FCC Product Aromatics Content.................................... 255 2.3.4.3 FCC Feed Pretreatment vs. FCC Gasoline HDS .................................................................... 256 2.3.4.4 Reducing the Endpoint in Gas Oil Hydrotreaters ................................................................... 257 2.3.4.5 Hydrotreating Heavy Coker Gas Oil ...................................................................................... 258 2.3.4.6 Predicting the Yield Pattern When Coprocessing LCGO in a VGO FCCU........................... 260 2.3.4.7 Improved Operation of a VGO Hydrotreater.......................................................................... 261 REFINING R&D ALERT! .................................................................................................................................... 262 2.4.1 Introduction .......................................................................................................................................... 262 2.4.2 Naphtha Hydrotreating......................................................................................................................... 268 2.4.2.1 Process .................................................................................................................................... 268 2.4.2.2 Catalyst ................................................................................................................................... 268 2.4.3 Middle Distillate Hydrotreating (Including ULSD Production)........................................................... 269 2.4.3.1 Process .................................................................................................................................... 269 2.4.3.1.1 Patents ................................................................................................................... 269 2.4.3.1.2 Research ................................................................................................................ 271 2.4.3.2 Catalyst ................................................................................................................................... 272

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2.7

2.4.4 LCO/SRGO............................................................................................................................................ 275 2.4.4.1 Process .................................................................................................................................... 275 2.4.4.2 Catalyst.................................................................................................................................... 276 2.4.5 Heavy Oil Hydrotreating....................................................................................................................... 277 2.4.5.1 Process .................................................................................................................................... 277 2.4.5.1.1 Patents.................................................................................................................... 277 2.4.5.1.2 Research................................................................................................................. 278 2.4.5.2 Catalyst.................................................................................................................................... 278 2.4.5.2.1 Patents.................................................................................................................... 278 2.4.5.2.2 Research................................................................................................................. 280 2.4.6 Resid Hydrotreating .............................................................................................................................. 282 2.4.6.1 Process .................................................................................................................................... 282 2.4.6.1.1 Patents.................................................................................................................... 282 2.4.6.1.2 Research................................................................................................................. 283 2.4.6.2 Catalyst.................................................................................................................................... 285 2.4.7 Renewable Feed Hydrotreating............................................................................................................. 285 2.4.7.1 Process .................................................................................................................................... 285 2.4.7.1.1 Patents.................................................................................................................... 285 2.4.7.1.2 Research................................................................................................................. 294 2.4.7.2 Catalyst.................................................................................................................................... 295 2.4.8 Upstream Heavy Crude Oil Upgrading ................................................................................................ 297 2.4.9 General Hydrotreating .......................................................................................................................... 297 2.4.9.1 Process .................................................................................................................................... 297 2.4.9.1.1 Patents.................................................................................................................... 297 2.4.9.1.2 Research................................................................................................................. 301 2.4.9.2 Hardware................................................................................................................................. 302 2.4.9.3 Catalyst.................................................................................................................................... 302 2.4.9.3.1 Promoter Effects .................................................................................................... 302 2.4.9.3.2 Effects of Additives and Contaminants ................................................................. 304 2.4.9.3.3 Carrier Supports ..................................................................................................... 305 2.4.9.3.3.1 Patents ............................................................................................. 305 2.4.9.3.3.2 Research .......................................................................................... 307 2.4.9.3.4 Preparation Procedures .......................................................................................... 308 2.4.9.3.4.1 Patents ............................................................................................. 308 2.4.9.3.4.2 Research .......................................................................................... 308 2.4.9.3.5 Catalyst Presulfiding and Activation ..................................................................... 310 2.4.9.3.5.1 Patents ............................................................................................. 310 2.4.9.3.5.2 Research .......................................................................................... 310 2.4.9.3.6 Catalyst Regeneration ............................................................................................ 311 2.4.9.3.7 Miscellaneous ........................................................................................................ 311 WORLDWIDE INSTALLED CAPACITY .................................................................................................................. 312 CONSTRUCTION ................................................................................................................................................. 316 2.6.1 Recent Construction Activity ................................................................................................................. 316 2.6.2 Completed Construction Projects.......................................................................................................... 324 REFERENCES ...................................................................................................................................................... 366

3. XTL.............................................................................................................................................. 399 3.1

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 399 3.1.1 Introduction........................................................................................................................................... 399 3.1.2 Market Conditions and Outlook ............................................................................................................ 400 3.1.2.1 Diesel Supply and Demand..................................................................................................... 400 3.1.2.2 Lube Oil Production................................................................................................................ 402

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3.3

3.1.3 Environmental Legislation.................................................................................................................... 403 3.1.3.1 Biofuels Mandates .................................................................................................................. 403 3.1.3.2 GTL for Stranded Gas/Flaring Applications to Reduce GHG Emissions in E&P.................. 406 3.1.4 Technology Competition, Directions, and Future Prospects................................................................ 408 3.1.4.1 Routes to Create Renewable and Alternative Transportation Fuels ....................................... 408 3.1.4.2 GTL Technologies.................................................................................................................. 410 3.1.4.3 BTL Technologies .................................................................................................................. 412 3.1.5 Conclusion ............................................................................................................................................ 413 STATE-OF-THE-ART TECHNOLOGY ................................................................................................................... 414 3.2.1 Introduction .......................................................................................................................................... 414 3.2.2 Gas-to-Liquids ...................................................................................................................................... 414 3.2.2.1 Complete GTL Processes ....................................................................................................... 418 3.2.2.1.1 Autothermal Reforming......................................................................................... 418 3.2.2.1.1.1 GTL.F1 ........................................................................................... 418 3.2.2.1.1.2 Sasol ............................................................................................... 419 3.2.2.1.1.3 Syncrude Technology ..................................................................... 422 3.2.2.1.1.4 Syntroleum...................................................................................... 423 3.2.2.1.2 Steam Reforming................................................................................................... 425 3.2.2.1.2.1 BP/Davy Process Technology ........................................................ 426 3.2.2.1.2.2 CompactGTL .................................................................................. 428 3.2.2.1.2.3 Oxford Catalysts Group.................................................................. 429 3.2.2.1.3 Combination Steam Reforming ............................................................................. 430 3.2.2.1.3.1 ExxonMobil .................................................................................... 431 3.2.2.1.3.2 Nippon GTL ................................................................................... 432 3.2.2.1.3.3 Shell................................................................................................ 433 3.2.2.1.4 Inactive GTL Technologies ................................................................................... 436 3.2.2.1.4.1 Energy Int. ...................................................................................... 436 3.2.2.1.4.2 ConocoPhillips................................................................................ 437 3.2.2.2 Additional GTL Technologies................................................................................................ 438 3.2.2.2.1 Axens..................................................................................................................... 438 3.2.2.2.2 Carbon Sciences .................................................................................................... 440 3.2.2.2.3 S端d-Chemie ........................................................................................................... 441 3.2.3 Biomass-to-Liquids ............................................................................................................................... 441 3.2.3.1 BTG ........................................................................................................................................ 442 3.2.3.2 Choren .................................................................................................................................... 443 3.2.3.3 Forschungszentrum Karlsruhe ................................................................................................ 444 3.2.3.4 IFP .......................................................................................................................................... 446 3.2.3.5 Oxford Catalysts Group.......................................................................................................... 447 3.2.3.6 Rentech ................................................................................................................................... 448 3.2.3.7 Syntroleum.............................................................................................................................. 450 3.2.4 Summary of Commercial and Near Commercial XTL Processes ......................................................... 453 REFINING R&D ALERT! .................................................................................................................................... 458 3.3.1 Introduction .......................................................................................................................................... 458 3.3.2 Biomass Gasification ............................................................................................................................ 468 3.3.3 Reforming.............................................................................................................................................. 469 3.3.3.1 Patents..................................................................................................................................... 469 3.3.3.2 Research.................................................................................................................................. 470 3.3.4 Cleaning-up Syngas .............................................................................................................................. 471 3.3.4.1 General ................................................................................................................................... 471 3.3.4.2 Biomass .................................................................................................................................. 471

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3.3.5 Fischer-Tropsch .................................................................................................................................... 473 3.3.5.1 Process and Hardware............................................................................................................. 473 3.3.5.1.1 Patents.................................................................................................................... 473 3.3.5.1.2 Research................................................................................................................. 475 3.3.5.2 Catalysts .................................................................................................................................. 478 3.3.5.2.1 Patents.................................................................................................................... 478 3.3.5.2.1.1 Iron Catalysts .................................................................................. 478 3.3.5.2.1.2 Cobalt Catalysts .............................................................................. 482 3.3.5.2.1.3 Other ............................................................................................... 486 3.3.5.2.2 Research................................................................................................................. 487 3.3.5.2.2.1 Iron Catalysts .................................................................................. 487 3.3.5.2.2.2 Cobalt Catalysts .............................................................................. 490 3.3.5.2.2.3 Ruthenium Catalysts ....................................................................... 494 3.3.5.2.2.4 Other ............................................................................................... 495 3.3.6 Refining Fischer-Tropsch Wax.............................................................................................................. 496 3.3.6.1 Hydroprocessing ..................................................................................................................... 496 3.3.6.1.1 Processes................................................................................................................ 496 3.3.6.1.1.1 Patents ............................................................................................. 496 3.3.6.1.1.2 Research .......................................................................................... 500 3.3.6.1.2 Catalysts................................................................................................................. 501 3.3.6.1.2.1 Patents ............................................................................................. 501 3.3.6.1.2.2 Research .......................................................................................... 503 3.3.6.2 Other ....................................................................................................................................... 504 3.3.6.2.1 Patents.................................................................................................................... 504 3.3.6.2.2 Research................................................................................................................. 505 3.3.7 Other...................................................................................................................................................... 505 3.3.7.1 Patents ..................................................................................................................................... 505 3.3.7.2 Research .................................................................................................................................. 507 REFERENCES ...................................................................................................................................................... 509

4. Latest Refining Technology Developments & Licensing ........................................................ 525 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11

FLUID CATALYTIC CRACKING ........................................................................................................................... 525 DESULFURIZATION (WITHOUT HYDROGEN) ....................................................................................................... 525 CONVENTIONAL AND RESID HYDROCRACKING ................................................................................................. 526 COKING ............................................................................................................................................................. 527 HEAVY OIL, EXTRA-HEAVY OIL, AND BITUMEN UPGRADING ............................................................................ 527 H2S REMOVAL AND SULFUR PLANT .................................................................................................................. 528 AROMATICS AND LIGHT OLEFINS PRODUCTION................................................................................................. 529 BIOFUELS PRODUCTION ..................................................................................................................................... 529 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION).............................................................................. 530 PLANT SAFETY .................................................................................................................................................. 531 REFERENCES ...................................................................................................................................................... 531