WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in One Single Source
Third Quarter 2013 Hydrotreating, and Product Treating and Blending Plus
Latest Refining Technology Developments & Licensing
HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability
P.O. Box 661 Southeastern, PA 19399 (U.S.A.)
SM
Phone: (610) 408-0117/ Fax: (610) 408-0118
Review@Hydrocarbonpublishing.com
TABLE OF CONTENTS 3Q 2013 Review Hydrotreating, and Product Treating and Blending 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 Transportation Fuels .................................................................................................. 5 2.1.2.1.2 Bunker Fuels.............................................................................................................. 8 2.1.2.2 Refined Products Demand ........................................................................................................ 10 2.1.2.3 Increasing Middle Distillate Production ................................................................................... 12 2.1.2.3.1 Diesel Supply and Demand ..................................................................................... 12 2.1.2.3.1.1 United States ..................................................................................... 13 2.1.2.3.1.2 European Union ................................................................................ 13 2.1.2.3.1.3 Russia ............................................................................................... 14 2.1.2.3.1.4 Middle East ....................................................................................... 15 2.1.2.3.1.5 Asia-Pacific ...................................................................................... 15 2.1.2.3.2 Renewable and Bio-based Diesel and Jet Fuel ........................................................ 17 2.1.2.3.2.1 Renewable Diesel and Bio-based Diesel .......................................... 17 2.1.2.3.2.2 Renewable Jet Fuel and Bio-based Jet Fuel...................................... 18 2.1.2.4 Shifting Crude Slate.................................................................................................................. 19 2.1.2.4.1 Opportunity Crudes ................................................................................................. 19 2.1.2.4.2 Tight or Shale Oil .................................................................................................... 22 2.1.2.5 Hydrotreating Capacity Expansion ........................................................................................... 24 2.1.2.6 Construction Projects and Unit Revamps ................................................................................. 25 2.1.2.7 Hydrogen Demand .................................................................................................................... 25 2.1.2.8 Hydrotreating Catalysts Market ................................................................................................ 26 2.1.3 Technology Competition, Directions, and Future Prospects .................................................................. 28 2.1.3.1 Conventional Hydrotreating ..................................................................................................... 30 2.1.3.2 Heavy Oil/Resid Hydrotreating ................................................................................................ 38 2.1.3.3 Renewable Feed Hydrotreating ................................................................................................ 40 2.1.4 Conclusion .............................................................................................................................................. 43 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 44 2.2.1 Introduction ............................................................................................................................................ 44 2.2.2 Commercial Catalysts and Guard Materials .......................................................................................... 45 2.2.2.1 Advanced Refining Technologies............................................................................................. 46 2.2.2.1.1 SmART .................................................................................................................... 47 2.2.2.1.2 ApART .................................................................................................................... 49 2.2.2.1.3 StART ...................................................................................................................... 51 2.2.2.2 Albemarle ................................................................................................................................. 51 2.2.2.2.1 STARS Series .......................................................................................................... 52 2.2.2.2.2 NEBULA Series ...................................................................................................... 57 2.2.2.2.3 Combined Implementation ...................................................................................... 60 2.2.2.2.4 KF 901, KF 902, KF 905, KF 859........................................................................... 62 2.2.2.2.5 KF 200 ..................................................................................................................... 62 2.2.2.2.6 Guard Catalysts ....................................................................................................... 63
3Q 2013 i Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS 2.2.2.3 Axens ........................................................................................................................................ 64 2.2.2.3.1 Impulse..................................................................................................................... 64 2.2.2.3.2 HR 400 Series .......................................................................................................... 65 2.2.2.3.3 HR 500 Series .......................................................................................................... 66 2.2.2.3.4 HR 600 Series .......................................................................................................... 67 2.2.2.3.5 HR 900 Series .......................................................................................................... 68 2.2.2.3.6 AX 740 Hydrogenation Catalysts ............................................................................ 68 2.2.2.3.7 ACT Grading Materials ........................................................................................... 68 2.2.2.4 BASF......................................................................................................................................... 69 2.2.2.5 Chevron Lummus Global .......................................................................................................... 69 2.2.2.6 Clariant ...................................................................................................................................... 70 2.2.2.7 Cosmo Oil ................................................................................................................................. 71 2.2.2.8 Criterion Catalysts & Technologies .......................................................................................... 71 2.2.2.8.1 CENTINEL .............................................................................................................. 72 2.2.2.8.2 CENTINEL GOLD .................................................................................................. 74 2.2.2.8.3 ASCENT .................................................................................................................. 76 2.2.2.8.4 CENTERA ............................................................................................................... 82 2.2.2.8.5 SDD-800/SDD-821 .................................................................................................. 86 2.2.2.8.6 Selective Hydrogenation Catalysts .......................................................................... 87 2.2.2.8.7 Guard Catalysts ........................................................................................................ 88 2.2.2.9 Crystaphase Products ................................................................................................................ 89 2.2.2.10 ExxonMobil .............................................................................................................................. 89 2.2.2.10.1 RT-225 ..................................................................................................................... 89 2.2.2.10.2 OCTGAIN Catalysts ................................................................................................ 90 2.2.2.11 Haldor Topsøe ........................................................................................................................... 90 2.2.2.11.1 Coker Naphtha Hydrotreating .................................................................................. 92 2.2.2.11.2 Naphtha and Kerosene Production........................................................................... 93 2.2.2.11.3 FCC Feed Pretreat .................................................................................................... 93 2.2.2.11.4 ULSD Production .................................................................................................... 94 2.2.2.11.5 Reduction of Diesel Density and Aromatics ............................................................ 96 2.2.2.11.6 Hydrocracker Pretreating ......................................................................................... 97 2.2.2.11.7 Graded Bed Products for Pressure Drop Control ..................................................... 97 2.2.2.12 JGC Catalysts & Chemicals Industries ..................................................................................... 99 2.2.2.13 Johnson Matthey Catalysts ...................................................................................................... 100 2.2.2.14 Nippon Oil .............................................................................................................................. 101 2.2.2.15 Sinopec .................................................................................................................................... 101 2.2.2.16 Saint Gobain NorPro ............................................................................................................... 102 2.2.2.17 TRICAT .................................................................................................................................. 102 2.2.2.18 UOP......................................................................................................................................... 103 2.2.2.19 Summary of Commercially Available Hydrotreating Catalysts .............................................. 104 2.2.3 Auxiliary Catalyst Technology .............................................................................................................. 108 2.2.3.1 Advanced Refining Technologies ........................................................................................... 109 2.2.3.1.1 PHOENIX .............................................................................................................. 109 2.2.3.2 Albemarle ................................................................................................................................ 109 2.2.3.2.1 EasyActive ............................................................................................................. 109 2.2.3.2.2 React ...................................................................................................................... 109 2.2.3.2.3 Stax ........................................................................................................................ 110 2.2.3.3 Axens ...................................................................................................................................... 112 2.2.3.4 Criterion Catalysts & Technologies ........................................................................................ 112 2.2.3.5 Eurecat .................................................................................................................................... 112 2.2.3.5.1 Sulficat ................................................................................................................... 113 2.2.3.5.2 Totsucat .................................................................................................................. 113 2.2.3.6 Haldor Topsøe ......................................................................................................................... 115
3Q 2013 ii Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS 2.2.3.7 Orient Catalyst/Advanced Refining Technologies ................................................................. 115 2.2.3.8 Oxford Catalysts ..................................................................................................................... 115 2.2.3.9 TRICAT Inc. ........................................................................................................................... 116 2.2.3.9.1 TRICAT Regeneration Process ............................................................................. 116 2.2.3.9.2 XpresS ................................................................................................................... 116 2.2.4 Commercial Process Technology.......................................................................................................... 116 2.2.4.1 Albemarle ............................................................................................................................... 117 2.2.4.1.1 UD-HDS ................................................................................................................ 117 2.2.4.1.2 HDAr ..................................................................................................................... 118 2.2.4.1.3 Cold Flow Improvement ........................................................................................ 120 2.2.4.1.4 PLEX Reactor Internals ......................................................................................... 121 2.2.4.2 Axens ...................................................................................................................................... 121 2.2.4.2.1 Prime-G+ ............................................................................................................... 121 2.2.4.2.2 Prime-D ................................................................................................................. 123 2.2.4.2.3 Benzene Saturation ................................................................................................ 126 2.2.4.2.4 Coker Naphtha Hydrotreating ............................................................................... 127 2.2.4.2.5 EquiFlow Reactor Internals ................................................................................... 127 2.2.4.3 Chevron Lummus Global ....................................................................................................... 128 2.2.4.4 DuPont Clean Technologies ................................................................................................... 130 2.2.4.5 ExxonMobil Research & Engineering/KBR........................................................................... 132 2.2.4.5.1 GO-Fining ............................................................................................................. 132 2.2.4.5.2 HYDROFINING ................................................................................................... 133 2.2.4.5.3 SCANfining ........................................................................................................... 134 2.2.4.5.4 EXOMER .............................................................................................................. 136 2.2.4.5.5 OCTGAIN ............................................................................................................. 136 2.2.4.5.6 MIDW ................................................................................................................... 137 2.2.4.6 Fushun Research Institute of Petroleum and Petrochemicals (Sinopec)................................. 139 2.2.4.6.1 FHI Diesel Hydro-upgrading/Isodewaxing Process .............................................. 140 2.2.4.6.2 FRS ........................................................................................................................ 141 2.2.4.6.3 OTA ....................................................................................................................... 141 2.2.4.6.4 OCT-M .................................................................................................................. 141 2.2.4.7 GTC Technology .................................................................................................................... 142 2.2.4.8 Haldor Topsøe ........................................................................................................................ 142 2.2.4.8.1 Conventional Hydrotreating .................................................................................. 142 2.2.4.8.2 Coker Naphtha Hydrotreating ............................................................................... 145 2.2.4.8.3 Diesel Dewaxing ................................................................................................... 146 2.2.4.8.4 Distillate HDS/HDA .............................................................................................. 146 2.2.4.8.5 Aroshift .................................................................................................................. 147 2.2.4.8.6 Reactor Internals .................................................................................................... 149 2.2.4.9 Instituto Mexicano del Petróleo .............................................................................................. 153 2.2.4.10 JGC Catalysts & Chemicals .................................................................................................... 153 2.2.4.10.1 JUST Refinery ....................................................................................................... 153 2.2.4.10.2 Gas Oil Ultra Deep Desulfurization ...................................................................... 154 2.2.4.10.3 GEFINERY ........................................................................................................... 154 2.2.4.10.4 LCO Upgrading ..................................................................................................... 155 2.2.4.11 Lummus Technology, a CB&I Company ............................................................................... 155 2.2.4.11.1 Conventional Hydrotreating .................................................................................. 155 2.2.4.11.2 Benzene CDHydro................................................................................................. 156 2.2.4.11.3 LCN CDHydro/CDHDS and CDHDS+................................................................. 158 2.2.4.12 MOL ....................................................................................................................................... 162 2.2.4.13 Neste Jacobs ........................................................................................................................... 163 2.2.4.14 Nippon Oil .............................................................................................................................. 164 2.2.4.15 RIPP/Sinopec .......................................................................................................................... 164
3Q 2013 iii Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
2.3
2.2.4.16 SK Corp. ................................................................................................................................. 165 2.2.4.17 Shaw Group/BASF ................................................................................................................. 167 2.2.4.18 Shell Global Solutions ............................................................................................................ 168 2.2.4.18.1 Hydrotreating Process ............................................................................................ 169 2.2.4.18.2 SMDH .................................................................................................................... 169 2.2.4.18.3 Pyrolysis Hydrogenation Unit................................................................................ 170 2.2.4.18.4 Reactor Internals .................................................................................................... 170 2.2.4.19 UOP......................................................................................................................................... 174 2.2.4.19.1 MQD Unionfining.................................................................................................. 175 2.2.4.19.2 VGO Unionfining .................................................................................................. 177 2.2.4.19.3 ISAL....................................................................................................................... 178 2.2.4.19.4 SelectFining ........................................................................................................... 180 2.2.4.19.5 BenSat .................................................................................................................... 181 2.2.4.19.6 Unisar ..................................................................................................................... 182 2.2.4.19.7 Unicracking/DW .................................................................................................... 183 2.2.4.19.8 UltraMix Reactor Internals .................................................................................... 184 2.2.4.20 Summary of Hydrotreating Process Technologies .................................................................. 185 2.2.5 Commercially Available Advanced Control and Optimization Systems................................................ 196 2.2.5.1 Aspen Technology .................................................................................................................. 196 2.2.5.2 Axens ...................................................................................................................................... 197 2.2.5.3 KBC Advanced Technologies ................................................................................................. 199 2.2.5.4 Repsol YPF ............................................................................................................................. 200 2.2.6 Resid Hydrotreating .............................................................................................................................. 200 2.2.7 Coprocessing of Renewable Feed with Conventional Petroleum Feed................................................. 204 2.2.7.1 Advanced Refining Technologies ........................................................................................... 205 2.2.7.2 Albemarle ................................................................................................................................ 205 2.2.7.3 Axens ...................................................................................................................................... 207 2.2.7.4 BP ............................................................................................................................................ 208 2.2.7.5 ConocoPhillips ........................................................................................................................ 208 2.2.7.6 Haldor Topsøe ......................................................................................................................... 209 2.2.7.6.1 Green Diesel Coprocessing Unit ............................................................................ 210 2.2.7.6.2 Standalone Renewable Diesel Hydrotreater........................................................... 212 2.2.7.7 Neste Oil ................................................................................................................................. 213 2.2.7.8 Petrobras ................................................................................................................................. 216 2.2.7.9 Repsol YPF ............................................................................................................................. 218 2.2.7.10 UOP/Eni .................................................................................................................................. 218 2.2.7.11 UPM ........................................................................................................................................ 222 2.2.7.12 Summary of Renewable Feed Hydrotreating .......................................................................... 222 PLANT OPERATIONS AND PRACTICES................................................................................................................. 223 2.3.1 General Hydrotreating Operations ....................................................................................................... 223 2.3.1.1 Feed Considerations, Process Configuration, and Hardware .................................................. 224 2.3.1.1.1 Feedstock Characterization .................................................................................... 224 2.3.1.1.2 Pre-hydrotreated Feeds .......................................................................................... 225 2.3.1.1.3 Upgrading Tight Oil............................................................................................... 226 2.3.1.1.4 Feed Drum Blanketing Gas .................................................................................... 227 2.3.1.1.5 Reactor Configuration ............................................................................................ 227 2.3.1.1.6 Minimize Fouling of Reactor Internals .................................................................. 227 2.3.1.1.7 Twisted Tube Exchanger Bundles for Preheat Service .......................................... 228 2.3.1.1.8 Thermal Enhancement System to Improve Heat Recovery ................................... 229
3Q 2013 iv Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS 2.3.1.2 Catalyst Management ............................................................................................................. 229 2.3.1.2.1 Measuring Hydrotreating Catalyst Activity........................................................... 230 2.3.1.2.2 Protecting HT Catalysts from Contamination ....................................................... 231 2.3.1.2.3 Determining and Mitigating HDS Catalyst Deactivation ...................................... 234 2.3.1.2.4 Minimizing HDS Activity Loss from Low Sulfur Feed ........................................ 236 2.3.1.2.5 In situ Catalyst Sulfiding vs. Ex situ Presulfiding ................................................. 236 2.3.1.2.6 Comparison of Various Sulfiding Agents ............................................................. 237 2.3.1.2.7 Using Regenerated Catalyst................................................................................... 239 2.3.1.2.8 Dry Dump vs. Wet Dump Catalyst Change-out Procedures ................................. 240 2.3.1.2.9 Catalyst Dense Loading ......................................................................................... 240 2.3.1.3 Operating Conditions and Hydrogen Consumption................................................................ 241 2.3.1.3.1 Effect of Process Severity/Variables on Hydrotreater Performance...................... 241 2.3.1.3.2 Using High-purity Hydrogen and/or Adjusting Hydrogen Partial Pressure .......... 243 2.3.1.3.3 Optimizing the Hydrogen-to-oil Ratio................................................................... 244 2.3.1.3.4 Mitigating High Temperature Hydrogen Attack ................................................... 244 2.3.1.3.5 Accurately Measuring Hydrogen Consumption in Hydrotreaters ......................... 245 2.3.1.3.6 Membranes for H2 Recovery from Hydrotreaters.................................................. 246 2.3.1.4 Operational Monitoring and Upset Detection ......................................................................... 247 2.3.1.4.1 Process Analyzer Placement .................................................................................. 247 2.3.1.4.2 Reactor Effluent Sampling .................................................................................... 247 2.3.1.4.3 Accurate Level Measurements in a Cold High Pressure Separator ....................... 248 2.3.1.4.4 Maldistribution in Hydrotreaters ........................................................................... 248 2.3.1.4.5 Reactor Pressure Drop Buildup: Causes and Remedies ........................................ 250 2.3.1.4.6 Detecting and Mitigating Leaks in Equipment ...................................................... 255 2.3.1.4.7 Fouling in Feed/Effluent Exchangers .................................................................... 257 2.3.1.4.8 Ammonium Chloride Fouling in Effluent Exchangers and H2 Gas Compressors . 258 2.3.1.5 Best Practices and Troubleshooting........................................................................................ 260 2.3.1.5.1 Reviewing and Updating Unit Operating Procedures ........................................... 260 2.3.1.5.2 Criteria for Selecting Remote Manual and/or Auto Depressuring Equipment and Instrumentation ...................................................................................................... 260 2.3.1.5.3 Interruption of Operations (Emergency or Planned) and Recommended Actions 261 2.3.1.5.4 Minimizing Exposure Risks during Reactor Shutdowns ....................................... 262 2.3.1.5.5 Preventing Flaring during Unit Startup or Shutdown Procedures ......................... 263 2.3.2 Distillate Hydrotreating ........................................................................................................................ 263 2.3.2.1 Diesel Quality Requirements .................................................................................................. 265 2.3.2.1.1 Cetane .................................................................................................................... 265 2.3.2.1.2 ULSD Cold Flow Properties ................................................................................. 267 2.3.2.1.3 ULSD Haze Point .................................................................................................. 268 2.3.2.1.4 Minimizing Diesel Color Degradation .................................................................. 268 2.3.2.1.5 Logistics ................................................................................................................ 269 2.3.2.2 Hardware Considerations ....................................................................................................... 270 2.3.2.2.1 Adjusting Hydrotreater Internals to Improve Diesel Production ........................... 270 2.3.2.2.2 Limitations of Single Bed or Undersized ULSD Reactors .................................... 271 2.3.2.2.3 Determining Sufficient Reserve Quench in ULSD Hydrotreaters......................... 271 2.3.2.2.4 Using Advanced-phase Separation Techniques .................................................... 271 2.3.2.2.5 Fouling on Disposable Feed Filters ....................................................................... 272 2.3.2.2.6 Improving Energy Efficiency ................................................................................ 272 2.3.2.3 Catalyst Management ............................................................................................................. 273 2.3.2.4 Feed Considerations ............................................................................................................... 277 2.3.2.4.1 Options for Converting FCC LCO to ULSD ......................................................... 277 2.3.2.4.2 Processing Distillate and Naphtha Blends in a Diesel Hydrotreater...................... 278 2.3.2.4.3 Coprocessing Renewable Feedstocks .................................................................... 279
3Q 2013 v Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
2.4
2.3.2.5 Process Monitoring ................................................................................................................. 280 2.3.2.5.1 Calculating Diesel Cetane Number from a Diesel Hydrotreater ............................ 280 2.3.2.6 Revamps for ULSD Production .............................................................................................. 280 2.3.2.6.1 Case Study 1 .......................................................................................................... 281 2.3.2.6.2 Case Study 2 .......................................................................................................... 282 2.3.2.6.3 Case Study 3 .......................................................................................................... 283 2.3.2.6.4 Case Study 4 .......................................................................................................... 284 2.3.2.6.5 Case Study 5 .......................................................................................................... 284 2.3.2.6.6 Case Study 6 .......................................................................................................... 286 2.3.2.6.7 Case Study 7 .......................................................................................................... 287 2.3.2.7 Ultra-low Sulfur Kerosene Production.................................................................................... 288 2.3.3 Naphtha Hydrotreating ......................................................................................................................... 289 2.3.3.1 Processing Coker and Visbreaker Naphtha ............................................................................. 289 2.3.3.2 Measuring Silicon Content in Coker Naphtha ........................................................................ 293 2.3.3.3 Hydrotreating FCC Naphtha—Octane Loss and Other Problems........................................... 294 2.3.3.4 Minimizing Fouling to Increase Catalyst Run Length ............................................................ 296 2.3.3.5 Separating Stripping and Splitting Applications ..................................................................... 297 2.3.4 Gas Oil Hydrotreating........................................................................................................................... 297 2.3.4.1 Modifying a FCC Feed Pretreater to Increase Yield of Diesel ............................................... 297 2.3.4.2 Impact of Feed Hydrotreatment on FCC Product Aromatics Content .................................... 298 2.3.4.3 FCC Feed Pretreatment vs. FCC Gasoline HDS ..................................................................... 298 2.3.4.4 Impact of Tier III Gasoline Standards on FCC Feed Pretreaters ............................................ 303 2.3.4.5 Reducing the Endpoint in Gas Oil Hydrotreaters.................................................................... 303 2.3.4.6 Hydrotreating Heavy Coker Gas Oil ....................................................................................... 304 2.3.4.7 Predicting the Yield Pattern When Coprocessing LCGO in a VGO FCCU ........................... 306 2.3.4.8 Improved Operation of a VGO Hydrotreater .......................................................................... 307 2.3.4.9 Operating a VGO Hydrotreater in Blocked Mode .................................................................. 308 REFINING R&D ALERT! ..................................................................................................................................... 308 2.4.1 Introduction ........................................................................................................................................... 308 2.4.2 General Hydrotreating .......................................................................................................................... 314 2.4.2.1 Process Designs....................................................................................................................... 314 2.4.2.1.1 Stripping and/or Fractionation ............................................................................... 314 2.4.2.1.2 Process Integration ................................................................................................. 316 2.4.2.1.3 Miscellaneous Process Schemes ............................................................................ 318 2.4.2.2 Catalyst Formulation and Preparation ..................................................................................... 319 2.4.2.2.1 Phosphorus-modified Carrier Supports.................................................................. 319 2.4.2.2.1.1 Patents ............................................................................................. 319 2.4.2.2.1.2 Research Literature ......................................................................... 321 2.4.2.2.2 Metal Oxides Carrier Supports .............................................................................. 322 2.4.2.2.2.1 Patents ............................................................................................. 322 2.4.2.2.2.2 Research Literature ......................................................................... 323 2.4.2.2.3 Promoters ............................................................................................................... 326 2.4.2.2.3.1 Transition Metal Sulfides ................................................................ 326 2.4.2.2.3.2 Zeolites ............................................................................................ 328 2.4.2.2.3.2.1 Patents ...................................................................... 328 2.4.2.2.3.2.2 Research Literature .................................................. 328 2.4.2.2.4 NiP-containing Catalysts........................................................................................ 328 2.4.2.2.5 Miscellaneous Catalyst Innovations....................................................................... 329 2.4.2.2.5.1 Patents ............................................................................................. 329 2.4.2.2.5.2 Research Literature ......................................................................... 330
3Q 2013 vi Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
2.5 2.6
2.7
2.4.2.2.6 Catalyst Activation Procedures ............................................................................. 332 2.4.2.2.7 Catalyst Regeneration ............................................................................................ 333 2.4.3 Naphtha and Pyrolysis Gasoline Hydrotreating ................................................................................... 334 2.4.4 Middle Distillate Hydrotreating (Including ULSD Production) ........................................................... 336 2.4.4.1 Process .................................................................................................................................... 336 2.4.4.1.1 Patents ................................................................................................................... 336 2.4.4.1.2 Research Literature ................................................................................................ 339 2.4.4.2 Catalyst ................................................................................................................................... 340 2.4.4.2.1 Patents ................................................................................................................... 340 2.4.4.2.2 Research Literature ................................................................................................ 341 2.4.5 LCO and Light Gas Oils Hydrotreating ............................................................................................... 342 2.4.5.1 Process .................................................................................................................................... 342 2.4.5.2 Catalyst ................................................................................................................................... 343 2.4.6 Heavy Oil Hydrotreating ...................................................................................................................... 344 2.4.6.1 Process .................................................................................................................................... 344 2.4.6.1.1 Patents ................................................................................................................... 344 2.4.6.1.2 Research Literature ................................................................................................ 348 2.4.6.2 Catalyst ................................................................................................................................... 348 2.4.6.2.1 Patents ................................................................................................................... 348 2.4.6.2.2 Research Literature ................................................................................................ 350 2.4.7 Resid Hydrotreating .............................................................................................................................. 351 2.4.7.1 Patents..................................................................................................................................... 351 2.4.7.2 Research Literature ................................................................................................................. 355 2.4.8 Renewable Feed Hydrotreating ............................................................................................................ 356 2.4.8.1 Process .................................................................................................................................... 356 2.4.8.1.1 Patents ................................................................................................................... 356 2.4.8.1.2 Research Literature ................................................................................................ 360 2.4.8.2 Catalyst ................................................................................................................................... 361 2.4.8.2.1 Patents ................................................................................................................... 361 2.4.8.2.2 Research Literature ................................................................................................ 362 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 363 CONSTRUCTION ................................................................................................................................................. 367 2.6.1 Recent Construction Activity ................................................................................................................. 367 2.6.2 Completed Construction Projects ......................................................................................................... 376 REFERENCES ..................................................................................................................................................... 419
3. Product Treating & Blending .................................................................................................... 457 3.1
MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ......................................................................................... 457 3.1.1 Introduction .......................................................................................................................................... 457 3.1.2 Market Conditions and Outlook............................................................................................................ 457 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 457 3.1.3.1 Product Treating ..................................................................................................................... 457 3.1.3.1.1 Commercial and Near-commercial Technologies ................................................. 459 3.1.3.1.2 Trends in R&D ...................................................................................................... 465 3.1.3.1.2.1 Adsorptive Desulfurization............................................................. 465 3.1.3.1.2.2 Oxidative Desulfurization ............................................................... 465 3.1.3.1.2.3 Membrane Desulfurization ............................................................. 468 3.1.3.1.2.4 Ionic Liquid Extraction ................................................................... 468 3.1.3.1.2.5 Benzene Removal ........................................................................... 470
3Q 2013 vii Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
3.2
3.3
3.1.3.2 Product Blending..................................................................................................................... 470 3.1.3.2.1 Commercial Technologies ..................................................................................... 472 3.1.3.2.2 Trends in R&D....................................................................................................... 478 3.1.4 Conclusion ............................................................................................................................................. 479 STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 480 3.2.1 Introduction ........................................................................................................................................... 480 3.2.2 Product Treating ................................................................................................................................... 483 3.2.2.1 Commercial Processes ............................................................................................................ 483 3.2.2.1.1 Axens ..................................................................................................................... 483 3.2.2.1.1.1 Sulfrex ............................................................................................. 483 3.2.2.1.1.2 Sweetening ...................................................................................... 484 3.2.2.1.1.3 Sweetn'K ......................................................................................... 485 3.2.2.1.1.4 OATS .............................................................................................. 485 3.2.2.1.2 ExxonMobil ........................................................................................................... 486 3.2.2.1.3 GTC Technology Inc. ............................................................................................ 488 3.2.2.1.4 Hielscher Ultrasonics ............................................................................................. 489 3.2.2.1.5 Indian Oil Corp. ..................................................................................................... 490 3.2.2.1.6 Merichem Chemicals & Refinery Services ............................................................ 492 3.2.2.1.6.1 Jet Fuel Treating.............................................................................. 494 3.2.2.1.6.2 Gasoline and LPG Treating............................................................. 496 3.2.2.1.6.3 Reformer and Alkylation Products Treating ................................... 497 3.2.2.1.7 Petreco Process Systems ........................................................................................ 498 3.2.2.1.8 Sinopec................................................................................................................... 498 3.2.2.1.9 UOP ....................................................................................................................... 501 3.2.2.1.9.1 Merox .............................................................................................. 501 3.2.2.1.9.1.1 Extraction ................................................................. 503 3.2.2.1.9.1.2 Sweetening ............................................................... 503 3.2.2.1.9.1.2.1 Fixed-bed ....................................... 504 3.2.2.1.9.1.2.2 Minalk ............................................ 504 3.2.2.1.9.1.2.3 Caustic Free Merox ........................ 505 3.2.2.1.9.1.2.4 Liquid-liquid Sweetening .............. 506 3.2.2.1.9.2 Sulfur-X .......................................................................................... 507 3.2.2.2 Catalysts, Adsorbents, and Other Technologies...................................................................... 508 3.2.2.2.1 Axens ..................................................................................................................... 508 3.2.2.2.2 Chemical Products Industries, Inc. ........................................................................ 509 3.2.2.2.3 CSIR-Indian Institute of Petroleum ....................................................................... 509 3.2.2.2.4 Gas Technology Products ...................................................................................... 510 3.2.2.2.5 No Heat Resources ................................................................................................. 510 3.2.2.2.6 UOP ....................................................................................................................... 511 3.2.2.3 Emerging Technologies .......................................................................................................... 512 3.2.2.3.1 Alternative Petroleum Technologies ...................................................................... 513 3.2.2.3.2 Grace ...................................................................................................................... 513 3.2.2.3.3 LyondellBasell Industries ...................................................................................... 515 3.2.2.3.4 RTI ......................................................................................................................... 516 3.2.2.3.5 SulphCo ................................................................................................................. 517 3.2.2.3.6 UniPure Energy...................................................................................................... 518 3.2.3 Summary of Commercial Product Treating Processes.......................................................................... 520 3.2.4 Product Blending................................................................................................................................... 525 PLANT OPERATIONS AND PRACTICES................................................................................................................. 529 3.3.1 General Non-hydrogen Product Treating ............................................................................................. 529 3.3.1.1 Predicting Sulfur Type, Levels in FCC Products .................................................................... 529 3.3.1.2 Methods of Removing Sulfur Compounds Without Hydrogen .............................................. 530 3.3.1.3 Analyzing Product Streams for Sulfur and Aromatics ............................................................ 531
3Q 2013 viii Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
3.4
3.3.1.4 LPG Treating .......................................................................................................................... 532 3.3.1.4.1 Minimizing Caustic Consumption in Product Treating ......................................... 532 3.3.1.4.2 Effects of H2S Content on Deethanizer ................................................................. 532 3.3.1.4.3 Mercury Removal .................................................................................................. 533 3.3.1.4.4 Commercial Methods of Removing COS from Propane/Propylene Streams ........ 534 3.3.1.5 Gasoline Treating ................................................................................................................... 534 3.3.1.5.1 Meeting 10 ppm Sulfur in Gasoline ...................................................................... 534 3.3.1.5.2 Liquid-Liquid Coalescence to Obtain On-spec FCC Gasoline .............................. 535 3.3.1.5.3 Utilizing Octane-enhancing FCC Additives in Product Treating Applications..... 536 3.3.1.5.4 Natural Gasoline Processing Problems.................................................................. 537 3.3.1.5.5 Minimizing Gasoline Color Degradation .............................................................. 537 3.3.1.6 Middle Distillates Treating ..................................................................................................... 538 3.3.1.6.1 Meeting Cloud Point and CFPP Specifications with Additives ............................ 538 3.3.1.6.2 Meeting Jet Fuel Specifications ............................................................................. 539 3.3.1.6.3 Minimizing Jet Fuel Color Degradation ................................................................ 539 3.3.2 Product Blending .................................................................................................................................. 540 3.3.2.1 Systematic Approach to Upgrading Refinery Blending Operations ....................................... 540 3.3.2.2 Benefits of Inline Blending over Storage ............................................................................... 543 3.3.2.3 Use of Process Analyzers and Models.................................................................................... 543 3.3.2.3.1 FTIR vs. Raman Spectroscopy for Inline Blending............................................... 544 3.3.2.3.2 Accurately Predicting Cetane Improver Impact .................................................... 545 3.3.2.4 Gasoline Blending .................................................................................................................. 545 3.3.2.4.1 Optimal Gasoline Blending ................................................................................... 545 3.3.2.4.1 Effect of RVP on Gasoline Loss During Blending................................................ 547 3.3.2.4.2 Summer Management of RVP and Butanes .......................................................... 547 3.3.2.4.3 Blending Opportunities for Heavy Naphtha .......................................................... 548 3.3.2.4.4 Online Analyzers Used for Gasoline Blending ..................................................... 549 3.3.2.4.5 Accurately Predicting Gasoline Octane Using ANN Models ................................ 551 3.3.2.5 Bunker Fuels Blending ........................................................................................................... 551 3.3.2.6 Biofuels Blending ................................................................................................................... 552 3.3.2.6.1 Flexible Fuel Terminals for Biofuels Blending ..................................................... 552 3.3.2.6.2 European Union Measuring Instruments Directive ............................................... 553 3.3.2.6.3 Ethanol Blending into the Gasoline Pool .............................................................. 553 3.3.2.6.3.1 Increasing Ethanol Blending........................................................... 553 3.3.2.6.3.2 Corrosion ........................................................................................ 554 3.3.2.6.3.3 Gasoline Blendstocks ..................................................................... 555 3.3.2.6.3.4 Gasoline Pool Components............................................................. 556 3.3.2.6.3.5 Isobutanol as an Alternative to Ethanol .......................................... 556 3.3.2.6.4 Biodiesel Blending into the Diesel Pool ................................................................ 557 3.3.2.7 Predicting Viscosity for Heavy Blends ................................................................................... 557 3.3.2.8 Incorporating Logistics in Blending Optimizations Systems ................................................. 558 REFINING R&D ALERT! .................................................................................................................................... 559 3.4.1 Introduction .......................................................................................................................................... 559 3.4.2 Product Treating ................................................................................................................................... 565 3.4.2.1 Adsorptive Desulfurization..................................................................................................... 565 3.4.2.1.1 Gasoline ................................................................................................................. 565 3.4.2.1.1.1 Patents............................................................................................. 565 3.4.2.1.1.2 Research Literature ......................................................................... 569 3.4.2.1.2 Diesel ..................................................................................................................... 570 3.4.2.1.2.1 Patents............................................................................................. 570 3.4.2.1.2.2 Research Literature ......................................................................... 572 3.4.2.1.3 Multiple fuel application ....................................................................................... 574 3.4.2.1.3.1 Patents............................................................................................. 574
3Q 2013 ix Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
3.5
3.6
3.4.2.1.3.2 Research Literature ......................................................................... 576 3.4.2.2 Oxidative Desulfurization ....................................................................................................... 578 3.4.2.2.1 Catalysts ................................................................................................................. 578 3.4.2.2.1.1 Patents ............................................................................................. 578 3.4.2.2.1.2 Research Literature ......................................................................... 580 3.4.2.2.2 Process ................................................................................................................... 583 3.4.2.2.2.1 Patents ............................................................................................. 583 3.4.2.2.2.2 Research Literature ......................................................................... 585 3.4.2.3 Ionic Liquid Extraction ........................................................................................................... 589 3.4.2.3.1 Patents .................................................................................................................... 589 3.4.2.3.2 Research Literature ................................................................................................ 591 3.4.2.4 Membrane Desulfurization...................................................................................................... 596 3.4.2.4.1 Process ................................................................................................................... 596 3.4.2.4.1.1 Patents ............................................................................................. 596 3.4.2.4.1.2 Research Literature ......................................................................... 597 3.4.2.4.2 Novel material ........................................................................................................ 597 3.4.2.4.2.1 Patents ............................................................................................. 597 3.4.2.4.2.2 Research Literature ......................................................................... 600 3.4.2.5 Benzene Removal.................................................................................................................... 602 3.4.2.5.1 Reactive ................................................................................................................. 602 3.4.2.5.1.1 Patents ............................................................................................. 602 3.4.2.5.1.2 Research Literature ......................................................................... 604 3.4.2.5.2 Non-reactive........................................................................................................... 605 3.4.2.5.2.1 Patent............................................................................................... 605 3.4.2.6 Miscellaneous.......................................................................................................................... 605 3.4.2.6.1 Scavengers ............................................................................................................. 605 3.4.2.6.1.1 Patents ............................................................................................. 605 3.4.2.6.2 Other ...................................................................................................................... 606 3.4.2.6.2.1 Patent............................................................................................... 606 3.4.2.6.2.2 Research Literature ......................................................................... 607 3.4.2.6.3 Other contaminants ................................................................................................ 607 3.4.2.6.3.1 Research Literature ......................................................................... 607 3.4.3 Product Blending................................................................................................................................... 608 3.4.3.1 Blending and Process Control ................................................................................................. 608 3.4.3.1.1 Patents .................................................................................................................... 608 3.4.3.1.2 Research Literature ................................................................................................ 612 3.4.3.2 Components/Additives ............................................................................................................ 614 3.4.3.2.1 Patents .................................................................................................................... 614 3.4.3.2.2 Research Literature ................................................................................................ 615 CONSTRUCTION ................................................................................................................................................. 616 3.5.1 Recent Construction Activity ................................................................................................................. 616 3.5.2 Completed Construction Projects.......................................................................................................... 619 REFERENCES ...................................................................................................................................................... 634
4. Latest Refining Technology Developments & Licensing ........................................................ 653 4.1 4.2 4.3 4.4 4.5 4.6
FLUID CATALYTIC CRACKING ........................................................................................................................... 653 HYDROCRACKING .............................................................................................................................................. 653 CRUDE DISTILLATION ........................................................................................................................................ 654 DEASPHALTING.................................................................................................................................................. 655 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 655 GAS CONCENTRATION PLANT/VAPOR RECOVERY ............................................................................................. 656
3Q 2013 x Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14
LUBE PRODUCTION ........................................................................................................................................... 656 AROMATICS, LIGHT OLEFINS, AND ETHANOL PRODUCTION .............................................................................. 656 PROCESS CONTROLS AND SIMULATION ............................................................................................................. 658 XTL (BIOMASS-, GAS-, AND COAL-TO-LIQUID) ................................................................................................ 658 BIOFUELS PRODUCTION..................................................................................................................................... 659 CO2 CAPTURE AND CONVERSION ...................................................................................................................... 661 PLANT SAFETY .................................................................................................................................................. 663 REFERENCES ..................................................................................................................................................... 664
3Q 2013 xi Hydrocarbon Publishing Co./Copyright Protected
TABLE OF CONTENTS
This page is intentionally left blank.
3Q 2013 xii Hydrocarbon Publishing Co./Copyright Protected