WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in One Single Source
Third Quarter 2014 Hydrotreating, and Alkylation Plus
Latest Refining Technology Developments & Licensing
HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability
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TABLE OF CONTENTS 3Q 2014 Review Hydrotreating and Alkylation 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 ......................................................................................................... 7 2.1.2.2 Refined Products Demand ....................................................................................................... 8 2.1.2.2.1 Renewable and Bio-based Diesel and Jet Fuel .................................................... 11 2.1.2.3 Shifting Crude Slate ............................................................................................................... 12 2.1.2.4 Hydrotreating Capacity Contraction ...................................................................................... 15 2.1.2.5 Construction Projects and Unit Revamps .............................................................................. 16 2.1.2.6 Hydrotreating Catalysts Market ............................................................................................. 16 2.1.3 Technology Competition, Directions, and Future Prospects .................................................................. 17 2.1.3.1 Conventional Hydrotreating .................................................................................................. 20 2.1.3.1.1 Diesel Hydrotreating ........................................................................................... 20 2.1.3.1.2 Gasoline Hydrotreating ....................................................................................... 23 2.1.3.1.3 Major Technology Offerings............................................................................... 24 2.1.3.1.4 H2 Consumption .................................................................................................. 25 2.1.3.1.5 Advanced Process Control .................................................................................. 26 2.1.3.1.6 Process Integration .............................................................................................. 27 2.1.3.2 Heavy Oil/Resid Hydrotreating ............................................................................................. 27 2.1.3.3 Renewable Feed Hydrotreating ............................................................................................. 29 2.1.4 Conclusion .............................................................................................................................................. 30 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 31 2.2.1 Introduction ............................................................................................................................................ 31 2.2.2 Commercial Catalysts and Guard Materials .......................................................................................... 31 2.2.2.1 Advanced Refining Technologies .......................................................................................... 32 2.2.2.1.1 SmART ............................................................................................................... 33 2.2.2.1.2 ApART ................................................................................................................ 37 2.2.2.1.3 StART ................................................................................................................. 39 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 .................................................................................. 48 2.2.2.2.4 KF 901, KF 902, KF 905, KF 859 ...................................................................... 49 2.2.2.2.5 KF 200................................................................................................................. 50 2.2.2.2.6 Guard Catalysts ................................................................................................... 51 2.2.2.3 Axens ..................................................................................................................................... 52 2.2.2.3.1 Impulse ................................................................................................................ 52 2.2.2.3.2 HR 400 Series ..................................................................................................... 53 2.2.2.3.3 HR 500 Series ..................................................................................................... 53 2.2.2.3.4 HR 600 Series ..................................................................................................... 55 2.2.2.3.5 HR 900 Series ..................................................................................................... 55 2.2.2.3.6 AX 740 Hydrogenation Catalysts ....................................................................... 56 2.2.2.3.7 ACT Grading Materials ....................................................................................... 56
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TABLE OF CONTENTS 2.2.2.4 2.2.2.5 2.2.2.6 2.2.2.7 2.2.2.8
BASF ...................................................................................................................................... 57 Chevron Lummus Global ....................................................................................................... 57 Clariant ................................................................................................................................... 57 Cosmo Oil .............................................................................................................................. 59 Criterion Catalysts & Technologies ....................................................................................... 59 2.2.2.8.1 CENTINEL .......................................................................................................... 60 2.2.2.8.2 CENTINEL GOLD.............................................................................................. 61 2.2.2.8.3 ASCENT.............................................................................................................. 64 2.2.2.8.4 CENTERA ........................................................................................................... 70 2.2.2.8.5 SDD-800/SDD-821 ............................................................................................. 74 2.2.2.8.6 Selective Hydrogenation Catalysts ...................................................................... 77 2.2.2.8.7 Guard Catalysts.................................................................................................... 77 2.2.2.9 Crystaphase Products ............................................................................................................. 78 2.2.2.10 ExxonMobil............................................................................................................................ 78 2.2.2.10.1 RT-225 ................................................................................................................. 79 2.2.2.10.2 RT-235 ................................................................................................................. 79 2.2.2.10.3 OCTGAIN Catalysts ............................................................................................ 79 2.2.2.11 Haldor Topsøe ........................................................................................................................ 80 2.2.2.11.1 Coker Naphtha Hydrotreating.............................................................................. 82 2.2.2.11.2 Naphtha and Kerosene Production ...................................................................... 83 2.2.2.11.3 FCC Feed Pretreat ............................................................................................... 83 2.2.2.11.4 ULSD Production ................................................................................................ 84 2.2.2.11.5 Reduction of Diesel Density and Aromatics........................................................ 86 2.2.2.11.6 Hydrocracker Pretreating ..................................................................................... 88 2.2.2.11.7 Graded Bed Products for Pressure Drop Control ................................................ 89 2.2.2.12 JGC Catalysts & Chemicals Industries................................................................................... 91 2.2.2.13 Johnson Matthey Catalysts ..................................................................................................... 92 2.2.2.14 Nippon Oil.............................................................................................................................. 92 2.2.2.15 Sinopec ................................................................................................................................... 93 2.2.2.16 Saint Gobain NorPro .............................................................................................................. 94 2.2.2.17 TRICAT ................................................................................................................................. 94 2.2.2.18 UOP ........................................................................................................................................ 95 2.2.2.19 Summary of Commercially Available Hydrotreating Catalysts ............................................. 96 2.2.3 Auxiliary Catalyst Technology .............................................................................................................. 100 2.2.3.1 Advanced Refining Technologies ........................................................................................ 100 2.2.3.2 Albemarle ............................................................................................................................. 100 2.2.3.2.1 EasyActive ......................................................................................................... 100 2.2.3.2.2 React .................................................................................................................. 101 2.2.3.2.3 Stax .................................................................................................................... 102 2.2.3.3 Axens ................................................................................................................................... 103 2.2.3.4 Criterion Catalysts & Technologies ..................................................................................... 103 2.2.3.5 Eurecat.................................................................................................................................. 104 2.2.3.5.1 Sulficat ............................................................................................................... 104 2.2.3.5.2 Totsucat ............................................................................................................. 105 2.2.3.6 Haldor Topsøe ...................................................................................................................... 106 2.2.3.7 HPA ...................................................................................................................................... 106 2.2.3.8 hte ......................................................................................................................................... 107 2.2.3.9 Orient Catalyst/Advanced Refining Technologies ............................................................... 107 2.2.3.10 TRICAT Inc. ........................................................................................................................ 108 2.2.3.10.1 TRICAT Regeneration Process ......................................................................... 108 2.2.3.10.2 XpresS ............................................................................................................... 108 2.2.3.11 Velocys ................................................................................................................................. 108
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TABLE OF CONTENTS 2.2.4 Commercial Process Technology.......................................................................................................... 108 2.2.4.1 Albemarle ............................................................................................................................ 109 2.2.4.1.1 UD-HDS............................................................................................................ 109 2.2.4.1.2 HDAr ................................................................................................................. 110 2.2.4.1.3 Cold Flow Improvement ................................................................................... 111 2.2.4.1.4 PLEX Reactor Internals .................................................................................... 112 2.2.4.2 Axens ................................................................................................................................... 113 2.2.4.2.1 Prime-G+ ........................................................................................................... 113 2.2.4.2.2 Prime-D ............................................................................................................. 115 2.2.4.2.3 Benzene Saturation............................................................................................ 117 2.2.4.2.4 Coker Naphtha Hydrotreating ........................................................................... 119 2.2.4.2.5 EquiFlow Reactor Internals ............................................................................... 119 2.2.4.3 Chevron Lummus Global..................................................................................................... 120 2.2.4.4 DuPont Clean Technologies ................................................................................................ 122 2.2.4.5 ExxonMobil Research & Engineering/KBR ........................................................................ 124 2.2.4.5.1 GO-Fining ......................................................................................................... 124 2.2.4.5.2 HYDROFINING ............................................................................................... 125 2.2.4.5.3 SCANfining....................................................................................................... 125 2.2.4.5.4 EXOMER .......................................................................................................... 127 2.2.4.5.5 OCTGAIN ......................................................................................................... 128 2.2.4.5.6 MIDW ............................................................................................................... 129 2.2.4.6 Fushun Research Institute of Petroleum and Petrochemicals (Sinopec) .............................. 131 2.2.4.6.1 FHI Diesel Hydro-upgrading/Isodewaxing Process .......................................... 131 2.2.4.6.2 FRS.................................................................................................................... 132 2.2.4.6.3 OTA .................................................................................................................. 133 2.2.4.6.4 OCT-M .............................................................................................................. 133 2.2.4.7 GTC Technology ................................................................................................................. 134 2.2.4.8 Haldor Topsøe ..................................................................................................................... 134 2.2.4.8.1 Conventional Hydrotreating .............................................................................. 134 2.2.4.8.2 Coker Naphtha Hydrotreating ........................................................................... 137 2.2.4.8.3 Diesel Dewaxing ............................................................................................... 138 2.2.4.8.4 Distillate HDS/HDA ......................................................................................... 138 2.2.4.8.5 Aroshift ............................................................................................................. 139 2.2.4.8.6 Reactor Internals ............................................................................................... 141 2.2.4.9 Instituto Mexicano del Petróleo ........................................................................................... 144 2.2.4.10 JGC Catalysts & Chemicals ................................................................................................. 145 2.2.4.10.1 JUST Refinery ................................................................................................... 145 2.2.4.10.2 Gas Oil Ultra Deep Desulfurization .................................................................. 146 2.2.4.10.3 GEFINERY ....................................................................................................... 146 2.2.4.10.4 LCO Upgrading ................................................................................................. 146 2.2.4.11 Lummus Technology, a CB&I Company ............................................................................ 147 2.2.4.11.1 Conventional Hydrotreating .............................................................................. 147 2.2.4.11.2 Benzene CDHydro ............................................................................................ 148 2.2.4.11.3 LCN CDHydro/CDHDS and CDHDS+ ............................................................ 149 2.2.4.12 MOL .................................................................................................................................... 153 2.2.4.13 Nippon Oil ........................................................................................................................... 155 2.2.4.14 RIPP/Sinopec ....................................................................................................................... 155 2.2.4.15 SK Corp. .............................................................................................................................. 157 2.2.4.16 Shaw Group/BASF .............................................................................................................. 158 2.2.4.17 Shell Global Solutions ......................................................................................................... 160 2.2.4.17.1 Hydrotreating Process ....................................................................................... 160 2.2.4.17.2 SMDH ............................................................................................................... 161 2.2.4.17.3 Pyrolysis Hydrogenation Unit ........................................................................... 161
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2.2.4.17.4 Reactor Internals ................................................................................................ 162 2.2.4.18 UOP ...................................................................................................................................... 165 2.2.4.18.1 MQD Unionfining ............................................................................................. 166 2.2.4.18.2 VGO Unionfining .............................................................................................. 169 2.2.4.18.3 ISAL .................................................................................................................. 170 2.2.4.18.4 SelectFining ....................................................................................................... 171 2.2.4.18.5 BenSat................................................................................................................ 172 2.2.4.18.6 Unisar ................................................................................................................ 174 2.2.4.18.7 Unicracking/DW ................................................................................................ 175 2.2.4.18.8 UltraMix Reactor Internals ................................................................................ 176 2.2.4.19 Summary of Hydrotreating Process Technologies ............................................................... 176 2.2.5 Commercially Available Advanced Control and Optimization Systems................................................ 187 2.2.5.1 Aspen Technology ............................................................................................................... 187 2.2.5.2 Axens ................................................................................................................................... 189 2.2.5.3 KBC Advanced Technologies .............................................................................................. 191 2.2.5.4 Petrobras............................................................................................................................... 192 2.2.5.5 Repsol YPF .......................................................................................................................... 192 2.2.6 Resid Hydrotreating .............................................................................................................................. 193 2.2.7 Coprocessing of Renewable Feed with Conventional Petroleum Feed................................................. 196 2.2.7.1 Advanced Refining Technologies ........................................................................................ 198 2.2.7.2 Albemarle ............................................................................................................................. 198 2.2.7.3 Axens ................................................................................................................................... 200 2.2.7.4 BP ......................................................................................................................................... 200 2.2.7.5 ConocoPhillips ..................................................................................................................... 201 2.2.7.6 Haldor Topsøe ...................................................................................................................... 202 2.2.7.6.1 Green Diesel Coprocessing Unit ....................................................................... 202 2.2.7.6.2 Standalone Renewable Diesel Hydrotreater ...................................................... 205 2.2.7.7 Neste Oil............................................................................................................................... 206 2.2.7.8 Petrobras............................................................................................................................... 209 2.2.7.9 Repsol YPF .......................................................................................................................... 211 2.2.7.10 UOP/Eni ............................................................................................................................... 211 2.2.7.11 UPM ..................................................................................................................................... 215 2.2.7.12 Summary of Renewable Feed Hydrotreating ....................................................................... 215 PLANT OPERATIONS AND PRACTICES................................................................................................................. 216 2.3.1 General Hydrotreating Operations ....................................................................................................... 216 2.3.1.1 Feed Considerations, Process Configuration, and Hardware ............................................... 217 2.3.1.1.1 Feedstock Characterization ................................................................................ 217 2.3.1.1.2 Pre-hydrotreated Feeds ...................................................................................... 218 2.3.1.1.3 Upgrading Tight Oil .......................................................................................... 219 2.3.1.1.4 Feed Drum Blanketing Gas ............................................................................... 221 2.3.1.1.5 Reactor Configuration ....................................................................................... 221 2.3.1.1.6 Minimize Fouling of Reactor Internals .............................................................. 221 2.3.1.1.7 Twisted Tube Exchanger Bundles for Preheat Service ..................................... 222 2.3.1.1.8 Thermal Enhancement System to Improve Heat Recovery ............................... 222 2.3.1.1.9 Welded Supports on Reactor Walls ................................................................... 223 2.3.1.2 Catalyst Management ........................................................................................................... 224 2.3.1.2.1 Measuring Hydrotreating Catalyst Activity ....................................................... 224 2.3.1.2.2 Protecting HT Catalysts from Contamination.................................................... 225 2.3.1.2.3 Determining and Mitigating HDS Catalyst Deactivation .................................. 230 2.3.1.2.4 Minimizing HDS Activity Loss from Low Sulfur Feed .................................... 231 2.3.1.2.5 In situ Catalyst Sulfiding vs. Ex situ Presulfiding ............................................. 231 2.3.1.2.6 Comparison of Various Sulfiding Agents.......................................................... 233 2.3.1.2.7 Determining HDM Range.................................................................................. 234
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TABLE OF CONTENTS 2.3.1.2.8 Using Regenerated Catalyst .............................................................................. 235 2.3.1.2.9 Dry Dump vs. Wet Dump Catalyst Change-out Procedures ............................. 236 2.3.1.2.10 Catalyst Removal for Non-free Flowing Catalysts ........................................... 236 2.3.1.2.11 Transportation and Disposal of Contaminant-laden Catalysts .......................... 236 2.3.1.2.12 Catalyst Dense Loading .................................................................................... 237 2.3.1.2.13 Catalyst Short Loading ...................................................................................... 239 2.3.1.3 Operating Conditions and Hydrogen Consumption ............................................................. 239 2.3.1.3.1 Effect of Process Severity/Variables on Hydrotreater Performance ................. 239 2.3.1.3.2 Using High-purity Hydrogen and/or Adjusting Hydrogen Partial Pressure ...... 241 2.3.1.3.3 Optimizing the Hydrogen-to-Oil Ratio ............................................................. 242 2.3.1.3.4 Carbon Oxide Contamination............................................................................ 243 2.3.1.3.5 Mitigating High Temperature Hydrogen Attack ............................................... 243 2.3.1.3.6 Accurately Measuring Hydrogen Consumption in Hydrotreaters ..................... 244 2.3.1.3.7 Membranes for H2 Recovery from Hydrotreaters ............................................. 245 2.3.1.4 Operational Monitoring and Upset Detection ...................................................................... 246 2.3.1.4.1 Process Analyzer Placement ............................................................................. 246 2.3.1.4.2 Temperature Monitoring During Startup and Shutdown .................................. 246 2.3.1.4.3 Reactor Effluent Sampling ................................................................................ 247 2.3.1.4.4 Accurate Level Measurements in a Cold High Pressure Separator ................... 248 2.3.1.4.5 Maldistribution in Hydrotreaters ....................................................................... 248 2.3.1.4.6 Reactor Pressure Drop Buildup: Causes and Remedies .................................... 250 2.3.1.4.6.1 Pressure Drop Issues Due to Catalyst .......................................... 250 2.3.1.4.6.2 Pressure Drop Issues Due to Plugging/Fouling ........................... 251 2.3.1.4.7 Detecting and Mitigating Leaks in Equipment .................................................. 255 2.3.1.4.8 Fouling in Feed/Effluent Exchangers ................................................................ 257 2.3.1.4.9 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 ................................................................................................. 261 2.3.1.5.3 Interruption of Operations (Emergency or Planned) and Recommended Actions.. 262 2.3.1.5.4 Minimizing Exposure Risks during Reactor Shutdowns................................... 263 2.3.1.5.5 Preventing Flaring during Unit Startup or Shutdown Procedures ..................... 263 2.3.1.5.6 Irregularities in Sulfur Content ......................................................................... 264 2.3.2 Distillate Hydrotreating ........................................................................................................................ 264 2.3.2.1 Diesel Quality Requirements ............................................................................................... 266 2.3.2.1.1 Cetane ................................................................................................................ 266 2.3.2.1.2 ULSD Cold Flow Properties ............................................................................. 268 2.3.2.1.3 ULSD Haze Point .............................................................................................. 269 2.3.2.1.4 Minimizing Diesel Color Degradation .............................................................. 269 2.3.2.1.5 Logistics ............................................................................................................ 270 2.3.2.2 Increasing Diesel Output ..................................................................................................... 270 2.3.2.2.1 Maximizing Volume Swell of Distillate Feeds ................................................. 270 2.3.2.2.2 Increasing Distillates Fed into a Hydrotreater ................................................... 271 2.3.2.3 Hardware Considerations ..................................................................................................... 272 2.3.2.3.1 Adjusting Hydrotreater Internals to Improve Diesel Production ...................... 272 2.3.2.3.2 Limitations of Single Bed or Undersized ULSD Reactors ................................ 273 2.3.2.3.3 Determining Sufficient Reserve Quench in ULSD Hydrotreaters .................... 274 2.3.2.3.4 Using Advanced-phase Separation Techniques ................................................ 274 2.3.2.3.5 Fouling on Disposable Feed Filters ................................................................... 274 2.3.2.3.6 Improving Energy Efficiency ............................................................................ 275 2.3.2.4 Catalyst Management........................................................................................................... 276
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TABLE OF CONTENTS 2.3.2.5
2.4
Feed Considerations ............................................................................................................. 280 2.3.2.5.1 Options for Converting FCC LCO to ULSD ..................................................... 280 2.3.2.5.2 Processing Distillate and Naphtha Blends in a Diesel Hydrotreater .................. 281 2.3.2.5.3 Coprocessing Renewable Feedstocks ................................................................ 282 2.3.2.6 Process Monitoring .............................................................................................................. 283 2.3.2.6.1 Calculating Diesel Cetane Number from a Diesel Hydrotreater ........................ 283 2.3.2.7 Revamps for ULSD Production ........................................................................................... 283 2.3.2.7.1 Case Study 1 ...................................................................................................... 284 2.3.2.7.2 Case Study 2 ...................................................................................................... 285 2.3.2.7.3 Case Study 3 ...................................................................................................... 286 2.3.2.7.4 Case Study 4 ...................................................................................................... 287 2.3.2.7.5 Case Study 5 ...................................................................................................... 288 2.3.2.7.6 Case Study 6 ...................................................................................................... 289 2.3.2.7.7 Case Study 7 ...................................................................................................... 290 2.3.2.8 Ultra-low Sulfur Kerosene Production ................................................................................. 292 2.3.2.9 Off-Color Products ............................................................................................................... 293 2.3.3 Naphtha Hydrotreating ......................................................................................................................... 293 2.3.3.1 Hydrotreating FCC Naphtha ................................................................................................ 293 2.3.3.2 Processing Coker and Visbreaker Naphtha .......................................................................... 295 2.3.3.3 Processing Coker Naphtha for Hydrogen Production .......................................................... 299 2.3.3.4 Measuring Silicon Content in Coker Naphtha ..................................................................... 300 2.3.3.5 Minimizing Fouling to Increase Catalyst Run Length ......................................................... 301 2.3.3.6 Separating Stripping and Splitting Applications .................................................................. 301 2.3.4 Gas Oil Hydrotreating........................................................................................................................... 301 2.3.4.1 Modifying a FCC Feed Pretreater to Increase Yield of Diesel............................................. 301 2.3.4.2 Impact of Feed Hydrotreatment on FCC Product Aromatics Content ................................. 302 2.3.4.3 Impact of Tier III Gasoline Standards on FCC Feed Pretreaters.......................................... 303 2.3.4.4 FCC Feed Pretreatment vs. FCC Gasoline HDS .................................................................. 303 2.3.4.5 Reducing the Endpoint in Gas Oil Hydrotreaters ................................................................. 308 2.3.4.6 Hydrotreating Heavy Coker Gas Oil .................................................................................... 309 2.3.4.7 Predicting the Yield Pattern When Coprocessing LCGO in a VGO FCCU ........................ 311 2.3.4.8 Improved Operation of a VGO Hydrotreater ....................................................................... 311 2.3.4.9 Operating a VGO Hydrotreater in Blocked Mode ............................................................... 312 REFINING R&D ALERT! ..................................................................................................................................... 313 2.4.1 Introduction ........................................................................................................................................... 313 2.4.2 General Hydrotreating .......................................................................................................................... 320 2.4.2.1 Process ................................................................................................................................. 320 2.4.2.1.1 Patents................................................................................................................ 320 2.4.2.1.1.1 Reduction of Refractory Aromatic Sulfur Compounds ................ 320 2.4.2.1.1.2 Dissolution of Hydrogen to Enhance Mass Transfer ................... 321 2.4.2.1.1.3 Other Process Innovations............................................................ 322 2.4.2.1.2 Research............................................................................................................. 322 2.4.2.2 Catalyst Formulation and Preparation .................................................................................. 323 2.4.2.2.1 Alumina Carrier Supports .................................................................................. 323 2.4.2.2.1.1 Patents .......................................................................................... 323 2.4.2.2.1.2 Research ....................................................................................... 324 2.4.2.2.2 Zeolite Carrier Supports .................................................................................... 325 2.4.2.2.2.1 Patents .......................................................................................... 325 2.4.2.2.2.2 Research ....................................................................................... 326 2.4.2.2.3 Titanium and Zirconium Carrier Supports......................................................... 327 2.4.2.2.3.1 Patents .......................................................................................... 327 2.4.2.2.3.2 Research ....................................................................................... 328
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TABLE OF CONTENTS 2.4.2.2.4 NiP-containing Catalysts ................................................................................... 329 2.4.2.2.5 Phosphorus-modified Carrier Supports ............................................................. 331 2.4.2.2.5.1 Patents .......................................................................................... 331 2.4.2.2.5.2 Research ....................................................................................... 332 2.4.2.2.6 Transition Metal Sulfides .................................................................................. 332 2.4.2.2.6.1 Patents .......................................................................................... 332 2.4.2.2.6.2 Research ....................................................................................... 333 2.4.2.2.7 Noble Metal Catalysts ....................................................................................... 334 2.4.2.2.7.1 Patents .......................................................................................... 334 2.4.2.2.7.2 Research ....................................................................................... 335 2.4.2.2.8 Unsupported Catalysts....................................................................................... 336 2.4.2.2.9 Use of Acids and/or Amines during Formulation and Preparation ................... 338 2.4.2.2.9.1 Patents .......................................................................................... 338 2.4.2.2.9.2 Research ....................................................................................... 338 2.4.2.2.10 Catalyst Regeneration ....................................................................................... 340 2.4.2.2.10.1 Patents .......................................................................................... 340 2.4.2.2.10.2 Research ....................................................................................... 341 2.4.2.2.11 Catalyst Sulfidation ........................................................................................... 342 2.4.2.2.12 Other Catalyst Innovations ................................................................................ 343 2.4.2.2.12.1 Patents .......................................................................................... 343 2.4.2.2.12.2 Research ....................................................................................... 345 2.4.3 Middle Distillate Hydrotreating (Including ULSD Production) ........................................................... 348 2.4.3.1 Process ................................................................................................................................. 348 2.4.3.1.1 Patents ............................................................................................................... 348 2.4.3.1.1.1 Integration of Hydrotreating and Hydrocracking Processes ........ 348 2.4.3.1.1.2 Aromatics Extraction to Improve Cetane..................................... 350 2.4.3.1.1.3 Combined Hydrotreating and Oxidation Treatment .................... 351 2.4.3.1.1.4 Combined Hydrotreating and Dewaxing ..................................... 352 2.4.3.1.1.5 Other Process Schemes ................................................................ 353 2.4.3.1.2 Research ............................................................................................................ 355 2.4.3.2 Catalyst ................................................................................................................................ 356 2.4.3.2.1 Patents ............................................................................................................... 356 2.4.3.2.1.1 Metal Oxide Supports .................................................................. 356 2.4.3.2.1.1.1 Patents .................................................................. 356 2.4.3.2.1.1.2 Research ............................................................... 358 2.4.3.2.1.2 Zeolites ........................................................................................ 358 2.4.3.2.1.3 Bulk Catalysts .............................................................................. 360 2.4.3.2.2 Research ............................................................................................................ 360 2.4.3.2.2.1 General Catalyst Studies .............................................................. 360 2.4.3.2.2.2 NiP Supported Catalyst ................................................................ 362 2.4.3.2.2.3 Unsupported Catalysts ................................................................. 362 2.4.4 Naphtha Hydrotreating ......................................................................................................................... 362 2.4.4.1 Process ................................................................................................................................. 362 2.4.4.1.1 Patents ............................................................................................................... 362 2.4.4.1.1.1 FCCU Posttreatment .................................................................... 362 2.4.4.1.1.2 Other Innovations ........................................................................ 364 2.4.4.2 Catalyst ................................................................................................................................ 366 2.4.4.2.1 Patents ............................................................................................................... 366 2.4.4.2.1.1 FCCU Posttreatment .................................................................... 366 2.4.4.2.1.2 Non-FCCU Naphtha Hydrotreating ............................................. 368 2.4.4.2.2 Research ............................................................................................................ 369 2.4.4.2.2.1 General Catalyst Studies .............................................................. 369 2.4.4.2.2.2 Catalyst Supports ......................................................................... 371
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2.5 2.6
2.7
2.4.4.2.2.3 Reaction Mechanism .................................................................... 372 2.4.5 Tight Oil Processing .............................................................................................................................. 372 2.4.6 Heavy Oil and Resid Hydrotreating ...................................................................................................... 373 2.4.6.1 Process ................................................................................................................................. 373 2.4.6.1.1 Patents................................................................................................................ 373 2.4.6.1.1.1 Integrated Processes ..................................................................... 373 2.4.6.1.1.2 Reactor Configuration .................................................................. 378 2.4.6.1.1.3 Bunker Fuel Production ............................................................... 380 2.4.6.1.2 Research............................................................................................................. 380 2.4.6.2 Catalyst ................................................................................................................................. 381 2.4.6.2.1 Patents................................................................................................................ 381 2.4.6.2.1.1 Resid HDM Catalysts ................................................................... 381 2.4.6.2.1.2 Resid HDS and/or HDN Catalysts ............................................... 384 2.4.6.2.2 Research............................................................................................................. 386 2.4.7 Renewable Feed Hydrotreating............................................................................................................. 389 2.4.7.1 Process ................................................................................................................................. 389 2.4.7.1.1 Patents................................................................................................................ 389 2.4.7.1.1.1 Process Integration ....................................................................... 389 2.4.7.1.1.2 Product Specific Processes ........................................................... 391 2.4.7.1.1.2.1 Gasoline/Naphtha ................................................ 391 2.4.7.1.1.2.2 Kerosene/Jet Fuel ................................................ 392 2.4.7.1.1.2.3 Biodiesel .............................................................. 394 2.4.7.1.1.2.4 Heavy Products ................................................... 396 2.4.7.1.1.3 Minimization of Coke Production ................................................ 397 2.4.7.1.1.4 Miscellaneous Process Schemes .................................................. 398 2.4.7.1.2 Research............................................................................................................. 400 2.4.7.2 Catalyst ................................................................................................................................. 402 2.4.7.2.1 Patents................................................................................................................ 402 2.4.7.2.1.1 Noble Metal .................................................................................. 402 2.4.7.2.1.2 Phosphided Catalysts.................................................................... 403 2.4.7.2.1.3 Metal Oxide Carrier Supports ...................................................... 404 2.4.7.2.1.4 Miscellaneous ............................................................................... 405 2.4.7.2.2 Research............................................................................................................. 406 WORLDWIDE INSTALLED CAPACITY .................................................................................................................. 406 CONSTRUCTION ................................................................................................................................................. 410 2.6.1 Recent Construction Activity ................................................................................................................. 410 2.6.2 Completed Construction Projects.......................................................................................................... 419 REFERENCES ...................................................................................................................................................... 462
3. Alkylation .................................................................................................................................... 507 3.1
MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 507 3.1.1 Introduction ........................................................................................................................................... 507 3.1.2 Market Conditions and Outlook ............................................................................................................ 507 3.1.2.1 Gasoline Supply and Demand .............................................................................................. 507 3.1.2.2 Alkylation Capacity and New Construction Projects ........................................................... 509 3.1.2.3 Mandated Blending of Ethanol and the Impact on the Gasoline Pool.................................. 511 3.1.2.4 Impact of Shale Boom on Alkylation Operations ................................................................ 512 3.1.2.5 Safety and Environmental Concerns .................................................................................... 513 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 516 3.1.3.1 Liquid Acid Alkylation ........................................................................................................ 516 3.1.3.1.1 HF ...................................................................................................................... 517 3.1.3.1.2 H2SO4................................................................................................................. 518
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TABLE OF CONTENTS 3.1.3.2
3.2
3.3
Alternative Alkylation Technologies ................................................................................... 518 3.1.3.2.1 Indirect Alkylation ............................................................................................ 519 3.1.3.2.2 Solid Acid.......................................................................................................... 519 3.1.3.2.3 Ionic Liquid ....................................................................................................... 520 3.1.3.3 Revamping Liquid Acid Units to Solid Acid and Ionic Liquid Units.................................. 522 3.1.3.4 R&D Trends......................................................................................................................... 523 3.1.4 Conclusion ............................................................................................................................................ 523 STATE-OF-THE-ART TECHNOLOGY ................................................................................................................... 524 3.2.1 Introduction .......................................................................................................................................... 524 3.2.2 Commercially Available Liquid Acid Alkylation Technologies ............................................................ 527 3.2.2.1 Feed Pretreatment ................................................................................................................ 527 3.2.2.1.1 Axens ................................................................................................................ 528 3.2.2.1.2 UOP ................................................................................................................... 529 3.2.2.2 HF Alkylation ...................................................................................................................... 530 3.2.2.2.1 UOP ................................................................................................................... 531 3.2.2.2.1.1 Gravity Circulated HF Alkylation ............................................... 532 3.2.2.2.1.2 Forced Circulation HF Alkylation ............................................... 533 3.2.2.2.1.3 ReVAP ......................................................................................... 535 3.2.2.2.1.4 Alkad ........................................................................................... 537 3.2.2.2.1.5 Inventory Management Process ................................................... 537 3.2.2.3 H2SO4 Alkylation ................................................................................................................. 538 3.2.2.3.1 CDTECH ........................................................................................................... 539 3.2.2.3.2 DuPont STRATCO ........................................................................................... 543 3.2.2.3.2.1 Feed Segregation ......................................................................... 543 3.2.2.3.2.2 Butenes Feed Fractionation ......................................................... 544 3.2.2.3.2.3 Effluent Refrigerated Alkylation ................................................. 545 3.2.2.3.2.4 ALKYSAFE ................................................................................ 548 3.2.2.3.2.5 Integrated Alkylation and Onsite SAR/SGR ............................... 549 3.2.2.3.3 ExxonMobil....................................................................................................... 550 3.2.2.3.4 Refining Hydrocarbon Technologies (RHT)..................................................... 553 3.2.3 Alternative Alkylation Technologies ..................................................................................................... 555 3.2.3.1 Solid Acid ............................................................................................................................ 555 3.2.3.1.1 Exelus ................................................................................................................ 556 3.2.3.1.2 Lummus Technology/Albemarle/Neste Oil....................................................... 560 3.2.3.1.3 Lurgi .................................................................................................................. 563 3.2.3.1.4 UOP ................................................................................................................... 564 3.2.3.2 Supported Liquid-phase Catalysts ....................................................................................... 567 3.2.3.2.1 Haldor Topsøe ................................................................................................... 567 3.2.3.3 Ionic Liquid Alkylation ....................................................................................................... 569 3.2.3.3.1 PetroChina ......................................................................................................... 569 3.2.3.4 Indirect Alkylation ............................................................................................................... 572 3.2.3.4.1 UOP ................................................................................................................... 572 3.2.3.5 Butane Oxydehydrogenation ............................................................................................... 575 3.2.3.5.1 Uhde .................................................................................................................. 575 3.2.3.6 Renewable Alkylation.......................................................................................................... 579 3.2.3.6.1 Exelus ................................................................................................................ 579 3.2.4 Summary of Alkylation Technologies .................................................................................................... 580 3.2.5 Comparison of Commercially Available Advanced Control and Optimization Systems ...................... 585 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 586 3.3.1 Feed Considerations ............................................................................................................................. 586 3.3.1.1 Feed Contaminants .............................................................................................................. 586
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3.4
Alkylating Alternative Feedstocks ....................................................................................... 587 3.3.1.2.1 Propylene ........................................................................................................... 588 3.3.1.2.2 Amylenes ........................................................................................................... 589 3.3.1.2.3 Isobutene............................................................................................................ 590 3.3.1.2.4 Isomerization Butane Slop Stream .................................................................... 591 3.3.1.2.5 Light Ends ......................................................................................................... 591 3.3.1.2.6 Feed from Cokers .............................................................................................. 592 3.3.2 HF Alkylation ........................................................................................................................................ 592 3.3.2.1 Disposing of Acid Soluble Oils from HF Plants .................................................................. 592 3.3.2.2 Corrosion .............................................................................................................................. 592 3.3.2.3 Chemical Cleaning in HF Alkylation Units Prior to Turnaround ........................................ 594 3.3.2.4 Online Monitoring of HF Acid Catalyst............................................................................... 594 3.3.2.5 Safety and Mitigation Techniques ........................................................................................ 595 3.3.2.6 Optimizing HF Alkylation Feed Nozzles ............................................................................. 597 3.3.2.7 Improved Valve Design ....................................................................................................... 597 3.3.2.8 Pump Seal Selection ............................................................................................................. 598 3.3.2.9 Inspecting Joints in HF Alkylation Unit............................................................................... 599 3.3.2.10 Treating HF Alkylation Products to Remove Organic Fluorides ......................................... 600 3.3.2.11 Revamping HF Alkylation Units .......................................................................................... 600 3.3.2.11.1 Revamping to H2SO4 Alkylation ....................................................................... 601 3.3.2.11.2 Revamping to Solid Acid Alkylation................................................................. 602 3.3.3 H2SO4 Alkylation ................................................................................................................................... 603 3.3.3.1 ASO Formation and Disposal .............................................................................................. 603 3.3.3.2 Corrosion and Fouling.......................................................................................................... 603 3.3.3.3 Spent H2SO4 Regeneration and Treatment ........................................................................... 607 3.3.3.3.1 Regeneration ...................................................................................................... 607 3.3.3.3.2 Treatment ........................................................................................................... 608 3.3.3.4 Electrostatic Precipitator Use in Caustic Wash Systems ...................................................... 608 3.3.4 Acid Management .................................................................................................................................. 609 3.3.4.1 Acid Runaway ...................................................................................................................... 609 3.3.4.2 Acid Storage ......................................................................................................................... 610 3.3.5 Process Control, Monitoring, and Optimization ................................................................................... 611 3.3.5.1 Dynamic Simulation for Debottlenecking a Deisobutanizer ................................................ 611 3.3.5.2 Measuring Circulating Acid Strength and Acid Levels ....................................................... 612 3.3.5.2.1 Employing Multi-objective Optimization to Alkylation Processes ................... 614 3.3.5.2.2 Isostripper Advanced Process Control (APC) ................................................... 614 REFINING R&D ALERT! ..................................................................................................................................... 615 3.4.1 Introduction ........................................................................................................................................... 615 3.4.2 Feedstock Preparation .......................................................................................................................... 616 3.4.3 General Alkylation ................................................................................................................................ 617 3.4.3.1 Patents .................................................................................................................................. 617 3.4.3.1.1 Hardware ........................................................................................................... 617 3.4.3.1.2 Alkylation Units for Producing Alkylate and/or Middle Distillate.................... 618 3.4.3.2 Research ............................................................................................................................... 619 3.4.4 HF Alkylation ........................................................................................................................................ 620 3.4.5 H2SO4 Alkylation ................................................................................................................................... 621 3.4.6 Solid Acid Alkylation ............................................................................................................................. 624 3.4.6.1 Process ................................................................................................................................. 624 3.4.6.2 Catalyst ................................................................................................................................. 625 3.4.6.2.1 Patents................................................................................................................ 625 3.4.6.2.2 Research............................................................................................................. 627
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3.5 3.6
3.7
3.4.7 Ionic Liquid Alkylation ......................................................................................................................... 627 3.4.7.1 Process ................................................................................................................................. 627 3.4.7.2 Catalyst ................................................................................................................................ 630 3.4.7.2.1 Patents ............................................................................................................... 630 3.4.7.2.1 Research ............................................................................................................ 632 3.4.7.3 Hardware.............................................................................................................................. 633 3.4.7.4 Revamping from Liquid Acid to Ionic Liquid ..................................................................... 635 3.4.7.5 Ionic Liquid Alkylation to Produce Alkylate and/or Distillate ............................................ 636 3.4.7.6 Integration ............................................................................................................................ 638 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 641 CONSTRUCTION ................................................................................................................................................. 643 3.6.1 Recent Construction Activity ................................................................................................................. 643 3.6.1 Completed Construction Projects ......................................................................................................... 645 REFERENCES ..................................................................................................................................................... 650
4. Latest Refining Technology Developments & Licensing......................................................... 661 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16
FLUID CATALYTIC CRACKING ........................................................................................................................... 661 HYDROCRACKING ............................................................................................................................................. 662 ISOMERIZATION ................................................................................................................................................. 663 BENZENE REDUCTION AND REMOVAL ............................................................................................................... 663 COKING ............................................................................................................................................................. 664 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 664 COGENERATION AND INTEGRATED GASIFICATION COMBINED CYCLE .............................................................. 664 LUBE PRODUCTION ........................................................................................................................................... 665 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................ 665 CATALYST AND CARRIER SUPPORT DEVELOPMENTS ........................................................................................ 669 PROCESS CONTROLS AND SIMULATION ............................................................................................................. 669 XTL (BIOMASS-, COAL-, AND GAS-TO-LIQUID) ................................................................................................ 670 BIOFUELS PRODUCTION..................................................................................................................................... 672 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) ............................................................................. 674 SITE EMISSIONS AND DISCHARGE...................................................................................................................... 676 REFERENCES ..................................................................................................................................................... 678
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