Hydrotreating and Environmental Controls by Hydrocarbon Publishing Company

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

Second Quarter 2012 Hydrotreating and Environmental Controls Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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

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

Review@Hydrocarbonpublishing.com

TABLE OF CONTENTS 2Q 2012 Review Hydrotreating and Environmental Controls 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 2.1.2.2 Refined Products Demand .......................................................................................................... 7 2.1.2.3 Increasing Middle Distillate Production ..................................................................................... 9 2.1.2.4 Hydrotreating Capacity Expansion ........................................................................................... 10 2.1.2.5 Construction Projects and Unit Revamps ................................................................................. 11 2.1.2.6 Shifting Crude Slate.................................................................................................................. 12 2.1.2.7 Heavy Crude Oil Upgrading ..................................................................................................... 15 2.1.2.8 Biofuel Production .................................................................................................................... 15 2.1.2.9 Hydrogen Demand .................................................................................................................... 16 2.1.2.10 Hydrotreating Catalysts Market ................................................................................................ 16 2.1.3 Technology Competition, Directions, and Future Prospects .................................................................. 17 2.1.3.1 Conventional Hydrotreating ..................................................................................................... 19 2.1.3.2 Resid Hydrotreating .................................................................................................................. 27 2.1.3.3 Renewable Feed Hydrotreating ................................................................................................ 28 2.1.4 Conclusion .............................................................................................................................................. 30 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 31 2.2.1 Introduction ............................................................................................................................................ 31 2.2.2 Commercial Catalysts and Guard Materials .......................................................................................... 32 2.2.2.1 Advanced Refining Technologies............................................................................................. 33 2.2.2.1.1 SmART .................................................................................................................... 33 2.2.2.1.2 ApART .................................................................................................................... 36 2.2.2.2 Albemarle ................................................................................................................................. 38 2.2.2.2.1 STARS Series .......................................................................................................... 39 2.2.2.2.2 NEBULA Series ...................................................................................................... 44 2.2.2.2.3 Combined Implementation ...................................................................................... 46 2.2.2.2.4 KF 901, KF 902, KF 905, KF 859........................................................................... 48 2.2.2.2.5 KF 200 ..................................................................................................................... 49 2.2.2.2.6 Guard Catalysts ....................................................................................................... 49 2.2.2.3 Axens ........................................................................................................................................ 50 2.2.2.3.1 HR 400 Series .......................................................................................................... 50 2.2.2.3.2 HR 500 Series .......................................................................................................... 51 2.2.2.3.3 HR 600 Series .......................................................................................................... 52 2.2.2.3.4 HR 900 Series .......................................................................................................... 53 2.2.2.3.5 AX 740 Hydrogenation Catalysts ............................................................................ 53 2.2.2.3.6 ACT Grading Materials ........................................................................................... 53 2.2.2.4 BASF ........................................................................................................................................ 54 2.2.2.5 Chevron Lummus Global ......................................................................................................... 55 2.2.2.6 Clariant ..................................................................................................................................... 55 2.2.2.7 Cosmo Oil ................................................................................................................................. 56

2Q 2012 i Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS 2.2.2.8 Criterion Catalysts & Technologies .......................................................................................... 56 2.2.2.8.1 CENTINEL .............................................................................................................. 57 2.2.2.8.2 CENTINEL GOLD .................................................................................................. 58 2.2.2.8.3 ASCENT .................................................................................................................. 61 2.2.2.8.4 CENTERA ............................................................................................................... 66 2.2.2.8.5 SDD-800/SDD-821 .................................................................................................. 68 2.2.2.8.6 Selective Hydrogenation Catalysts .......................................................................... 70 2.2.2.8.7 Guard Catalysts ........................................................................................................ 70 2.2.2.9 Crystaphase Products ................................................................................................................ 71 2.2.2.10 ExxonMobil .............................................................................................................................. 71 2.2.2.10.1 RT-225 ..................................................................................................................... 71 2.2.2.10.2 OCTGAIN Catalysts ................................................................................................ 72 2.2.2.11 Haldor Topsøe ........................................................................................................................... 72 2.2.2.11.1 Coker Naphtha Hydrotreating .................................................................................. 73 2.2.2.11.2 FCC Feed Pretreat .................................................................................................... 74 2.2.2.11.3 ULSD Production .................................................................................................... 75 2.2.2.11.4 Reduction of Diesel Density and Aromatics ............................................................ 78 2.2.2.11.5 Hydrocracker Pretreating ......................................................................................... 79 2.2.2.11.6 Graded Bed Products for Pressure Drop Control ..................................................... 79 2.2.2.12 JGC Catalysts & Chemicals Industries ..................................................................................... 81 2.2.2.13 Johnson Matthey Catalysts ........................................................................................................ 82 2.2.2.14 Nippon Oil ................................................................................................................................ 82 2.2.2.15 Sinopec ...................................................................................................................................... 83 2.2.2.16 Saint Gobain NorPro ................................................................................................................. 84 2.2.2.17 TRICAT .................................................................................................................................... 84 2.2.2.18 UOP........................................................................................................................................... 85 2.2.2.19 Summary of Commercially Available Hydrotreating Catalysts ................................................ 86 2.2.3 Auxiliary Catalyst Technology ................................................................................................................ 90 2.2.3.1 Advanced Refining Technologies ............................................................................................. 90 2.2.3.1.1 PHOENIX ................................................................................................................ 90 2.2.3.2 Albemarle .................................................................................................................................. 90 2.2.3.2.1 EasyActive ............................................................................................................... 90 2.2.3.2.2 REACT .................................................................................................................... 91 2.2.3.2.3 STAX ....................................................................................................................... 91 2.2.3.3 Axens ........................................................................................................................................ 92 2.2.3.4 Criterion Catalysts & Technologies .......................................................................................... 93 2.2.3.5 Eurecat ...................................................................................................................................... 93 2.2.3.5.1 Sulficat ..................................................................................................................... 93 2.2.3.5.2 Totsucat .................................................................................................................... 94 2.2.3.6 Haldor Topsøe ........................................................................................................................... 95 2.2.3.7 Orient Catalyst/Advanced Refining Technologies .................................................................... 95 2.2.3.8 Oxford Catalysts ....................................................................................................................... 95 2.2.3.9 TRICAT Inc. ............................................................................................................................. 96 2.2.3.9.1 TRICAT Regeneration Process ................................................................................ 96 2.2.3.9.2 XpresS ...................................................................................................................... 96 2.2.4 Commercial Process Technology ............................................................................................................ 96 2.2.4.1 Albemarle .................................................................................................................................. 96 2.2.4.1.1 UD-HDS .................................................................................................................. 97 2.2.4.1.2 HDAr ....................................................................................................................... 98 2.2.4.1.3 Cold Flow Improvement .......................................................................................... 99 2.2.4.1.4 PLEX Reactor Internals ......................................................................................... 100

2Q 2012 ii Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS 2.2.4.2 Axens ...................................................................................................................................... 100 2.2.4.2.1 Prime-G+ ............................................................................................................... 101 2.2.4.2.2 Prime-D ................................................................................................................. 103 2.2.4.2.3 Benzene Saturation ................................................................................................ 105 2.2.4.2.4 EquiFlow Reactor Internals ................................................................................... 106 2.2.4.3 Chevron Lummus Global ....................................................................................................... 107 2.2.4.4 DuPont .................................................................................................................................... 109 2.2.4.5 ExxonMobil Research & Engineering/KBR........................................................................... 111 2.2.4.5.1 GO-Fining ............................................................................................................. 111 2.2.4.5.2 HYDROFINING ................................................................................................... 112 2.2.4.5.3 SCANfining ........................................................................................................... 112 2.2.4.5.4 EXOMER .............................................................................................................. 114 2.2.4.5.5 OCTGAIN ............................................................................................................. 115 2.2.4.5.6 MIDW ................................................................................................................... 116 2.2.4.6 Fushun Research Institute of Petroleum and Petrochemicals (Sinopec)................................. 118 2.2.4.6.1 FHI Diesel Hydro-upgrading/Isodewaxing Process .............................................. 118 2.2.4.6.2 FRS ........................................................................................................................ 119 2.2.4.6.3 OTA ....................................................................................................................... 119 2.2.4.6.4 OCT-M .................................................................................................................. 120 2.2.4.7 GTC Technology .................................................................................................................... 120 2.2.4.8 Haldor Topsøe ........................................................................................................................ 121 2.2.4.8.1 Conventional Hydrotreating .................................................................................. 121 2.2.4.8.2 Coker Naphtha Hydrotreating ............................................................................... 123 2.2.4.8.3 Distillate HDS/HDA .............................................................................................. 123 2.2.4.8.4 Diesel Dewaxing ................................................................................................... 125 2.2.4.8.5 Aroshift .................................................................................................................. 125 2.2.4.8.6 Reactor Internals .................................................................................................... 127 2.2.4.9 Instituto Mexicano del Petróleo .............................................................................................. 129 2.2.4.10 JGC Catalysts & Chemicals .................................................................................................... 130 2.2.4.10.1 JUST Refinery ....................................................................................................... 130 2.2.4.10.2 Gas Oil Ultra Deep Desulfurization ...................................................................... 131 2.2.4.10.3 GEFINERY ........................................................................................................... 131 2.2.4.10.4 LCO Upgrading ..................................................................................................... 131 2.2.4.11 Lummus Technology, a CB&I Company ............................................................................... 132 2.2.4.11.1 Conventional Hydrotreating .................................................................................. 132 2.2.4.11.2 Benzene CDHydro................................................................................................. 133 2.2.4.11.3 LCN CDHydro/CDHDS and CDHDS+................................................................. 134 2.2.4.12 MOL ....................................................................................................................................... 138 2.2.4.13 Neste Jacobs ........................................................................................................................... 139 2.2.4.14 Nippon Oil .............................................................................................................................. 140 2.2.4.15 RIPP ........................................................................................................................................ 140 2.2.4.16 SK Corp. ................................................................................................................................. 142 2.2.4.17 Shaw Group/BASF ................................................................................................................. 143 2.2.4.18 Shell Global Solutions ............................................................................................................ 145 2.2.4.18.1 Hydrotreating Process ........................................................................................... 145 2.2.4.18.2 SMDH ................................................................................................................... 145 2.2.4.18.3 Pyrolysis Hydrogenation Unit ............................................................................... 146 2.2.4.18.4 Reactor Internals .................................................................................................... 146

2Q 2012 iii Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

2.3

2.2.4.19 UOP......................................................................................................................................... 150 2.2.4.19.1 MQD Unionfining.................................................................................................. 151 2.2.4.19.2 VGO Unionfining .................................................................................................. 153 2.2.4.19.3 ISAL....................................................................................................................... 154 2.2.4.19.4 SelectFining ........................................................................................................... 155 2.2.4.19.5 BenSat .................................................................................................................... 156 2.2.4.19.6 Unisar ..................................................................................................................... 158 2.2.4.19.7 Unicracking/DW .................................................................................................... 159 2.2.4.19.8 UltraMix Reactor Internals .................................................................................... 160 2.2.4.20 Summary of Hydrotreating Process Technologies .................................................................. 160 2.2.5 Commercially Available Advanced Control and Optimization Systems................................................ 171 2.2.5.1 Aspen Technology .................................................................................................................. 171 2.2.5.2 Axens ...................................................................................................................................... 172 2.2.5.3 KBC Advanced Technologies ................................................................................................. 174 2.2.5.4 Repsol YPF ............................................................................................................................. 175 2.2.6 Resid Hydrotreating .............................................................................................................................. 175 2.2.7 Coprocessing of Renewable Feed with Conventional Petroleum Feed................................................. 178 2.2.7.1 Advanced Refining Technologies ........................................................................................... 180 2.2.7.2 Albemarle ................................................................................................................................ 180 2.2.7.3 Axens ...................................................................................................................................... 182 2.2.7.4 BP ............................................................................................................................................ 182 2.2.7.5 ConocoPhillips ........................................................................................................................ 183 2.2.7.6 Haldor Topsøe ......................................................................................................................... 184 2.2.7.6.1 Green Diesel Coprocessing Unit ............................................................................ 184 2.2.7.6.2 Standalone Renewable Diesel Hydrotreater........................................................... 186 2.2.7.7 Neste Oil ................................................................................................................................. 187 2.2.7.8 Petrobras ................................................................................................................................. 191 2.2.7.9 Repsol YPF ............................................................................................................................. 193 2.2.7.10 UOP/Eni .................................................................................................................................. 193 2.2.7.11 UPM ........................................................................................................................................ 196 2.2.7.12 Summary of Renewable Feed Hydrotreating .......................................................................... 197 PLANT OPERATIONS AND PRACTICES................................................................................................................. 198 2.3.1 General Hydrotreating Operations ....................................................................................................... 198 2.3.1.1 Feed Considerations, Process Configuration, and Hardware .................................................. 199 2.3.1.1.1 Feedstock Characterization .................................................................................... 199 2.3.1.1.2 Pre-hydrotreated Feeds .......................................................................................... 200 2.3.1.1.3 Feed Drum Blanketing Gas .................................................................................... 200 2.3.1.1.4 Reactor Configuration ............................................................................................ 201 2.3.1.1.5 Minimize Fouling of Reactor Internals .................................................................. 201 2.3.1.1.6 Twisted Tube Exchanger Bundles for Preheat Service .......................................... 202 2.3.1.1.7 Thermal Enhancement System to Improve Heat Recovery ................................... 202 2.3.1.2 Catalyst Management .............................................................................................................. 203 2.3.1.2.1 Measuring Hydrotreating Catalyst Activity ........................................................... 203 2.3.1.2.2 Protecting HT Catalysts from Contamination ........................................................ 203 2.3.1.2.3 Catalyst Deactivation by Carbon Monoxide in Selective HDS Units .................... 206 2.3.1.2.4 Minimizing HDS Activity Loss from Low Sulfur Feed ........................................ 207 2.3.1.2.5 In situ Catalyst Sulfiding vs. Ex situ Presulfiding.................................................. 207 2.3.1.2.6 Comparison of Various Sulfiding Agents .............................................................. 208 2.3.1.2.7 Using Regenerated Catalyst ................................................................................... 210 2.3.1.2.8 Dry Dump vs. Wet Dump Catalyst Change-out Procedures .................................. 211 2.3.1.2.9 Catalyst Dense Loading ......................................................................................... 211

2Q 2012 iv Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS 2.3.1.3 Operating Conditions and Hydrogen Consumption................................................................ 212 2.3.1.3.1 Effect of Process Severity/Variables on Hydrotreater Performance...................... 212 2.3.1.3.2 Using High-purity Hydrogen and/or Adjusting Hydrogen Partial Pressure .......... 214 2.3.1.3.3 Optimizing the Hydrogen-to-oil Ratio................................................................... 215 2.3.1.3.4 Mitigating High Temperature Hydrogen Attack ................................................... 215 2.3.1.3.5 Accurately Measuring Hydrogen Consumption in Hydrotreaters ......................... 216 2.3.1.4 Operational Monitoring and Upset Detection ......................................................................... 217 2.3.1.4.1 Process Analyzer Placement .................................................................................. 217 2.3.1.4.2 Reactor Effluent Sampling .................................................................................... 218 2.3.1.4.3 Accurate Level Measurements in a Cold High Pressure Separator ....................... 218 2.3.1.4.4 Maldistribution in Hydrotreaters ........................................................................... 219 2.3.1.4.5 Reactor Pressure Drop Buildup: Causes and Remedies ........................................ 220 2.3.1.4.6 Detecting and Mitigating Leaks in Equipment ...................................................... 226 2.3.1.4.7 Fouling in Feed/Effluent Exchangers .................................................................... 227 2.3.1.4.8 Ammonium Chloride Fouling in Effluent Exchangers and H2 Gas Compressors . 228 2.3.1.5 Best Practices and Troubleshooting........................................................................................ 230 2.3.1.5.1 Reviewing and Updating Unit Operating Procedures ........................................... 230 2.3.1.5.2 Criteria for Selecting Remote Manual and/or Auto Depressuring Equipment and Instrumentation ...................................................................................................... 230 2.3.1.5.3 Interruption of Operations (Emergency or Planned) and Recommended Actions 231 2.3.1.5.4 Minimizing Exposure Risks during Reactor Shutdowns ....................................... 232 2.3.1.5.5 Preventing Flaring during Unit Startup or Shutdown Procedures ......................... 232 2.3.2 Distillate Hydrotreating ........................................................................................................................ 233 2.3.2.1 Diesel Quality Requirements .................................................................................................. 235 2.3.2.1.1 Cetane .................................................................................................................... 235 2.3.2.1.2 ULSD Cold Flow Properties ................................................................................. 237 2.3.2.1.3 ULSD Haze Point .................................................................................................. 237 2.3.2.1.4 Logistics ................................................................................................................ 238 2.3.2.2 Hardware Considerations ....................................................................................................... 238 2.3.2.2.1 Adjusting Hydrotreater Internals to Improve Diesel Production ........................... 238 2.3.2.2.2 Limitations of Single Bed or Undersized ULSD Reactors .................................... 239 2.3.2.2.3 Determining Sufficient Reserve Quench in ULSD Hydrotreaters......................... 239 2.3.2.2.4 Using Advanced-phase Separation Techniques .................................................... 240 2.3.2.2.5 Fouling on Disposable Feed Filters ....................................................................... 240 2.3.2.2.6 Improving Energy Efficiency ................................................................................ 240 2.3.2.3 Catalyst Management ............................................................................................................. 241 2.3.2.4 Feed Considerations ............................................................................................................... 245 2.3.2.4.1 Options for Converting FCC LCO to ULSD ......................................................... 245 2.3.2.4.2 Processing Distillate and Naphtha Blends in a Diesel Hydrotreater...................... 247 2.3.2.4.3 Coprocessing Renewable Feedstocks .................................................................... 247 2.3.2.5 Process Monitoring ................................................................................................................. 248 2.3.2.5.1 Calculating Diesel Cetane Number from a Diesel Hydrotreater ........................... 248 2.3.2.6 Revamps for ULSD Production .............................................................................................. 248 2.3.2.6.1 Case Study 1 .......................................................................................................... 249 2.3.2.6.2 Case Study 2 .......................................................................................................... 250 2.3.2.6.3 Case Study 3 .......................................................................................................... 251 2.3.2.6.4 Case Study 4 .......................................................................................................... 252 2.3.2.6.5 Case Study 5 .......................................................................................................... 252 2.3.2.6.6 Case Study 6 .......................................................................................................... 254 2.3.2.6.7 Case Study 7 .......................................................................................................... 255 2.3.2.7 Ultra Low Sulfur Kerosene Production .................................................................................. 256 2.3.3 Naphtha Hydrotreating ......................................................................................................................... 257 2.3.3.1 Processing Coker and Visbreaker Naphtha ............................................................................ 257

2Q 2012 v Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

2.4

2.3.3.2 Measuring Silicon Content in Coker Naphtha ........................................................................ 261 2.3.3.3 Hydrotreating FCC Naphtha—Octane Loss and Other Problems........................................... 261 2.3.3.4 Minimizing Fouling to Increase Catalyst Run Length ............................................................ 263 2.3.3.5 Separating Stripping and Splitting Applications ..................................................................... 264 2.3.4 Gas Oil Hydrotreating........................................................................................................................... 264 2.3.4.1 Modifying a FCC Feed Pretreater to Increase Yield of Diesel ............................................... 264 2.3.4.2 Impact of Feed Hydrotreatment on FCC Product Aromatics Content .................................... 265 2.3.4.3 FCC Feed Pretreatment vs. FCC Gasoline HDS ..................................................................... 266 2.3.4.4 Reducing the Endpoint in Gas Oil Hydrotreaters.................................................................... 267 2.3.4.5 Hydrotreating Heavy Coker Gas Oil ....................................................................................... 268 2.3.4.6 Predicting the Yield Pattern When Coprocessing LCGO in a VGO FCCU ........................... 270 2.3.4.7 Improved Operation of a VGO Hydrotreater .......................................................................... 271 REFINING R&D ALERT! ..................................................................................................................................... 272 2.4.1 Introduction ........................................................................................................................................... 272 2.4.2 General Hydrotreating .......................................................................................................................... 280 2.4.2.1 Process Schemes ..................................................................................................................... 280 2.4.2.1.1 Process Schemes .................................................................................................... 280 2.4.2.1.2 Integrated Configurations ...................................................................................... 281 2.4.2.1.2.1 Stripping and/or Fractionation ........................................................ 281 2.4.2.1.2.2 Adsorption....................................................................................... 283 2.4.2.1.2.3 Oxidative Desulfurization ............................................................... 284 2.4.2.1.2.4 Other ............................................................................................... 285 2.4.2.2 Catalyst Formulation and Preparation ..................................................................................... 286 2.4.2.2.1 Supports ................................................................................................................. 286 2.4.2.2.1.1 Phosphorus-containing Carriers ...................................................... 286 2.4.2.2.1.1.1 Patents ...................................................................... 286 2.4.2.2.1.1.2 Research ................................................................... 286 2.4.2.2.1.2 Metal Oxides ................................................................................... 287 2.4.2.2.1.2.1 Patents ...................................................................... 287 2.4.2.2.1.2.2 Research ................................................................... 288 2.4.2.2.1.3 Zeolites ............................................................................................ 292 2.4.2.2.1.3.1 Patents ...................................................................... 292 2.4.2.2.1.3.2 Research ................................................................... 293 2.4.2.2.2 Promoters ............................................................................................................... 294 2.4.2.2.2.1 Phosphorus ...................................................................................... 294 2.4.2.2.2.1.1 Patents ...................................................................... 294 2.4.2.2.2.1.2 Research ................................................................... 295 2.4.2.2.2.2 Metal Oxides ................................................................................... 296 2.4.2.2.2.3 Transition Metal Sulfides ................................................................ 296 2.4.2.2.2.4 Zeolites ............................................................................................ 297 2.4.2.2.2.5 Organics .......................................................................................... 298 2.4.2.2.3 Catalyst Activation Procedures .............................................................................. 298 2.4.2.2.3.1 Patents ............................................................................................. 298 2.4.2.2.3.2 Research .......................................................................................... 299 2.4.2.3 Catalyst Regeneration ............................................................................................................. 300 2.4.2.4 Miscellaneous Catalyst Innovations ........................................................................................ 300 2.4.2.4.1 Patents .................................................................................................................... 300 2.4.2.4.2 Research ................................................................................................................. 301 2.4.3 Naphtha Hydrotreating ......................................................................................................................... 302 2.4.3.1 Patents ..................................................................................................................................... 302 2.4.3.2 Research .................................................................................................................................. 302 2.4.4 Middle Distillate Hydrotreating (Including ULSD Production) ........................................................... 303 2.4.4.1 Process .................................................................................................................................... 303

2Q 2012 vi Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

2.5 2.6

2.7

2.4.4.2 Catalyst ................................................................................................................................... 305 2.4.4.2.1 Patents ................................................................................................................... 305 2.4.4.2.2 Research ................................................................................................................ 307 2.4.5 LCO/SRGO ........................................................................................................................................... 308 2.4.5.1 Process .................................................................................................................................... 308 2.4.5.1.1 Patents ................................................................................................................... 308 2.4.5.1.2 Research ................................................................................................................ 308 2.4.5.2 Catalyst ................................................................................................................................... 309 2.4.6 Heavy Oil Hydrotreating ...................................................................................................................... 311 2.4.6.1 Process .................................................................................................................................... 311 2.4.6.1.1 Patents ................................................................................................................... 311 2.4.6.1.2 Research ................................................................................................................ 313 2.4.6.2 Catalyst ................................................................................................................................... 313 2.4.6.2.1 Patents ................................................................................................................... 313 2.4.6.2.2 Research ................................................................................................................ 315 2.4.7 Resid Hydrotreating .............................................................................................................................. 316 2.4.7.1 Patents..................................................................................................................................... 316 2.4.7.2 Research.................................................................................................................................. 317 2.4.8 Renewable Feed Hydrotreating ............................................................................................................ 319 2.4.8.1 Process .................................................................................................................................... 319 2.4.8.1.1 Patents ................................................................................................................... 319 2.4.8.1.2 Research ................................................................................................................ 326 2.4.8.2 Catalyst ................................................................................................................................... 327 2.4.8.2.1 Patents ................................................................................................................... 327 2.4.8.2.2 Research ................................................................................................................ 327 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 328 CONSTRUCTION ................................................................................................................................................. 332 2.6.1 Recent Construction Activity ................................................................................................................. 332 2.6.2 Completed Construction Projects ......................................................................................................... 338 REFERENCES ..................................................................................................................................................... 377

3. Environmental Controls ............................................................................................................. 413 3.1

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ......................................................................................... 413 3.1.1 Introduction .......................................................................................................................................... 413 3.1.2 Market Conditions and Outlook............................................................................................................ 414 3.1.2.1 Refinery Emissions Considerations ........................................................................................ 414 3.1.2.1.1 Refinery Unit Emissions ........................................................................................ 414 3.1.2.1.2 Flaring ................................................................................................................... 416 3.1.2.1.3 GHG Emissions ..................................................................................................... 418 3.1.2.2 Compliance Costs ................................................................................................................... 419 3.1.2.3 Effect of Rare Earth Materials on FCC SOX Reduction Additives ......................................... 421 3.1.3 Technology Directions, Competition, and Future Prospects ................................................................ 423 3.1.3.1 General Pollution Control Technologies ................................................................................ 424 3.1.3.1.1 Flue Gas Scrubbing for SOX and PM Control ....................................................... 424 3.1.3.1.2 Electrostatic Precipitators for PM Control ............................................................ 425 3.1.3.1.3 Selective Catalytic Reduction for NOX Control .................................................... 426 3.1.3.1.4 Selective Non-catalytic Reduction for NOX Control ............................................. 426 3.1.3.1.5 Low and Ultra-low NOX Burners for NOX Control ............................................... 427 3.1.3.1.6 Flaring for VOCs Control ...................................................................................... 428 3.1.3.2 Unit Specific Pollution Control Technologies ........................................................................ 429

2Q 2012 vii Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

3.2

3.1.3.2.1 FCC ........................................................................................................................ 429 3.1.3.2.2 Sulfur Plant ............................................................................................................ 430 3.1.3.2.2.1 Acid Gas Removal .......................................................................... 431 3.1.3.2.2.2 Claus Process .................................................................................. 432 3.1.3.2.2.3 Tailgas Treating .............................................................................. 433 3.1.4 Conclusion ............................................................................................................................................. 434 STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 435 3.2.1 Introduction ........................................................................................................................................... 435 3.2.2 Commercial Processes and Hardware for General Pollution Control ................................................. 436 3.2.2.1 Flue Gas Scrubbing for SOX and PM Control......................................................................... 436 3.2.2.1.1 CANSOLV............................................................................................................. 436 3.2.2.1.2 DuPont Clean Technologies .................................................................................. 437 3.2.2.1.2.1 EDV ................................................................................................ 437 3.2.2.1.2.2 LABSORB ...................................................................................... 439 3.2.2.1.3 ExxonMobil ........................................................................................................... 440 3.2.2.1.4 Fischer-Klosterman ................................................................................................ 442 3.2.2.1.5 Haldor Topsøe........................................................................................................ 442 3.2.2.1.6 MECS..................................................................................................................... 444 3.2.2.1.7 Marsulex Environmental Technologies ................................................................. 446 3.2.2.1.7.1 Wet Flue Gas Scrubbing ................................................................. 446 3.2.2.1.7.2 Regenerable Scrubbing ................................................................... 447 3.2.2.1.8 Met-Pro .................................................................................................................. 448 3.2.2.1.9 Pollution Systems................................................................................................... 448 3.2.2.1.10 Tri-Mer................................................................................................................... 449 3.2.2.1.10.1 Cloud Chamber Scrubber ................................................................ 449 3.2.2.1.10.2 Tri-NOX ........................................................................................... 451 3.2.2.2 Electrostatic Precipitators for PM Control .............................................................................. 451 3.2.2.2.1 Buell ....................................................................................................................... 454 3.2.2.2.2 CoorsTek ................................................................................................................ 455 3.2.2.2.3 Hamon Research-Cottrell ....................................................................................... 455 3.2.2.2.4 Marsulex Environmental Technologies ................................................................. 455 3.2.2.2.5 Nestec..................................................................................................................... 455 3.2.2.2.6 PPC ........................................................................................................................ 455 3.2.2.3 Selective Catalytic Reduction for NOX Control ...................................................................... 455 3.2.2.3.1 BASF ..................................................................................................................... 456 3.2.2.3.2 Clariant................................................................................................................... 457 3.2.2.3.3 Cormetech .............................................................................................................. 457 3.2.2.3.4 Haldor Topsøe........................................................................................................ 458 3.2.2.3.5 Johnson Matthey .................................................................................................... 461 3.2.2.3.6 Mitsubishi Power Systems ..................................................................................... 461 3.2.2.4 Selective Non-catalytic Reduction for NOX Control............................................................... 462 3.2.2.4.1 ExxonMobil ........................................................................................................... 463 3.2.2.5 Low and Ultra-low NOX Burners for NOX Control ................................................................ 463 3.2.2.5.1 Alzeta ..................................................................................................................... 464 3.2.2.5.2 Callidus .................................................................................................................. 464 3.2.2.5.2.1 Low NOX......................................................................................... 464 3.2.2.5.2.2 Ultra-low NOX ................................................................................ 465 3.2.2.5.2.3 CUBL .............................................................................................. 465 3.2.2.5.3 John Zink ............................................................................................................... 466 3.2.2.5.4 NAO ....................................................................................................................... 466

2Q 2012 viii Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS 3.2.2.6 Clean Burn Flaring for VOCs Control.................................................................................... 467 3.2.2.6.1 Baker Hughes ........................................................................................................ 467 3.2.2.6.2 John Zink ............................................................................................................... 468 3.2.2.6.2.1 Steam-assisted Flares ...................................................................... 468 3.2.2.6.2.2 Air-assisted Flares .......................................................................... 468 3.2.2.6.2.3 Enclosed Flares ............................................................................... 469 3.2.2.6.3 NAO ...................................................................................................................... 470 3.2.2.7 Other Commercial Processes and Hardware........................................................................... 471 3.2.2.7.1 DuPont Clean Technologies .................................................................................. 471 3.2.2.7.2 Eco Power Solutions.............................................................................................. 471 3.2.2.8 Summary of Commercially Available Environmental Control Technologies ........................ 472 3.2.3 Unit Specific Pollution Control Technology ......................................................................................... 479 3.2.3.1 FCC......................................................................................................................................... 479 3.2.3.1.1 FCC Hardware ....................................................................................................... 479 3.2.3.1.1.1 Feed Injection Technology ............................................................. 479 3.2.3.1.1.1.1 ExxonMobil/KBR .................................................... 479 3.2.3.1.1.1.2 Lummus Technology ............................................... 480 3.2.3.1.1.2 Third and Fourth Stage Separators ................................................. 481 3.2.3.1.1.2.1 KBR ......................................................................... 481 3.2.3.1.1.2.2 Shell ......................................................................... 481 3.2.3.1.1.2.3 UOP ......................................................................... 482 3.2.3.1.1.3 Low-NOX Regenerators .................................................................. 483 3.2.3.1.1.3.1 KBR ......................................................................... 483 3.2.3.1.1.3.2 Praxair/Shell ............................................................ 484 3.2.3.1.1.3.3 UOP ......................................................................... 486 3.2.3.1.1.4 Other FCC Hardware ...................................................................... 487 3.2.3.1.1.4.1 Fischer-Klosterman .................................................. 487 3.2.3.1.1.4.2 UOP ......................................................................... 487 3.2.3.1.1.4.2.1 RxCat ............................................. 487 3.2.3.1.1.4.2.2 Emergency Interlock System ......... 488 3.2.3.1.1.5 Summary of FCC Hardware ........................................................... 489 3.2.3.1.2 Commercial Catalysts and Additives ..................................................................... 491 3.2.3.1.2.1 SOX Reduction Additives ............................................................... 491 3.2.3.1.2.1.1 Albemarle ................................................................ 491 3.2.3.1.2.1.2 Baker Petrolite ......................................................... 492 3.2.3.1.2.1.3 BASF ....................................................................... 492 3.2.3.1.2.1.4 Grace Davison ......................................................... 493 3.2.3.1.2.1.5 INTERCAT.............................................................. 494 3.2.3.1.2.1.6 JGC Catalysts and Chemicals .................................. 496 3.2.3.1.2.2 CO Combustion Promoters ............................................................. 496 3.2.3.1.2.2.1 Albemarle ................................................................ 496 3.2.3.1.2.2.2 Ambur Chemical Co. ............................................... 497 3.2.3.1.2.2.3 BASF ....................................................................... 497 3.2.3.1.2.2.4 Grace Davison ......................................................... 498 3.2.3.1.2.2.5 Inst. Mexicano del Petróleo ..................................... 499 3.2.3.1.2.2.6 INTERCAT.............................................................. 499 3.2.3.1.2.2.7 JGC Catalysts and Chemicals .................................. 500 3.2.3.1.2.3 Microfine Reduction Catalyst Technology ..................................... 500 3.2.3.1.2.3.1 Albemarle ................................................................ 500 3.2.3.1.2.3.2 BASF ....................................................................... 501 3.2.3.1.2.4Summary of Commercially Available Catalyst and Additive Technologies .............................................................................................................................. 502

2Q 2012 ix Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

3.3

3.4

3.2.3.2 Sulfur Plant ............................................................................................................................. 503 3.2.3.2.1 Summary of Commercially Available Sulfur Plant Technologies ......................... 505 3.2.3.2.2 Summary of Commercially Available Sulfur Plant Catalysts ................................ 515 3.2.4 Advanced Process Control/Process Models and Simulation ................................................................ 516 3.2.4.1 ABB ........................................................................................................................................ 516 3.2.4.2 Computational Particle Fluid Dynamics ................................................................................. 517 PLANT OPERATIONS AND PRACTICES................................................................................................................. 517 3.3.1 Minimizing Flaring During Unit Startup .............................................................................................. 517 3.3.2 Treating and Recovering VOCs ............................................................................................................ 518 3.3.3 Upgrading to Low or Ultra-low NOX Burners....................................................................................... 519 3.3.4 Calculating Emissions from Furnace and Heater Stacks ...................................................................... 520 3.3.5 Unit Specific Environmental Considerations ........................................................................................ 521 3.3.5.1 Coker ....................................................................................................................................... 521 3.3.5.1.1 Coke Drum Emission Reduction............................................................................ 521 3.3.5.1.2 CO2 Emissions Considerations .............................................................................. 521 3.3.5.1.3 Reduce Flaring from Closed Blowdown System ................................................... 522 3.3.5.1.4 Minimizing Coke Particulate Emissions ................................................................ 522 3.3.5.2 FCC ......................................................................................................................................... 523 3.3.5.2.1 FCC Feed Pretreatment .......................................................................................... 523 3.3.5.2.2 Use of Electrostatic Precipitators to Reduce FCC Emissions ................................ 524 3.3.5.2.3 Proper Two-stage Cyclone System Design ............................................................ 526 3.3.5.2.4 Effect of FCC Operating Variables on SOX Emissions ......................................... 526 3.3.5.2.5 Flue Gas Scrubbers to Reduce FCC SOX Emissions ............................................. 527 3.3.5.2.6 Effect of Regenerator Operations on NOX Emissions ........................................... 529 3.3.5.2.7 Effect of O2 Availability and Discharge Design on Regenerator NOX Emissions . 530 3.3.5.2.8 Utilizing NOX Reduction Additives ....................................................................... 531 3.3.5.2.9 Lowering CO Emissions During FCCU Startup .................................................... 532 3.3.5.2.10 Options to Reduce Particulate Matter Emissions from Regenerators .................... 532 3.3.5.2.11 Preventing Clogging of FCC Flue Gas Equipment ................................................ 534 3.3.5.2.12 Measuring Sulfur Content in FCC Flue Gas .......................................................... 535 3.3.5.3 Sulfur Plant ............................................................................................................................. 536 3.3.5.3.1 Acid Gas Removal ................................................................................................. 537 3.3.5.3.1.1 Amine Solvent Replacement ........................................................... 537 3.3.5.3.1.2 Optimizing an Amine Unit .............................................................. 538 3.3.5.3.1.3 Amine System Operating Issues ..................................................... 540 3.3.5.3.1.3.1 Wet Acid Gas Corrosion .......................................... 540 3.3.5.3.1.3.2 Amine Solution Corrosion ....................................... 540 3.3.5.3.1.3.3 Foaming.................................................................... 542 3.3.5.3.1.3.4 Amine Losses ........................................................... 542 3.3.5.3.1.3.5 Carbon Filters in Amine Systems ............................. 543 3.3.5.3.1.4 Safe Acid Gas Handling .................................................................. 544 3.3.5.3.1.5 Fuel Gas Sweetening in a Hydrocracker Fractionation Section ...... 545 3.3.5.3.2 Claus Process ......................................................................................................... 546 3.3.5.3.2.1 Increasing Sulfur Recovery Capacity.............................................. 546 3.3.5.3.2.2 The Effects of Extreme Turndowns ................................................ 548 3.3.5.3.2.3 Benefits and Drawbacks of Oxygen Enrichment ............................ 548 3.3.5.3.2.4 Claus Unit Shutdowns ..................................................................... 550 3.3.5.3.2.5 Claus Catalyst Life and Reuse ........................................................ 550 3.3.5.3.2.6 Analyzing Sulfur Content in Claus Tailgas..................................... 551 3.3.5.3.3 Tailgas Treating ..................................................................................................... 552 3.3.5.3.3.1 Experience with Designing a TGTU ............................................... 552 3.3.5.3.3.2 Proper TGT Catalyst Selection ....................................................... 554 REFINING R&D ALERT! ..................................................................................................................................... 554

2Q 2012 x Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

3.5

3.4.1 Introduction .......................................................................................................................................... 554 3.4.2 General Pollution Control Technologies .............................................................................................. 557 3.4.2.1 Flue Gas Scrubbing for SOX and PM Control ........................................................................ 557 3.4.2.1.1 Patents ................................................................................................................... 557 3.4.2.1.2 Research ................................................................................................................ 563 3.4.2.2 Selective Catalytic Reduction for NOX Control ..................................................................... 564 3.4.2.2.1 Process ................................................................................................................... 564 3.4.2.2.1.1 Patents............................................................................................. 564 3.4.2.2.1.2 Research.......................................................................................... 565 3.4.2.2.2 Catalyst .................................................................................................................. 565 3.4.2.2.2.1 Patents............................................................................................. 565 3.4.2.2.2.2 Research.......................................................................................... 570 3.4.2.3 Selective Non-catalytic Reduction for NOX Control .............................................................. 571 3.4.2.3.1 Patents ................................................................................................................... 571 3.4.2.3.2 Research ................................................................................................................ 573 3.4.2.4 Flaring for VOCs Control ....................................................................................................... 573 3.4.3 Unit Specific Control Technologies ...................................................................................................... 575 3.4.3.1 FCC......................................................................................................................................... 575 3.4.3.1.1 Hardware Improvements ....................................................................................... 575 3.4.3.1.1.1 CO Boiler ........................................................................................ 575 3.4.3.1.1.2 Third Stage Separator ..................................................................... 575 3.4.3.1.1.3 Catalyst Regeneration ..................................................................... 576 3.4.3.1.1.3.1 Patents ...................................................................... 576 3.4.3.1.1.3.2 Research ................................................................... 578 3.4.3.1.2 Catalyst and Additive Improvements .................................................................... 578 3.4.3.1.2.1 Attrition Resistant Catalysts ........................................................... 578 3.4.3.1.2.2 SOX Reduction Additives ............................................................... 579 3.4.3.1.2.2.1 Patents ...................................................................... 579 3.4.3.1.2.2.2 Research ................................................................... 581 3.4.3.1.2.3 NOX Reduction Additives ............................................................... 582 3.4.3.1.2.4 CO Combustion Promoters ............................................................. 583 3.4.3.1.2.4.1 Patents ...................................................................... 583 3.4.3.1.2.4.2 Research ................................................................... 585 3.4.3.1.2.5 Multipurpose Additives .................................................................. 585 3.4.3.2 Sulfur Plant ............................................................................................................................. 586 REFERENCES ..................................................................................................................................................... 590

4. Latest Refining Technology Developments & Licensing......................................................... 605 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

HYDROCRACKING ............................................................................................................................................. 605 COKING ............................................................................................................................................................. 606 VISBREAKING .................................................................................................................................................... 606 SOLVENT DEASPHALTING ................................................................................................................................. 606 HEAVY OIL, EXTRA-HEAVY OIL, AND BITUMEN UPGRADING ........................................................................... 607 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 608 COGENERATION AND INTEGRATED GASIFICATION COMBINED CYCLE .............................................................. 609 SULFUR PLANT .................................................................................................................................................. 610 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................ 610 CATALYST AND CARRIER SUPPORT DEVELOPMENTS ........................................................................................ 612 GAS-TO-LIQUID ................................................................................................................................................. 613 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) ............................................................................. 613 REFERENCES ..................................................................................................................................................... 614