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

Third Quarter 2016

Hydrotreating and Gas Processing

Plus

Latest Refining Technology Developments & Licensing

3Q 2016

Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

3Q 2016 i


3Q 2016 Review Hydrotreating and Gas Processing

1. INTRODUCTION ...................................................................................................................................................... 1

2. HYDROTREATING ................................................................................................................................................... 5

2.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .............................................................................................................. 5 2.1.1 Introduction.................................................................................................................................................. 5 2.1.2 Market Conditions and Outlook ................................................................................................................... 5

2.1.2.1 Global Transportation Fuels Specifications .................................................................................................... 5 2.1.2.1.1 Motor Gasoline ........................................................................................................................... 6 2.1.2.1.2 Middle Distillates ........................................................................................................................ 8 2.1.2.1.3 Bunker Fuel ................................................................................................................................. 9

2.1.2.2 Refined Products Demand ............................................................................................................................ 10 2.1.2.2.1 Gasoline vs. Diesel .................................................................................................................... 10

2.1.2.2.1.1 Diesel Demand in Decline ................................................................................. 12 2.1.2.2.1.2 But Growth Opportunities Still Exist ................................................................. 14

2.1.2.2.2 Renewable and Bio‐based Diesel .............................................................................................. 16 2.1.2.2.3 Renewable and Bio‐based Jet Fuel ........................................................................................... 18

2.1.2.3 Shifting Crude Slate ...................................................................................................................................... 20 2.1.2.3.1 Opportunity Crudes .................................................................................................................. 20 2.1.2.3.2 Tight Oil .................................................................................................................................... 22

2.1.2.4 Hydrogen Demand ....................................................................................................................................... 23 2.1.2.5 Hydrotreating Capacity Expansion ............................................................................................................... 24 2.1.2.6 Construction Projects and Unit Revamps ..................................................................................................... 26 2.1.2.7 Hydrotreating Catalysts Market ................................................................................................................... 26

2.1.3 Technology Competition, Latest Trends, Research Developments, and Future Prospects......................... 27 2.1.3.1 Conventional Hydrotreating ......................................................................................................................... 28

2.1.3.1.1 Diesel Hydrotreating ................................................................................................................. 29 2.1.3.1.2 Gasoline Hydrotreating ............................................................................................................. 33 2.1.3.1.3 Major Technology Offerings ..................................................................................................... 35 2.1.3.1.4 Reactor Internals ...................................................................................................................... 37 2.1.3.1.5 H2 Consumption ........................................................................................................................ 38 2.1.3.1.6 Advanced Process Control ........................................................................................................ 38 2.1.3.1.7 Process Integration ................................................................................................................... 39

2.1.3.2 Heavy Oil/Resid Hydrotreating ..................................................................................................................... 40 2.1.3.3 Renewable Feed Hydrotreating .................................................................................................................... 42 2.1.3.4 Latest R&D Trends ........................................................................................................................................ 44

2.1.4 Conclusion .................................................................................................................................................. 45 2.2 STATE‐OF‐THE‐ART TECHNOLOGY ................................................................................................................................... 47

2.2.1 Introduction................................................................................................................................................ 47 2.2.2 Commercial Catalysts and Guard Materials .............................................................................................. 48

2.2.2.1 Advanced Refining Technologies .................................................................................................................. 49 2.2.2.1.1 SmART....................................................................................................................................... 50 2.2.2.1.2 ApART ....................................................................................................................................... 55 2.2.2.1.3 StART ........................................................................................................................................ 57

2.2.2.2 Albemarle ..................................................................................................................................................... 58 2.2.2.2.1 STARS Series ............................................................................................................................. 59 2.2.2.2.2 NEBULA Series .......................................................................................................................... 68 2.2.2.2.3 Combined Implementation ....................................................................................................... 71 2.2.2.2.4 KF 901, KF 902, KF 905, KF 859 ................................................................................................. 73 2.2.2.2.5 KF 200 ....................................................................................................................................... 73 2.2.2.2.6 Guard Catalysts ......................................................................................................................... 74

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2.2.2.3 Axens ............................................................................................................................................................ 75 2.2.2.3.1 Impulse ..................................................................................................................................... 75 2.2.2.3.2 HR 400 Series............................................................................................................................ 77 2.2.2.3.3 HR 500 Series............................................................................................................................ 77 2.2.2.3.4 HR 600 Series............................................................................................................................ 79 2.2.2.3.5 HR 900 Series............................................................................................................................ 80 2.2.2.3.6 AX 740 Hydrogenation Catalysts .............................................................................................. 80 2.2.2.3.7 ACT Grading Materials.............................................................................................................. 81

2.2.2.4 BASF ............................................................................................................................................................. 82 2.2.2.5 Chevron Lummus Global .............................................................................................................................. 82 2.2.2.6 Clariant ......................................................................................................................................................... 84 2.2.2.7 Cosmo Oil ..................................................................................................................................................... 85 2.2.2.8 Criterion Catalysts & Technologies .............................................................................................................. 85

2.2.2.8.1 CENTINEL .................................................................................................................................. 86 2.2.2.8.2 CENTINEL GOLD ........................................................................................................................ 88 2.2.2.8.3 ASCENT ..................................................................................................................................... 90 2.2.2.8.4 CENTERA ................................................................................................................................... 97 2.2.2.8.5 SDD‐800/SDD‐821 .................................................................................................................. 105 2.2.2.8.6 Selective Hydrogenation Catalysts ......................................................................................... 108 2.2.2.8.7 Guard Catalysts ...................................................................................................................... 108

2.2.2.9 Crystaphase Products ................................................................................................................................. 109 2.2.2.10 ExxonMobil ................................................................................................................................................ 111

2.2.2.10.1 RT‐225 .................................................................................................................................... 111 2.2.2.10.2 RT‐235 .................................................................................................................................... 111 2.2.2.10.3 OCTGAIN Catalysts ................................................................................................................. 111

2.2.2.11 Haldor Topsøe ............................................................................................................................................ 112 2.2.2.11.1 Coker Naphtha Hydrotreating ................................................................................................ 115 2.2.2.11.2 Naphtha and Kerosene Production ........................................................................................ 116 2.2.2.11.3 FCC Feed Pretreat ................................................................................................................... 117 2.2.2.11.4 ULSD Production .................................................................................................................... 118 2.2.2.11.5 FCC Gasoline Posttreat ........................................................................................................... 121 2.2.2.11.6 Reduction of Diesel Density and Aromatics ........................................................................... 122 2.2.2.11.7 Hydrocracker Pretreating ....................................................................................................... 123 2.2.2.11.8 Graded Bed Products for Pressure Drop Control ................................................................... 124

2.2.2.12 JGC Catalysts & Chemicals Industries ......................................................................................................... 127 2.2.2.13 Johnson Matthey Catalysts ........................................................................................................................ 128 2.2.2.14 Nippon Oil .................................................................................................................................................. 128 2.2.2.15 Sinopec ....................................................................................................................................................... 128 2.2.2.16 Saint Gobain NorPro .................................................................................................................................. 130 2.2.2.17 TRICAT ........................................................................................................................................................ 130 2.2.2.18 UOP ............................................................................................................................................................ 131 2.2.2.19 Summary of Commercially Available Hydrotreating Catalysts ................................................................... 134

2.2.3 Auxiliary Catalyst Technology ................................................................................................................... 139 2.2.3.1 Advanced Refining Technologies ............................................................................................................... 139 2.2.3.2 Albemarle ................................................................................................................................................... 140

2.2.3.2.1 EasyActive .............................................................................................................................. 140 2.2.3.2.2 REACT ..................................................................................................................................... 140 2.2.3.2.3 STAX ....................................................................................................................................... 141

2.2.3.3 Axens .......................................................................................................................................................... 147 2.2.3.3.1 Catapac ................................................................................................................................... 147 2.2.3.3.2 Orchestra ................................................................................................................................ 147

2.2.3.4 Criterion Catalysts & Technologies ............................................................................................................ 148 2.2.3.5 Eurecat ....................................................................................................................................................... 148

2.2.3.5.1 Sulficat .................................................................................................................................... 149 2.2.3.5.2 Totsucat .................................................................................................................................. 149

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2.2.3.6 Haldor Topsøe ............................................................................................................................................ 152 2.2.3.7 HPA ............................................................................................................................................................. 152 2.2.3.8 hte .............................................................................................................................................................. 152 2.2.3.9 Orient Catalyst/Advanced Refining Technologies ...................................................................................... 153 2.2.3.10 TRICAT Inc. .................................................................................................................................................. 153

2.2.3.10.1 TRICAT Regeneration Process ................................................................................................. 153 2.2.3.10.2 XpresS ..................................................................................................................................... 154

2.2.3.11 Velocys ....................................................................................................................................................... 154 2.2.4 Commercial Process Technology .............................................................................................................. 154

2.2.4.1 Albemarle ................................................................................................................................................... 155 2.2.4.1.1 UD‐HDS ................................................................................................................................... 155 2.2.4.1.2 HDAr ....................................................................................................................................... 156 2.2.4.1.3 Cold Flow Improvement ......................................................................................................... 157 2.2.4.1.4 PLEX Reactor Internals ............................................................................................................ 158

2.2.4.2 Axens .......................................................................................................................................................... 158 2.2.4.2.1 Prime‐G+ ................................................................................................................................. 159 2.2.4.2.2 Prime‐D ................................................................................................................................... 162 2.2.4.2.3 Benzene Saturation ................................................................................................................ 164 2.2.4.2.4 Coker Naphtha Hydrotreating ................................................................................................ 166 2.2.4.2.5 EquiFlow Reactor Internals ..................................................................................................... 166

2.2.4.3 Chevron Lummus Global ............................................................................................................................ 167 2.2.4.3.1 ISOTREATING .......................................................................................................................... 167 2.2.4.3.2 Reactor Internals .................................................................................................................... 169

2.2.4.4 DuPont Clean Technologies ........................................................................................................................ 170 2.2.4.5 ExxonMobil Research & Engineering/KBR .................................................................................................. 172

2.2.4.5.1 GO‐Fining ................................................................................................................................ 172 2.2.4.5.2 HYDROFINING ......................................................................................................................... 173 2.2.4.5.3 SCANfining .............................................................................................................................. 173 2.2.4.5.4 EXOMER .................................................................................................................................. 176 2.2.4.5.5 OCTGAIN ................................................................................................................................. 176 2.2.4.5.6 MIDW ...................................................................................................................................... 177

2.2.4.6 Fushun Research Institute of Petroleum and Petrochemicals (Sinopec) .................................................... 180 2.2.4.6.1 FHI Diesel Hydro‐upgrading/Isodewaxing Process ................................................................. 180 2.2.4.6.2 FRS .......................................................................................................................................... 181 2.2.4.6.3 OTA ......................................................................................................................................... 182 2.2.4.6.4 OCT‐M ..................................................................................................................................... 182

2.2.4.7 GTC Technology .......................................................................................................................................... 183 2.2.4.8 Haldor Topsøe ............................................................................................................................................ 183

2.2.4.8.1 Conventional Hydrotreating ................................................................................................... 183 2.2.4.8.2 Coker Naphtha Hydrotreating ................................................................................................ 186 2.2.4.8.3 Diesel Dewaxing ...................................................................................................................... 187 2.2.4.8.4 Distillate HDS/HDA.................................................................................................................. 187 2.2.4.8.5 Aroshift ................................................................................................................................... 188 2.2.4.8.6 Reactor Internals .................................................................................................................... 190

2.2.4.9 Instituto Mexicano del Petróleo ................................................................................................................. 193 2.2.4.10 JGC Catalysts & Chemicals .......................................................................................................................... 193

2.2.4.10.1 JUST Refinery .......................................................................................................................... 193 2.2.4.10.2 Gas Oil Ultra Deep Desulfurization ......................................................................................... 194 2.2.4.10.3 GEFINERY ................................................................................................................................ 195 2.2.4.10.4 LCO Upgrading ........................................................................................................................ 195

2.2.4.11 Lummus Technology, a CB&I Company ...................................................................................................... 195 2.2.4.11.1 Conventional Hydrotreating ................................................................................................... 196 2.2.4.11.2 Benzene CDHydro ................................................................................................................... 196 2.2.4.11.3 LCN CDHydro/CDHDS and CDHDS+ ......................................................................................... 198

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2.2.4.12 MOL ............................................................................................................................................................ 202 2.2.4.13 Neste Jacobs .............................................................................................................................................. 203 2.2.4.14 Nippon Oil .................................................................................................................................................. 204 2.2.4.15 RIPP/Sinopec .............................................................................................................................................. 204 2.2.4.16 SK Corp. ...................................................................................................................................................... 206 2.2.4.17 Shell Global Solutions ................................................................................................................................. 207

2.2.4.17.1 Hydrotreating Process ............................................................................................................ 207 2.2.4.17.2 SMDH ..................................................................................................................................... 208 2.2.4.17.3 Pyrolysis Hydrogenation Unit ................................................................................................. 209 2.2.4.17.4 Reactor Internals .................................................................................................................... 209

2.2.4.18 Technip Stone & Webster/BASF................................................................................................................. 213 2.2.4.19 UOP ............................................................................................................................................................ 215

2.2.4.19.1 MQD Unionfining ................................................................................................................... 217 2.2.4.19.2 VGO Unionfining ..................................................................................................................... 219 2.2.4.19.3 ISAL ......................................................................................................................................... 220 2.2.4.19.4 SelectFining ............................................................................................................................ 222 2.2.4.19.5 BenSat .................................................................................................................................... 223 2.2.4.19.6 Unisar ..................................................................................................................................... 225 2.2.4.19.7 Unicracking/DW ..................................................................................................................... 226 2.2.4.19.8 Reactor Internals .................................................................................................................... 227

2.2.4.20 Summary of Hydrotreating Process Technologies ..................................................................................... 229 2.2.5 Commercially Available Advanced Control and Optimization Systems .................................................... 240

2.2.5.1 Aspen Technology ...................................................................................................................................... 240 2.2.5.2 Axens .......................................................................................................................................................... 241 2.2.5.3 KBC Advanced Technologies ...................................................................................................................... 244 2.2.5.4 Petrobras .................................................................................................................................................... 245 2.2.5.5 Repsol YPF .................................................................................................................................................. 245

2.2.6 Resid Hydrotreating .................................................................................................................................. 246 2.2.7 Coprocessing of Renewable Feed with Conventional Petroleum Feed ..................................................... 252

2.2.7.1 A*STAR ....................................................................................................................................................... 253 2.2.7.2 Advanced Refining Technologies ............................................................................................................... 254 2.2.7.3 Albemarle ................................................................................................................................................... 254 2.2.7.4 Axens .......................................................................................................................................................... 256 2.2.7.5 BP ............................................................................................................................................................... 256 2.2.7.6 Cepsa .......................................................................................................................................................... 257 2.2.7.7 ConocoPhillips (now Phillips 66) ................................................................................................................ 260 2.2.7.8 Grace .......................................................................................................................................................... 260 2.2.7.9 Haldor Topsøe ............................................................................................................................................ 260

2.2.7.9.1 Green Diesel Coprocessing Unit ............................................................................................. 261 2.2.7.9.2 Standalone Renewable Diesel Hydrotreater .......................................................................... 264

2.2.7.10 Neste Oil ..................................................................................................................................................... 264 2.2.7.11 Petrobras .................................................................................................................................................... 268 2.2.7.12 Repsol ........................................................................................................................................................ 270 2.2.7.13 Total‐Amyris ............................................................................................................................................... 270 2.2.7.14 UOP ............................................................................................................................................................ 271

2.2.7.14.1 EcoFining ................................................................................................................................ 271 2.2.7.14.2 Renewable Jet Fuel ................................................................................................................. 274

2.2.7.15 Summary of Renewable Feed Hydrotreating ............................................................................................. 276 2.3 PLANT OPERATIONS AND PRACTICES .............................................................................................................................. 278

2.3.1 General Hydrotreating Operations ........................................................................................................... 278 2.3.1.1 Feed Considerations, Process Configuration, and Hardware ..................................................................... 279

2.3.1.1.1 Feedstock Characterization .................................................................................................... 279 2.3.1.1.2 Pre‐hydrotreated Feeds ......................................................................................................... 280 2.3.1.1.3 Upgrading Tight Oil ................................................................................................................. 281 2.3.1.1.4 Feed Drum Blanketing Gas ..................................................................................................... 283 2.3.1.1.5 Reactor Configuration ............................................................................................................ 283

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2.3.1.1.6 Minimize Fouling of Reactor Internals .................................................................................... 285 2.3.1.1.7 Twisted Tube Exchanger Bundles for Preheat Service ............................................................ 286 2.3.1.1.8 Thermal Enhancement System to Improve Heat Recovery .................................................... 286 2.3.1.1.9 Improving Recycle Gas Compressor Operation ...................................................................... 287 2.3.1.1.10 Welded Supports on Reactor Walls ........................................................................................ 288

2.3.1.2 Catalyst Management ................................................................................................................................ 288 2.3.1.2.1 Measuring Hydrotreating Catalyst Activity ............................................................................. 289 2.3.1.2.2 Protecting HT Catalysts from Contamination ......................................................................... 290 2.3.1.2.3 Determining and Mitigating HDS Catalyst Deactivation ......................................................... 295 2.3.1.2.4 Minimizing HDS Activity Loss from Low Sulfur Feed ............................................................... 296 2.3.1.2.5 In situ Catalyst Sulfiding vs. Ex situ Presulfiding ...................................................................... 297 2.3.1.2.6 Comparison of Various Sulfiding Agents ................................................................................. 299 2.3.1.2.7 Determining HDM Range ........................................................................................................ 300 2.3.1.2.8 Using Regenerated Catalyst .................................................................................................... 301 2.3.1.2.9 Dry Dump vs. Wet Dump Catalyst Change‐out Procedures .................................................... 302 2.3.1.2.10 Catalyst Removal for Non‐free Flowing Catalysts ................................................................... 302 2.3.1.2.11 Transportation and Disposal of Contaminant‐laden Catalysts ............................................... 303 2.3.1.2.12 Catalyst Dense Loading ........................................................................................................... 303 2.3.1.2.13 Catalyst Short Loading ............................................................................................................ 305

2.3.1.3 Operating Conditions and Hydrogen Consumption.................................................................................... 306 2.3.1.3.1 Effect of Process Severity/Variables on Hydrotreater Performance....................................... 306 2.3.1.3.2 Control of Maximum Reactor Temperature ........................................................................... 307 2.3.1.3.3 Using High‐purity Hydrogen and/or Adjusting Hydrogen Partial Pressure ............................. 308 2.3.1.3.4 Optimizing the Hydrogen‐to‐Oil Ratio .................................................................................... 309 2.3.1.3.5 Carbon Oxide Contamination ................................................................................................. 310 2.3.1.3.6 Mitigating High Temperature Hydrogen Attack...................................................................... 310 2.3.1.3.7 Accurately Measuring Hydrogen Consumption in Hydrotreaters ........................................... 311 2.3.1.3.8 Membranes for H2 Recovery from Hydrotreaters .................................................................. 312

2.3.1.4 Operational Monitoring and Upset Detection ............................................................................................ 313 2.3.1.4.1 Process Analyzer Placement ................................................................................................... 313 2.3.1.4.2 Temperature Monitoring During Startup and Shutdown ....................................................... 313 2.3.1.4.3 Reactor Effluent Sampling ...................................................................................................... 314 2.3.1.4.4 Accurate Level Measurements in a Cold High Pressure Separator ......................................... 315 2.3.1.4.5 Maldistribution in Hydrotreaters ............................................................................................ 315 2.3.1.4.6 Reactor Pressure Drop Buildup: Causes and Remedies .......................................................... 317

2.3.1.4.6.1 Pressure Drop Issues Due to Catalyst ............................................................. 317 2.3.1.4.6.2 Pressure Drop Issues Due to Plugging/Fouling ............................................... 318

2.3.1.4.7 Detecting and Mitigating Leaks in Equipment ........................................................................ 323 2.3.1.4.8 Fouling in Feed/Effluent Exchangers ...................................................................................... 324 2.3.1.4.9 Ammonium Chloride Fouling in Effluent Exchangers and H2 Gas Compressors ..................... 326

2.3.1.5 Best Practices and Troubleshooting ........................................................................................................... 328 2.3.1.5.1 Reviewing and Updating Unit Operating Procedures ............................................................. 328 2.3.1.5.2 Criteria for Selecting Remote Manual and/or Auto Depressuring Equipment and Instrumentation ......................................................................................................................................... 328 2.3.1.5.3 Interruption of Operations (Emergency or Planned) and Recommended Actions ................. 330 2.3.1.5.4 Minimizing Exposure Risks during Reactor Shutdowns .......................................................... 331 2.3.1.5.5 Preventing Flaring during Unit Startup or Shutdown Procedures .......................................... 331 2.3.1.5.6 Irregularities in Sulfur Content ............................................................................................... 332

2.3.2 Distillate Hydrotreating ............................................................................................................................ 332 2.3.2.1 Diesel Quality Requirements ...................................................................................................................... 334

2.3.2.1.1 Cetane .................................................................................................................................... 334 2.3.2.1.2 ULSD Cold Flow Properties ..................................................................................................... 337 2.3.2.1.3 ULSD Haze Point ..................................................................................................................... 338 2.3.2.1.4 Minimizing Diesel Color Degradation ..................................................................................... 338 2.3.2.1.5 Logistics .................................................................................................................................. 340

2.3.2.2 Increasing Diesel Output ............................................................................................................................ 340 2.3.2.2.1 Maximizing Volume Swell of Distillate Feeds ......................................................................... 340

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2.3.2.2.2 Increasing Distillates Fed into a Hydrotreater ........................................................................ 341 2.3.2.3 Hardware Considerations........................................................................................................................... 343

2.3.2.3.1 Adjusting Hydrotreater Internals to Improve Diesel Production ............................................ 343 2.3.2.3.2 Limitations of Single Bed or Undersized ULSD Reactors......................................................... 344 2.3.2.3.3 Determining Sufficient Reserve Quench in ULSD Hydrotreaters ............................................ 344 2.3.2.3.4 Using Advanced‐phase Separation Techniques ...................................................................... 345 2.3.2.3.5 Fouling on Disposable Feed Filters ......................................................................................... 345 2.3.2.3.6 Designing and Operating a Diesel Salt Dryer .......................................................................... 345 2.3.2.3.7 Improving Energy Efficiency ................................................................................................... 346

2.3.2.4 Catalyst Management ................................................................................................................................ 347 2.3.2.5 Feed Considerations................................................................................................................................... 351

2.3.2.5.1 Options for Converting FCC LCO to ULSD ............................................................................... 351 2.3.2.5.2 Processing Distillate and Naphtha Blends in a Diesel Hydrotreater ....................................... 353 2.3.2.5.3 Coprocessing Renewable Feedstocks ..................................................................................... 354

2.3.2.6 Revamps for ULSD Production ................................................................................................................... 355 2.3.2.6.1 Case Study 1 ........................................................................................................................... 356 2.3.2.6.2 Case Study 2 ........................................................................................................................... 357 2.3.2.6.3 Case Study 3 ........................................................................................................................... 358 2.3.2.6.4 Case Study 4 ........................................................................................................................... 358 2.3.2.6.5 Case Study 5 ........................................................................................................................... 359 2.3.2.6.6 Case Study 6 ........................................................................................................................... 361 2.3.2.6.7 Case Study 7 ........................................................................................................................... 362

2.3.2.7 Ultra‐low Sulfur Kerosene Production ....................................................................................................... 363 2.3.2.8 Off‐color Products ...................................................................................................................................... 364

2.3.3 Naphtha Hydrotreating ............................................................................................................................ 365 2.3.3.1 Hydrotreating FCC Naphtha ....................................................................................................................... 365 2.3.3.2 Processing Coker and Visbreaker Naphtha ................................................................................................ 367 2.3.3.3 Processing Coker Naphtha for Hydrogen Production ................................................................................ 371 2.3.3.4 Measuring Silicon Content in Coker Naphtha ............................................................................................ 372 2.3.3.5 Minimizing Fouling to Increase Catalyst Run Length.................................................................................. 373 2.3.3.6 Separating Stripping and Splitting Applications ......................................................................................... 374

2.3.4 Gas Oil Hydrotreating ............................................................................................................................... 374 2.3.4.1 Modifying a FCC Feed Pretreater to Increase Yield of Diesel ..................................................................... 375 2.3.4.2 Impact of Feed Hydrotreatment on FCC Product Aromatics Content ........................................................ 377 2.3.4.3 Impact of Tier III Gasoline Standards on FCC Feed Pretreaters ................................................................. 378 2.3.4.4 FCC Feed Pretreatment vs. FCC Gasoline HDS ........................................................................................... 379 2.3.4.5 Reducing the Endpoint in Gas Oil Hydrotreaters ....................................................................................... 384 2.3.4.6 Hydrotreating Heavy Coker Gas Oil ............................................................................................................ 385 2.3.4.7 Predicting the Yield Pattern When Coprocessing LCGO in a VGO FCCU .................................................... 388 2.3.4.8 Improved Operation of a VGO Hydrotreater ............................................................................................. 388 2.3.4.9 Operating a VGO Hydrotreater in Blocked Mode ...................................................................................... 389

2.4 REFINING R&D ALERT! ............................................................................................................................................... 389 2.4.1 Introduction .............................................................................................................................................. 389 2.4.2 General Hydrotreating .............................................................................................................................. 395

2.4.2.1 Process ....................................................................................................................................................... 395 2.4.2.1.1 Patents ................................................................................................................................... 395

2.4.2.1.1.1 Saturation of PNA Compounds ....................................................................... 395 2.4.2.1.1.2 Dissolution of Hydrogen to Enhance Mass Transfer ....................................... 395 2.4.2.1.1.3 Hydrotreating Feed Pretreatment .................................................................. 395 2.4.2.1.1.4 Catalyst Regeneration .................................................................................... 396 2.4.2.1.1.5 Reducing Capital and Operating Costs ............................................................ 397

2.4.2.1.2 Research ................................................................................................................................. 399 2.4.2.2 Catalyst Formulation, Preparation, and Presulfidation .............................................................................. 400

2.4.2.2.1 Patents ................................................................................................................................... 400 2.4.2.2.1.1 Modified Alumina and Silica‐Alumina Carrier Supports ................................. 400 2.4.2.2.1.2 Titanium and Zirconium Carrier Supports....................................................... 402

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2.4.2.2.1.3 Use of Acids and/or Amines during Formulation and Preparation ................. 403 2.4.2.2.1.4 Catalyst Presulfiding ........................................................................................ 404 2.4.2.2.1.5 Other ............................................................................................................... 405

2.4.2.2.2 Research ................................................................................................................................. 406 2.4.2.2.2.1 Modified Alumina Carrier Supports ................................................................ 406 2.4.2.2.2.2 Titanium and Zirconium Carrier Supports ....................................................... 407 2.4.2.2.2.3 NiP‐containing Catalysts ................................................................................. 407 2.4.2.2.2.4 Unsupported Catalysts .................................................................................... 409 2.4.2.2.2.5 Other ............................................................................................................... 409

2.4.3 Middle Distillate Hydrotreating (Including ULSD Production) .................................................................. 410 2.4.3.1 Process ....................................................................................................................................................... 410

2.4.3.1.1 Patents .................................................................................................................................... 410 2.4.3.1.1.1 Integration of Hydrotreating and Hydrocracking Processes ........................... 410 2.4.3.1.1.2 Integration of Hydrotreating and Mild Hydrocracking to Improve Cetane ..... 411 2.4.3.1.1.3 Integration of Hydrotreating and Oxidation Treatment ................................. 411 2.4.3.1.1.4 Integration of Hydrotreating and Dewaxing ................................................... 412 2.4.3.1.1.5 Multi‐stage Hydrotreating .............................................................................. 412 2.4.3.1.1.6 Other ............................................................................................................... 413

2.4.3.1.2 Research ................................................................................................................................. 414 2.4.3.2 Catalyst ....................................................................................................................................................... 415

2.4.3.2.1 Patents .................................................................................................................................... 415 2.4.3.2.1.1 Titania‐alumina Carrier Supports .................................................................... 415 2.4.3.2.1.2 Other Metal Oxide Supports ........................................................................... 416 2.4.3.2.1.3 High Surface‐area Alumina Carrier Supports .................................................. 417 2.4.3.2.1.4 Zeolites ............................................................................................................ 418 2.4.3.2.1.5 Other ............................................................................................................... 419

2.4.3.2.2 Research ................................................................................................................................. 419 2.4.3.2.2.1 Modified Alumina Carrier Supports ................................................................ 419 2.4.3.2.2.2 Zeolite Carrier Supports .................................................................................. 420

2.4.4 FCCU Pretreatment .................................................................................................................................. 420 2.4.5 FCCU Posttreatment ................................................................................................................................. 422 2.4.6 Naphtha Hydrotreating ............................................................................................................................ 423

2.4.6.1 Process ....................................................................................................................................................... 423 2.4.6.2 Catalyst ....................................................................................................................................................... 425

2.4.6.2.1 Patents .................................................................................................................................... 425 2.4.6.2.2 Research ................................................................................................................................. 425

2.4.7 Heavy Oil and Resid Hydrotreating .......................................................................................................... 426 2.4.7.1 Process ....................................................................................................................................................... 426

2.4.7.1.1 Integrated Processes .............................................................................................................. 426 2.4.7.1.2 Heavy FCC Oil for Bunker Fuel Production .............................................................................. 428 2.4.7.1.3 Other ...................................................................................................................................... 428

2.4.7.2 Catalyst ....................................................................................................................................................... 429 2.4.7.2.1 Patents .................................................................................................................................... 429

2.4.7.2.1.1 HDM Catalysts ................................................................................................. 429 2.4.7.2.1.2 HDS and/or HDN Catalysts .............................................................................. 430 2.4.7.2.1.3 Other ............................................................................................................... 431

2.4.7.2.2 Research ................................................................................................................................. 433 2.4.7.2.2.1 Catalyst Deactivation ...................................................................................... 433 2.4.7.2.2.2 Other ............................................................................................................... 434

2.4.8 Hydrotreating for Aromatics and Light Olefins Production...................................................................... 435 2.4.9 Renewable Feed Hydrotreating ............................................................................................................... 438

2.4.9.1 Process ....................................................................................................................................................... 438 2.4.9.1.1 Patents .................................................................................................................................... 438

2.4.9.1.1.1 Coprocessing Renewable and Conventional Feeds ......................................... 438 2.4.9.1.1.2 Other ............................................................................................................... 439

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2.4.9.1.2 Research ................................................................................................................................. 439 2.4.9.1.2.1 Coprocessing Renewable and Conventional Feeds ........................................ 439 2.4.9.1.2.2 Integrated Processes ...................................................................................... 440 2.4.9.1.2.3 Other .............................................................................................................. 441

2.4.9.2 Catalyst ...................................................................................................................................................... 442 2.4.9.2.1 Patents ................................................................................................................................... 442

2.4.9.2.1.1 Metal Oxide Carrier Supports ......................................................................... 442 2.4.9.2.1.2 Other .............................................................................................................. 443

2.4.9.2.2 Research ................................................................................................................................. 443 2.4.9.2.2.1 Zeolite Supports .............................................................................................. 443 2.4.9.2.2.2 Other .............................................................................................................. 445

2.5 WORLDWIDE INSTALLED CAPACITY ................................................................................................................................ 446 2.6 CONSTRUCTION ......................................................................................................................................................... 449

2.6.1 Recent Construction Activity ..................................................................................................................... 449 2.6.2 Completed Construction Projects ............................................................................................................. 459

2.7 REFERENCES .............................................................................................................................................................. 502

3. GAS PROCESSING ................................................................................................................................................ 547

3.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................................... 547 3.1.1 Introduction .............................................................................................................................................. 547 3.1.2 Market Conditions and Outlook ............................................................................................................... 549

3.1.2.1 Liquefied Petroleum Gas ............................................................................................................................ 549 3.1.2.2 Ethylene ..................................................................................................................................................... 549 3.1.2.3 Propylene ................................................................................................................................................... 550 3.1.2.4 Hydrogen.................................................................................................................................................... 551

3.1.3 Technology Competition, Directions, and Future Prospects ..................................................................... 552 3.1.3.1 LPG and Olefins .......................................................................................................................................... 553 3.1.3.2 Hydrogen.................................................................................................................................................... 554 3.1.3.3 Research and Development ....................................................................................................................... 555

3.1.4 Conclusion ................................................................................................................................................ 556 3.2 STATE‐OF‐THE‐ART TECHNOLOGY ................................................................................................................................. 556

3.2.1 Introduction .............................................................................................................................................. 556 3.2.2 Gas Plant Configuration ........................................................................................................................... 559

3.2.2.1 Saturated Gas Plant.................................................................................................................................... 559 3.2.2.2 Unsaturated Gas Plant ............................................................................................................................... 560

3.2.3 Gas Separation Mechanisms .................................................................................................................... 561 3.2.4 Commercially Available Process Technology ............................................................................................ 564

3.2.4.1 Advanced Extraction Technologies ............................................................................................................ 564 3.2.4.1.1 Light Olefin Recovery ............................................................................................................. 564 3.2.4.1.2 LPG Recovery from Saturated Offgas ..................................................................................... 565 3.2.4.1.3 Hydrogen Recovery Unit ........................................................................................................ 566

3.2.4.2 Air Liquide .................................................................................................................................................. 567 3.2.4.3 Air Products and Chemicals ........................................................................................................................ 568

3.2.4.3.1 Cryogenic System ................................................................................................................... 568 3.2.4.3.2 Membrane Technology .......................................................................................................... 569

3.2.4.4 BASF ........................................................................................................................................................... 569 3.2.4.5 Black & Veatch ........................................................................................................................................... 570 3.2.4.6 CB&I ........................................................................................................................................................... 571 3.2.4.7 Compact Membrane Systems .................................................................................................................... 572 3.2.4.8 Costain Oil, Gas & Process ......................................................................................................................... 573

3.2.4.8.1 Light Olefins Recovery ............................................................................................................ 574 3.2.4.8.2 LPG Recovery .......................................................................................................................... 576

3.2.4.9 Eurofilm ...................................................................................................................................................... 578 3.2.4.9.1 LPG Recovery .......................................................................................................................... 578 3.2.4.9.2 Hydrogen Recovery ................................................................................................................ 579

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3.2.4.10 ExxonMobil/Xebec ..................................................................................................................................... 579 3.2.4.11 Fluor ........................................................................................................................................................... 580

3.2.4.11.1 CO2LDSep ................................................................................................................................ 580 3.2.4.12 Generon IGS‐Global .................................................................................................................................... 581

3.2.4.12.1 H2S Removal ........................................................................................................................... 581 3.2.4.12.2 Hydrogen Recovery ................................................................................................................ 582

3.2.4.12.2.1 HYDROSWING PSA .......................................................................................... 582 3.2.4.12.2.2 Membrane Technology ................................................................................... 583

3.2.4.13 Linde Engineering North America ............................................................................................................... 584 3.2.4.13.1 Light Olefins Recovery ............................................................................................................ 584

3.2.4.13.1.1 Cryo‐Plus ......................................................................................................... 584 3.2.4.13.1.2 Cryo‐Plus C2= ................................................................................................... 586

3.2.4.13.2 Hydrogen Recovery ................................................................................................................ 587 3.2.4.13.2.1 Options for Utilizing Hydrogen from Refinery Offgas (ROG) ........................... 587

3.2.4.14 Membrane Technology and Research. ....................................................................................................... 589 3.2.4.14.1 VaporSep‐H2 ........................................................................................................................... 589 3.2.4.14.2 VaporSep‐LPG ......................................................................................................................... 590

3.2.4.15 Praxair ........................................................................................................................................................ 591 3.2.4.16 ThyssenKrupp ............................................................................................................................................. 591 3.2.4.17 UOP ............................................................................................................................................................ 592

3.2.4.17.1 Propylene Recovery ................................................................................................................ 592 3.2.4.17.2 Polybed PSA ............................................................................................................................ 593 3.2.4.17.3 Membrane Separation ............................................................................................................ 593

3.2.4.18 Xebec Adsorption Inc. ................................................................................................................................ 594 3.2.4.19 Other Technologies .................................................................................................................................... 595

3.2.5 Summary of Commercially Available Gas Processing Technologies ........................................................ 595 3.3 PLANT OPERATIONS AND PRACTICES .............................................................................................................................. 599

3.3.1 General Refinery Offgas Treatment ......................................................................................................... 599 3.3.2 Holistic Approach to FCC Gas Plant Optimization .................................................................................... 600 3.3.3 Improving FCC Propylene Recovery and Purity ........................................................................................ 602

3.3.3.1 Propylene Splitter ....................................................................................................................................... 602 3.3.3.1.1 Economic Feasibility ............................................................................................................... 602 3.3.3.1.2 Optimization ........................................................................................................................... 604 3.3.3.1.3 Control of Propylene Splitters ................................................................................................ 605

3.3.3.1.3.1 Dynamic Simulation ........................................................................................ 605 3.3.3.1.3.2 Inferential Model ............................................................................................ 605

3.3.3.1.4 Exotherms Safety .................................................................................................................... 606 3.3.3.2 Improving FCC Gas Plant Operations to Increase Propylene Yield ............................................................. 607 3.3.3.3 Processes Used to Purify FCC Propylene .................................................................................................... 607 3.3.3.4 Control Issues for Propylene‐Propane Separators ..................................................................................... 609

3.3.4 Improving Hydrogen Recovery ................................................................................................................. 610 3.3.4.1 Feed Properties That Influence Hydrogen Recovery .................................................................................. 610 3.3.4.2 Hydrogen Recovery PSA Configurations ..................................................................................................... 611

3.3.4.2.1 Combined Feed of Refinery Offgas and Steam Reformer Gas to PSA Unit ............................. 611 3.3.4.2.2 Separate PSA Unit for ROG ..................................................................................................... 612 3.3.4.2.3 Direct ROG Feed to HGU ......................................................................................................... 612 3.3.4.2.4 PSA with TSA ........................................................................................................................... 612

3.3.4.3 Lowering PSA Hydrogen Purity to Boost Recovery ..................................................................................... 612 3.3.5 Capacity Limitations Due to Stripper Flooding ......................................................................................... 613

3.3.5.1 Process Configuration................................................................................................................................. 615 3.3.5.2 Operating Conditions ................................................................................................................................. 615 3.3.5.3 Internals ..................................................................................................................................................... 617 3.3.5.4 HP Receiver ................................................................................................................................................ 618 3.3.5.5 Water Draw ................................................................................................................................................ 618

3.3.6 Overcoming Hardware Limitations Through Revamp .............................................................................. 619 3.3.7 Controlling LPG Weathering in a Gas Plant ............................................................................................. 620

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3.3.8 Decreasing LPG Content in Fuel Gas (Dry Gas) ......................................................................................... 621 3.3.9 Optimizing Light Ends Recovery from Refinery Fuel Gas Streams ............................................................ 621

3.3.9.1 Chevron Salt Lake City Refinery ................................................................................................................. 621 3.3.9.2 Motiva Enterprises Refinery ....................................................................................................................... 622

3.3.10 Debottlenecking Debutanizer Feed .......................................................................................................... 624 3.3.11 Pressure Safety Valves for Light Hydrocarbon Separations...................................................................... 625 3.3.12 Vacuum Tower Air Leakage and Offgas Quality ....................................................................................... 626 3.3.13 Minimizing FCC Startup Flaring ................................................................................................................ 627 3.3.14 Conversion from Solvent CO2 Removal to PSA .......................................................................................... 628 3.3.15 PSA Unit Inspections ................................................................................................................................. 628

3.4 REFINING R&D ALERT! ............................................................................................................................................... 629 3.4.1 Introduction .............................................................................................................................................. 629 3.4.2 Absorption of Ethane/Ethylene and Other Dry Gases .............................................................................. 632

3.4.2.1 Patents ....................................................................................................................................................... 632 3.4.2.2 Research ..................................................................................................................................................... 635

3.4.3 Membrane ................................................................................................................................................ 637 3.4.4 Adsorption ................................................................................................................................................ 637

3.4.4.1 Hydrogen.................................................................................................................................................... 637 3.4.4.1.1 Patents ................................................................................................................................... 637 3.4.4.1.2 Research ................................................................................................................................. 638

3.4.4.2 Light Hydrocarbons and Hydrogen ............................................................................................................ 638 3.4.5 Hybrid Separation (Combination of Absorption, Membrane, and/or Adsorption) ................................... 640

3.4.5.1 Hydrogen.................................................................................................................................................... 640 3.4.5.2 C2 Hydrocarbons ........................................................................................................................................ 642 3.4.5.3 Light Hydrocarbons and Hydrogen ............................................................................................................ 643

3.4.6 Treatment ................................................................................................................................................. 646 3.4.6.1 Patents ....................................................................................................................................................... 646 3.4.6.1 Research ..................................................................................................................................................... 647

3.4.7 Paraffin/Olefin Separation ....................................................................................................................... 647 3.5 REFERENCES .............................................................................................................................................................. 651

4. LATEST REFINING TECHNOLOGY DEVELOPMENTS & LICENSING ........................................................................... 661

4.1 FLUID CATALYTIC CRACKING ......................................................................................................................................... 661 4.2 HYDROCRACKING ....................................................................................................................................................... 662 4.3 BENZENE REDUCTION AND REMOVAL ............................................................................................................................. 662 4.4 ALKYLATION .............................................................................................................................................................. 662 4.5 HEAVY OIL, EXTRA‐HEAVY OIL, AND BITUMEN UPGRADING ................................................................................................ 664 4.6 HYDROGEN PRODUCTION AND PURIFICATION .................................................................................................................. 664 4.7 SULFUR PLANT ........................................................................................................................................................... 664 4.8 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................................ 665 4.9 PROCESS CONTROLS AND SIMULATION ........................................................................................................................... 666 4.10 INDUSTRIAL INTERNET OF THINGS (IIOT) ......................................................................................................................... 668 4.11 XTL (BIOMASS‐, COAL‐, AND GAS‐TO‐LIQUID) ................................................................................................................ 669 4.12 METHANE‐TO‐CHEMICALS ........................................................................................................................................... 670 4.13 BIOFUELS PRODUCTION ............................................................................................................................................... 671 4.14 ENERGY MANAGEMENT .............................................................................................................................................. 673 4.15 CARBON CAPTURE AND SEQUESTRATION ........................................................................................................................ 674 4.16 SITE AIR POLLUTION AND WASTE DISCHARGE .................................................................................................................. 675 4.17 PLANT SAFETY ........................................................................................................................................................... 677 4.18 REFERENCES .............................................................................................................................................................. 678

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