Review2q16toce by Hydrocarbon Publishing Company

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

Second Quarter 2016 Hydrocracking, and Lube Oil Production Plus

Latest Refining Technology Developments & Licensing

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1Q 2016 Hydrocarbon Publishing Co./Copyright Protected

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

Second Quarter 2016 Hydrocracking, and Lube Oil Production Plus Latest Refining Technology Developments & Licensing

http://www.hydrocarbonpublishing.com

WORLDWIDE REFINERY PROCESSING REVIEW is published by Hydrocarbon Publishing Co. every quarter. Copyright 2007-2016. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or translated into any language or by any means—electronic, mechanical, photocopying, recording or otherwise—without prior written permission of Hydrocarbon Publishing Company. P.O. Box 815, Paoli, PA 19301-0815 (USA). Tel: (610) 408-0117, Fax: (610) 408-0118. E-mail: review@hydrocarbonpublishing.com

1Q, 2Q, 3Q, 4Q .. (the) first, second, third, and fourth quarters, respectively AAA ................... American Automobile Association (US) ANS .................... Alaskan North Slope crude API...................... American Petroleum Institute (US) ARA.................... Antwerp, Rotterdam, Amsterdam ASTM ................. American Society for Testing & Materials b or bbl................ barrel(s) B ......................... billion boe ...................... barrel(s) of oil equivalent CA ...................... California CAA.................... Clean Air Act (US) CARB ................. California Air Resources Board cf ......................... cubic foot, cubic feet cfr........................ cost and freight cif ........................ cost, insurance, and freight Concawe ............. Conservation of Clean Air and Water Europe CIS ...................... Commonwealth of Independent States CNG.................... compressed natural gas cst........................ centistoke d .......................... day DOE .................... Department of Energy EEC .................... European Economic Community EIA ....................... US Energy Information Administration EPA .................... US Environmental Protection Agency EPC(M) .............. engineering, procurement, and construction (management) EU15 ................... 15 original EU members EU25 ................... EU15 and the 10 new members admitted in May 2004 EUROPIA ........... European Petroleum Industry Association (Brussels) FCV .................... fuel cell vehicle fd......................... free delivered FEED .................. front-end engineering design fob....................... free on board gal ....................... gallon GTL .................... gas to liquid(s) h .......................... hour H1 or H2 ............. first or second half of the year ICE...................... Int'l Commodity Exchange (UK— formerly Int'l Petroleum Exchange) IEA ..................... Int'l Energy Agency (Paris-based)

IPAA ................... Independent Petr. Assoc. of America IPO...................... initial public offering j.v. ....................... joint venture LPG .................... liquefied petroleum gas K ......................... thousand kL........................ kiloliter lb ......................... pound(s) METI .................. Ministry of Economy, Trade and Industry (Japan) MM ..................... million MOU ................... memorandum of understanding mpg ..................... miles per gallon mt ........................ metric ton MW ..................... megawatt N.A. .................... not applicable or not available NAAQS .............. national ambient air quality standards NESCAUM ........ Northeast States for Coordinated Air Use Management NG ...................... natural gas NGL .................... natural gas liquid NPRA ................. National Petrochemical & Refiners Association (US) NWE ................... Northwest Europe NYMEX ............. New York Mercantile Exchange (US) OECD ................. Organization for Economic Cooperation & Development OPEC .................. Organization of the Petroleum Exporting Countries OSHA ................. Occupational, Safety and Health Administration (US) PC ....................... petrochemical(s) PM ...................... particulate matter RBOB ................. RFG before oxygenate blending RFG .................... reformulated gasoline RMT ..................... refining, marketing, and transportation RVP .................... Reid vapor pressure SCAQMD ........... South Coast Air Quality Management District (California) VLCC ................. very large crude carrier WTI .................... West Texas Intermediate y .......................... year ¢ .......................... US cent(s) € .......................... EU euro(s) £ .......................... UK pound(s) $ .......................... US dollar(s) ¥ .......................... Japanese yen

Please note that other international currencies are abbreviated using International Standards Organization codes, which can be found at www.xe.com.

TABLE OF CONTENTS 2Q 2016 Review Hydrocracking and Lube Oil Production 1. INTRODUCTION ...................................................................................................................................................... 1 2. HYDROCRACKING ................................................................................................................................................... 5 2.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .............................................................................................................. 5 2.1.1 Introduction.................................................................................................................................................. 5 2.1.2 Market Conditions and Outlook ................................................................................................................... 6 2.1.2.1 Global Transportation Fuels Specifications .................................................................................................... 6 2.1.2.2 Global Refined Products Demand ................................................................................................................ 10 2.1.2.2.1 Diesel Demand in Decline in Parts of the World ....................................................................... 13 2.1.2.2.2 But Growth Opportunities Still Exist ......................................................................................... 15 2.1.2.3 Shifting Crude Slate ...................................................................................................................................... 15 2.1.2.3.1 Opportunity Crudes .................................................................................................................. 16 2.1.2.3.2 Tight Oil .................................................................................................................................... 19 2.1.2.4 Hydrogen Demand ....................................................................................................................................... 20 2.1.2.5 Capacity Expansion ....................................................................................................................................... 20 2.1.2.6 Construction Projects and Unit Revamps ..................................................................................................... 22 2.1.2.7 Hydrocracking Catalyst Market .................................................................................................................... 22

2.1.3 Technology Competition, Direction, and Future Prospects ........................................................................ 24 2.1.3.1 Market Layout and Strategic Alliances ......................................................................................................... 24 2.1.3.2 Recent Technology Developments ............................................................................................................... 30 2.1.3.2.1 Catalyst Developments ............................................................................................................. 30 2.1.3.2.2 Process and Hardware Developments ...................................................................................... 32 2.1.3.2.2.1 Two‐phase Hydrocracking ................................................................................... 33 2.1.3.2.2.2 Reactor Internals ................................................................................................. 34 2.1.3.2.2.3 HPNAs Removal .................................................................................................. 34 2.1.3.2.3 Conventional and Mild Hydrocracking ...................................................................................... 35 2.1.3.2.4 Resid Hydrocracking ................................................................................................................. 35 2.1.3.2.5 Alternative Feed Hydrocracking ............................................................................................... 38 2.1.3.2.6 Revamp and Integration Options .............................................................................................. 39 2.1.3.2.7 Process Modeling ..................................................................................................................... 40 2.1.3.3 Latest R&D Trends ........................................................................................................................................ 41

2.1.4 Conclusion .................................................................................................................................................. 42 2.2 STATE‐OF‐THE‐ART TECHNOLOGY ................................................................................................................................... 43 2.2.1 Introduction................................................................................................................................................ 43 2.2.2 Commercial Process Technology ................................................................................................................ 44 2.2.2.1 Axens ............................................................................................................................................................ 45 2.2.2.1.1 Mild Hydrocracking ................................................................................................................... 45 2.2.2.1.1.1 Mild‐HCK ............................................................................................................. 45 2.2.2.1.1.2 HyC‐10/HyC‐10+.................................................................................................. 46 2.2.2.1.2 H‐OilDC ....................................................................................................................................... 50 2.2.2.1.3 Medium‐pressure Hydrocracking ............................................................................................. 51 2.2.2.1.4 Conventional (High‐pressure) Hydrocracking ........................................................................... 51 2.2.2.1.5 HPNA Removal .......................................................................................................................... 55 2.2.2.1.6 Reactor Internals ...................................................................................................................... 56 2.2.2.2 Chevron Lummus Global .............................................................................................................................. 56 2.2.2.2.1 ISOCRACKING ............................................................................................................................ 57 2.2.2.2.1.1 Single‐stage Once Through and Single‐stage Recycle ......................................... 58 2.2.2.2.1.2 Two‐stage Recycle............................................................................................... 60 2.2.2.2.1.3 Optimized Partial Conversion ............................................................................. 63 2.2.2.2.1.4 Selective Staging ................................................................................................. 65 2.2.2.2.1.5 Split‐feed Injection .............................................................................................. 68

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TABLE OF CONTENTS

2.2.2.3 2.2.2.4

2.2.2.5

2.2.2.6

2.2.2.7

2.2.2.8

2.2.2.9

2.2.2.2.1.6 Single‐stage Reaction Sequencing ...................................................................... 68 2.2.2.2.2 ISOFLEX ..................................................................................................................................... 69 2.2.2.2.3 Reactor Internals ...................................................................................................................... 71 DuPont Clean Technologies ......................................................................................................................... 73 ExxonMobil .................................................................................................................................................. 76 2.2.2.4.1 Single‐stage MPHC ................................................................................................................... 77 2.2.2.4.2 MPHC‐PTU ................................................................................................................................ 81 2.2.2.4.3 MPHC‐LCO ................................................................................................................................ 83 2.2.2.4.4 Two‐stage MPHC ...................................................................................................................... 85 2.2.2.4.5 MIDW ....................................................................................................................................... 87 2.2.2.4.6 Spider‐Vortex Reactor Internals ............................................................................................... 89 Haldor Topsøe .............................................................................................................................................. 89 2.2.2.5.1 Mild Hydrocracking .................................................................................................................. 90 2.2.2.5.1.1 Staged Partial Conversion Hydrocracking ........................................................... 92 2.2.2.5.1.2 Back‐End Shift (BES) Process .............................................................................. 93 2.2.2.5.2 Conventional (High‐pressure) Hydrocracking ........................................................................... 93 2.2.2.5.3 HPNA Trim ................................................................................................................................ 94 2.2.2.5.4 Reactor Internals ...................................................................................................................... 96 Shell Global Solutions ................................................................................................................................... 98 2.2.2.6.1 Mild Hydrocracking .................................................................................................................. 99 2.2.2.6.2 Conventional Hydrocracking .................................................................................................. 101 2.2.2.6.3 Reactor Internals .................................................................................................................... 103 Sinopec ....................................................................................................................................................... 108 2.2.2.7.1 Flexible Hydrotreating/Mild Hydrocracking ........................................................................... 108 2.2.2.7.2 Medium‐pressure Hydro‐Upgrading ...................................................................................... 109 2.2.2.7.3 Moderate‐pressure Hydrocracking ........................................................................................ 112 2.2.2.7.4 High‐pressure Hydrocracking ................................................................................................. 112 2.2.2.7.4.1 Single‐stage Hydrocracking ............................................................................... 113 2.2.2.7.4.2 Single‐stage in Series Hydrocracking ................................................................ 113 2.2.2.7.4.3 Two‐stage Hydrocracking ................................................................................. 116 2.2.2.7.4.4 Flexible Hydrocracking ...................................................................................... 116 UOP ............................................................................................................................................................ 117 2.2.2.8.1 MHC Unicracking .................................................................................................................... 118 2.2.2.8.2 Unicracking ............................................................................................................................. 120 2.2.2.8.2.1 Single‐stage Once Through or with Recycle...................................................... 120 2.2.2.8.2.2 Two‐stage ......................................................................................................... 122 2.2.2.8.3 Partial‐conversion Unicracking ............................................................................................... 127 2.2.2.8.4 Dieselmax ............................................................................................................................... 130 2.2.2.8.5 HyCycle Unicracking ............................................................................................................... 132 2.2.2.8.6 Advanced Partial Conversion Unicracking .............................................................................. 134 2.2.2.8.7 HPNA Removal Systems ......................................................................................................... 135 2.2.2.8.8 Reactor Internals .................................................................................................................... 136 Summary of Hydrocracking Process Technologies ..................................................................................... 138

2.2.3 Commercial Catalysts ............................................................................................................................... 144 2.2.3.1 2.2.3.2 2.2.3.3 2.2.3.4 2.2.3.5 2.2.3.6 2.2.3.7 2.2.3.8 2.2.3.9 2.2.3.10

Albemarle ................................................................................................................................................... 145 Axens .......................................................................................................................................................... 145 Clariant Catalysts ........................................................................................................................................ 148 Chevron Lummus Global ............................................................................................................................ 149 Criterion Catalysts & Technologies ............................................................................................................ 156 Haldor Topsøe ............................................................................................................................................ 167 JGC Catalysts & Chemicals ......................................................................................................................... 170 Sinopec Catalyst Co. ................................................................................................................................... 171 UOP ............................................................................................................................................................ 173 Summary of Commercially Available Hydrocracking Catalysts .................................................................. 178

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TABLE OF CONTENTS 2.2.4 Auxiliary Catalyst Technology .................................................................................................................. 180 2.2.4.1 2.2.4.2 2.2.4.3 2.2.4.4

Axens .......................................................................................................................................................... 181 Crystaphase Products ................................................................................................................................. 181 Eurecat ....................................................................................................................................................... 181 TRICAT ........................................................................................................................................................ 182

2.2.5 Control and Optimization Systems ........................................................................................................... 183 2.2.6 Resid Hydrocracking ................................................................................................................................. 188 2.2.7 Renewable Hydrocracking ....................................................................................................................... 197 2.3 PLANT OPERATIONS AND PRACTICES .............................................................................................................................. 202 2.3.1 General Hydrocracking Operations .......................................................................................................... 202 2.3.1.1 Feed Considerations, Operational Variables, Process Configurations, and Hardware ............................... 203 2.3.1.1.1 Feedstock Characterization .................................................................................................... 203 2.3.1.1.2 Contaminant Metals ............................................................................................................... 203 2.3.1.1.3 Upgrading Tight Oil ................................................................................................................. 204 2.3.1.1.4 Increasing Conversion for Heavier Feedstocks ....................................................................... 205 2.3.1.1.5 Upgrading LCO and/or HCO in Hydrocrackers ........................................................................ 206 2.3.1.1.6 Undercutting LVGO to Increase Hydrocracker Utilization ...................................................... 208 2.3.1.1.7 Optimizing Operational Variables ........................................................................................... 209 2.3.1.1.7.1 Recycle Rate in Two‐stage Units ....................................................................... 209 2.3.1.1.7.2 Setting Operational Pressure ............................................................................ 209 2.3.1.1.7.3 Flow Control on Feeds from Coking Unit .......................................................... 211 2.3.1.1.8 Reactor Configuration ............................................................................................................. 211 2.3.1.1.9 Optimized Hydrocracker Reactor Internals ............................................................................. 212 2.3.1.1.10 Removing Welded Attachments from Reactor Internals ........................................................ 214 2.3.1.1.11 Changing Unit Configuration to Boost Yields and Process Alternative Feeds ......................... 214 2.3.1.1.12 Large Single Process Train vs. Smaller Parallel Trains in Hydrocrackers ................................. 215 2.3.1.1.13 Reactor Fabrication and Metallurgy ....................................................................................... 216 2.3.1.1.14 Comparison of Quench Systems ............................................................................................. 217 2.3.1.1.15 Revamping the Overhead Condenser of a Hydrocracker........................................................ 218 2.3.1.1.16 Hydrocracker Stripper Revamp: From Packing to Trays ......................................................... 218 2.3.1.1.17 Designing Hydrocracker Charge Heater .................................................................................. 219 2.3.1.1.18 Hydrocracker Pump Selection ................................................................................................. 219 2.3.1.1.19 Membranes for H2 Recovery from Hydrocrackers .................................................................. 220 2.3.1.2 Fouling, Particulate Deposition, and Corrosion .......................................................................................... 220 2.3.1.2.1 Causes of Hydroprocesser Fouling and Possible Treatments ................................................. 220 2.3.1.2.2 Chlorides Fouling in Effluent Exchangers ................................................................................ 223 2.3.1.2.3 Elimination of Polynuclear Aromatics (PNA) Buildup.............................................................. 224 2.3.1.2.4 Preventing Sedimentation in Ebullated‐bed Hydrocrackers ................................................... 225 2.3.1.2.5 Iron Sulfide Buildup in VGO Hydrocrackers ............................................................................ 226 2.3.1.2.6 Feed Filter Operation .............................................................................................................. 228 2.3.1.2.7 Mitigating High Temperature Hydrogen Attack...................................................................... 229 2.3.1.2.8 Fouling in Furnace Tubes ........................................................................................................ 230 2.3.1.2.9 Corrosion in Overhead System ............................................................................................... 231 2.3.1.2.10 Corrosion in Auxiliary Equipment ........................................................................................... 231 2.3.1.2.11 Reducing Foaming in an Amine Scrubber ............................................................................... 232 2.3.1.3 Operational Problems ................................................................................................................................ 233 2.3.1.3.1 Increased Yield Using Multivariable Predictive Control (MPC) ............................................... 233 2.3.1.3.2 Improving Hydrocracker Temperature Control ...................................................................... 236 2.3.1.3.3 Detecting Radial Temperature Spread and Preventing Reactor Runaway ............................. 238 2.3.1.3.4 Hydrocracker Furnace Operations .......................................................................................... 241 2.3.1.3.5 Causes of Overcracking ........................................................................................................... 242 2.3.1.3.6 Improving the Performance of a Debutanizer ........................................................................ 243 2.3.1.3.7 Preventing Off‐color Naphtha Product ................................................................................... 245 2.3.1.3.8 Reducing the Level of Sulfur in Naphtha at EOR Conditions ................................................... 245 2.3.1.3.9 Limiting Ammonia Concentration in the Cold High‐pressure Separator Overhead ................ 246 2.3.1.3.10 Inline Hydrocracker Cleaning System ..................................................................................... 247

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TABLE OF CONTENTS 2.3.1.3.11 Improving Recycle Gas Compressor Operation ...................................................................... 247 2.3.1.4 Catalyst Management ................................................................................................................................ 248 2.3.1.4.1 Selection Process for Hydrocracking Catalysts ....................................................................... 248 2.3.1.4.2 Catalyst Testing on Different Scales ....................................................................................... 249 2.3.1.4.3 Catalyst Loading Precautions ................................................................................................. 250 2.3.1.4.4 Measuring Hydrocracking Catalyst Activity ............................................................................ 251 2.3.1.4.5 Catalysts for Processing Tight Oil ........................................................................................... 252 2.3.1.4.6 Catalysts for Processing Various Feeds .................................................................................. 252 2.3.1.4.7 Replacing a Noble Metal Catalyst with a Base Metal Catalyst ............................................... 254 2.3.1.4.8 Catalyst Structure: Homogeneous vs. Stacked ....................................................................... 255 2.3.1.4.9 Ex‐Situ Sulfiding (Presulfiding) of Hydrocracking Catalysts .................................................... 255 2.3.1.4.10 Hydrocracking Catalyst Passivation ........................................................................................ 258 2.3.1.4.11 Disproportionate Catalyst Deactivation in the First Bed of a Hydrocracker ........................... 259 2.3.1.4.12 Designing a Posttreat Bed for Hydrocracking Reactors .......................................................... 260 2.3.1.4.13 Asphaltene Contribution to Catalyst Deactivation ................................................................. 260 2.3.1.4.14 Impact of HPNAs on Catalyst Activity and Stability ................................................................ 261 2.3.1.4.15 Regenerated Hydrocracking Catalyst Use .............................................................................. 262 2.3.1.4.16 Catalyst Removal for Non‐free Flowing Catalysts .................................................................. 264 2.3.1.4.17 Recovering Spent Hydroprocessing Catalysts and Metal Reclamation .................................. 265 2.3.1.5 Reducing Hydrocracker Energy and Hydrogen Use .................................................................................... 266 2.3.1.5.1 Advanced Process Control and Modeling ............................................................................... 267 2.3.1.5.2 Cleaning .................................................................................................................................. 268 2.3.1.5.3 Heat Integration ..................................................................................................................... 268 2.3.1.5.4 Power Recovery ...................................................................................................................... 268 2.3.1.5.5 Process Heaters ...................................................................................................................... 269 2.3.1.5.6 Compressors ........................................................................................................................... 269 2.3.1.5.7 Impact of Catalysts ................................................................................................................. 269 2.3.1.6 Hydrocracker Safety ................................................................................................................................... 270 2.3.1.6.1 Hydrocracker Safety Incidents ................................................................................................ 270 2.3.1.6.2 Emergency Depressurization: Triggering Criteria, Rates and Modes ..................................... 272 2.3.1.6.3 Operational Status of Emergency Depressurizing Valves and Interlocks ............................... 274 2.3.1.6.4 Safely Performing Inter‐reactor Sampling in Hydrocrackers .................................................. 274 2.3.1.6.5 Sampling of Light Streams around High‐Pressure Equipment ................................................ 275

2.3.2 Mild Hydrocracking (MHC) ....................................................................................................................... 275 2.3.2.1 Mild Hydrocracking: Feedstock, Conversion, and Product Quality ............................................................ 275 2.3.2.2 Converting a Cat Feed or Distillate Hydrotreater to a Mild Hydrocracker ................................................. 276 2.3.2.3 Options for Improving the Cycle Length of Mild Hydrocrackers ................................................................ 279

2.3.3 Distillate Hydrocracking ........................................................................................................................... 280 2.3.3.1 2.3.3.2 2.3.3.3 2.3.3.4 2.3.3.5 2.3.3.6 2.3.3.7 2.3.3.8 2.3.3.9 2.3.3.10

Shifting from Maximum Naphtha to Maximum Middle Distillate Yields .................................................... 280 Maximizing Diesel Production in VGO Hydrocrackers ................................................................................ 283 Benefits of Moderate Pressure Hydrocracking (MPHC) in Clean Diesel Production .................................. 285 Adjusting CAT to Maximize Diesel Production ........................................................................................... 286 Reactor Revamp to Improve ULSD Production .......................................................................................... 287 Optimizing Saturation and Volume Swell in ULSD Service ......................................................................... 289 Loading Hydrocracking Catalyst in the Last Bed of a ULSD Unit ................................................................. 289 Process Revamp for Added H2S Removal to Meet ULSD Standards ........................................................... 290 Improving Diesel Cetane from Hydrocrackers ........................................................................................... 291 Hydrocracking Catalysts for Cold Flow Property Improvements ................................................................ 292

2.3.4 Integrated Processing Schemes ................................................................................................................ 293 2.3.4.1 2.3.4.2 2.3.4.3 2.3.4.4

Delayed Coker with Hydrocracker .............................................................................................................. 293 Solvent Deasphalting with Hydrocracker ................................................................................................... 296 Mild Hydrocracker with FCC ....................................................................................................................... 297 Integrated Processes for Heavy Oil Upgrading........................................................................................... 298

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TABLE OF CONTENTS 2.4 REFINING R&D ALERT! ............................................................................................................................................... 299 2.4.1 Introduction.............................................................................................................................................. 299 2.4.2 General Hydrocracking ............................................................................................................................. 304 2.4.2.1 Process ....................................................................................................................................................... 304 2.4.2.2 Catalyst ....................................................................................................................................................... 305 2.4.2.2.1 Patents .................................................................................................................................... 305 2.4.2.2.1.1 Novel Composition ............................................................................................ 305 2.4.2.2.1.2 Preparation Method ......................................................................................... 307 2.4.2.2.2 Research ................................................................................................................................. 308 2.4.2.2.2.1 Novel Composition ............................................................................................ 308 2.4.2.2.2.2 Preparation Method ......................................................................................... 309 2.4.2.3 Hardware .................................................................................................................................................... 309 2.4.2.3.1 Patents .................................................................................................................................... 309 2.4.2.3.2 Research ................................................................................................................................. 310 2.4.2.4 Integrated Operations (Conventional Feeds) ............................................................................................. 311 2.4.2.5 Mild Hydrocracking and Hydrotreating to Improve Cetane ....................................................................... 312 2.4.2.6 Process Modeling ....................................................................................................................................... 313 2.4.2.6.1 Patents .................................................................................................................................... 313 2.4.2.6.2 Research ................................................................................................................................. 313

2.4.3 Product Selective Hydrocracking .............................................................................................................. 315 2.4.3.1 Middle Distillates ........................................................................................................................................ 315 2.4.3.1.1 Process .................................................................................................................................... 315 2.4.3.1.2 Catalyst ................................................................................................................................... 318 2.4.3.1.2.1 Patents .............................................................................................................. 318 2.4.3.1.2.1.1 Support with Improved Porosity ............................................................................................................. 318 2.4.3.1.2.1.2 Catalysts Enhancing Aromatics Saturation ............................................................................................. 319 2.4.3.1.2.1.3 Other ...................................................................................................................................................... 319 2.4.3.1.2.2 Research ........................................................................................................... 322 2.4.3.2 Production of Aromatics‐rich, High‐octane Heavy Naphtha ...................................................................... 323 2.4.3.2.1 Patents .................................................................................................................................... 323 2.4.3.2.2 Research ................................................................................................................................. 324 2.4.3.3 Production of Gasoline ............................................................................................................................... 324 2.4.3.3.1 Patents .................................................................................................................................... 324 2.4.3.3.2 Research ................................................................................................................................. 325 2.4.3.4 BTX ............................................................................................................................................................. 325 2.4.3.4.1 Patents .................................................................................................................................... 325 2.4.3.4.2 Research ................................................................................................................................. 327

2.4.4 Resid Hydrocracking ................................................................................................................................. 328 2.4.4.1 Ebullated‐bed Reactor ................................................................................................................................ 328 2.4.4.1.1 Patents .................................................................................................................................... 328 2.4.4.1.2 Research ................................................................................................................................. 329 2.4.4.2 Slurry‐bed Reactor ...................................................................................................................................... 330 2.4.4.2.1 Process .................................................................................................................................... 330 2.4.4.2.1.1 Patents .............................................................................................................. 330 2.4.4.2.1.2 Research ........................................................................................................... 334 2.4.4.2.2 Catalyst ................................................................................................................................... 334 2.4.4.2.2.1 Patents .............................................................................................................. 334 2.4.4.2.2.2 Research ........................................................................................................... 336 2.4.4.3 Other .......................................................................................................................................................... 337 2.4.4.3.1 Catalyst ................................................................................................................................... 337

2.4.5 Hydrocracking Alternative Feedstocks ..................................................................................................... 337 2.4.5.1 Fischer‐Tropsch Liquids .............................................................................................................................. 337 2.4.5.1.1 Process .................................................................................................................................... 337 2.4.5.1.2 Catalyst ................................................................................................................................... 339 2.4.5.1.2.1 Patents .............................................................................................................. 339 2.4.5.1.2.2 Research ........................................................................................................... 340

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TABLE OF CONTENTS 2.4.5.2 Renewable Feedstocks ............................................................................................................................... 341 2.4.5.2.1 Coprocessing Hydrocarbon and Bio‐oil Feeds ........................................................................ 341 2.4.5.2.2 Production of Fuels ................................................................................................................ 341 2.4.5.2.2.1 Patents .............................................................................................................. 341 2.4.5.2.2.2 Research ........................................................................................................... 343 2.4.5.2.3 Making Bio‐chemicals ............................................................................................................. 345 2.4.5.2.3.1 Patents .............................................................................................................. 345 2.4.5.2.3.2 Research ........................................................................................................... 346 2.4.5.2.4 Other ...................................................................................................................................... 346

2.5 WORLDWIDE INSTALLED CAPACITY ................................................................................................................................ 347 2.6 CONSTRUCTION ......................................................................................................................................................... 351 2.6.1 Recent Construction Activity ..................................................................................................................... 351 2.6.2 Completed Construction Projects ............................................................................................................. 356 2.7 REFERENCES .............................................................................................................................................................. 368 3. LUBE OIL PRODUCTION ....................................................................................................................................... 395 3.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................................... 395 3.1.1 Introduction .............................................................................................................................................. 395 3.1.1 Market Conditions and Outlook ............................................................................................................... 396 3.1.1.1 3.1.1.2 3.1.1.3 3.1.1.4 3.1.1.5 3.1.1.6 3.1.1.7 3.1.1.8

Base Oil Market In The Midst of Oversupply ............................................................................................. 397 New Regulations, Overcapacity Drive Base Oil Switch ............................................................................... 397 Poor Economics Driving Out European Group I Lubes ............................................................................... 399 Vehicle Ownership to Contribute to Rise in Asian Lube Demand .............................................................. 399 Middle East Refiners Add Base Oil Capacity ............................................................................................... 400 Crude Feedstock Impacts Lubes Output .................................................................................................... 400 Lube Prices Track Crude Higher ................................................................................................................. 401 Installed Capacity and Future Projects ....................................................................................................... 402

3.1.2 Technology Competition, Direction, and Future Prospects ...................................................................... 403 3.1.2.1 3.1.2.2 3.1.2.3 3.1.2.4

Hydroprocessing‐based Technology .......................................................................................................... 405 Hybrid Processes ........................................................................................................................................ 407 Alternative Feeds ....................................................................................................................................... 408 Converting from Solvent‐based to Hydroprocessing‐based Lubes Production .......................................... 409

3.1.3 Conclusion ................................................................................................................................................ 410 3.2 STATE‐OF‐THE‐ART TECHNOLOGY ................................................................................................................................. 410 3.2.1 Introduction .............................................................................................................................................. 410 3.2.2 Commercial Processes .............................................................................................................................. 414 3.2.2.1 Axens .......................................................................................................................................................... 415 3.2.2.1.1 Solvent Refining ..................................................................................................................... 415 3.2.2.1.2 Hydroprocessing ..................................................................................................................... 415 3.2.2.1.2.1 Hydrorefining .................................................................................................... 416 3.2.2.1.2.2 High Conversion Hydrocracking ........................................................................ 417 3.2.2.1.2.3 Lube Oil Hydrofinishing .................................................................................... 417 3.2.2.1.2.4 White Oils Hydrotreatment .............................................................................. 418 3.2.2.1.2.5 Wax Hydrotreatment (Wax HDT) ...................................................................... 418 3.2.2.2 Bechtel ....................................................................................................................................................... 419 3.2.2.2.1 Solvent Refining ..................................................................................................................... 419 3.2.2.2.1.1 MP Refining ...................................................................................................... 419 3.2.2.2.1.2 Furfural Refining ............................................................................................... 420 3.2.2.2.1.3 Solvent Dewaxing ............................................................................................. 421 3.2.2.2.1.4 Wax Fractionation ............................................................................................ 422 3.2.2.2.2 Hydroprocessing ..................................................................................................................... 423 3.2.2.2.2.1 Hy‐Raff .............................................................................................................. 423 3.2.2.2.2.2 Hy‐Finishing ...................................................................................................... 425 3.2.2.2.2.3 Hy‐Starting ........................................................................................................ 425 3.2.2.2.2.4 Wax Hy‐Finishing .............................................................................................. 425

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TABLE OF CONTENTS 3.2.2.2.2.5 White Oil Hy‐Finishing ....................................................................................... 426 3.2.2.3 Chevron Lummus Global ............................................................................................................................ 426 3.2.2.3.1 Hydroprocessing ..................................................................................................................... 426 3.2.2.3.1.1 ISOCRACKING .................................................................................................... 428 3.2.2.3.1.2 ISODEWAXING .................................................................................................. 429 3.2.2.3.1.3 ISOFINISHING .................................................................................................... 433 3.2.2.3.1.4 Integration Opportunities ................................................................................. 433 3.2.2.4 ExxonMobil ................................................................................................................................................. 435 3.2.2.4.1 Solvent Refining ...................................................................................................................... 436 3.2.2.4.1.1 EXOL N Extraction ............................................................................................. 436 3.2.2.4.1.2 DILCHILL ............................................................................................................ 438 3.2.2.4.1.3 Propane Dewaxing ............................................................................................ 439 3.2.2.4.2 Hydroprocessing ..................................................................................................................... 441 3.2.2.4.2.1 Lube HYDROFINING .......................................................................................... 441 3.2.2.4.2.2 LHDC ................................................................................................................. 442 3.2.2.4.2.3 Raffinate Hydroconversion ............................................................................... 443 3.2.2.4.2.4 MSDW ............................................................................................................... 444 3.2.2.4.2.5 MLDW ............................................................................................................... 447 3.2.2.4.2.6 MWI .................................................................................................................. 447 3.2.2.4.2.7 Wax HYDROFINING ........................................................................................... 448 3.2.2.4.2.8 MAXSAT ............................................................................................................ 449 3.2.2.4.3 Membrane Separation ............................................................................................................ 449 3.2.2.4.4 Integration Opportunities ....................................................................................................... 449 3.2.2.5 Process Dynamics ....................................................................................................................................... 451 3.2.2.5.1 Integrated Extraction/Dewaxing ............................................................................................. 451 3.2.2.5.2 IsoTherming ............................................................................................................................ 453 3.2.2.6 Shell Global Solutions ................................................................................................................................. 453 3.2.2.6.1 Solvent Refining ...................................................................................................................... 454 3.2.2.6.2 Hydroprocessing ..................................................................................................................... 454 3.2.2.6.2.1 Pretreating/Hydrofinishing ............................................................................... 454 3.2.2.6.2.2 Hydrocracking ................................................................................................... 455 3.2.2.6.2.3 Catalytic Dewaxing and Wax Isomerization ...................................................... 455 3.2.2.6.2.4 Food Grade Oils and Wax .................................................................................. 455 3.2.2.6.3 Hybrid Process ........................................................................................................................ 456 3.2.2.7 Suncor Energy ............................................................................................................................................. 457 3.2.2.7.1 HT Severe Hydrocracking ........................................................................................................ 457 3.2.2.7.2 HydroIsomerization ................................................................................................................ 457 3.2.2.8 Uhde ........................................................................................................................................................... 458 3.2.2.8.1 Solvent Refining ...................................................................................................................... 458 3.2.2.8.1.1 Solvent Dewaxing and Wax Deoiling ................................................................. 458 3.2.2.8.1.2 Slack Wax Deoiling ............................................................................................ 459 3.2.2.8.1.3 Liquid‐liquid Extraction ..................................................................................... 460 3.2.2.8.2 Hydroprocessing ..................................................................................................................... 460 3.2.2.8.2.1 Hydrofinishing ................................................................................................... 460 3.2.2.8.2.2 White Oil and Wax Hydrotreating ..................................................................... 461 3.2.2.9 Washington Group Int./SK Innovation ....................................................................................................... 462 3.2.2.10 Summary of Commercial Lube Oil Manufacturing Processes ..................................................................... 464

3.2.3 Summary of Commercial Lube Oil Manufacturing Catalysts ................................................................... 468 3.3 PLANT OPERATIONS AND PRACTICES .............................................................................................................................. 470 3.3.1 Process ..................................................................................................................................................... 470 3.3.1.1 Selecting a Lube Production Process .......................................................................................................... 470 3.3.1.2 Breakeven Cost Comparison ...................................................................................................................... 470 3.3.1.3 Improvements in Plant Efficiency, Performance, and Profitability ............................................................. 470 3.3.1.3.1 Converting Fuel Hydrocracking to Lube Hydrocracking .......................................................... 471 3.3.1.3.2 Revamps to Existing Equipment ............................................................................................. 471 3.3.1.3.2.1 Vacuum Distillation Unit ................................................................................... 472

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3.3.1.3.3

3.3.1.3.4

3.3.1.3.5

3.3.1.3.2.2 Solvent Extraction Unit ..................................................................................... 473 3.3.1.3.2.3 Solvent Dewaxing Unit ...................................................................................... 474 Optimization of Operating Conditions ................................................................................... 475 3.3.1.3.3.1 Vacuum Distillation Unit ................................................................................... 475 3.3.1.3.3.2 Solvent Extraction Unit ..................................................................................... 476 3.3.1.3.3.3 Solvent Dewaxing Unit ...................................................................................... 476 3.3.1.3.3.4 Lube and Wax Hydrofinishing Unit ................................................................... 478 Retrofitting ............................................................................................................................. 478 3.3.1.3.4.1 Solvent Extraction Unit ..................................................................................... 479 3.3.1.3.4.2 Solvent Dewaxing Unit ...................................................................................... 479 3.3.1.3.4.3 Hydrofinishing Unit ........................................................................................... 479 Use of Additives and Aids ....................................................................................................... 480 3.3.1.3.5.1 Improvements to Additives and Lubricant Blending ........................................ 480 3.3.1.3.5.2 Dewaxing Aids .................................................................................................. 481

3.3.2 Alternative Base Oil Sources ..................................................................................................................... 481 3.3.2.1 Recycled Used Lubricants ........................................................................................................................... 481 3.3.2.2 Bio‐lubricants and GTL Lubricants .............................................................................................................. 482 3.3.2.3 Other Chemicals ......................................................................................................................................... 482

3.3.3 Wax Production ........................................................................................................................................ 483 3.3.3.1 Waxes from Fischer‐Tropsch ...................................................................................................................... 484 3.3.3.2 Hybrid Installations .................................................................................................................................... 485

3.4 REFINING R&D ALERT! ............................................................................................................................................... 485 3.4.1 Introduction .............................................................................................................................................. 485 3.4.2 Fractionation ............................................................................................................................................ 490 3.4.3 Solvent‐based Lube Production ................................................................................................................ 491 3.4.3.1 Solvent Extraction ...................................................................................................................................... 491 3.4.3.2 Solvent Dewaxing ....................................................................................................................................... 492 3.4.3.2.1 Patents ................................................................................................................................... 492 3.4.3.2.2 Research ................................................................................................................................. 494

3.4.4 Hydroprocessing‐based Lube Production ................................................................................................. 495 3.4.4.1 Hydrocracking ............................................................................................................................................ 495 3.4.4.1.1 Process ................................................................................................................................... 495 3.4.4.1.2 Catalyst ................................................................................................................................... 497 3.4.4.1.2.1 Patents .............................................................................................................. 497 3.4.4.1.2.2 Research ........................................................................................................... 498 3.4.4.2 Hydroisomerization/Dewaxing................................................................................................................... 498 3.4.4.2.1 Process ................................................................................................................................... 498 3.4.4.2.2 Catalyst ................................................................................................................................... 503 3.4.4.3 Combined Hydrocracking and Dewaxing Process ...................................................................................... 508 3.4.4.3.1 Process ................................................................................................................................... 508 3.4.4.3.2 Catalyst ................................................................................................................................... 518

3.4.5 Alternative Processes ................................................................................................................................ 520 3.4.5.1 Oligomerization/Alkylation ........................................................................................................................ 520

3.4.6 Alternative Feeds ...................................................................................................................................... 522 3.4.6.1 F‐T Wax ...................................................................................................................................................... 522 3.4.6.2 Bio and Unconventional Feeds................................................................................................................... 531 3.4.6.2.1 Process ................................................................................................................................... 531 3.4.6.2.1.1 Patents .............................................................................................................. 531 3.4.6.2.1.1.1 Lube ........................................................................................................................................................ 531 3.4.6.2.1.1.2 Grease .................................................................................................................................................... 542 3.4.6.2.1.2 Research ........................................................................................................... 543 3.4.6.2.2 Catalyst ................................................................................................................................... 545

3.4.7 Miscellaneous ........................................................................................................................................... 546 3.4.7.1 Patents ....................................................................................................................................................... 546 3.4.7.2 Research ..................................................................................................................................................... 548

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TABLE OF CONTENTS 3.5 WORLDWIDE INSTALLED CAPACITY ................................................................................................................................ 549 3.6 CONSTRUCTION ......................................................................................................................................................... 551 3.6.1 Recent Construction Activity .................................................................................................................... 551 3.6.2 Completed Construction Projects ............................................................................................................. 555 3.7 REFERENCES ............................................................................................................................................................. 563 4. LATEST REFINING TECHNOLOGY DEVELOPMENTS & LICENSING ........................................................................... 579 4.1 FLUID CATALYTIC CRACKING ......................................................................................................................................... 579 4.2 HYDROTREATING (INCLUDING HDS) .............................................................................................................................. 580 4.3 BENZENE REDUCTION AND REMOVAL ............................................................................................................................ 580 4.4 ALKYLATION .............................................................................................................................................................. 581 4.5 COKING ................................................................................................................................................................... 581 4.6 SULFUR PLANT .......................................................................................................................................................... 582 4.7 GAS CONCENTRATION PLANT/VAPOR RECOVERY ............................................................................................................. 582 4.8 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................................ 583 4.9 PROCESS CONTROLS AND SIMULATION ........................................................................................................................... 586 4.10 XTL (BIOMASS‐, COAL‐, AND GAS‐TO‐LIQUID) ................................................................................................................ 587 4.11 BIOFUELS PRODUCTION .............................................................................................................................................. 588 4.12 ENERGY MANAGEMENT .............................................................................................................................................. 590 4.13 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) ............................................................................................... 590 4.14 SITE AIR POLLUTION AND WASTE DISCHARGE ................................................................................................................. 592 4.15 REFERENCES ............................................................................................................................................................. 593

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