Worldwide Refinery Processing Review by Hydrocarbon Publishing Company

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

Second Quarter 2014 Hydrocracking, and Solvent Extraction & Deasphalting Plus

Latest Refining Technology Developments & Licensing

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

Second Quarter 2014 Hydrocracking, and Solvent Extraction & Deasphalting Plus Latest Refining Technology Developments & Licensing

http://www.hydrocarbonpublishing.com

WORLDWIDE REFINERY PROCESSING REVIEW is published by Hydrocarbon Publishing Co. every quarter. Copyright 2007-2014. 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 661, Southeastern, PA 19399 (USA). Tel: (610) 408-0117, Fax: (610) 408-0118. E-mail: review@hydrocarbonpublishing.com

Abbreviations 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 2014 Review Hydrocracking and Solvent Extraction and Deasphalting 1. Introduction ..................................................................................................................................... 1 2. Hydrocracking ................................................................................................................................ 5 2.1

2.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 5 2.1.1 Introduction .............................................................................................................................................. 5 2.1.2 Market Conditions and Outlook................................................................................................................ 6 2.1.2.1 Refined Products Legislation ................................................................................................... 6 2.1.2.1.1 Transportation Fuels.............................................................................................. 6 2.1.2.1.2 Bunker Fuels ......................................................................................................... 7 2.1.2.2 Refined Products Demand ....................................................................................................... 7 2.1.2.3 Increasing Middle Distillate Production ................................................................................ 10 2.1.2.3.1 Diesel Market Conditions.................................................................................... 10 2.1.2.3.1.1 United States .................................................................................. 10 2.1.2.3.1.2 South America ............................................................................... 11 2.1.2.3.1.3 European Union ............................................................................. 11 2.1.2.3.1.4 Russia ............................................................................................. 12 2.1.2.3.1.5 Middle East .................................................................................... 13 2.1.2.3.1.6 Asia-Pacific.................................................................................... 13 2.1.2.4 Shifting Crude Slate ............................................................................................................... 14 2.1.2.4.1 Opportunity Crudes ............................................................................................. 14 2.1.2.4.2 Tight Oil .............................................................................................................. 17 2.1.2.5 Hydrogen Demand ................................................................................................................. 18 2.1.2.6 Capacity Expansion ............................................................................................................... 19 2.1.2.7 Construction Projects and Unit Revamps .............................................................................. 22 2.1.2.8 Hydrocracking Catalyst Market ............................................................................................. 22 2.1.3 Technology Competition, Direction, and Future Prospects ................................................................... 23 2.1.3.1 Market Layout and Strategic Alliances.................................................................................. 23 2.1.3.2 Latest R&D Trends ................................................................................................................ 28 2.1.3.3 Recent Technology Developments ........................................................................................ 29 2.1.3.3.1 Catalyst Developments ........................................................................................ 29 2.1.3.3.2 Process and Hardware Developments ................................................................. 31 2.1.3.3.3 Conventional and Mild Hydrocracking ............................................................... 32 2.1.3.3.4 Resid Hydrocracking ........................................................................................... 33 2.1.3.3.5 Alternative Feed Hydrocracking ......................................................................... 35 2.1.3.3.6 Revamp and Integration Options......................................................................... 37 2.1.4 Conclusion .............................................................................................................................................. 38 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 40 2.2.1 Introduction ............................................................................................................................................ 40 2.2.2 Commercial Process Technology............................................................................................................ 41 2.2.2.1 Axens ..................................................................................................................................... 42 2.2.2.1.1 Mild Hydrocracking ............................................................................................ 42 2.2.2.1.1.1 Mild-HCK ...................................................................................... 42 2.2.2.1.1.2 HyC-10/HyC-10+ .......................................................................... 43 2.2.2.1.2 H-OilDC ................................................................................................................ 47 2.2.2.1.3 HyTail ................................................................................................................. 48 2.2.2.1.4 Medium-pressure Hydrocracking ........................................................................ 49 2.2.2.1.5 Conventional (High-pressure) Hydrocracking .................................................... 50 2.2.2.1.6 Reactor Internals ................................................................................................. 53

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Chevron Lummus Global ....................................................................................................... 54 2.2.2.2.1 ISOCRACKING .................................................................................................. 54 2.2.2.2.1.1 Single-stage Once Through and Single-stage Recycle ................... 55 2.2.2.2.1.2 Two-stage Recycle ......................................................................... 57 2.2.2.2.1.3 Optimized Partial Conversion ........................................................ 61 2.2.2.2.1.4 Selective Staging ............................................................................ 63 2.2.2.2.1.5 Split-feed Injection ......................................................................... 65 2.2.2.2.1.6 Single-stage Reaction Sequencing ................................................. 66 2.2.2.2.2 ISOFLEX ............................................................................................................. 67 2.2.2.2.3 Reactor Internals .................................................................................................. 69 2.2.2.3 DuPont Clean Technologies ................................................................................................... 70 2.2.2.4 ExxonMobil............................................................................................................................ 72 2.2.2.4.1 Single-stage MPHC ............................................................................................. 73 2.2.2.4.2 MPHC-PTU ......................................................................................................... 78 2.2.2.4.3 MPHC-LCO......................................................................................................... 79 2.2.2.4.4 Two-stage MPHC ................................................................................................ 81 2.2.2.4.5 MIDW.................................................................................................................. 83 2.2.2.4.6 Spider-Vortex Reactor Internals .......................................................................... 84 2.2.2.5 Haldor Topsøe ........................................................................................................................ 85 2.2.2.5.1 Mild Hydrocracking ............................................................................................ 85 2.2.2.5.1.1 Staged Partial Conversion Hydrocracking ..................................... 87 2.2.2.5.1.2 Back-End Shift (BES) Process ....................................................... 89 2.2.2.5.2 Conventional (High-pressure) Hydrocracking .................................................... 89 2.2.2.5.3 Reactor Internals .................................................................................................. 90 2.2.2.6 Shell Global Solutions............................................................................................................ 92 2.2.2.6.1 Mild Hydrocracking ............................................................................................ 92 2.2.2.6.2 Conventional Hydrocracking ............................................................................... 94 2.2.2.6.3 Reactor Internals .................................................................................................. 96 2.2.2.7 Sinopec ................................................................................................................................... 99 2.2.2.7.1 Flexible Hydrotreating/Mild Hydrocracking ..................................................... 100 2.2.2.7.2 Medium-pressure Hydro-Upgrading ................................................................. 101 2.2.2.7.3 Moderate-pressure Hydrocracking .................................................................... 103 2.2.2.7.4 High-pressure Hydrocracking............................................................................ 104 2.2.2.7.4.1 Single-stage Hydrocracking ......................................................... 104 2.2.2.7.4.2 Single-stage in Series Hydrocracking .......................................... 105 2.2.2.7.4.3 Single-stage, Double-catalyst Hydrocracking .............................. 106 2.2.2.7.4.4 Two-stage Hydrocracking ............................................................ 107 2.2.2.7.4.5 Flexible Hydrocracking ................................................................ 108 2.2.2.8 UOP ...................................................................................................................................... 109 2.2.2.8.1 MHC Unicracking ............................................................................................. 109 2.2.2.8.2 Unicracking ....................................................................................................... 111 2.2.2.8.2.1 Single-stage Once Through or with Recycle ................................ 111 2.2.2.8.2.2 Two-stage ..................................................................................... 113 2.2.2.8.3 Partial-conversion Unicracking ......................................................................... 117 2.2.2.8.4 Dieselmax .......................................................................................................... 122 2.2.2.8.5 HyCycle Unicracking ........................................................................................ 123 2.2.2.8.6 Advanced Partial Conversion Unicracking ....................................................... 125 2.2.2.8.7 HPNA Removal Systems ................................................................................... 126 2.2.2.8.8 Reactor Internals ................................................................................................ 127 2.2.2.9 Summary of Hydrocracking Process Technologies ............................................................. 128 2.2.3 Commercial Catalysts ........................................................................................................................... 133 2.2.3.1 Albemarle ............................................................................................................................. 134 2.2.3.2 Axens ................................................................................................................................... 134

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2.2.3.3 Clariant ................................................................................................................................ 136 2.2.3.4 Chevron Lummus Global..................................................................................................... 137 2.2.3.5 Criterion Catalysts & Technologies ..................................................................................... 143 2.2.3.6 Haldor Topsøe ..................................................................................................................... 149 2.2.3.7 JGC Catalysts & Chemicals ................................................................................................. 151 2.2.3.8 Sinopec ................................................................................................................................ 152 2.2.3.9 UOP ..................................................................................................................................... 152 2.2.3.10 Summary of Commercially Available Hydrocracking Catalysts ......................................... 156 2.2.4 Auxiliary Catalyst Technology .............................................................................................................. 159 2.2.4.1 Axens ................................................................................................................................... 159 2.2.4.2 Crystaphase Products ........................................................................................................... 159 2.2.4.3 Eurecat ................................................................................................................................. 160 2.2.4.4 TRICAT ............................................................................................................................... 160 2.2.5 Control and Optimization Systems........................................................................................................ 161 2.2.6 Resid Hydrocracking ............................................................................................................................ 165 2.2.7 Renewable Hydrocracking .................................................................................................................... 172 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 176 2.3.1 General Hydrocracking Operations ..................................................................................................... 176 2.3.1.1 Feed Considerations, Operational Variables, Process Configurations, and Hardware ........ 177 2.3.1.1.1 Feedstock Characterization ............................................................................... 177 2.3.1.1.2 Upgrading Tight Oil .......................................................................................... 177 2.3.1.1.3 Increasing Conversion for Heavier Feedstocks ................................................. 178 2.3.1.1.4 Upgrading LCO and/or HCO in Hydrocrackers ............................................... 179 2.3.1.1.5 Undercutting LVGO to Increase Hydrocracker Utilization .............................. 180 2.3.1.1.6 Optimizing Operational Variables..................................................................... 180 2.3.1.1.6.1 Recycle Rate in Two-stage Units ................................................. 181 2.3.1.1.6.2 Setting Operational Pressure ........................................................ 181 2.3.1.1.6.3 Flow Control on Feeds from Coking Unit ................................... 182 2.3.1.1.7 Reactor Configuration ....................................................................................... 183 2.3.1.1.8 Optimized Hydrocracker Reactor Internals ....................................................... 183 2.3.1.1.9 Removing Welded Attachments from Reactor Internals ................................... 185 2.3.1.1.10 Changing Unit Configuration to Boost Yields and Process Alternative Feeds . 186 2.3.1.1.11 Large Single Process Train vs. Smaller Parallel Trains in Hydrocrackers ........ 187 2.3.1.1.12 Reactor Fabrication and Metallurgy .................................................................. 187 2.3.1.1.13 Comparison of Quench Systems ....................................................................... 189 2.3.1.1.14 Hydrocracker Stripper Revamp: From Packing to Trays .................................. 189 2.3.1.1.15 Hydrocracker Pump Selection ........................................................................... 190 2.3.1.1.16 Membranes for H2 Recovery from Hydrocrackers ............................................ 190 2.3.1.2 Fouling, Particulate Deposition, and Corrosion ................................................................... 191 2.3.1.2.1 Causes of Hydroprocesser Fouling and Possible Treatments............................ 191 2.3.1.2.2 Ammonium Chloride Fouling in Effluent Exchangers ..................................... 193 2.3.1.2.3 Elimination of Polynuclear Aromatics (PNA) Buildup..................................... 194 2.3.1.2.4 Iron Sulfide Buildup in VGO Hydrocrackers ................................................... 195 2.3.1.2.5 Feed Filter Operation ........................................................................................ 198 2.3.1.2.6 Mitigating High Temperature Hydrogen Attack ............................................... 198 2.3.1.2.7 Fouling in Furnace Tubes.................................................................................. 199 2.3.1.2.8 Corrosion in Overhead System ......................................................................... 200 2.3.1.2.9 Corrosion in Auxiliary Equipment .................................................................... 200 2.3.1.2.10 Redcuing Foaming in an Amine Scrubber ........................................................ 201 2.3.1.3 Operational Problems .......................................................................................................... 202 2.3.1.3.1 Increased Yield Using Multivariable Predictive Control (MPC) ...................... 202 2.3.1.3.2 Improving Hydrocracker Temperature Control ................................................ 205 2.3.1.3.3 Detecting Radial Temperature Spread and Preventing Reactor Runaway ........ 207

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TABLE OF CONTENTS 2.3.1.3.4 2.3.1.3.5 2.3.1.3.6 2.3.1.3.7 2.3.1.3.8 2.3.1.3.9

Hydrocracker Furnace Operations ..................................................................... 210 Causes of Overcracking ..................................................................................... 210 Improving the Performance of a Debutanizer.................................................... 211 Preventing Off-color Naphtha Product .............................................................. 214 Reducing the Level of Sulfur in Naphtha at EOR Conditions ........................... 214 Limiting Ammonia Concentration in the Cold High-pressure Separator Overhead ........................................................................................................................... 215 2.3.1.3.10 Inline Hydrocracker Cleaning System ............................................................... 215 2.3.1.3.11 Improving Recycle Gas Compressor Operation ................................................ 216 2.3.1.4 Catalyst Management ........................................................................................................... 217 2.3.1.4.1 Selection Process for Hydrocracking Catalysts ................................................. 217 2.3.1.4.2 Catalyst Testing on Different Scales ................................................................. 218 2.3.1.4.3 Catalyst Loading Precautions ............................................................................ 218 2.3.1.4.4 Measuring Hydrocracking Catalyst Activity ..................................................... 219 2.3.1.4.5 Catalysts for Processing Tight Oil ..................................................................... 220 2.3.1.4.6 Catalysts for Processing Various Feeds ............................................................. 220 2.3.1.4.7 Replacing a Noble Metal Catalyst with a Base Metal Catalyst ......................... 221 2.3.1.4.8 Catalyst Structure: Homogeneous vs. Stacked .................................................. 222 2.3.1.4.9 Ex-Situ Sulfiding (Presulfiding) of Hydrocracking Catalysts ........................... 222 2.3.1.4.10 Ammoniation Passivation during Startup .......................................................... 224 2.3.1.4.11 Disproportionate Catalyst Deactivation in the First Bed of a Hydrocracker ..... 225 2.3.1.4.12 Asphaltene Contribution to Catalyst Deactivation ............................................ 225 2.3.1.4.13 Impact of HPNAs on Catalyst Activity and Stability ........................................ 226 2.3.1.4.14 Regenerated Hydrocracking Catalyst Use ......................................................... 226 2.3.1.4.15 Catalyst Removal for Non-free Flowing Catalysts ............................................ 229 2.3.1.4.16 Recovering Spent Hydroprocessing Catalysts and Metal Reclamation ............. 229 2.3.1.5 Reducing Hydrocracker Energy Use .................................................................................... 231 2.3.1.5.1 Modeling............................................................................................................ 231 2.3.1.5.2 Cleaning ............................................................................................................. 232 2.3.1.5.3 Heat Integration ................................................................................................. 232 2.3.1.5.4 Power Recovery ................................................................................................. 232 2.3.1.5.5 Process Heaters .................................................................................................. 232 2.3.1.5.6 Impact of Catalysts ............................................................................................ 233 2.3.1.6 Hydrocracker Safety............................................................................................................. 233 2.3.1.6.1 Hydrocracker Safety Incidents .......................................................................... 233 2.3.1.6.2 Emergency Depressurization: Triggering Criteria, Rates and Modes ............... 235 2.3.1.6.3 Operational Status of Emergency Depressurizing Valves and Interlocks ......... 238 2.3.1.6.4 Safely Performing Inter-reactor Sampling in Hydrocrackers ............................ 238 2.3.1.6.5 Sampling of Light Streams around High-Pressure Equipment .......................... 238 2.3.2 Mild Hydrocracking (MHC) .................................................................................................................. 239 2.3.2.1 Mild Hydrocracking: Feedstock, Conversion, and Product Quality .................................... 239 2.3.2.2 Converting a Cat Feed or Distillate Hydrotreater to a Mild Hydrocracker .......................... 240 2.3.2.3 Options for Improving the Cycle Length of Mild Hydrocrackers ........................................ 243 2.3.3 Distillate Hydrocracking ....................................................................................................................... 243 2.3.3.1 Shifting from Maximum Naphtha to Maximum Middle Distillate Yields ........................... 243 2.3.3.2 Maximizing Diesel Production in VGO Hydrocrackers ...................................................... 246 2.3.3.3 Benefits of Moderate Pressure Hydrocracking (MPHC) in Clean Diesel Production.......... 248 2.3.3.4 Adjusting CAT to Maximize Diesel Production .................................................................. 249 2.3.3.5 Reactor Revamp to Improve ULSD Production................................................................... 250 2.3.3.6 Optimizing Saturation and Volume Swell in ULSD Service ............................................... 251 2.3.3.7 Loading Hydrocracking Catalyst in the Last Bed of a ULSD Unit ...................................... 252 2.3.3.8 Process Revamp for Added H2S Removal to Meet ULSD Standards .................................. 253 2.3.3.9 Improving Diesel Cetane from Hydrocrackers..................................................................... 253

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2.5 2.6

2.7

2.3.3.10 Hydrocracking Catalysts for Cold Flow Property Improvements........................................ 254 2.3.4 Integrated Processing Schemes ............................................................................................................ 255 2.3.4.1 Delayed Coker with Hydrocracker ...................................................................................... 255 2.3.4.2 Solvent Deasphalting with Hydrocracker ............................................................................ 258 2.3.4.3 Mild Hydrocracker with FCC .............................................................................................. 260 2.3.4.4 Integrated Processes for Heavy Oil Upgrading ................................................................... 261 REFINING R&D ALERT! .................................................................................................................................... 262 2.4.1 Introduction .......................................................................................................................................... 262 2.4.2 General Hydrocracking ........................................................................................................................ 266 2.4.2.1 Process ................................................................................................................................. 266 2.4.2.1.1 Patents ............................................................................................................... 266 2.4.2.1.2 Research ............................................................................................................ 268 2.4.2.2 Catalyst ................................................................................................................................ 269 2.4.2.2.1 Patents ............................................................................................................... 269 2.4.2.2.1.1 Novel Composition ...................................................................... 269 2.4.2.2.1.2 Preparation Method ..................................................................... 271 2.4.2.2.2 Research ............................................................................................................ 274 2.4.2.3 Hardware.............................................................................................................................. 275 2.4.2.3.1 Patents ............................................................................................................... 275 2.4.2.3.2 Research ............................................................................................................ 278 2.4.2.4 Integrated Operations (Conventional Feeds) ....................................................................... 279 2.4.3 Product Selective Hydrocracking ......................................................................................................... 280 2.4.3.1 Middle Distillates ................................................................................................................. 280 2.4.3.1.1 Process .............................................................................................................. 280 2.4.3.1.1.1 Patents .......................................................................................... 280 2.4.3.1.1.2 Research ....................................................................................... 282 2.4.3.1.2 Catalyst .............................................................................................................. 283 2.4.3.1.2.1 Patents .......................................................................................... 283 2.4.3.1.2.2 Research ....................................................................................... 287 2.4.3.2 Naphtha ................................................................................................................................ 289 2.4.3.3 BTX ..................................................................................................................................... 291 2.4.3.3.1 Patents ............................................................................................................... 291 2.4.3.3.2 Research ............................................................................................................ 293 2.4.4 Resid Hydrocracking ............................................................................................................................ 293 2.4.4.1 Process ................................................................................................................................. 293 2.4.4.1.1 Patents ............................................................................................................... 293 2.4.4.1.2 Research ............................................................................................................ 297 2.4.4.2 Catalyst ................................................................................................................................ 299 2.4.4.2.1 Patents ............................................................................................................... 299 2.4.4.2.2 Research ............................................................................................................ 302 2.4.5 Hydrocracking Alternative Feedstocks ................................................................................................. 304 2.4.5.1 Fischer-Tropsch Liquids ...................................................................................................... 304 2.4.5.1.1 Patents ............................................................................................................... 304 2.4.5.1.2 Research ............................................................................................................ 308 2.4.5.2 Renewable Feedstocks ......................................................................................................... 308 2.4.5.2.1 Patents ............................................................................................................... 308 2.4.5.2.2 Research ............................................................................................................ 311 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 313 CONSTRUCTION ................................................................................................................................................. 316 2.6.1 Recent Construction Activity ................................................................................................................. 316 2.6.2 Completed Construction Projects ......................................................................................................... 321 REFERENCES ..................................................................................................................................................... 332

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TABLE OF CONTENTS 3. Solvent Extraction and Deasphalting ....................................................................................... 359 3.1

3.2

3.3

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 359 3.1.1 Market Conditions and Outlook ............................................................................................................ 359 3.1.1.1 Refined Product Demand ..................................................................................................... 359 3.1.1.2 Resid Upgrading and Solvent Deasphalting Capacity.......................................................... 360 3.1.1.3 Construction Projects ........................................................................................................... 362 3.1.2 Technology Competition, Directions, and Future Prospects ................................................................ 363 3.1.2.1 Upstream Applications ......................................................................................................... 364 3.1.2.2 Integration with Other Bottom-of-the-Barrel Conversion Technologies ............................. 364 3.1.2.3 Utilization of Pitch/Asphaltene for Increased Margins ........................................................ 365 3.1.2.4 Trends in R&D ..................................................................................................................... 367 3.1.3 Conclusion ............................................................................................................................................. 368 STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 369 3.2.1 Introduction ........................................................................................................................................... 369 3.2.2 Commercial Processes .......................................................................................................................... 369 3.2.2.1 Axens ................................................................................................................................... 370 3.2.2.1.1 Solvahl ............................................................................................................... 370 3.2.2.1.2 Integrated Applications...................................................................................... 371 3.2.2.2 Foster Wheeler/UOP ............................................................................................................ 373 3.2.2.2.1 UOP/FWUSA Solvent Deasphalting ................................................................. 373 3.2.2.2.2 ASCOT .............................................................................................................. 377 3.2.2.3 ExxonMobil.......................................................................................................................... 380 3.2.2.4 KBR ..................................................................................................................................... 380 3.2.2.4.1 ROSE ................................................................................................................. 380 3.2.2.4.2 ROSEFLOW ...................................................................................................... 386 3.2.2.4.3 AQUAFORM .................................................................................................... 387 3.2.2.4.4 Integrated Solvent Deasphalting-Coking ........................................................... 388 3.2.2.5 Petrobras............................................................................................................................... 389 3.2.2.6 Uhde/ThyssenKrupp ............................................................................................................ 390 3.2.2.7 Well Resources..................................................................................................................... 391 3.2.3 Summary of Commercial Solvent Extraction and Deasphalting Processes .......................................... 395 PLANT OPERATIONS AND PRACTICES................................................................................................................. 398 3.3.1 Feed and Product Considerations ......................................................................................................... 398 3.3.1.1 Controlling Product Quality and Yield ................................................................................ 400 3.3.1.1.1 Solvent Selection ............................................................................................... 401 3.3.1.1.2 Temperature ....................................................................................................... 404 3.3.1.1.3 Pressure.............................................................................................................. 405 3.3.1.1.4 Solvent-to-oil Ratio and Circulation .................................................................. 405 3.3.1.2 Lubes Production vs. Fuels Production ................................................................................ 406 3.3.1.3 Three-product Configuration: The Value of Resins ............................................................. 406 3.3.1.4 Uncovering Economical Outlets for Asphaltene Products ................................................... 409 3.3.1.4.1 Conversion to Synthetic Fuels via F-T Processing ............................................ 410 3.3.1.4.2 Conversion to Bitumen ...................................................................................... 411 3.3.2 Synergies with Solvent Deasphalting .................................................................................................... 412 3.3.2.1 Implementing SDA Operations with Conventional or Deep-cut Vacuum Distillation ........ 412 3.3.2.2 DAO as a Feedstock for Downstream Conversion Units (conventional FCC and HC) ....... 415 3.3.2.3 Solvent Deasphalting in Conjunction with Bottoms Conversion Units ............................... 417 3.3.2.3.1 Coker ................................................................................................................. 417 3.3.2.3.2 Visbreaker.......................................................................................................... 418 3.3.2.3.3 Gasifier .............................................................................................................. 419 3.3.2.3.4 Resid Hydroprocessing ...................................................................................... 419 3.3.2.4 Energy Efficiency, Integration, and CO2 Emissions Considerations ................................... 420

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3.5

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3.3.2.5 Comparison of Various Refinery Configurations ................................................................ 422 3.3.3 Performance Issues and Process Monitoring ....................................................................................... 423 3.3.3.1 Crude Type and Asphaltene Carryover................................................................................ 423 3.3.3.2 H2S in Deasphalter Circulating Solvent ............................................................................... 424 3.3.3.3 H2S in Asphalt Storage Tanks ............................................................................................. 425 3.3.3.4 Level Indicators for Asphaltene Separators ......................................................................... 425 REFINING R&D ALERT! .................................................................................................................................... 425 3.4.1 Introduction .......................................................................................................................................... 425 3.4.2 Upstream ............................................................................................................................................... 429 3.4.2.1 Upgrading ............................................................................................................................ 429 3.4.2.1.1 Patents ............................................................................................................... 429 3.4.2.1.2 Research ............................................................................................................ 431 3.4.2.2 Asphaltene Conversion ........................................................................................................ 431 3.4.2.3 Integration ............................................................................................................................ 432 3.4.3 Downstream .......................................................................................................................................... 433 3.4.3.1 Process ................................................................................................................................. 433 3.4.3.1.1 Patents ............................................................................................................... 433 3.4.3.1.2 Research ............................................................................................................ 436 3.4.3.2 Hardware.............................................................................................................................. 439 3.4.3.3 Integration ............................................................................................................................ 440 3.4.3.3.1 Hydroprocessing ............................................................................................... 440 3.4.3.3.1.1 Patents .......................................................................................... 440 3.4.3.3.1.2 Research ....................................................................................... 443 3.4.3.3.2 Thermal/Catalytic Cracking .............................................................................. 444 3.4.3.3.2.1 Patents .......................................................................................... 444 3.4.3.3.2.2 Research ....................................................................................... 445 3.4.3.3.3 Steam Pyrolysis ................................................................................................. 446 3.4.3.3.4 Coking ............................................................................................................... 447 3.4.3.3.5 Gasification ....................................................................................................... 447 3.4.3.4 Specialty Products................................................................................................................ 448 3.4.3.4.1 Oil Products ....................................................................................................... 448 3.4.3.4.2 Asphalt .............................................................................................................. 450 3.4.3.4.3 Other.................................................................................................................. 451 3.4.3.5 Modeling .............................................................................................................................. 451 CONSTRUCTION ................................................................................................................................................. 452 3.5.1 Recent Construction Activity ................................................................................................................. 452 3.5.2 Completed Construction Projects ......................................................................................................... 454 REFERENCES ..................................................................................................................................................... 455

4. Latest Refining Technology Developments & Licensing......................................................... 465 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10

FLUID CATALYTIC CRACKING ........................................................................................................................... 465 ISOMERIZATION ................................................................................................................................................. 465 DESALTING ....................................................................................................................................................... 465 CRUDE DISTILLATION ....................................................................................................................................... 466 COKING ............................................................................................................................................................. 466 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 467 COGENERATION AND INTEGRATED GASIFICATION COMBINED CYCLE .............................................................. 468 SULFUR PLANT .................................................................................................................................................. 468 LUBE PRODUCTION ........................................................................................................................................... 469 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................ 469

2Q 2014 vii Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS 4.11 4.12 4.13 4.14 4.15 4.16

PROCESS CONTROLS AND SIMULATION ............................................................................................................. 471 XTL (BIOMASS-, COAL-, AND GAS-TO-LIQUID) ................................................................................................. 473 BIOFUELS PRODUCTION ..................................................................................................................................... 474 ENERGY MANAGEMENT..................................................................................................................................... 475 SITE EMISSIONS ................................................................................................................................................. 477 REFERENCES ...................................................................................................................................................... 478