Worldwide Refinery Processing Review - 1Q2014 by Hydrocarbon Publishing Company

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

First Quarter 2014 Sulfur Plant and Coking Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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

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

Review@Hydrocarbonpublishing.com

TABLE OF CONTENTS 1Q 2014 Review Sulfur Plant and Coking 1. Introduction ..................................................................................................................................... 1 2. Sulfur Plant ..................................................................................................................................... 5 2.1

2.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 5 2.1.1 Introduction .............................................................................................................................................. 5 2.1.2 Market Conditions and Outlook................................................................................................................ 5 2.1.2.1 Fuel Specifications and Unit Emissions Considerations.......................................................... 5 2.1.2.1.1 Transportation Fuels.............................................................................................. 5 2.1.2.1.2 Bunker Fuels ......................................................................................................... 7 2.1.2.1.3 Refinery Units Emitting Sulfur ............................................................................. 8 2.1.2.2 Sulfur Production, Demand, and Pricing ................................................................................. 8 2.1.2.2.1 Global Sulfur Production and Demand ................................................................. 8 2.1.2.2.2 Sulfur Prices ........................................................................................................ 10 2.1.2.3 Sulfur Plant Capacity and Expansion .................................................................................... 11 2.1.3 Technology Competition, Directions, and Future Prospects .................................................................. 13 2.1.3.1 Acid Gas Removal ................................................................................................................. 14 2.1.3.2 Claus ...................................................................................................................................... 17 2.1.3.3 Tailgas Treating ..................................................................................................................... 22 2.1.3.4 Alternative Sulfur Production and Handling Methods .......................................................... 26 2.1.3.5 Advanced Process Control ..................................................................................................... 27 2.1.4 Conclusion .............................................................................................................................................. 27 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 28 2.2.1 Introduction ............................................................................................................................................ 28 2.2.2 Commercial Process Technology............................................................................................................ 29 2.2.2.1 Acid Gas Removal ................................................................................................................. 29 2.2.2.1.1 BASF ................................................................................................................... 30 2.2.2.1.1.1 PuraTreat R .................................................................................... 30 2.2.2.1.1.2 aMDEA .......................................................................................... 30 2.2.2.1.2 Dow Gas Treating Products and Services ........................................................... 32 2.2.2.1.3 ExxonMobil......................................................................................................... 33 2.2.2.1.4 Fluor .................................................................................................................... 36 2.2.2.1.5 Huntsman ............................................................................................................ 37 2.2.2.1.6 INEOS Oxide ...................................................................................................... 37 2.2.2.1.7 Lurgi/Air Liquide ................................................................................................ 39 2.2.2.1.8 Shell Global Solutions......................................................................................... 40 2.2.2.1.8.1 ADIP .............................................................................................. 40 2.2.2.1.8.2 Sulfinol .......................................................................................... 41 2.2.2.1.8.3 ADIP-X and Sulfinol-X ................................................................. 41 2.2.2.1.9 Uhde .................................................................................................................... 42 2.2.2.1.9.1 Morphysorb.................................................................................... 42 2.2.2.1.9.2 Genosorb ........................................................................................ 43 2.2.2.1.10 UOP ..................................................................................................................... 44 2.2.2.2 Acid Gas Enrichment ............................................................................................................. 44 2.2.2.2.1 BASF ................................................................................................................... 45 2.2.2.2.2 ExxonMobil......................................................................................................... 46 2.2.2.2.3 Fluor .................................................................................................................... 48 2.2.2.2.4 TKK .................................................................................................................... 49

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2.2.2.4

Claus....................................................................................................................................... 50 2.2.2.3.1 Oxygen Enriched Claus ....................................................................................... 51 2.2.2.3.1.1 Air Liquide ..................................................................................... 51 2.2.2.3.1.2 CB&I .............................................................................................. 52 2.2.2.3.1.3 Duiker Combustion Engineers ....................................................... 53 2.2.2.3.1.4 Fluor ............................................................................................... 53 2.2.2.3.1.5 Goar, Allison & Associates ............................................................ 54 2.2.2.3.1.6 Linde/BOC Gases/WorleyParsons ................................................. 56 2.2.2.3.1.6.1 Low- Level Enrichment ............................................. 57 2.2.2.3.1.6.2 SURE Single Combustion .......................................... 57 2.2.2.3.1.6.3 SURE Double Combustion ........................................ 58 2.2.2.3.1.7 Lurgi/Air Liquide/Black & Veatch ................................................ 59 2.2.2.3.2 Sub-dew Point Claus ........................................................................................... 61 2.2.2.3.2.1 BP ................................................................................................... 61 2.2.2.3.2.2 DEG-ITS ........................................................................................ 62 2.2.2.3.2.3 Jacobs Comprimo Sulfur Solutions ................................................ 64 2.2.2.3.2.4 Linde .............................................................................................. 64 2.2.2.3.2.5 Lurgi/Air Liquide ........................................................................... 65 2.2.2.3.2.6 WorleyParsons ............................................................................... 66 2.2.2.3.3 Direct Oxidation .................................................................................................. 68 2.2.2.3.3.1 GTC Technology ............................................................................ 69 2.2.2.3.3.2 Jacobs Comprimo Sulfur Solutions ................................................ 69 2.2.2.3.3.2.1 SUPERCLAUS .......................................................... 70 2.2.2.3.3.2.2 EUROCLAUS ............................................................ 72 2.2.2.3.3.3 Linde .............................................................................................. 73 2.2.2.3.3.4 Lurgi/Air Liquide ........................................................................... 74 2.2.2.3.3.5 UOP/WorleyParsons ...................................................................... 74 2.2.2.3.4 Other Claus Processes ......................................................................................... 75 2.2.2.3.4.1 Foster Wheeler ............................................................................... 75 2.2.2.3.4.2 GTC Technology ............................................................................ 76 2.2.2.3.4.3 Siirtec Nigi ..................................................................................... 77 2.2.2.3.4.3.1 Modified Claus Process .............................................. 77 2.2.2.3.4.3.2 Advanced Ammonia Claus Technology..................... 78 2.2.2.3.4.4 WorleyParsons ............................................................................... 80 2.2.2.3.4.4.1 Modified Claus Process .............................................. 80 2.2.2.3.4.4.2 Ammonia Destruction ................................................ 81 Tailgas Treatment ................................................................................................................... 81 2.2.2.4.1 BASF ................................................................................................................... 81 2.2.2.4.2 CANSOLV Technologies .................................................................................... 82 2.2.2.4.3 CB&I ................................................................................................................... 85 2.2.2.4.4 DuPont Clean Technologies ................................................................................ 86 2.2.2.4.5 Fluor .................................................................................................................... 88 2.2.2.4.6 Linde .................................................................................................................... 88 2.2.2.4.7 Lurgi/Air Liquide ................................................................................................ 89 2.2.2.4.8 MECS .................................................................................................................. 90 2.2.2.4.8.1 DynaWave ...................................................................................... 90 2.2.2.4.8.2 SUPERCLAUS/DynaWave ........................................................... 93 2.2.2.4.8.3 ClausMaster.................................................................................... 94 2.2.2.4.9 Prosernat IFP Group Technologies...................................................................... 94 2.2.2.4.9.1 CLAUSPOL ................................................................................... 94 2.2.2.4.9.2 Sultimate ........................................................................................ 96 2.2.2.4.10 Shell Global Solutions ......................................................................................... 97 2.2.2.4.11 Siirtec Nigi ........................................................................................................... 99

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TABLE OF CONTENTS 2.2.2.4.12 SWAPSOL ........................................................................................................ 100 2.2.2.4.13 Technip.............................................................................................................. 102 2.2.2.4.13.1 Reduction Absorption Recycle .................................................... 102 2.2.2.4.13.2 Multipurpose Reduction Absorption Recycle .............................. 103 2.2.2.4.14 TKK .................................................................................................................. 104 2.2.2.4.15 UOP/WorleyParsons ......................................................................................... 105 2.2.2.4.15.1 Beavon Sulfur Removal ............................................................... 105 2.2.2.4.15.2 Catalytic Thermal Incineration .................................................... 108 2.2.2.4.15.3 Ammonia Combustion ................................................................. 109 2.2.2.5 Alternative Sulfur Removal Processes................................................................................. 109 2.2.2.5.1 Adding a Redox Process for Increased Sulfur Recovery .................................. 110 2.2.2.5.1.1 Gas Technology Products (GTP) ................................................. 110 2.2.2.5.1.1.1 LO-CAT .................................................................... 110 2.2.2.5.1.1.2 LO-CAT II ................................................................ 111 2.2.2.5.1.1.3 MINI-CAT ................................................................ 113 2.2.2.5.1.2 Prosernat IFP Group Technologies/Le Gaz Integral .................... 113 2.2.2.5.1.3 Shell Global Solutions ................................................................. 114 2.2.2.5.2 Production of Sulfuric Acid .............................................................................. 115 2.2.2.5.2.1 DuPont STRATCO ...................................................................... 115 2.2.2.5.2.2 Haldor Topsøe ............................................................................. 115 2.2.2.5.2.2.1 Wet Gas Sulfuric Acid (WSA) ................................. 115 2.2.2.5.2.2.2 SNOX ....................................................................... 120 2.2.2.5.3 Other Processes ................................................................................................. 122 2.2.2.5.3.1 Black & Veatch............................................................................ 122 2.2.2.5.3.2 CrystaTech/URS .......................................................................... 122 2.2.2.5.3.3 Paques BV/Shell Global Solutions .............................................. 124 2.2.2.5.3.4 Paques BV/Shell Global Solutions/UOP ..................................... 126 2.2.2.6 Sulfur Degasification ........................................................................................................... 128 2.2.2.6.1 Black & Veatch ................................................................................................. 129 2.2.2.6.2 Brimrock Group Inc. ......................................................................................... 130 2.2.2.6.3 Enersul .............................................................................................................. 130 2.2.2.6.4 ExxonMobil....................................................................................................... 130 2.2.2.6.5 Goar, Allison & Associates ............................................................................... 131 2.2.2.6.6 Lurgi/Air Liquide .............................................................................................. 132 2.2.2.6.7 Shell Global Solutions....................................................................................... 133 2.2.2.6.8 Siirtec Nigi ........................................................................................................ 133 2.2.2.6.9 WorleyParsons .................................................................................................. 134 2.2.2.7 Sulfur Finishing Processes ................................................................................................... 134 2.2.2.7.1 Brimrock Group Inc. ......................................................................................... 134 2.2.2.7.2 Devco USA ....................................................................................................... 135 2.2.2.7.3 Enersul .............................................................................................................. 136 2.2.2.7.3.1 GX ............................................................................................... 137 2.2.2.7.3.2 WetPrill ........................................................................................ 138 2.2.2.7.4 Sandvik.............................................................................................................. 138 2.2.3 Commercial Catalysts ........................................................................................................................... 140 2.2.3.1 Axens ................................................................................................................................... 141 2.2.3.1.1 Claus Catalysts .................................................................................................. 141 2.2.3.1.2 Tailgas Treating Catalysts ................................................................................. 142 2.2.3.2 BASF Catalysts .................................................................................................................... 144 2.2.3.3 Clariant Catalysts ................................................................................................................. 146 2.2.3.4 Criterion Catalysts & Technologies ..................................................................................... 147 2.2.3.5 UOP ..................................................................................................................................... 148

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2.2.4 Advanced Process Control and Simulation ........................................................................................... 149 2.2.4.1 Axens ................................................................................................................................... 149 2.2.4.2 Aspen Tech........................................................................................................................... 149 2.2.4.3 Bryan Research and Engineering ......................................................................................... 149 2.2.4.4 Jacobs Comprimo Sulfur Solutions ...................................................................................... 150 2.2.4.5 Optimized Gas Treating ....................................................................................................... 150 2.2.4.6 Shell Global Solutions.......................................................................................................... 151 2.2.5 Analyzers and Instrumentation .............................................................................................................. 151 2.2.5.1 AMETEK ............................................................................................................................. 151 2.2.5.2 Applied Analytics................................................................................................................. 152 2.2.5.3 PAC LP ................................................................................................................................ 152 2.2.6 Summary of Commercially Available Sulfur Plant Technologies ......................................................... 152 2.2.7 Comparison of Commercial Sulfur Plant Catalysts .............................................................................. 163 PLANT OPERATIONS AND PRACTICES................................................................................................................. 165 2.3.1 Acid Gas Removal ................................................................................................................................. 165 2.3.1.1 Amine Solvent Replacement ................................................................................................ 165 2.3.1.2 Optimizing an Amine Unit ................................................................................................... 166 2.3.1.3 Amine System Operating Issues........................................................................................... 169 2.3.1.3.1 Contaminants ..................................................................................................... 169 2.3.1.3.1.1 Importance of Chemical Analysis ................................................ 169 2.3.1.3.1.2 Hydrocarbon Carryover in Amine Acid Gas ................................ 170 2.3.1.3.1.3 Filtration and Separation of Contaminants ................................... 172 2.3.1.3.1.4 Removal of HCN.......................................................................... 173 2.3.1.3.2 Wet Acid Gas Corrosion.................................................................................... 174 2.3.1.3.3 Amine Solution Corrosion ................................................................................. 174 2.3.1.3.4 Foaming ............................................................................................................. 177 2.3.1.3.5 Amine Losses .................................................................................................... 178 2.3.1.3.6 Instability in Amine Regenerator ....................................................................... 179 2.3.1.4 Proper Heat Exchanger Design for Acid Gas Removal Units .............................................. 180 2.3.1.5 Safe Acid Gas Handling ....................................................................................................... 181 2.3.1.6 Refractory Upgrade .............................................................................................................. 182 2.3.1.7 Fuel Gas Sweetening in a Hydrocracker Fractionation Section ........................................... 183 2.3.2 Claus Process ........................................................................................................................................ 184 2.3.2.1 Increasing Sulfur Recovery Capacity ................................................................................... 184 2.3.2.2 The Effects of Extreme Turndowns ..................................................................................... 186 2.3.2.3 Benefits and Drawbacks of Oxygen Enrichment ................................................................. 187 2.3.2.4 Claus Unit Shutdowns .......................................................................................................... 188 2.3.2.5 Claus Catalyst Life and Reuse.............................................................................................. 189 2.3.2.6 Advanced Control Systems for Claus Plants ........................................................................ 190 2.3.2.7 Preventing Overpressure in Claus Units .............................................................................. 191 2.3.2.8 Processing SWS Offgas in Claus Units................................................................................ 192 2.3.2.9 Analyzing Sulfur Content in Claus Tailgas .......................................................................... 193 2.3.2.10 Neural Network for Claus Temperature Control .................................................................. 194 2.3.2.11 Benefits of Partial Oxidation Process vs. Modified Claus ................................................... 195 2.3.3 Tailgas Treating .................................................................................................................................... 196 2.3.3.1 Experience with Designing a TGTU .................................................................................... 196 2.3.3.2 Proper TGT Catalyst Selection............................................................................................. 197 2.3.3.3 Cold Bed Adsorption Units for Tailgas Treating ................................................................. 198 2.3.4 Small Scale Sulfur Plants ...................................................................................................................... 200 2.3.5 Improving Energy Efficiency of Sulfur Plants ....................................................................................... 200 2.3.6 Liquid Scavengers for H2S Removal...................................................................................................... 201

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2.5 2.6

2.7

2.3.7 Sulfur Storage and Handling ................................................................................................................ 202 2.3.7.1 Premium Sulfur Specifications ............................................................................................ 202 2.3.7.2 Liquid Loading and Transport ............................................................................................. 203 2.3.7.3 Blocking ............................................................................................................................... 205 REFINING R&D ALERT! .................................................................................................................................... 206 2.4.1 Introduction .......................................................................................................................................... 206 2.4.2 Acid Gas Removal ................................................................................................................................. 208 2.4.2.1 Simultaneous Removal of SOx and CO2 ............................................................................. 208 2.4.2.2 Absorbent Materials ............................................................................................................. 209 2.4.2.3 Amine Regeneration ............................................................................................................ 211 2.4.2.4 Miscellaneous ...................................................................................................................... 212 2.4.2.4.1 Patents ............................................................................................................... 212 2.4.2.4.2 Research ............................................................................................................ 212 2.4.3 Claus Technology ................................................................................................................................. 212 2.4.3.1 Process ................................................................................................................................. 212 2.4.3.1.1 Multiple Claus Reactors .................................................................................... 212 2.4.3.1.2 Oxygen Enrichment........................................................................................... 213 2.4.3.1.2.1 Patents .......................................................................................... 213 2.4.3.1.2.2 Research ....................................................................................... 214 2.4.3.1.3 Miscellaneous Claus Process Improvements..................................................... 215 2.4.3.1.3.1 Patents .......................................................................................... 215 2.4.3.1.3.2 Research ....................................................................................... 217 2.4.3.2 Catalyst ................................................................................................................................ 218 2.4.3.3 Hardware.............................................................................................................................. 218 2.4.4 Tailgas Treating .................................................................................................................................... 220 2.4.4.1 Process ................................................................................................................................. 220 2.4.4.2 Catalyst ................................................................................................................................ 221 2.4.4.2.1 Patents ............................................................................................................... 221 2.4.4.2.2 Research ............................................................................................................ 222 2.4.5 Sulfur Degasification ............................................................................................................................ 222 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 224 CONSTRUCTION ................................................................................................................................................. 226 2.6.1 Recent Construction Activity ................................................................................................................. 226 2.6.2 Completed Construction Projects ......................................................................................................... 231 REFERENCES ..................................................................................................................................................... 267

3. Coking .......................................................................................................................................... 283 3.1

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ......................................................................................... 283 3.1.1 Introduction .......................................................................................................................................... 283 3.1.2 Market Conditions and Outlook............................................................................................................ 283 3.1.2.1 Refined Products Supply and Demand ................................................................................ 283 3.1.2.2 Increasing Use of Opportunity Crudes ................................................................................ 286 3.1.2.3 Bottoms Upgrading Capacity and Expansion: Focus on Coking ......................................... 291 3.1.2.4 Construction ......................................................................................................................... 292 3.1.2.5 Petroleum Coke Production, Quality, and Use .................................................................... 292 3.1.2.6 Government Legislation ...................................................................................................... 295 3.1.3 Technology Competition, Directions, and Future Prospects ................................................................ 296 3.1.3.1 Bottom-of-the-Barrel Upgrading Technology Trends ......................................................... 296 3.1.3.2 Latest Developments in Coking Technology ....................................................................... 300 3.1.4 Conclusion ............................................................................................................................................ 304

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STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 305 3.2.1 Introduction ........................................................................................................................................... 305 3.2.2 Commercial Processes .......................................................................................................................... 307 3.2.2.1 Bechtel.................................................................................................................................. 307 3.2.2.1.1 ThruPlus ............................................................................................................ 307 3.2.2.1.2 Integration with Power Generation .................................................................... 310 3.2.2.2 ExxonMobil.......................................................................................................................... 312 3.2.2.2.1 FLUID COKING ............................................................................................... 313 3.2.2.2.2 FLEXICOKING ................................................................................................ 315 3.2.2.3 Foster Wheeler/UOP ............................................................................................................ 319 3.2.2.3.1 SYDEC .............................................................................................................. 319 3.2.2.3.2 Integration Opportunities ................................................................................... 323 3.2.2.3.2.1 Combined Coking and Deasphalting............................................ 323 3.2.2.3.2.2 Petropower and Combined Gasification-CFB Plants ................... 326 3.2.2.4 KBR ..................................................................................................................................... 328 3.2.2.4.1 Delayed Coking ................................................................................................. 328 3.2.2.4.2 Integrated Solvent Deasphalting-Coking ........................................................... 330 3.2.2.5 Lummus Technology, a CB&I Company ............................................................................. 330 3.2.2.5.1 Delayed Coking ................................................................................................. 330 3.2.2.5.2 Maruzen-Lummus Process ................................................................................ 333 3.2.2.5.3 Vertical Plate Coke Drum .................................................................................. 333 3.2.2.6 Petrobras............................................................................................................................... 335 3.2.2.7 Sinopec & LPEC .................................................................................................................. 335 3.2.3 Summary of Commercial Coking Processes.......................................................................................... 337 3.2.4 Additional Coking Technologies ........................................................................................................... 339 3.2.4.1 Automated/Remote Unheading ............................................................................................ 339 3.2.4.1.1 CITGO ............................................................................................................... 339 3.2.4.1.2 Curtiss Wright Flow Control ............................................................................. 340 3.2.4.1.3 Flowserve .......................................................................................................... 340 3.2.4.1.4 Metso ................................................................................................................. 341 3.2.4.1.5 SIS-Tech ............................................................................................................ 342 3.2.4.1.6 Zimmermann & Jansen ...................................................................................... 342 3.2.4.2 Hydrocyclones...................................................................................................................... 342 3.2.4.3 Coker Heater Tube Coating.................................................................................................. 342 3.2.5 Alternatives to Conventional Coking Technologies .............................................................................. 343 3.2.5.1 Chiyoda ................................................................................................................................ 343 3.2.5.2 ETX Systems ........................................................................................................................ 347 3.2.5.3 Toyo Engineering ................................................................................................................. 348 3.2.5.4 Non-commercial Coking Process Technologies .................................................................. 349 3.2.6 Comparison of Commercially Available Advanced Control and Optimization Systems ....................... 350 PLANT OPERATIONS AND PRACTICES................................................................................................................. 353 3.3.1 Meeting Feed Challenges ...................................................................................................................... 353 3.3.1.1 Processing Refinery Sludge ................................................................................................. 353 3.3.1.2 Hydrotreated VGO and Resid Streams ................................................................................ 354 3.3.1.3 FCC Slurry Oil Addition ...................................................................................................... 355 3.3.1.4 Coping with High Asphaltene and CCR Feeds .................................................................... 356 3.3.1.5 Processing Tight Oil ............................................................................................................. 357 3.3.2 Process Operating Variables ................................................................................................................ 357 3.3.2.1 Impact on Product Distribution ............................................................................................ 357 3.3.2.2 Significance of Coke Drum Pressure and Recycle Rate ...................................................... 358 3.3.2.3 Influence of Operating Conditions on Heater Run Lengths ................................................. 360 3.3.2.4 Operational Recommendations to Avoid Feed Line Plugging ............................................. 360 3.3.2.5 Optimal Transfer Line Quench Injection Angle to Improve Heat Transfer ......................... 361

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TABLE OF CONTENTS 3.3.2.6 Impact of Steam Rates ......................................................................................................... 361 3.3.2.7 Effect of Changing Coke Drum Cycle Time ....................................................................... 362 3.3.3 Mitigating Coker Fouling and Corrosion ............................................................................................. 362 3.3.3.1 Handling of Solids ............................................................................................................... 362 3.3.3.2 Minimizing Heater Tube Coking ......................................................................................... 363 3.3.3.3 Online vs. Offline Cleaning Methods: Spalling and Pigging............................................... 367 3.3.3.4 Frequency of Overhead Vapor Line Cleanings ................................................................... 370 3.3.3.5 Fractionator Fouling ............................................................................................................ 371 3.3.3.6 Coker Naphtha Reboiler Fouling ......................................................................................... 372 3.3.3.7 Plugging in Resid Lines ....................................................................................................... 373 3.3.4 Coke Drum Foaming Issues .................................................................................................................. 373 3.3.4.1 Primary Causes and Solutions ............................................................................................. 373 3.3.4.2 Antifoam Additive Use in Coke Drums and Associated Problems ..................................... 375 3.3.5 Enhancing Liquid Products .................................................................................................................. 376 3.3.5.1 Balancing LCGO and HCGO Yield to Optimize Refinery Products ................................... 376 3.3.5.2 Methods to Desulfurize Coker Naphtha .............................................................................. 377 3.3.5.3 Coker Additives to Increase Liquid Yield ........................................................................... 378 3.3.5.4 Reducing Naphtha Yield to Increase Liquid Yield .............................................................. 379 3.3.6 Coke Product Considerations ............................................................................................................... 379 3.3.6.1 Coke Grades and Morphology ............................................................................................. 379 3.3.6.2 Coke Density ....................................................................................................................... 381 3.3.6.3 Influencing Coke Quality..................................................................................................... 381 3.3.6.4 Controlling Shot Coke Formation........................................................................................ 383 3.3.7 Synergies with Other Bottoms Conversion Units .................................................................................. 385 3.3.7.1 Vacuum Distillation ............................................................................................................. 385 3.3.7.2 Solvent Deasphalting ........................................................................................................... 386 3.3.7.3 Hydrocracker ....................................................................................................................... 388 3.3.7.4 Gasification and/or CFB for Utilities Cogeneration ............................................................ 391 3.3.8 Hardware Solutions .............................................................................................................................. 393 3.3.8.1 Metallurgy for Coker Heater Tubes ..................................................................................... 393 3.3.8.2 Selecting Main Fractionator Internals .................................................................................. 394 3.3.8.3 Valve Selection: Pros and Cons ........................................................................................... 395 3.3.8.4 Coker Drum Insulation Concerns ........................................................................................ 396 3.3.9 Revamps and Turnarounds ................................................................................................................... 397 3.3.9.1 Revamps to Boost Coker Capacity ...................................................................................... 397 3.3.9.1.1 Increasing Drum Size ........................................................................................ 397 3.3.9.1.2 Reducing Cycle Time and Adjusting Operating Parameters ............................. 400 3.3.9.2 Revamping to Recover Coke Drum Blowdown Vapor ....................................................... 403 3.3.9.3 Furnace Tube Revamp to Handle Significantly Heavier Feed............................................. 403 3.3.9.4 Retrofitting a Visbreaker to Eliminate Fuel Oil Production ................................................ 403 3.3.9.5 EPC Management Service to Optimize Coker Revamp Process ......................................... 404 3.3.9.6 New Revamp Approach Incorporating Modular Equipment ............................................... 404 3.3.9.7 Benefits of Structural Engineering Contractors ................................................................... 405 3.3.10 Energy Efficiency and Environmental Emissions ................................................................................. 405 3.3.10.1 Energy Characteristics ......................................................................................................... 405 3.3.10.1.1 Heat Integration ................................................................................................. 406 3.3.10.1.2 Steam Generation and Heat Recovery from Overhead Vapors ......................... 406 3.3.10.1.3 Saving Energy in the Main Fractionator ........................................................... 406 3.3.10.1.4 Optimization ...................................................................................................... 407 3.3.10.2 Controlling Emissions.......................................................................................................... 407 3.3.10.2.1 Coke Drum Emission Reduction ....................................................................... 407 3.3.10.2.2 CO2 Emissions Considerations .......................................................................... 408 3.3.10.2.3 Reduce Flaring from Closed Blowdown System .............................................. 408

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3.4

3.3.10.2.4 Minimizing Post-Drum Coke Particulate Emissions ......................................... 409 3.3.11 Process Monitoring, Analytical Methods, and Instrumentation............................................................ 409 3.3.11.1 Key Process Indicators ......................................................................................................... 409 3.3.11.2 Heater Tube Fouling: Utilizing a Coke Stability Index to Characterize Potential Feeds ..... 410 3.3.11.3 Methods of Coke Drum Level Detection ............................................................................. 413 3.3.11.4 Flowmeter Selection ............................................................................................................. 414 3.3.11.5 Utilizing Artificial Neural Networks to Model Coker Heater Performance......................... 414 3.3.11.6 Monitoring Drum Wall Condition........................................................................................ 415 3.3.12 Improving Coker Safety ......................................................................................................................... 416 3.3.12.1 General Guidelines ............................................................................................................... 416 3.3.12.2 Unheading and Coke Cutting Safety Measures .................................................................... 418 3.3.12.3 Avoid Low Heater-outlet Temperatures and Conditions for Hot Spots Formation ............. 419 3.3.12.4 Implement Independent Review of Practices and Management of Change Procedures ...... 420 3.3.12.5 Identifying and Preventing Drum Cracks and Pipe Failure.................................................. 421 3.3.12.6 Avoiding Exposure to H2S ................................................................................................... 423 3.3.12.7 Mitigating Leak Issues ......................................................................................................... 423 3.3.12.8 Closed Processes .................................................................................................................. 424 3.3.12.8.1 Closed Coke Slurry System ............................................................................... 424 3.3.12.8.2 Continuous Coking ............................................................................................ 425 3.3.13 Coker Plant Water System ..................................................................................................................... 426 3.3.13.1 Reducing Coker Fines in Cutting Water .............................................................................. 426 3.3.13.2 Performing a Coker Water Balance to Optimize Steam Purging and Sour Water Make ..... 427 3.3.14 Coke Bed Instability .............................................................................................................................. 428 REFINING R&D ALERT! ..................................................................................................................................... 428 3.4.1 Introduction ........................................................................................................................................... 428 3.4.2 Delayed Coking ..................................................................................................................................... 432 3.4.2.1 Patents .................................................................................................................................. 432 3.4.2.1.1 Improving Liquid Quality/Yields ...................................................................... 433 3.4.2.1.2 Improved Decoking ........................................................................................... 436 3.4.2.1.3 Resolve Fouling/Foaming Issues ....................................................................... 438 3.4.2.1.4 Continuous Delayed Coking .............................................................................. 442 3.4.2.1.5 Delayed Coking of Particular Feedstocks .......................................................... 443 3.4.2.1.6 Miscellaneous .................................................................................................... 444 3.4.2.2 Research ............................................................................................................................... 448 3.4.3 Fluidized-bed Coking ............................................................................................................................ 449 3.4.4 Integration ............................................................................................................................................. 450 3.4.4.1 Patents .................................................................................................................................. 450 3.4.4.2 Research ............................................................................................................................... 452 3.4.5 Specialized and Unconventional Feeds (excluding Bitumen) ............................................................... 453 3.4.5.1 Patents .................................................................................................................................. 453 3.4.5.2 Research ............................................................................................................................... 456 3.4.6 Product Fractionation and Treatment .................................................................................................. 457 3.4.6.1 Patents .................................................................................................................................. 457 3.4.6.2 Research ............................................................................................................................... 461 3.4.7 Coke Quality and Morphology .............................................................................................................. 461 3.4.8 Coker Additives ..................................................................................................................................... 465 3.4.9 Monitoring and Control ........................................................................................................................ 470 3.4.9.1 Patents .................................................................................................................................. 470 3.4.9.1.1 Remote Controlled Decoking ............................................................................ 470 3.4.9.1.2 Valves ................................................................................................................ 475 3.4.9.1.3 Analysis and Control ......................................................................................... 477 3.4.9.2 Research ............................................................................................................................... 480

1Q 2014 viii Hydrocarbon Publishing Co./Copyright Protected

TABLE OF CONTENTS

3.5 3.6

3.7

3.4.10 Furnace ................................................................................................................................................. 480 3.4.10.1 Furnaces and Furnace Equipment ........................................................................................ 480 3.4.10.2 Furnace Fouling Prevention ................................................................................................. 486 3.4.11 Maintenance.......................................................................................................................................... 489 3.4.12 Hardware .............................................................................................................................................. 490 3.4.12.1 Coke Drums ......................................................................................................................... 490 3.4.12.2 Cutting Tools ....................................................................................................................... 491 3.4.12.3 Miscellaneous ...................................................................................................................... 493 3.4.13 Petroleum Coke Handling and Usage .................................................................................................. 495 3.4.14 Water Handling and Treatment ............................................................................................................ 495 3.4.14.1 Patents .................................................................................................................................. 495 3.4.14.2 Research ............................................................................................................................... 499 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 501 CONSTRUCTION ................................................................................................................................................. 503 3.6.1 Recent Construction Activity ................................................................................................................. 503 3.6.2 Completed Construction Projects ......................................................................................................... 507 REFERENCES ..................................................................................................................................................... 516

4. Latest Refining Technology Developments & Licensing......................................................... 537 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15

HYDROTREATING (INCLUDING HDS) ................................................................................................................ 537 ISOMERIZATION ................................................................................................................................................. 537 HEAVY OIL, EXTRA-HEAVY OIL, AND BITUMEN UPGRADING ........................................................................... 537 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 538 ASPHALT PRODUCTION ..................................................................................................................................... 538 COGENERATION AND INTEGRATED GASIFICATION COMBINED CYCLE .............................................................. 539 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................ 539 CATALYST AND CARRIER SUPPORT DEVELOPMENTS ........................................................................................ 541 XTL (BIOMASS-, COAL-, AND GAS-TO-LIQUID) ................................................................................................ 541 BIOFUELS PRODUCTION..................................................................................................................................... 543 ENERGY MANAGEMENT .................................................................................................................................... 544 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) ............................................................................. 544 SITE EMISSIONS ................................................................................................................................................. 545 PLANT SAFETY .................................................................................................................................................. 546 REFERENCES ..................................................................................................................................................... 546