WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in One Single Source
First Quarter 2016 Sulfur Plant, and Aromatics Production Plus
Latest Refining Technology Developments & Licensing
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TABLE OF CONTENTS 1Q 2016 Review Sulfur Plant, and Aromatics Production 1. INTRODUCTION 2. SULFUR PLANT ....................................................................................................................................................... 5 2.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .............................................................................................................. 5 2.1.1 Introduction.................................................................................................................................................. 5 2.1.2 Market Conditions and Outlook ................................................................................................................... 5 2.1.2.1 Fuel Specifications and Unit Emissions Considerations .................................................................................. 5 2.1.2.1.1 Transportation Fuels ................................................................................................................... 5 2.1.2.1.2 Refinery Units Emitting Sulfur .................................................................................................... 8 2.1.2.1.3 GHG Emissions ............................................................................................................................ 8 2.1.2.2 Sulfur Production, Demand, and Pricing ........................................................................................................ 9 2.1.2.2.1 Global Sulfur Production and Demand ....................................................................................... 9 2.1.2.2.1.1 Sulfur Production ................................................................................................ 9 2.1.2.2.1.2 Sulfur Demand .................................................................................................. 12 2.1.2.2.2 Sulfur Prices .............................................................................................................................. 14 2.1.2.3 Sulfur Plant Capacity and Expansion ............................................................................................................ 15
2.1.3 Technology Competition, Directions, and Future Prospects ...................................................................... 16 2.1.3.1 2.1.3.2 2.1.3.3 2.1.3.4 2.1.3.5
Acid Gas Removal ......................................................................................................................................... 17 Claus ............................................................................................................................................................. 21 Tailgas Treating ............................................................................................................................................ 28 Alternative Sulfur Production and Handling Methods ................................................................................. 33 Advanced Process Control ............................................................................................................................ 35
2.1.4 Conclusion .................................................................................................................................................. 36 2.2 STATE‐OF‐THE‐ART TECHNOLOGY ................................................................................................................................... 37 2.2.1 Introduction................................................................................................................................................ 37 2.2.2 Commercial Process Technology ................................................................................................................ 38 2.2.2.1 Acid Gas Removal ......................................................................................................................................... 38 2.2.2.1.1 BASF .......................................................................................................................................... 39 2.2.2.1.1.1 PuraTreat R ....................................................................................................... 39 2.2.2.1.1.2 aMDEA .............................................................................................................. 39 2.2.2.1.2 Dow Gas Treating Products and Services .................................................................................. 41 2.2.2.1.3 ExxonMobil ............................................................................................................................... 42 2.2.2.1.4 Fluor .......................................................................................................................................... 45 2.2.2.1.5 Huntsman ................................................................................................................................. 46 2.2.2.1.6 INEOS Oxide .............................................................................................................................. 47 2.2.2.1.7 Lurgi/Air Liquide ....................................................................................................................... 48 2.2.2.1.8 Shell Global Solutions ............................................................................................................... 49 2.2.2.1.8.1 ADIP .................................................................................................................. 50 2.2.2.1.8.2 Sulfinol .............................................................................................................. 50 2.2.2.1.8.3 ADIP‐X and Sulfinol‐X ........................................................................................ 51 2.2.2.1.9 Uhde ......................................................................................................................................... 52 2.2.2.1.9.1 Morphysorb ...................................................................................................... 52 2.2.2.1.9.2 Genosorb .......................................................................................................... 53 2.2.2.1.10 UOP ........................................................................................................................................... 54 2.2.2.2 Acid Gas Enrichment .................................................................................................................................... 55 2.2.2.2.1 BASF .......................................................................................................................................... 56 2.2.2.2.2 ExxonMobil ............................................................................................................................... 57 2.2.2.2.3 Fluor .......................................................................................................................................... 59 2.2.2.2.4 TKK Technology Co. .................................................................................................................. 60 2.2.2.2.4.1 HIGHSULF PLUS ................................................................................................. 60 2.2.2.2.4.2 TC ...................................................................................................................... 61
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TABLE OF CONTENTS 2.2.2.3 Claus ............................................................................................................................................................. 62 2.2.2.3.1 Oxygen Enriched Claus ............................................................................................................. 63 2.2.2.3.1.1 Air Liquide ......................................................................................................... 63 2.2.2.3.1.2 CB&I .................................................................................................................. 64 2.2.2.3.1.3 Duiker Combustion Engineers .......................................................................... 64 2.2.2.3.1.4 Fluor .................................................................................................................. 65 2.2.2.3.1.5 Goar, Allison & Associates ................................................................................ 65 2.2.2.3.1.6 Linde/BOC Gases/WorleyParsons ..................................................................... 68 2.2.2.3.1.6.1 Low‐ level Enrichment .............................................................. 68 2.2.2.3.1.6.2 SURE Single Combustion ........................................................... 69 2.2.2.3.1.6.3 SURE Double Combustion ......................................................... 70 2.2.2.3.1.7 Lurgi/Air Liquide/Black & Veatch ...................................................................... 72 2.2.2.3.2 Sub‐dew Point Claus ................................................................................................................. 73 2.2.2.3.2.1 BP ...................................................................................................................... 73 2.2.2.3.2.2 DEG‐ITS ............................................................................................................. 74 2.2.2.3.2.3 Jacobs Comprimo Sulfur Solutions ................................................................... 76 2.2.2.3.2.4 Lurgi/Air Liquide ............................................................................................... 77 2.2.2.3.3 Direct Oxidation ....................................................................................................................... 78 2.2.2.3.3.1 GTC Technology ................................................................................................ 78 2.2.2.3.3.2 Jacobs Comprimo Sulfur Solutions ................................................................... 79 2.2.2.3.3.2.1 SUPERCLAUS ............................................................................. 79 2.2.2.3.3.2.2 EUROCLAUS............................................................................... 81 2.2.2.3.3.3 Lurgi/Air Liquide ............................................................................................... 83 2.2.2.3.3.4 Prosernat .......................................................................................................... 83 2.2.2.3.3.5 UOP/WorleyParsons ......................................................................................... 86 2.2.2.3.4 Other Claus Processes .............................................................................................................. 87 2.2.2.3.4.1 Amec Foster Wheeler ....................................................................................... 87 2.2.2.3.4.2 GTC Technology ................................................................................................ 89 2.2.2.3.4.2.1 GT‐SPOC .................................................................................... 89 2.2.2.3.4.2.2 GT‐Claus .................................................................................... 90 2.2.2.3.4.2.3 GT‐SSR ....................................................................................... 90 2.2.2.3.4.2.4 GT‐SULFCAT .............................................................................. 91 2.2.2.3.4.3 Siirtec Nigi ......................................................................................................... 93 2.2.2.3.4.3.1 Modified Claus Process ............................................................. 93 2.2.2.3.4.3.2 Advanced Ammonia Claus Technology ..................................... 94 2.2.2.3.4.4 Sulfur Operations Support, Inc. ........................................................................ 95 2.2.2.3.4.5 WorleyParsons .................................................................................................. 96 2.2.2.3.4.5.1 Modified Claus Process ............................................................. 96 2.2.2.3.4.5.2 Ammonia Destruction ............................................................... 97 2.2.2.4 Tailgas Treatment ........................................................................................................................................ 98 2.2.2.4.1 Amec Foster Wheeler ............................................................................................................... 98 2.2.2.4.2 BASF ......................................................................................................................................... 98 2.2.2.4.3 CANSOLV Technologies ............................................................................................................ 99 2.2.2.4.4 CB&I........................................................................................................................................ 102 2.2.2.4.5 CS Combustion Solutions ........................................................................................................ 104 2.2.2.4.6 DuPont Sustainable Solutions ................................................................................................ 104 2.2.2.4.7 Fluor ....................................................................................................................................... 106 2.2.2.4.7.1 Direct Contacting Condenser .......................................................................... 106 2.2.2.4.7.2 SOX Clean‐up Process ...................................................................................... 107 2.2.2.4.8 GTC Technology ...................................................................................................................... 107 2.2.2.4.9 John Zink Hamworthy Combustion ........................................................................................ 107 2.2.2.4.10 Lurgi/Air Liquide ..................................................................................................................... 107 2.2.2.4.11 MECS ...................................................................................................................................... 108 2.2.2.4.11.1 DynaWave ...................................................................................................... 108 2.2.2.4.11.2 SUPERCLAUS/DynaWave ................................................................................ 111 2.2.2.4.11.3 ClausMaster .................................................................................................... 112
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TABLE OF CONTENTS
2.2.2.5
2.2.2.6
2.2.2.7
2.2.2.4.12 Prosernat ................................................................................................................................ 112 2.2.2.4.12.1 CLAUSPOL ....................................................................................................... 113 2.2.2.4.12.2 Sultimate ......................................................................................................... 114 2.2.2.4.13 Shell Global Solutions ............................................................................................................. 116 2.2.2.4.13.1 SCOT ................................................................................................................ 116 2.2.2.4.13.2 LS‐SCOT ........................................................................................................... 118 2.2.2.4.14 Siirtec Nigi ............................................................................................................................... 119 2.2.2.4.15 SWAPSOL ................................................................................................................................ 120 2.2.2.4.16 Technip ................................................................................................................................... 122 2.2.2.4.16.1 Reduction Absorption Recycle ........................................................................ 122 2.2.2.4.16.2 Multipurpose Reduction Absorption Recycle.................................................. 123 2.2.2.4.17 TKK Technology Co. ................................................................................................................ 124 2.2.2.4.18 UOP/WorleyParsons ............................................................................................................... 126 2.2.2.4.18.1 Beavon Sulfur Removal ................................................................................... 126 2.2.2.4.18.2 Catalytic Thermal Incineration ........................................................................ 128 2.2.2.4.18.3 Ammonia Combustion .................................................................................... 129 Alternative Sulfur Removal Processes ........................................................................................................ 130 2.2.2.5.1 Adding a Redox Process for Increased Sulfur Recovery .......................................................... 130 2.2.2.5.1.1 Gas Technology Products (GTP) ...................................................................... 131 2.2.2.5.1.1.1 LO‐CAT ..................................................................................... 131 2.2.2.5.1.1.2 LO‐CAT II .................................................................................. 132 2.2.2.5.1.1.3 MINI‐CAT ................................................................................. 134 2.2.2.5.1.2 Prosernat/Le Gaz Integral ............................................................................... 135 2.2.2.5.1.3 Shell Global Solutions ...................................................................................... 135 2.2.2.5.2 Production of Sulfuric Acid ..................................................................................................... 136 2.2.2.5.2.1 DuPont STRATCO ............................................................................................ 136 2.2.2.5.2.2 Haldor Topsøe ................................................................................................. 137 2.2.2.5.2.2.1 WSA ......................................................................................... 137 2.2.2.5.2.2.2 SNOX ....................................................................................... 142 2.2.2.5.3 Other Processes ...................................................................................................................... 144 2.2.2.5.3.1 Black & Veatch ................................................................................................ 144 2.2.2.5.3.2 CrystaTech/URS .............................................................................................. 144 2.2.2.5.3.3 Paques BV/Shell Global Solutions ................................................................... 146 2.2.2.5.3.4 Paques BV/Shell Global Solutions/UOP .......................................................... 147 2.2.2.5.3.5 ThioSolv ........................................................................................................... 150 Sulfur Degasification ................................................................................................................................... 153 2.2.2.6.1 Black & Veatch ........................................................................................................................ 153 2.2.2.6.2 Brimrock Group Inc. ................................................................................................................ 154 2.2.2.6.3 Enersul .................................................................................................................................... 155 2.2.2.6.4 ExxonMobil ............................................................................................................................. 155 2.2.2.6.5 Goar, Allison & Associates ...................................................................................................... 156 2.2.2.6.6 Prosernat ................................................................................................................................ 157 2.2.2.6.7 Shell Global Solutions ............................................................................................................. 158 2.2.2.6.8 Siirtec Nigi ............................................................................................................................... 158 2.2.2.6.9 WorleyParsons ........................................................................................................................ 159 Sulfur Finishing Processes .......................................................................................................................... 159 2.2.2.7.1 Brimrock Group Inc. ................................................................................................................ 159 2.2.2.7.2 Devco USA .............................................................................................................................. 160 2.2.2.7.3 Enersul .................................................................................................................................... 160 2.2.2.7.3.1 GX .................................................................................................................... 162 2.2.2.7.3.2 WetPrill ........................................................................................................... 163 2.2.2.7.4 Sandvik Process Systems ........................................................................................................ 164
2.2.3 Commercial Catalysts ............................................................................................................................... 166 2.2.3.1 Axens .......................................................................................................................................................... 167 2.2.3.1.1 Claus Catalysts ........................................................................................................................ 167 2.2.3.1.2 Tailgas Treating Catalysts ....................................................................................................... 169 2.2.3.2 BASF Catalysts ............................................................................................................................................ 171
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TABLE OF CONTENTS 2.2.3.3 2.2.3.4 2.2.3.5 2.2.3.6
Clariant Catalysts ........................................................................................................................................ 173 Criterion Catalysts & Technologies ............................................................................................................ 174 Haldor Topsøe ............................................................................................................................................ 175 UOP ............................................................................................................................................................ 176
2.2.4 Advanced Process Control and Simulation ............................................................................................... 176 2.2.4.1 2.2.4.2 2.2.4.3 2.2.4.4 2.2.4.5 2.2.4.6
Axens .......................................................................................................................................................... 176 Aspen Tech ................................................................................................................................................. 177 Bryan Research and Engineering ................................................................................................................ 177 Jacobs Comprimo Sulfur Solutions ............................................................................................................. 177 Optimized Gas Treating .............................................................................................................................. 178 Shell Global Solutions ................................................................................................................................. 179
2.2.5 Analyzers and Instrumentation ................................................................................................................ 179 2.2.5.1 2.2.5.2 2.2.5.3 2.2.5.4 2.2.5.5
AMETEK Process Instruments .................................................................................................................... 179 Applied Analytics ........................................................................................................................................ 180 Fives Pillard ................................................................................................................................................ 181 Metso ......................................................................................................................................................... 182 PAC LP ........................................................................................................................................................ 182
2.2.6 Summary of Commercially Available Sulfur Plant Technologies .............................................................. 182 2.2.7 Comparison of Commercial Sulfur Plant Catalysts ................................................................................... 196 2.3 PLANT OPERATIONS AND PRACTICES .............................................................................................................................. 197 2.3.1 Acid Gas Removal ..................................................................................................................................... 197 2.3.1.1 Amine Solvent Replacement ...................................................................................................................... 197 2.3.1.2 Optimizing an Amine Unit .......................................................................................................................... 198 2.3.1.3 Amine System Operating Issues ................................................................................................................. 201 2.3.1.3.1 Contaminants ......................................................................................................................... 201 2.3.1.3.1.1 Importance of Chemical Analysis .................................................................... 201 2.3.1.3.1.2 Hydrocarbon Carryover in Amine Acid Gas .................................................... 202 2.3.1.3.1.3 Filtration and Separation of Contaminants .................................................... 205 2.3.1.3.1.4 Removal of HCN .............................................................................................. 206 2.3.1.3.2 Wet Acid Gas Corrosion.......................................................................................................... 207 2.3.1.3.3 Amine Solution Corrosion ...................................................................................................... 207 2.3.1.3.4 Foaming .................................................................................................................................. 211 2.3.1.3.5 Amine Losses .......................................................................................................................... 212 2.3.1.3.6 Instability in Amine Regenerator ............................................................................................ 213 2.3.1.4 Proper Heat Exchanger Design for Acid Gas Removal Units ...................................................................... 215 2.3.1.5 Safe Acid Gas Handling............................................................................................................................... 215 2.3.1.6 Refractory Upgrade .................................................................................................................................... 216 2.3.1.7 Fuel Gas Sweetening in a Hydrocracker Fractionation Section .................................................................. 217
2.3.2 Claus Process ............................................................................................................................................ 218 2.3.2.1 2.3.2.2 2.3.2.3 2.3.2.4 2.3.2.5 2.3.2.6 2.3.2.7 2.3.2.8 2.3.2.9 2.3.2.10 2.3.2.11 2.3.2.12
Increasing Sulfur Recovery Capacity .......................................................................................................... 218 The Effects of Extreme Turndowns ............................................................................................................ 222 Benefits and Drawbacks of Oxygen Enrichment ........................................................................................ 222 Claus Unit Shutdowns ................................................................................................................................ 224 Claus Catalyst Life and Reuse ..................................................................................................................... 225 Advanced Control Systems for Claus Plants ............................................................................................... 226 Preventing Overpressure in Claus Units ..................................................................................................... 227 Preventing Liquid Sulfur Accumulation in Claus Units ............................................................................... 228 Processing SWS Offgas in Claus Units ........................................................................................................ 229 Analyzing Sulfur Content in Claus Tailgas ................................................................................................... 231 Neural Network for Claus Temperature Control ........................................................................................ 232 Benefits of Partial Oxidation Process vs. Modified Claus ........................................................................... 232
2.3.3 Tailgas Treating ........................................................................................................................................ 233 2.3.3.1 2.3.3.2 2.3.3.3 2.3.3.4
Experience with Designing a TGTU ............................................................................................................ 233 Proper TGT Catalyst Selection .................................................................................................................... 238 Cold Bed Adsorption Units for Tailgas Treating ......................................................................................... 239 MDEA Degradation in TGTUs ..................................................................................................................... 241
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TABLE OF CONTENTS 2.3.3.5 Preventing Corrosion in TGTUs................................................................................................................... 242
2.3.4 2.3.5 2.3.6 2.3.7
Small‐scale Sulfur Plants .......................................................................................................................... 243 Improving Energy Efficiency of Sulfur Plants ............................................................................................ 243 Liquid Scavengers for H2S Removal .......................................................................................................... 244 Sulfur Storage and Handling .................................................................................................................... 245 2.3.7.1 Premium Sulfur Specifications .................................................................................................................... 245 2.3.7.2 Liquid Loading and Transport ..................................................................................................................... 246 2.3.7.3 Blocking ...................................................................................................................................................... 248
2.4 REFINING R&D ALERT! ............................................................................................................................................... 249 2.4.1 Introduction.............................................................................................................................................. 249 2.4.2 Acid Gas Removal ..................................................................................................................................... 253 2.4.2.1 Simultaneous Removal of H2S and CO2 ...................................................................................................... 253 2.4.2.2 Sorbent Materials ....................................................................................................................................... 254 2.4.2.2.1 Solid Adsorbents ..................................................................................................................... 254 2.4.2.2.1.1 Patents ............................................................................................................ 254 2.4.2.2.1.2 Research.......................................................................................................... 254 2.4.2.2.2 Liquid Absorbents ................................................................................................................... 255 2.4.2.2.2.1 Patents ............................................................................................................ 255 2.4.2.2.2.2 Research.......................................................................................................... 258 2.4.2.3 Miscellaneous ............................................................................................................................................. 259 2.4.2.3.1 Patents .................................................................................................................................... 259 2.4.2.3.2 Research ................................................................................................................................. 259
2.4.3 Claus Technology ..................................................................................................................................... 260 2.4.3.1 Process ....................................................................................................................................................... 260 2.4.3.1.1 Multiple Claus Reactors .......................................................................................................... 260 2.4.3.1.2 Oxygen Enrichment ................................................................................................................ 260 2.4.3.1.2.1 Patents ............................................................................................................ 260 2.4.3.1.2.2 Research.......................................................................................................... 261 2.4.3.1.3 Miscellaneous Claus Process Improvements .......................................................................... 261 2.4.3.1.3.1 Patents ............................................................................................................ 261 2.4.3.1.3.2 Research.......................................................................................................... 263 2.4.3.2 Catalyst ....................................................................................................................................................... 264 2.4.3.2.1 Patents .................................................................................................................................... 264 2.4.3.2.2 Research ................................................................................................................................. 265 2.4.3.3 Process Control ........................................................................................................................................... 265
2.4.4 Tailgas Treating ....................................................................................................................................... 265 2.4.4.1 Process ....................................................................................................................................................... 265 2.4.4.1.1 Patents .................................................................................................................................... 265 2.4.4.1.2 Research ................................................................................................................................. 269 2.4.4.2 Catalyst ....................................................................................................................................................... 270
2.4.5 Sulfur Degasification ................................................................................................................................ 272 2.4.6 Other ........................................................................................................................................................ 273 2.5 WORLDWIDE INSTALLED CAPACITY ................................................................................................................................ 276 2.6 CONSTRUCTION ......................................................................................................................................................... 278 2.6.1 Recent Construction Activity .................................................................................................................... 278 2.6.2 Completed Construction Projects ............................................................................................................. 283 2.7 REFERENCES ............................................................................................................................................................. 319 3. AROMATICS PRODUCTION ................................................................................................................................. 341 3.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................................... 341 3.1.1 Introduction.............................................................................................................................................. 341 3.1.2 Market Conditions and Outlook ............................................................................................................... 342 3.1.2.1 US Could Be Fertile Ground for On‐Purpose Benzene ................................................................................ 343 3.1.2.2 Shifting Prices in Europe in the Face of Volatile Crude ............................................................................... 345
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TABLE OF CONTENTS 3.1.2.3 Mideast PCs Look to Expand, Downstream and Abroad ............................................................................ 345 3.1.2.4 Asia Remains Active in the PC Industry ...................................................................................................... 346 3.1.2.5 Continued Emergence of Bio‐BTX .............................................................................................................. 347
3.1.3 Technology Competition, Directions, and Future Prospects ..................................................................... 349 3.1.3.1 BTX Production & Recovery Technologies ................................................................................................. 350 3.1.3.1.1 Catalytic Reforming ................................................................................................................ 350 3.1.3.1.2 Toluene Disproportionation/Transalkylation ......................................................................... 351 3.1.3.1.3 Xylene Isomerization & Recovery ........................................................................................... 352 3.1.3.1.3.1 Isomerization .................................................................................................. 352 3.1.3.1.3.2 Separation and Purification of Xylene Isomers ............................................... 352 3.1.3.1.4 Alternative Production Processes .......................................................................................... 353 3.1.3.1.5 Hydrodealkylation .................................................................................................................. 354 3.1.3.1.6 Aromatics Recovery by Extraction or Extractive Distillation ................................................... 354 3.1.3.2 Integrated Refining and Aromatics Production .......................................................................................... 355 3.1.3.2.1 FCC ......................................................................................................................................... 355 3.1.3.2.2 Hydrocracking ........................................................................................................................ 356 3.1.3.2.3 Integrated Refinery and PC Complexes .................................................................................. 356
3.1.4 Conclusion ................................................................................................................................................ 357 3.2 STATE‐OF‐THE‐ART TECHNOLOGY ................................................................................................................................. 359 3.2.1 Introduction .............................................................................................................................................. 359 3.2.2 Catalytic Reforming .................................................................................................................................. 359 3.2.2.1 Process ....................................................................................................................................................... 360 3.2.2.1.1 Axens ...................................................................................................................................... 361 3.2.2.1.2 Chevron Phillips Chemicals ..................................................................................................... 364 3.2.2.1.3 UOP ........................................................................................................................................ 365 3.2.2.1.3.1 CCR Platforming .............................................................................................. 365 3.2.2.1.3.2 RZ Platforming ................................................................................................ 367 3.2.2.2 Catalyst ...................................................................................................................................................... 368
3.2.3 Aromatics from the FCCU ......................................................................................................................... 370 3.2.3.1 Sinopec ....................................................................................................................................................... 370 3.2.3.2 Technip Stone & Webster .......................................................................................................................... 372 3.2.3.3 UOP ............................................................................................................................................................ 373
3.2.4 Aromatics via Hydrocracking .................................................................................................................... 374 3.2.4.1 UOP ............................................................................................................................................................ 374
3.2.5 Alternative Production Processes ............................................................................................................. 375 3.2.5.1 Aromatics from LPG ................................................................................................................................... 375 3.2.5.2 Aromatics from Olefin‐rich Streams ........................................................................................................... 376 3.2.5.2.1 ExxonMobil Chemical ............................................................................................................. 376 3.2.5.2.2 Green Chem ........................................................................................................................... 377 3.2.5.2.3 Technip Stone & Webster ...................................................................................................... 377
3.2.6 Conversion of Toluene and/or Heavy Aromatics ...................................................................................... 378 3.2.6.1 Hydrodealkylation ...................................................................................................................................... 378 3.2.6.1.1 CB&I........................................................................................................................................ 378 3.2.6.1.1.1 DETOL ............................................................................................................. 378 3.2.6.1.1.2 LITOL ............................................................................................................... 380 3.2.6.1.1.3 PYROTOL ......................................................................................................... 381 3.2.6.1.2 UOP ........................................................................................................................................ 381 3.2.6.2 Disproportionation/Transalkylation ........................................................................................................... 382 3.2.6.2.1 ExxonMobil Chemical ............................................................................................................. 382 3.2.6.2.1.1 MTDP‐3 ........................................................................................................... 383 3.2.6.2.1.2 TransPlus ........................................................................................................ 384 3.2.6.2.1.3 PxMax ............................................................................................................. 385 3.2.6.2.2 GTC Technology ...................................................................................................................... 386 3.2.6.2.2.1 GT‐STDP .......................................................................................................... 386 3.2.6.2.2.2 GT‐TransAlk .................................................................................................... 387 3.2.6.2.2.3 GT‐TolAlk ........................................................................................................ 388
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TABLE OF CONTENTS
3.2.6.2.3 3.2.6.2.4
3.2.6.2.5
3.2.6.2.2.4 GT‐G2A ............................................................................................................ 388 Sinopec ................................................................................................................................... 388 UOP ......................................................................................................................................... 389 3.2.6.2.4.1 Tatoray ............................................................................................................ 389 3.2.6.2.4.2 TAC9 ................................................................................................................ 392 3.2.6.2.4.3 PX‐Plus ............................................................................................................ 393 Zeolyst International. .............................................................................................................. 395
3.2.7 Xylene Isomerization and Recovery ......................................................................................................... 396 3.2.7.1 Isomerization .............................................................................................................................................. 396 3.2.7.1.1 Clariant (Formerly Süd‐Chemie) ............................................................................................. 397 3.2.7.1.2 ExxonMobil Chemical ............................................................................................................. 397 3.2.7.1.2.1 Advanced MHAI .............................................................................................. 397 3.2.7.1.2.2 XyMax ............................................................................................................. 398 3.2.7.1.3 GTC Technology ...................................................................................................................... 399 3.2.7.1.4 IFP and Zeolyst ........................................................................................................................ 400 3.2.7.1.5 UOP ......................................................................................................................................... 402 3.2.7.2 Separation and Purification of Xylene Isomers........................................................................................... 404 3.2.7.2.1 Crystallization ......................................................................................................................... 405 3.2.7.2.1.1 BEFS Technologies .......................................................................................... 405 3.2.7.2.1.2 GTC Technology .............................................................................................. 406 3.2.7.2.1.3 Sulzer Chemtech ............................................................................................. 407 3.2.7.2.1.3.1 Falling Film Crystallization ....................................................... 407 3.2.7.2.1.3.2 Meta‐Xylene Process ............................................................... 408 3.2.7.2.1.4 UOP ................................................................................................................. 408 3.2.7.2.2 Adsorption .............................................................................................................................. 409 3.2.7.2.2.1 Axens ............................................................................................................... 409 3.2.7.2.2.2 BASF ................................................................................................................ 411 3.2.7.2.2.3 UOP ................................................................................................................. 411 3.2.7.2.2.3.1 Parex ....................................................................................... 411 3.2.7.2.2.3.2 MX Sorbex ............................................................................... 413
3.2.8 Recovery of Aromatics by Extraction or Extractive Distillation ................................................................ 414 3.2.8.1 3.2.8.2 3.2.8.3 3.2.8.4 3.2.8.5
3.2.8.6
Air Liquide .................................................................................................................................................. 415 GTC Technology .......................................................................................................................................... 415 Sinopec ....................................................................................................................................................... 419 Sulzer Chemtech ......................................................................................................................................... 420 ThyssenUhde Krupp Engineering Services .................................................................................................. 421 3.2.8.5.1 Morphylane ............................................................................................................................ 422 3.2.8.5.2 Octenar ................................................................................................................................... 424 3.2.8.5.3 Morphylex .............................................................................................................................. 424 UOP ............................................................................................................................................................ 425 3.2.8.6.1 Sulfolane ................................................................................................................................. 426 3.2.8.6.2 Carom ..................................................................................................................................... 427 3.2.8.6.3 Udex/Tetra .............................................................................................................................. 428
3.2.9 Summary of Commercially Available Aromatics Production Technologies .............................................. 429 3.3 PLANT OPERATIONS AND PRACTICES .............................................................................................................................. 437 3.3.1 Catalytic Reformer Aromatics Production ................................................................................................ 437 3.3.1.1 Increasing Aromatics Yield ......................................................................................................................... 437 3.3.1.1.1 Naphtha Feed Properties ........................................................................................................ 437 3.3.1.1.2 Catalysts.................................................................................................................................. 438 3.3.1.2 Reducing Coke Formation .......................................................................................................................... 439 3.3.1.3 Removing Chlorides from Hydrocarbon Streams ....................................................................................... 440
3.3.2 Dedicated Aromatics Production Units .................................................................................................... 442 3.3.2.1 3.3.2.2 3.3.2.3 3.3.2.4
Removing Olefins from Aromatic Streams ................................................................................................. 442 Improving Tray Technology in Aromatic Extraction Units .......................................................................... 444 Reducing Corrosion/Foaming in Aromatics Extraction Units ...................................................................... 445 Controlling the Feed Composition to a Paraxylene Crystallization Unit ..................................................... 447
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TABLE OF CONTENTS 3.3.2.5 Improvements to Process Control and Optimization ................................................................................. 447
3.3.3 FCCU Aromatics Production ...................................................................................................................... 448 3.4 REFINING R&D ALERT! ............................................................................................................................................... 448 3.4.1 Introduction .............................................................................................................................................. 448 3.4.2 Catalytic Reforming .................................................................................................................................. 452 3.4.2.1 Patents ....................................................................................................................................................... 452 3.4.2.2 Research ..................................................................................................................................................... 453
3.4.3 Hydrocracking ........................................................................................................................................... 455 3.4.4 FCC ............................................................................................................................................................ 457 3.4.4.1 Patents ....................................................................................................................................................... 457 3.4.4.2 Research ..................................................................................................................................................... 458
3.4.5 Integration of Refining and BTX Processes ............................................................................................... 459 3.4.5.1 Patents ....................................................................................................................................................... 459 3.4.5.2 Research ..................................................................................................................................................... 463
3.4.6 Conversion of Toluene and/or Heavier Aromatics .................................................................................... 463 3.4.6.1 Disproportionation/Transalkylation ........................................................................................................... 463 3.4.6.1.1 Process ................................................................................................................................... 463 3.4.6.1.1.1 Patents ............................................................................................................ 463 3.4.6.1.1.2 Research ......................................................................................................... 467 3.4.6.1.2 Catalyst ................................................................................................................................... 467 3.4.6.1.2.1 Patents ............................................................................................................ 467 3.4.6.1.2.2 Research ......................................................................................................... 469 3.4.6.2 Toluene Alkylation ..................................................................................................................................... 470
3.4.7 Xylene Isomerization and Recovery .......................................................................................................... 471 3.4.7.1 Isomerization ............................................................................................................................................. 471 3.4.7.1.1 Process ................................................................................................................................... 471 3.4.7.1.1.1 Preparation of Feedstock Prior to Isomerization ............................................ 471 3.4.7.1.1.2 Dual‐phase Processes ..................................................................................... 472 3.4.7.1.1.3 Heat Integration between Isomerization and Recovery Sections ................... 473 3.4.7.1.1.4 Miscellaneous ................................................................................................. 474 3.4.7.1.2 Catalyst ................................................................................................................................... 475 3.4.7.1.2.1 Patents ............................................................................................................ 475 3.4.7.1.2.2 Research ......................................................................................................... 476 3.4.7.2 Separation and Purification of Xylene Isomers .......................................................................................... 477 3.4.7.2.1 Adsorption .............................................................................................................................. 477 3.4.7.2.1.1 Patents ............................................................................................................ 477 3.4.7.2.1.1.1 Zeolitic Adsorbents ................................................................. 477 3.4.7.2.1.1.2 Integration with Fractionation ................................................ 477 3.4.7.2.1.1.3 Miscellaneous ......................................................................... 479 3.4.7.2.1.2 Research ......................................................................................................... 480 3.4.7.2.2 Crystallization ......................................................................................................................... 483 3.4.7.2.3 Combined Adsorption and Crystallization .............................................................................. 485
3.4.8 Alternative Production Technologies ........................................................................................................ 486 3.4.8.1 Patents ....................................................................................................................................................... 486 3.4.8.2 Research ..................................................................................................................................................... 487
3.4.9 Recovery of Aromatics by Extraction, Extractive Distillation, or Distillation ............................................ 487 3.4.9.1 Patents ....................................................................................................................................................... 487 3.4.9.2 Research ..................................................................................................................................................... 489
3.5 WORLDWIDE INSTALLED CAPACITY ................................................................................................................................ 490 3.6 CONSTRUCTION ......................................................................................................................................................... 492 3.6.1 Recent Construction Activity ..................................................................................................................... 492 3.6.2 Completed Construction Projects ............................................................................................................. 494 3.7 REFERENCES .............................................................................................................................................................. 506
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TABLE OF CONTENTS 4. LATEST REFINING TECHNOLOGY DEVELOPMENTS & LICENSING ........................................................................... 519 4.1 FLUID CATALYTIC CRACKING ......................................................................................................................................... 519 4.2 HYDROTREATING (INCLUDING HDS) .............................................................................................................................. 519 4.3 HYDROCRACKING ....................................................................................................................................................... 520 4.4 ISOMERIZATION ......................................................................................................................................................... 520 4.5 CRUDE TREATMENT .................................................................................................................................................... 520 4.6 DEASPHALTING .......................................................................................................................................................... 521 4.7 HYDROGEN PRODUCTION AND PURIFICATION .................................................................................................................. 521 4.8 LIGHT OLEFINS PRODUCTION ....................................................................................................................................... 522 4.9 METHANOL PRODUCTION ............................................................................................................................................ 523 4.10 PROCESS CONTROLS AND SIMULATION ........................................................................................................................... 524 4.11 XTL (BIOMASS‐, COAL‐, AND GAS‐TO‐LIQUID) ................................................................................................................ 524 4.12 BIOFUELS PRODUCTION .............................................................................................................................................. 525 4.13 ENERGY MANAGEMENT .............................................................................................................................................. 528 4.14 CO2 EMISSIONS (CARBON CAPTURE AND SEQUESTRATION) ............................................................................................... 529 4.15 SITE WASTEWATER DISCHARGE .................................................................................................................................... 530 4.16 AUTOMOBILE ENGINE DESIGN INNOVATIONS .................................................................................................................. 531 4.17 REFERENCES ............................................................................................................................................................. 531
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