Sulfur Plant and Refinery Aromatics Production

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

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability 速

P.O. Box 815, Paoli, PA 19301-0815 (U.S.A.)

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

Review@Hydrocarbonpublishing.com

Copyright Š Hydrocarbon Publishing Company, Inc. All Rights Reserved.

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

1Q 2016 i Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 ii Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 iii Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 iv Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 v Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 vi Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 vii Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 viii Hydrocarbon Publishing Co./Copyright Protected

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

1Q 2016 ix Hydrocarbon Publishing Co./Copyright Protected