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

First Quarter 2011 Alkylation; Isooctane Production; and Maintenance, Reliability, and Safety Plus

Latest Refining Technology Developments & Licensing

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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TABLE OF CONTENTS 1Q 2011 Review Alkylation; Isooctane Production; and Maintenance, Reliability, and Safety 1. Introduction.....................................................................................................................................1 2. Alkylation ........................................................................................................................................5 2.1

2.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 5 2.1.1 Introduction .............................................................................................................................................. 5 2.1.2 Market Conditions and Outlook................................................................................................................ 5 2.1.2.1 Gasoline Supply and Demand .................................................................................................... 5 2.1.2.2 Alkylation Capacity and New Construction Projects ................................................................. 7 2.1.2.3 Shifting Olefin Feedstock to Alkylation..................................................................................... 8 2.1.2.4 Mandated Blending of Ethanol and the Impact on the Gasoline Pool ...................................... 10 2.1.2.5 Safety and Environmental Concerns......................................................................................... 12 2.1.3 Technology Competition, Directions, and Future Prospects.................................................................. 13 2.1.3.1 Status of Technology Licensers................................................................................................ 13 2.1.3.2 Liquid Acid Alkylation............................................................................................................. 14 2.1.3.2.1 HF............................................................................................................................ 14 2.1.3.2.2 H2SO4 ...................................................................................................................... 15 2.1.3.3 Alternative Alkylation Technologies........................................................................................ 17 2.1.3.3.1 Solid Acid................................................................................................................ 17 2.1.3.3.2 Ionic Liquid ............................................................................................................. 18 2.1.3.3.3 Renewable Alkylation ............................................................................................. 19 2.1.3.4 Revamping HF Units to H2SO4 and Solid Acid Units.............................................................. 19 2.1.4 Conclusion .............................................................................................................................................. 20 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 21 2.2.1 Introduction ............................................................................................................................................ 21 2.2.2 Commercially Available Liquid Acid Alkylation Technologies .............................................................. 24 2.2.2.1 Feed Pretreatment ..................................................................................................................... 24 2.2.2.1.1 Axens....................................................................................................................... 24 2.2.2.1.2 UOP ......................................................................................................................... 25 2.2.2.2 HF Alkylation ........................................................................................................................... 26 2.2.2.2.1 UOP ......................................................................................................................... 27 2.2.2.2.1.1 Gravity Circulated HF Alkylation .................................................... 27 2.2.2.2.1.2 Forced Circulation HF Alkylation .................................................... 29 2.2.2.2.1.3 ReVAP.............................................................................................. 30 2.2.2.2.1.4 Alkad ................................................................................................ 32 2.2.2.2.1.5 Inventory Management Process........................................................ 33 2.2.2.3 H2SO4 Alkylation...................................................................................................................... 33 2.2.2.3.1 CDTECH ................................................................................................................. 35 2.2.2.3.1.1 CDAlky.............................................................................................. 35 2.2.2.3.1.2 CDAlkyPlus ...................................................................................... 39 2.2.2.3.2 DuPont STRATCO.................................................................................................. 41 2.2.2.3.2.1 Feed Segregation .............................................................................. 41 2.2.2.3.2.2 Butenes Feed Fractionation .............................................................. 42 2.2.2.3.2.3 Effluent Refrigerated Alkylation ...................................................... 43 2.2.2.3.2.4 ALKYSAFE ..................................................................................... 46 2.2.2.3.2.5 Integrated Alkylation and Onsite SAR/SGR .................................... 47

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2.3

2.4

2.2.2.3.3 ExxonMobil ............................................................................................................. 48 2.2.2.3.4 Refining Hydrocarbon Technologies (RHT) ........................................................... 50 2.2.3 Alternative Alkylation Technologies........................................................................................................ 52 2.2.3.1 Solid Acid ................................................................................................................................. 53 2.2.3.1.1 Exelus....................................................................................................................... 53 2.2.3.1.2 Lummus Technology/Albemarle/Neste Oil ............................................................. 57 2.2.3.1.3 Lurgi......................................................................................................................... 60 2.2.3.1.4 UOP ......................................................................................................................... 61 2.2.3.2 Supported Liquid-phase Catalysts............................................................................................. 64 2.2.3.2.1 Haldor Topsøe.......................................................................................................... 64 2.2.3.3 Ionic Liquid Alkylation............................................................................................................. 66 2.2.3.3.1 PetroChina ............................................................................................................... 67 2.2.3.4 Renewable Alkylation............................................................................................................... 69 2.2.3.4.1 Exelus....................................................................................................................... 69 2.2.4 Summary of Alkylation Technologies ...................................................................................................... 70 2.2.5 Comparison of Commercially Available Advanced Control and Optimization Systems......................... 74 PLANT OPERATIONS AND PRACTICES................................................................................................................... 76 2.3.1 Feed Considerations................................................................................................................................ 76 2.3.1.1 Feed Contaminants.................................................................................................................... 76 2.3.1.2 Alkylating Alternative Feedstocks ............................................................................................ 77 2.3.1.2.1 Propylene ................................................................................................................. 77 2.3.1.2.2 Amylenes ................................................................................................................. 78 2.3.1.2.3 Isobutene.................................................................................................................. 79 2.3.1.2.4 Isomerization Butane Slop Stream........................................................................... 80 2.3.1.2.5 Light Ends................................................................................................................ 81 2.3.1.2.6 Feed from Cokers..................................................................................................... 81 2.3.2 HF Alkylation .......................................................................................................................................... 81 2.3.2.1 Disposing of Acid Soluble Oils from HF Plants ....................................................................... 81 2.3.2.2 Corrosion................................................................................................................................... 82 2.3.2.3 Chemical Cleaning in HF Alkylation Units Prior to Turnaround ............................................. 83 2.3.2.4 Safety and Mitigation Techniques ............................................................................................ 83 2.3.2.5 Improved Valve Design ............................................................................................................ 84 2.3.2.6 Pump Seal Selection.................................................................................................................. 85 2.3.2.7 Inspecting Joints in HF Alkylation Unit ................................................................................... 86 2.3.2.8 Revamping HF Alkylation Units .............................................................................................. 86 2.3.2.8.1 Revamping to H2SO4 Alkylation ............................................................................. 87 2.3.2.8.2 Revamping to Solid Acid Alkylation....................................................................... 88 2.3.3 H2SO4 Alkylation ..................................................................................................................................... 89 2.3.3.1 ASO Formation and Disposal ................................................................................................... 89 2.3.3.2 Corrosion and Fouling .............................................................................................................. 90 2.3.3.3 Spent H2SO4 Regeneration and Treatment................................................................................ 93 2.3.3.3.1 Regeneration ............................................................................................................ 93 2.3.3.3.2 Treatment ................................................................................................................. 94 2.3.3.4 Electrostatic Precipitator Use in Caustic Wash Systems........................................................... 94 2.3.4 Acid Management.................................................................................................................................... 95 2.3.4.1 Acid Runaway........................................................................................................................... 95 2.3.4.2 Acid Storage.............................................................................................................................. 96 2.3.5 Process Control, Monitoring, and Optimization..................................................................................... 96 2.3.5.1 Measuring Circulating Acid Strength and Acid Levels ............................................................ 96 2.3.5.2 Employing Multi-objective Optimization to Alkylation Processes........................................... 98 2.3.5.3 Isostripper Advanced Process Control (APC)........................................................................... 99 REFINING R&D ALERT!....................................................................................................................................... 99

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TABLE OF CONTENTS 2.4.1 2.4.2 2.4.3 2.4.4

2.5 2.6

2.7

Introduction ............................................................................................................................................ 99 General Alkylation ................................................................................................................................ 100 HF Alkylation........................................................................................................................................ 102 H2SO4 Alkylation................................................................................................................................... 103 2.4.4.1 Patents..................................................................................................................................... 103 2.4.4.2 Research.................................................................................................................................. 104 2.4.5 Solid Acid Alkylation............................................................................................................................. 104 2.4.5.1 Patents..................................................................................................................................... 104 2.4.5.2 Research.................................................................................................................................. 105 2.4.6 Ionic Liquid Alkylation ......................................................................................................................... 110 2.4.6.1 Patents..................................................................................................................................... 110 2.4.6.2 Research.................................................................................................................................. 113 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 114 CONSTRUCTION ................................................................................................................................................. 117 2.6.1 Recent Construction Activity................................................................................................................. 117 2.6.2 Completed Construction Projects ......................................................................................................... 118 REFERENCES ..................................................................................................................................................... 123

3. Isooctane Production ..................................................................................................................131 3.1

3.2

3.3

3.4

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ......................................................................................... 131 3.1.1 Introduction .......................................................................................................................................... 131 3.1.2 Market Conditions and Outlook............................................................................................................ 132 3.1.2.1 Gasoline Supply and Demand ................................................................................................ 132 3.1.2.2 MTBE and Ethanol Blending ................................................................................................. 132 3.1.2.3 Isooctene/Isooctane as a Blending Component ...................................................................... 135 3.1.3 Technology Competition, Directions, and Future Prospects................................................................ 136 3.1.3.1 Market Competition................................................................................................................ 136 3.1.3.2 Revamping MTBE Units ........................................................................................................ 137 3.1.3.3 Gasoline Additive Production and Blending .......................................................................... 138 3.1.4 Conclusion ............................................................................................................................................ 139 STATE-OF-THE-ART TECHNOLOGY ................................................................................................................... 139 3.2.1 Introduction .......................................................................................................................................... 139 3.2.2 Commercially Available Isooctane/Isooctene Production Processes ................................................... 141 3.2.2.1 Axens...................................................................................................................................... 142 3.2.2.1.1 Dimersol-G ............................................................................................................ 142 3.2.2.1.2 Selectopol and Polynaphtha .................................................................................. 142 3.2.2.2 LyondellBasell/Kvaerner........................................................................................................ 144 3.2.2.3 Neste Jacobs/KBR .................................................................................................................. 146 3.2.2.4 Refining Hydrocarbon Technologies...................................................................................... 148 3.2.2.5 Snamprogetti/CDTECH.......................................................................................................... 149 3.2.2.6 UOP ........................................................................................................................................ 152 3.2.3 Summary of Commercial Isooctane Production Processes .................................................................. 155 PLANT OPERATIONS AND PRACTICES ................................................................................................................ 157 3.3.1 Impact of Feed Source on Dimerization Products................................................................................ 157 3.3.2 Impact of Reaction Selectivity on Additive Quality............................................................................... 157 3.3.3 Conversion of MTBE Units to Isooctane Production ........................................................................... 158 REFINING R&D ALERT! .................................................................................................................................... 159 3.4.1 Introduction .......................................................................................................................................... 159 3.4.1.1 General Process, Catalysts, and Operating Conditions........................................................... 160

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3.5

3.4.1.1.1 Patents.................................................................................................................... 160 3.4.1.1.2 Research................................................................................................................. 161 3.4.1.2 Product Quality Improvement................................................................................................. 162 3.4.1.2.1 Patents.................................................................................................................... 162 3.4.1.2.2 Research................................................................................................................. 163 3.4.1.3 Catalyst Modifiers................................................................................................................... 163 REFERENCES ...................................................................................................................................................... 165

4. Maintenance, Reliability, and Safety ........................................................................................ 169 4.1

4.2

4.3

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES .......................................................................................... 169 4.1.1 Introduction........................................................................................................................................... 169 4.1.2 Market Conditions................................................................................................................................. 169 4.1.2.1 Industry Challenges and Technology Drivers......................................................................... 169 4.1.2.2 Economic Impact of Maintenance, Reliability, and Safety Issues .......................................... 171 4.1.3 Technology Directions, Competition, and Future Outlook ................................................................... 173 4.1.3.1 Technology Vendors Focus on Turnkey Offerings................................................................. 173 4.1.3.2 Unit-by-Unit Reliability and Safety Issues ............................................................................. 173 4.1.3.3 Latest Developments in Refinery Maintenance, Reliability, and Safety................................. 174 4.1.4 Conclusion............................................................................................................................................. 176 STATE-OF-THE-ART TECHNOLOGY .................................................................................................................... 176 4.2.1 Optimization of Plant Reliability with Asset Management.................................................................... 176 4.2.1.1 Reliability Centered Maintenance ........................................................................................... 177 4.2.1.2 Risk-based Inspection ............................................................................................................. 178 4.2.1.3 Root Cause Analysis ............................................................................................................... 178 4.2.1.4 Reactive Maintenance vs. Predictive Maintenance ................................................................. 179 4.2.2 Intelligent Field Devices........................................................................................................................ 179 4.2.2.1 Standard Communication Protocols........................................................................................ 179 4.2.2.2 Incorporating Wireless Technologies into Refineries............................................................. 180 4.2.3 Inspection and Monitoring .................................................................................................................... 181 4.2.3.1 Non-destructive Testing .......................................................................................................... 181 4.2.3.2 Laboratory Evaluation............................................................................................................. 183 4.2.4 Identifying Gaps in Reliability and Maintenance Practices via Benchmarking.................................... 183 4.2.4.1 AP Networks ........................................................................................................................... 183 4.2.4.2 Solomon Associates ................................................................................................................ 184 4.2.5 Commercially Available Automation, Control, and Asset Management Technologies......................... 185 4.2.5.1 AP Networks ........................................................................................................................... 185 4.2.5.2 ABB Automation .................................................................................................................... 186 4.2.5.3 AspenTech .............................................................................................................................. 187 4.2.5.4 Emerson Process Management................................................................................................ 188 4.2.5.5 Flowserve ................................................................................................................................ 190 4.2.5.6 Honeywell Process Solutions.................................................................................................. 190 4.2.5.7 Invensys Operations Management .......................................................................................... 192 4.2.5.8 KBC ........................................................................................................................................ 193 4.2.5.9 Metso....................................................................................................................................... 194 4.2.5.10 Rockwell Automation ............................................................................................................. 195 4.2.5.11 Yokogawa ............................................................................................................................... 196 PLANT OPERATIONS AND PRACTICES................................................................................................................. 196

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TABLE OF CONTENTS 4.3.1 4.3.2 4.3.3 4.3.4 4.3.5

4.4

Case Study: Improving Plant Turnaround Strategy ............................................................................. 196 Impact of Materials Science on Refinery Reliability............................................................................. 197 Refinery Process Safety Management................................................................................................... 199 Case Study: Implementing PSM Metrics .............................................................................................. 200 Maintenance, Reliability, and Safety Issues for Individual Processing Units ...................................... 201 4.3.5.1 Crude Blending, Treating, and Desalting ............................................................................... 201 4.3.5.2 CDU/VDU and Crude Preheat Train...................................................................................... 203 4.3.5.3 Fluid Catalytic Cracking......................................................................................................... 206 4.3.5.4 Hydrocracking ........................................................................................................................ 209 4.3.5.5 Hydrotreating.......................................................................................................................... 211 4.3.5.6 Catalytic Reforming................................................................................................................ 212 4.3.5.7 Isomerization .......................................................................................................................... 214 4.3.5.8 Coking and Visbreaking/Thermal Cracking ........................................................................... 215 4.3.5.9 Solvent Deasphalting .............................................................................................................. 218 4.3.5.10 Alkylation ............................................................................................................................... 219 4.3.5.11 Gas Plant and Flare Gas System ............................................................................................. 220 4.3.5.12 Product Treating, Sulfur Plant, and Amine Systems .............................................................. 222 4.3.5.13 Hydrogen Plant ....................................................................................................................... 224 4.3.5.14 Lube Oil Production ............................................................................................................... 225 4.3.5.15 Utilities Systems and Auxiliary Equipment/Processes ........................................................... 226 REFERENCES ..................................................................................................................................................... 229

5. Latest Refining Technology Developments & Licensing.........................................................235 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14

FLUID CATALYTIC CRACKING ........................................................................................................................... 235 HYDROTREATING (INCLUDING HDS) ................................................................................................................ 235 HYDROCRACKING ............................................................................................................................................. 236 BENZENE REDUCTION AND REMOVAL ............................................................................................................... 236 CRUDE TREATMENT (E.G., DESALTING) ............................................................................................................ 237 DEASPHALTING ................................................................................................................................................. 237 PRODUCT TREATING AND BLENDING ................................................................................................................ 237 HYDROGEN PRODUCTION AND PURIFICATION ................................................................................................... 238 GASIFICATION ................................................................................................................................................... 238 AROMATICS AND LIGHT OLEFINS PRODUCTION ................................................................................................ 238 BIOFUELS PRODUCTION..................................................................................................................................... 240 SITE EMISSIONS ................................................................................................................................................. 242 AUTOMOBILE ENGINE DESIGN INNOVATIONS AND EXHAUST EMISSIONS REDUCTION ...................................... 242 REFERENCES ..................................................................................................................................................... 243

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Alkylation, Isooctane