WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in One Single Source
Third Quarter 2013 Product Treating and Blending Plus
Latest Refining Technology Developments & Licensing
HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability
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TABLE OF CONTENTS 3Q2013 Review Product Treating and Blending 1. Product Treating and Blending ................................................................................................... 1 1.1
1.2
MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 1 1.1.1 Introduction .............................................................................................................................................. 1 1.1.2 Market Conditions and Outlook................................................................................................................ 1 1.1.3 Technology Competition, Directions, and Future Prospects .................................................................... 1 1.1.3.1 Product Treating ......................................................................................................................... 1 1.1.3.1.1 Commercial and Near-commercial Technologies ..................................................... 3 1.1.3.1.2 Trends in R&D .......................................................................................................... 9 1.1.3.1.2.1 Adsorptive Desulfurization................................................................. 9 1.1.3.1.2.2 Oxidative Desulfurization ................................................................... 9 1.1.3.1.2.3 Membrane Desulfurization ............................................................... 12 1.1.3.1.2.4 Ionic Liquid Extraction ..................................................................... 12 1.1.3.1.2.5 Benzene Removal ............................................................................. 14 1.1.3.2 Product Blending ...................................................................................................................... 14 1.1.3.2.1 Commercial Technologies ....................................................................................... 16 1.1.3.2.2 Trends in R&D ........................................................................................................ 22 1.1.4 Conclusion .............................................................................................................................................. 23 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 24 1.2.1 Introduction ............................................................................................................................................ 24 1.2.2 Product Treating ..................................................................................................................................... 27 1.2.2.1 Commercial Processes .............................................................................................................. 27 1.2.2.1.1 Axens ....................................................................................................................... 27 1.2.2.1.1.1 Sulfrex .............................................................................................. 27 1.2.2.1.1.2 Sweetening........................................................................................ 28 1.2.2.1.1.3 Sweetn'K ........................................................................................... 29 1.2.2.1.1.4 OATS ................................................................................................ 29 1.2.2.1.2 ExxonMobil ............................................................................................................. 30 1.2.2.1.3 GTC Technology Inc. .............................................................................................. 32 1.2.2.1.4 Hielscher Ultrasonics............................................................................................... 33 1.2.2.1.5 Indian Oil Corp. ....................................................................................................... 34 1.2.2.1.6 Merichem Chemicals & Refinery Services ............................................................. 36 1.2.2.1.6.1 Jet Fuel Treating ............................................................................... 38 1.2.2.1.6.2 Gasoline and LPG Treating .............................................................. 40 1.2.2.1.6.3 Reformer and Alkylation Products Treating ..................................... 41 1.2.2.1.7 Petreco Process Systems .......................................................................................... 42 1.2.2.1.8 Sinopec .................................................................................................................... 42 1.2.2.1.9 UOP ......................................................................................................................... 45 1.2.2.1.9.1 Merox ............................................................................................... 45 1.2.2.1.9.1.1 Extraction .................................................................... 47 1.2.2.1.9.1.2 Sweetening .................................................................. 47 1.2.2.1.9.1.2.1 Fixed-bed ..................................... 48
1.2.2.1.9.2
1.2.2.1.9.1.2.2
Minalk .......................................... 48
1.2.2.1.9.1.2.3
Caustic Free Merox ...................... 49
1.2.2.1.9.1.2.4
Liquid-liquid Sweetening ............ 50
Sulfur-X ............................................................................................ 51
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1.2.2.2 Catalysts, Adsorbents, and Other Technologies........................................................................ 52 1.2.2.2.1 Axens ....................................................................................................................... 52 1.2.2.2.2 Chemical Products Industries, Inc. .......................................................................... 53 1.2.2.2.3 CSIR-Indian Institute of Petroleum ......................................................................... 53 1.2.2.2.4 Gas Technology Products ........................................................................................ 54 1.2.2.2.5 No Heat Resources ................................................................................................... 54 1.2.2.2.6 UOP ......................................................................................................................... 55 1.2.2.3 Emerging Technologies ............................................................................................................ 56 1.2.2.3.1 Alternative Petroleum Technologies ........................................................................ 57 1.2.2.3.2 Grace ........................................................................................................................ 57 1.2.2.3.3 LyondellBasell Industries ........................................................................................ 59 1.2.2.3.4 RTI ........................................................................................................................... 60 1.2.2.3.5 SulphCo ................................................................................................................... 61 1.2.2.3.6 UniPure Energy........................................................................................................ 62 1.2.3 Summary of Commercial Product Treating Processes............................................................................ 64 1.2.4 Product Blending..................................................................................................................................... 69 PLANT OPERATIONS AND PRACTICES................................................................................................................... 73 1.3.1 General Non-hydrogen Product Treating ............................................................................................... 73 1.3.1.1 Predicting Sulfur Type, Levels in FCC Products ...................................................................... 73 1.3.1.2 Methods of Removing Sulfur Compounds Without Hydrogen ................................................ 74 1.3.1.3 Analyzing Product Streams for Sulfur and Aromatics .............................................................. 75 1.3.1.4 LPG Treating............................................................................................................................. 76 1.3.1.4.1 Minimizing Caustic Consumption in Product Treating ........................................... 76 1.3.1.4.2 Effects of H2S Content on Deethanizer.................................................................... 76 1.3.1.4.3 Mercury Removal .................................................................................................... 77 1.3.1.4.4 Commercial Methods of Removing COS from Propane/Propylene Streams .......... 78 1.3.1.5 Gasoline Treating ...................................................................................................................... 78 1.3.1.5.1 Meeting 10 ppm Sulfur in Gasoline ......................................................................... 78 1.3.1.5.2 Liquid-Liquid Coalescence to Obtain On-spec FCC Gasoline ................................ 79 1.3.1.5.3 Utilizing Octane-enhancing FCC Additives in Product Treating Applications ....... 80 1.3.1.5.4 Natural Gasoline Processing Problems .................................................................... 81 1.3.1.5.5 Minimizing Gasoline Color Degradation ................................................................. 81 1.3.1.6 Middle Distillates Treating ....................................................................................................... 82 1.3.1.6.1 Meeting Cloud Point and CFPP Specifications with Additives ............................... 82 1.3.1.6.2 Meeting Jet Fuel Specifications ............................................................................... 83 1.3.1.6.3 Minimizing Jet Fuel Color Degradation .................................................................. 83 1.3.2 Product Blending..................................................................................................................................... 84 1.3.2.1 Systematic Approach to Upgrading Refinery Blending Operations ......................................... 84 1.3.2.2 Benefits of Inline Blending over Storage .................................................................................. 87 1.3.2.3 Use of Process Analyzers and Models ...................................................................................... 87 1.3.2.3.1 FTIR vs. Raman Spectroscopy for Inline Blending ................................................. 88 1.3.2.3.2 Accurately Predicting Cetane Improver Impact ....................................................... 89 1.3.2.4 Gasoline Blending ..................................................................................................................... 89 1.3.2.4.1 Optimal Gasoline Blending ...................................................................................... 89 1.3.2.4.1 Effect of RVP on Gasoline Loss During Blending .................................................. 91 1.3.2.4.2 Summer Management of RVP and Butanes............................................................. 91 1.3.2.4.3 Blending Opportunities for Heavy Naphtha ............................................................ 92 1.3.2.4.4 Online Analyzers Used for Gasoline Blending ........................................................ 93 1.3.2.4.5 Accurately Predicting Gasoline Octane Using ANN Models .................................. 95 1.3.2.5 Bunker Fuels Blending.............................................................................................................. 95
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1.3.2.6 Biofuels Blending ..................................................................................................................... 96 1.3.2.6.1 Flexible Fuel Terminals for Biofuels Blending ....................................................... 96 1.3.2.6.2 European Union Measuring Instruments Directive ................................................. 97 1.3.2.6.3 Ethanol Blending into the Gasoline Pool ................................................................ 97 1.3.2.6.3.1 Increasing Ethanol Blending............................................................. 97 1.3.2.6.3.2 Corrosion .......................................................................................... 98 1.3.2.6.3.3 Gasoline Blendstocks ....................................................................... 99 1.3.2.6.3.4 Gasoline Pool Components............................................................. 100 1.3.2.6.3.5 Isobutanol as an Alternative to Ethanol .......................................... 100 1.3.2.6.4 Biodiesel Blending into the Diesel Pool ................................................................ 101 1.3.2.7 Predicting Viscosity for Heavy Blends ................................................................................... 101 1.3.2.8 Incorporating Logistics in Blending Optimizations Systems ................................................. 102 REFINING R&D ALERT! .................................................................................................................................... 103 1.4.1 Introduction .......................................................................................................................................... 103 1.4.2 Product Treating ................................................................................................................................... 109 1.4.2.1 Adsorptive Desulfurization..................................................................................................... 109 1.4.2.1.1 Gasoline ................................................................................................................. 109 1.4.2.1.1.1 Patents............................................................................................. 109 1.4.2.1.1.2 Research Literature ......................................................................... 113 1.4.2.1.2 Diesel ..................................................................................................................... 114 1.4.2.1.2.1 Patents............................................................................................. 114 1.4.2.1.2.2 Research Literature ......................................................................... 116 1.4.2.1.3 Multiple fuel application ....................................................................................... 118 1.4.2.1.3.1 Patents............................................................................................. 118 1.4.2.1.3.2 Research Literature ......................................................................... 120 1.4.2.2 Oxidative Desulfurization ....................................................................................................... 122 1.4.2.2.1 Catalysts ................................................................................................................ 122 1.4.2.2.1.1 Patents............................................................................................. 122 1.4.2.2.1.2 Research Literature ......................................................................... 124 1.4.2.2.2 Process ................................................................................................................... 127 1.4.2.2.2.1 Patents............................................................................................. 127 1.4.2.2.2.2 Research Literature ......................................................................... 129 1.4.2.3 Ionic Liquid Extraction ........................................................................................................... 133 1.4.2.3.1 Patents ................................................................................................................... 133 1.4.2.3.2 Research Literature ................................................................................................ 135 1.4.2.4 Membrane Desulfurization ..................................................................................................... 140 1.4.2.4.1 Process ................................................................................................................... 140 1.4.2.4.1.1 Patents............................................................................................. 140 1.4.2.4.1.2 Research Literature ......................................................................... 141 1.4.2.4.2 Novel material ....................................................................................................... 141 1.4.2.4.2.1 Patents............................................................................................. 141 1.4.2.4.2.2 Research Literature ......................................................................... 144 1.4.2.5 Benzene Removal ................................................................................................................... 146 1.4.2.5.1 Reactive ................................................................................................................. 146 1.4.2.5.1.1 Patents............................................................................................. 146 1.4.2.5.1.2 Research Literature ......................................................................... 148 1.4.2.5.2 Non-reactive .......................................................................................................... 149 1.4.2.5.2.1 Patent .............................................................................................. 149 1.4.2.6 Miscellaneous ......................................................................................................................... 149 1.4.2.6.1 Scavengers ............................................................................................................. 149 1.4.2.6.1.1 Patents............................................................................................. 149
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1.4.2.6.2 Other ...................................................................................................................... 150 1.4.2.6.2.1 Patent............................................................................................... 150 1.4.2.6.2.2 Research Literature ......................................................................... 151 1.4.2.6.3 Other contaminants ................................................................................................ 151 1.4.2.6.3.1 Research Literature ......................................................................... 151 1.4.3 Product Blending................................................................................................................................... 152 1.4.3.1 Blending and Process Control ................................................................................................. 152 1.4.3.1.1 Patents .................................................................................................................... 152 1.4.3.1.2 Research Literature ................................................................................................ 156 1.4.3.2 Components/Additives ............................................................................................................ 158 1.4.3.2.1 Patents .................................................................................................................... 158 1.4.3.2.2 Research Literature ................................................................................................ 159 CONSTRUCTION ................................................................................................................................................. 160 1.5.1 Recent Construction Activity ................................................................................................................. 160 1.5.2 Completed Construction Projects.......................................................................................................... 163 REFERENCES ...................................................................................................................................................... 178
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