Product Treating and Blending

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

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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

TABLE OF CONTENTS

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3Q2013 Review Product Treating and Blending

1. Product Treating and Blending ................................................................................................... 1

1.1 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

1.2 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

1.2.2.1.9.1.2.2 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

1.2.2.1.9.2 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

1.3 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

1.4 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


1.4.2.2.2 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


1.4.2.4.2 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


1.4.2.5.2 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

1.5 CONSTRUCTION ................................................................................................................................................. 160 1.5.1 Recent Construction Activity ................................................................................................................. 160 1.5.2 Completed Construction Projects .......................................................................................................... 163

1.6 REFERENCES ...................................................................................................................................................... 178

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