Catalytic Reforming by Hydrocarbon Publishing Company

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

Second Quarter 2013 Catalytic Reforming

HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability

P.O. Box 661 Southeastern, PA 19399 (U.S.A.)

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

Review@Hydrocarbonpublishing.com

TABLE OF CONTENTS 2Q 2013 Review Catalytic Reforming

1. Catalytic Reforming ....................................................................................................................... 1 1.1

1.2

MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 1 1.1.1 Introduction .............................................................................................................................................. 1 1.1.2 Market Conditions and Outlook................................................................................................................ 2 1.1.2.1.1 Refined Product Supply and Demand ....................................................................... 2 1.1.2.1.1.1 Gasoline .............................................................................................. 3 1.1.2.1.1.2 Rise of Aromatics (BTX).................................................................... 5 1.1.2.1.1.3 Pricing Trends..................................................................................... 7 1.1.2.1.1.4 Reforming Catalyst Market ................................................................ 8 1.1.2.1.2 New Construction and Expansion ............................................................................. 9 1.1.2.1.3 Catalytic Reforming Capacity ................................................................................... 9 1.1.3 Technology Competition, Directions, and Future Prospects .................................................................. 10 1.1.3.1 Process and Catalyst Advancements......................................................................................... 11 1.1.3.1.1 Process and Hardware Improvements ..................................................................... 11 1.1.3.1.2 Catalyst Innovations ................................................................................................ 13 1.1.3.2 Trends in R&D ......................................................................................................................... 14 1.1.4 Conclusion .............................................................................................................................................. 17 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 18 1.2.1 Introduction ............................................................................................................................................ 18 1.2.2 Commercial Process Technology............................................................................................................ 18 1.2.2.1 Axens ........................................................................................................................................ 20 1.2.2.1.1 Semi-regenerative .................................................................................................... 20 1.2.2.1.2 Octanizing ............................................................................................................... 21 1.2.2.1.3 Aromizing ................................................................................................................ 23 1.2.2.1.4 Dualforming/Dualforming Plus ............................................................................... 24 1.2.2.2 Chevron Phillips Chemical ....................................................................................................... 25 1.2.2.3 UOP .......................................................................................................................................... 26 1.2.2.3.1 Platforming .............................................................................................................. 27 1.2.2.3.2 CCR Platforming ..................................................................................................... 27 1.2.2.3.3 RZ Platforming ........................................................................................................ 30 1.2.2.3.4 CycleX ..................................................................................................................... 31 1.2.2.3.5 Chlorsorb ................................................................................................................. 33 1.2.2.4 Zeosit ........................................................................................................................................ 33 1.2.3 Summary of Commercial Process Technology ....................................................................................... 35 1.2.4 Commercial Catalysts ............................................................................................................................. 38 1.2.4.1 Axens ........................................................................................................................................ 39 1.2.4.1.1 CCR Catalysts ......................................................................................................... 40 1.2.4.1.2 Fixed-bed Catalysts ................................................................................................. 42 1.2.4.2 BASF Catalysts......................................................................................................................... 46 1.2.4.3 ExxonMobil .............................................................................................................................. 46 1.2.4.4 Indian Petrochemical Corp. ...................................................................................................... 46 1.2.4.5 Sinopec ..................................................................................................................................... 46 1.2.4.5.1 CCR Catalysts ......................................................................................................... 46 1.2.4.5.2 Fixed-bed Catalysts ................................................................................................. 47

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TABLE OF CONTENTS

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1.2.4.6 UOP........................................................................................................................................... 47 1.2.4.6.1 CCR Catalysts .......................................................................................................... 47 1.2.4.6.2 Fixed-bed Catalysts .................................................................................................. 50 1.2.5 Comparison of Commercially Available Catalysts ................................................................................. 53 1.2.6 Additional Catalyst and Adsorbent Technology ...................................................................................... 55 1.2.6.1 Axens ........................................................................................................................................ 55 1.2.6.2 Johnson Matthey Catalysts ........................................................................................................ 55 1.2.6.3 Süd-Chemie ............................................................................................................................... 56 1.2.6.4 UOP........................................................................................................................................... 56 1.2.7 Comparison of Commercially Available Advanced Control and Optimization Systems ......................... 56 PLANT OPERATIONS AND PRACTICES................................................................................................................... 61 1.3.1 Feedstock Management ........................................................................................................................... 61 1.3.1.1 Product Slate and Feed Type..................................................................................................... 61 1.3.1.2 Feedrate Considerations ............................................................................................................ 63 1.3.1.3 Sulfur Management ................................................................................................................... 63 1.3.1.4 Iron ............................................................................................................................................ 65 1.3.1.5 Nitrogen .................................................................................................................................... 65 1.3.1.6 Mercury ..................................................................................................................................... 66 1.3.2 Operational Challenges and Mitigation Strategies ................................................................................. 66 1.3.2.1 Problems Encountered when Processing Non-straight Run Naphthas ...................................... 66 1.3.2.2 Chloride, Water, and Fouling Monitoring and Control............................................................. 69 1.3.2.3 Red Oil in the Reformer ............................................................................................................ 71 1.3.2.4 High Temperature Hydrogen Attack (HTHA) .......................................................................... 72 1.3.2.5 Problems in the Catalyst Circulation Loop ............................................................................... 72 1.3.2.6 Preventing Failure in Reactor Internals..................................................................................... 73 1.3.3 Catalyst Management .............................................................................................................................. 74 1.3.3.1 Justifying a Change of Catalyst................................................................................................. 74 1.3.3.2 Tracking Coke on Catalyst ........................................................................................................ 75 1.3.3.3 Separating Useable Catalyst Pills from Fines ........................................................................... 75 1.3.3.4 Using Pre-reduced and Pre-sulfided Catalyst............................................................................ 76 1.3.3.5 Platinum Losses from Reforming Catalyst ............................................................................... 76 1.3.3.6 Catalyst Modeling for Improved Unit Performance.................................................................. 77 1.3.3.7 Catalyst Improvements for Extending Semi-regenerative Reformer Cycle Length .................. 77 1.3.3.8 In-situ Regeneration and its Importance for Reclamation......................................................... 78 1.3.4 Process Control and Modeling................................................................................................................ 79 1.3.4.1 Model-based Inferential Properties ........................................................................................... 79 1.3.4.2 Advanced Process Control in Catalytic Reforming Units ......................................................... 80 1.3.4.3 Online Measuring Tools: NMR Spectroscopy and Gas Chromatography ................................ 81 1.3.5 Product Slate ........................................................................................................................................... 82 1.3.5.1 Reformate Benzene and Aromatics Reduction ......................................................................... 82 1.3.5.2 Maximizing Hydrogen Production ............................................................................................ 84 1.3.5.3 Aromatics Production in Catalytic Reforming .......................................................................... 85 1.3.5.4 Flexibility in Naphtha Conversion for Integration with Petrochemical Plants ......................... 85 1.3.6 Revamp Strategies ................................................................................................................................... 86 1.3.6.1 Revamping Fixed-bed Units to CCR Reformers or Hybrid Units ............................................ 86 1.3.6.2 Revamping Semi-regenerative Reformers to Low-pressure Operations ................................... 88 1.3.7 Improving Energy Efficiency and Reducing CO2 Emissions ................................................................... 88 1.3.7.1 Reformer Heat Exchanger Types .............................................................................................. 89 1.3.7.1.1 Welded Plate ............................................................................................................ 90 1.3.7.1.2 Twisted Tube ........................................................................................................... 93 1.3.7.1.3 Rod Baffle ................................................................................................................ 93

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TABLE OF CONTENTS

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1.5 1.6

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1.3.7.2 Fired Heater Capacity and Efficiency ....................................................................................... 94 1.3.7.2.1 General Strategies .................................................................................................... 94 1.3.7.2.2 CCR Reformer Furnace Upgrade ............................................................................ 94 1.3.7.2.3 Ceramic Refractory Coating .................................................................................... 95 1.3.7.2.4 Rebalancing heat load among furnaces for CCR Platforming ................................. 96 REFINING R&D ALERT! ...................................................................................................................................... 97 1.4.1 Introduction ............................................................................................................................................ 97 1.4.2 Product Selective Cat Reforming .......................................................................................................... 101 1.4.2.1 Aromatics................................................................................................................................ 101 1.4.2.1.1 Patents ................................................................................................................... 101 1.4.2.1.2 Research ................................................................................................................ 105 1.4.2.2 Reformate Octane ................................................................................................................... 107 1.4.2.3 Hydrogen ................................................................................................................................ 108 1.4.2.3.1 Patents ................................................................................................................... 108 1.4.2.3.2 Research ................................................................................................................ 109 1.4.3 Catalyst Improvements.......................................................................................................................... 110 1.4.3.1 Coking and Deactivation ........................................................................................................ 110 1.4.3.2 Composition............................................................................................................................ 111 1.4.3.2.1 Patents ................................................................................................................... 111 1.4.3.2.2 Research ................................................................................................................ 113 1.4.3.3 Preparation Method ................................................................................................................ 115 1.4.3.3.1 Patents ................................................................................................................... 115 1.4.3.3.2 Research ................................................................................................................ 117 1.4.4 Process Improvements .......................................................................................................................... 119 1.4.4.1 Design ..................................................................................................................................... 119 1.4.4.2 Energy Efficiency ................................................................................................................... 120 1.4.4.2.1 Patent ..................................................................................................................... 120 1.4.4.2.2 Research ................................................................................................................ 122 1.4.4.3 Reactor Modeling ................................................................................................................... 122 1.4.4.4 Improved Feed Flexibility and Conversion ............................................................................ 124 1.4.4.5 Optimization ........................................................................................................................... 125 1.4.5 Other ..................................................................................................................................................... 126 WORLDWIDE INSTALLED CAPACITY.................................................................................................................. 128 CONSTRUCTION ................................................................................................................................................. 129 1.6.1 Recent Construction Activity ................................................................................................................. 129 1.6.2 Completed Construction Projects ......................................................................................................... 132 REFERENCES ..................................................................................................................................................... 136