Catalytic Reforming

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

Second Quarter 2013 Catalytic Reforming

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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

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