WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in One Single Source Fourth Quarter 2014 Isomerization HYDROCARBON PUBLISHING COMPANY SM Translating Knowledge into Profitability P.O. Box 661 Southeastern, PA 19399 (U.S.A.) Phone: (610) 408-0117/ Fax: (610) 408-0118 [email protected] TABLE OF CONTENTS 4Q 2014 Review Isomerization 1. Isomerization ................................................................................................................................... 1 1.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES ............................................................................................. 1 1.1.1 Introduction .............................................................................................................................................. 1 1.1.2 Market Conditions and Outlook ................................................................................................................ 1 1.1.2.1 Gasoline Supply and Demand .................................................................................................. 1 1.1.2.2 Isomerization Capacity and Recent Construction Activity ...................................................... 3 1.1.2.3 Environmental Considerations ................................................................................................. 4 1.1.2.4 Changing Crude Slate .............................................................................................................. 6 1.1.2.5 Isomerization Catalysts Market ............................................................................................... 7 1.1.3 Technology Direction, Competition, and Future Prospects ..................................................................... 8 1.1.3.1 Process Developments ............................................................................................................. 8 1.1.3.2 Catalyst Developments .......................................................................................................... 10 1.1.3.3 R&D Trends ........................................................................................................................... 12 1.1.4 Conclusion .............................................................................................................................................. 13 1.2 STATE-OF-THE-ART TECHNOLOGY ..................................................................................................................... 14 1.2.1 Commercial Processes ............................................................................................................................ 17 1.2.1.1 Axens ..................................................................................................................................... 17 1.2.1.2 CEPSA/KBR/Clariant ............................................................................................................ 22 1.2.1.3 GTC Technology/NPP Neftekhim ......................................................................................... 23 1.2.1.4 RRT Global ............................................................................................................................ 25 1.2.1.5 UOP ....................................................................................................................................... 26 1.2.1.5.1 Butamer ............................................................................................................... 26 1.2.1.5.2 TIP ....................................................................................................................... 28 1.2.1.5.3 Penex ................................................................................................................... 29 1.2.1.5.4 Par-Isom .............................................................................................................. 31 1.2.1.6 Summary of Commercial Isomerization Processes ................................................................ 34 1.2.2 Commercial Catalysts ............................................................................................................................. 35 1.2.2.1 C4 Isomerization Catalysts ..................................................................................................... 37 1.2.2.1.1 Albemarle ............................................................................................................ 37 1.2.2.1.2 Axens .................................................................................................................. 38 1.2.2.1.3 UOP ..................................................................................................................... 38 1.2.2.2 C5-C6 Isomerization Catalysts ................................................................................................ 39 1.2.2.2.1 Albemarle ............................................................................................................ 39 1.2.2.2.2 Axens .................................................................................................................. 41 1.2.2.2.3 Clariant ................................................................................................................ 41 1.2.2.2.4 Japan Energy Corp. ............................................................................................. 42 1.2.2.2.5 NPP Neftekhim ................................................................................................... 42 1.2.2.2.6 Research Institute of Petroleum Processing (RIPP)/Sinopec .............................. 43 1.2.2.2.7 UOP ..................................................................................................................... 44 1.2.2.2.8 VNIINeftekhim ................................................................................................... 47 1.2.2.3 Comparison of Commercially Available Isomerization Catalysts ......................................... 47 1.3 PLANT OPERATIONS AND PRACTICES .................................................................................................................. 48 1.3.1 Feedstock Quality and Benzene Reduction ............................................................................................. 48 1.3.1.1 Removal of CO from H2 Feedstream ..................................................................................... 48 1.3.1.2 Adverse Effects of Benzene and Benzene Precursors, C6+ Cyclics, C7s, and Cyclohexane . 48 1.3.1.3 Chlorination Agents ............................................................................................................... 50 1.3.1.4 Contaminants in Isomerization Feedstocks ............................................................................ 50 4Q 2014 i Hydrocarbon Publishing Co./Copyright Protected TABLE OF CONTENTS 1.3.1.5 Sulfur Detection in Isomerization Feeds ................................................................................ 51 1.3.1.6 Moisture Control for Isomerization Feeds ............................................................................. 52 1.3.1.7 Optimizing the Feed to a Light Naphtha Isomerization Unit ................................................. 53 1.3.2 Process Improvements ............................................................................................................................. 53 1.3.2.1 Problems Encountered with Isomerization Units ................................................................... 53 1.3.2.2 Causes of Temperature Runaway in C4 and C5-C6 Isomerization Units ................................ 54 1.3.2.3 Detecting Leaks in an Isomerization Heat Exchanger/System ............................................... 55 1.3.2.4 Preventing Fouling in C4 Isomerization Units Dryer Beds .................................................... 55 1.3.2.5 Comparison of Light Straight Run Isomerization Configurations ......................................... 55 1.3.2.6 Ways to Minimize RVP of C5-C6 Isomerate .......................................................................... 56 1.3.3 Unit Revamps and Integration ................................................................................................................ 56 1.3.3.1 Commercial Experience in Revamps from a Reformer to an Isomerization Unit .................. 56 1.3.3.2 Addition of a Deisopentanizer ................................................................................................ 5 7 1.3.3.3 Reformer/Isomerization Unit Integration ............................................................................... 58 1.3.4 Catalyst Performance .............................................................................................................................. 60 1.3.4.1 Catalyst Deactivation due to Steam Charge Heater Leakage ................................................. 60 1.3.4.2 Typical Run Lengths of Isomerization Catalysts ................................................................... 60 1.3.4.3 Advantages and Disadvantages of Regenerable Isomerization Catalysts .............................. 61 1.3.4.4 Recycling Spent Catalyst........................................................................................................ 62 1.3.5 Safety ....................................................................................................................................................... 62 1.3.5.1 Use of Safety Integrated Systems on Isomerization Units ....................................................