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Refining & Petrochemical Technology Center Manufacturing Department

Refining Technology Overview for Clean Fuels Production in IDEMITSU . Refining & Petrochemical Technology Center Manufacturing Department. IDEMITSU Kosan Co., Ltd. . CONTENTS Chapter 1 Outline of IDEMITSU 1-1 IDEMITSU’s Refineries 1-2 Crude Source of IDEMITSU

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Refining & Petrochemical Technology Center Manufacturing Department

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  1. Refining Technology Overview for Clean Fuels Production in IDEMITSU Refining & Petrochemical Technology Center Manufacturing Department IDEMITSU Kosan Co., Ltd.

  2. CONTENTS Chapter 1Outline of IDEMITSU 1-1IDEMITSU’s Refineries 1-2Crude Source of IDEMITSU 1-3History of Clean Fuels Production in IDEMITSU Chapter 2 Major Accomplishments 2-1 IDEMITSU’s Strategy 2-2Ultra-Low Sulfur Gasoline 2-3 Ultra-Low Sulfur Diesel 2-4Conclusions

  3. 1-1 IDEMITSU’s Refineries Aichi / Since 1975 Hokkaido / Since 1973 CDUDiesel-HDS Resid-HDS Resid-FCC ALKY ： 160 kBPSD ： 34 kBPSD ： 60 kBPSD ： 50 kBPSD ： 10 kBPSD CDUDiesel-HDS/HDW※ Resid-HDS Resid-FCC ： 140 kBPSD ： 25 kBPSD ： 42 kBPSD ： 33 kBPSD ※：CFI Process Chiba / Since 1963 Petrochemical complexLubricants Tokuyama / Since 1957 Petrochemical complex CDUDiesel-HDS Resid-HDSFCC ： 220 kBPSD ： 60 kBPSD ： 40 kBPSD ： 45 kBPSD CDUDiesel-HDS FCC ： 120 kBPSD ： 24 kBPSD ： 26 kBPSD

  4. 1-2 Crude Source of IDEMITSU Crude oils are mainly from the Middle East. Middle Eastern crude oils contain a large amount of sulfur. IDEMITSU has supplied low sulfur petroleum products.

  5. 1-3 History of Clean Fuels Production in IDEMITSU 1967~ The world’s first ARDS unit was installed at Chiba Refinery in 1967. (followed by Aichi in 1975, Hokkaido in 1994) 1975~ Unleaded Gasoline (Government regulation started in 1986) 1993~ Low Benzene Gasoline, 1 % > (Government regulation started in 1999) 1997~ Low Sulfur Diesel , 500 ppm > (Government regulation started in 1997) 2005~ Ultra-Low Sulfur Gasoline and Diesel, 10ppm > (Government regulation started in 2007) IDEMITSU started to produce clean fuels earlier than government mandatory regulation.

  6. 2-1 IDEMITSU’s Strategy Making full use of catalyst testing technology to select optimum catalyst for maximizing profit of existing units IDEMITSU Pilot Center has 31 fixed-bed bench reactor units (50 cc – 2,000 cc scale), 8 fixed-bed micro reactor units (10 cc scale) and 1 riser bench unit, for the development and testing of new catalysts, and for optimum-operation.

  7. 2-2 Ultra-Low Sulfur Gasoline Production Sulfur in regular gasoline originates in FCC gasoline, thus desulfurization of FCC gasoline is needed. How to reduce Sulfur in FCC Gasoline? Existing Unit Caustic Wash Resid-FCC or VGO-FCC Resid-HDS or VGO-HDS HDS unit (1)Reduce sulfur in FCC feedstock(pre-treatment) - Increase severity of HDS unit, but catalyst life is shortened. (2) Install new unit (post-treatment) to reduce sulfur with - Caustic Wash unit only. - HDS unit only. - combination of both units.

  8. (1) VGO-HDS-FCC Type Refinery Before modification FCC Gasoline S = 30 ppm VGO-HDS VGO-FCC S = 0.20 wt% Sulfur in FCC gasoline is relatively low. Sulfur in FCC gasoline wtppm Sulfur less than 10 ppm cannot be achieved only by pre-treatment. applicable Sulfur in FCC feedstock, wtppm Higher severity operation in HDS shortens catalyst life. The combination of high HDS severity operation and essential post-treat process is applicable.

  9. (1) VGO-HDS-FCC Type Refinery (cont’d) After modification High severity operation Desulfurized FCC Gasoline S = 10 ppm VGO-HDS VGO-FCC Caustic Wash (New) S = 0.07 wt% S = 20 ppm 10 ppm operation was achieved by both higher severity operation of VGO-HDS unit with new catalyst and installation of Caustic wash unit. EOR Temp Cat-B showed good performance at lower severity, but poor performance at higher severity. Cat-B, target S = 0.07 wt% +30 Correct WAT, degC +20 Cat-B, target S = 0.2 wt% +10 Base Time on stream, month

  10. (1) VGO-HDS-FCC Type Refinery (cont’d) After modification High severity operation Desulfurized FCC Gasoline S = 10 ppm VGO-HDS VGO-FCC Caustic Wash (New) S = 0.07 wt% S = 20 ppm target S = 0.07 wt% EOR Temp new Cat-A Summary: Catalyst life is sensitive to severity (sulfur target). Best catalyst suited to operating condition should be selected. new Cat-C Cat-B +30 +20 Correct WAT, degC +10 Base Time on stream, month

  11. (2) AR-Conversion Type Refinery Before modification Resid-FCC Gasoline S = 50 ppm Resid-HDS Resid-FCC Caustic Wash (Existing) S = 0.3 wt% Feature of Resid-FCC gasoline Sulfur distribution Olefin distribution Light Heavy Light Heavy HDS is available. Octane loss of olefin is inevitable in HDS treatment. Caustic wash is available.

  12. Resid-HDS Resid-FCC S = 0.3 wt% (2) AR-Conversion Type Refinery (cont’d) After modification light Caustic Wash (Existing) Desulfurized Resid-FCC Gasoline S = 10 ppm Splitter (New) HDS unit (New) heavy Prime-G+ Higher severity operation of Resid-HDS unit was not applicable because simulation suggested that catalyst life was too short. Summary: Existing Caustic Wash unit reduced sulfur in light FCC gasoline. Post-treat process (Prime-G+) helped to reduce thiophen-type sulfur species in heavy FCC gasoline, minimizing investment and operating costs. Split of FCC gasoline is crucial to reduce octane loss.

  13. (2) AR-Conversion Type Refinery (cont’d) Performance of Prime-G+ HDS unit Summary: The HDS catalyst of Prime-G+ process shows good performance. (without catalyst replacement)

  14. (3) Conclusion for Ultra-Low Sulfur Gasoline Production The production of ultra-low sulfur gasoline was achieved by investigation of properties of FCC gasoline. Best catalyst selection contributed to higher severity operation of VGO-HDS unit without shortage of catalyst life. Both maximum utilization of existing units and installation of essential process saved investment and operating costs significantly.

  15. 2-3 Ultra-Low Sulfur Diesel Production (1) Regulations and IDEMITSU’s efforts 2,000 ppm 500 ppm 50 ppm IDEMITSU added HDS units. Sulfur in diesel, wtppm 10 ppm Calendar year IDEMITSU started to produce ultra-low sulfur diesel earlier than government target.

  16. S (2) Towards 50 ppm Substituted dibenzothiophenes remain after deep HDS treatment. 4,6-Dimethyl- dibenzothiophene Product S = 148 wtppm C2+ C3+ C4+ C5+ Product S = 48 wtppm How to reduce such refractory sulfur species? One answer is choice of highly active NiMo catalyst. (1) No additional reactor (2) Replace IDEMITSU CoMo with highly active IDEMITSU NiMo catalyst (3) Increase of make-up compressor capacity if necessary

  17. Refinery Chiba Aichi Tokuyama 50 ppm since 2005 Catalyst highly active IDEMITSU NiMo catalyst Modification none +amine scrubber +make-up compressor capacity (min.cost) none (2) Towards 50 ppm (Cont’d) Pilot test results: Initial Activity Test: LGO: 90 % = 347.0 degC, N = 99 ppm, S = 11,500 ppm, d = 0.8522 g/cm3, LHSV = 1.5 h-1, PH2 = 4.9 MPa, H2/Oil = 250 Nm3/kl 500 ppm cat Sulfur, wtppm 50 ppm cat IDEMITSU developed NiMo Catalyst successfully. Base +10 +20 +30 +40 +50 Rx WAT, degC Decision:

  18. H2 Consumption, Nm3/kl 50 ppm operation +20 +10 500 ppm operation Base Correct condition: Prod.S = 40 wtppm +40 Correct WAT, degC +30 +20 +10 Base Time on stream, day (2) Towards 50 ppm (Cont’d) Achievement of 50 ppm operation: Summary: IDEMITSU NiMo catalyst showed better performance than expected. Hydrogen consumption increased as expected.

  19. CH3 CH3 CH3 S S CH3 CH3 CH3 CH3 CH3 (3) How to reduce hydrogen consumption? HDS Reaction network HDS activity : less active H2 consumption : lower CoMo prefers Direct HDS HDS activity : more active H2 consumption : higher NiMo prefers Indirect HDS Hydrogenation 4,6-Dimethyl- dibenzothiophene (refractory sulfur species) HDS easily desulfurized species with mitigated steric hindrance Summary: CoMo catalyst prefers direct HDS route. H2 consumption is lower than that of NiMo catalyst. If catalyst life is long enough , CoMo catalyst is attractive in terms of lower H2 consumption.

  20. Sulfur, wtppm - 5 Nm3/kl Base +10 +20 +30 +40 Rx WAT, degC (4) Towards 10 ppm (ULSD) (1) Design of reactor size (LHSV) for one or two-year operation (2) Proper catalyst selection (3) Decrease of hydrogen consumption if possible (4) Increase of make-up compressor capacity if necessary Pilot test results: LHSV was designed 1.0 h-1 for two-year operation as a result of pilot testing. Activity of CoMo catalyst is high enough for two-year operation with lower H2 consumption.

  21. Target 500 ppm> 50 ppm> Catalyst CoMo NiMo Activity very high low high middle Stability BASE H2 consumption - 18 Nm3/kl 10 ppm> CoMo high high ULSD Operation +7 NiMo to CoMo – 5 Total = +2 Nm3/kl Decision: Refinery Chiba Aichi Tokuyama 10 ppm since 2005 Catalyst CoMo catalyst for lower H2 cons. Modification none +additional Rx. +make-up compressor capacity (4) Towards 10 ppm (cont’d) Pilot test summary: IDEMITSU selected CoMo catalyst because of stability and H2 consumption.

  22. H2 Consumption Nm3/kl 10 ppm operation +20 50 ppm operation +10 Base Correct condition: Prod.S = 8 wtppm +40 Correct WAT, degC +30 +20 +10 Base Time on stream, day (4) Towards 10 ppm (cont’d) Achievement of ULSD operation: The stability of CoMo catalyst is satisfactory and increase of hydrogen consumption is minimized. As a result, investment and operating costs were saved.

  23. (5) Conclusions for Diesel HDS Minimum reactor sizes were designed for ULSD operation by proper catalyst testing. Best catalyst selection enabled ULSD operation without significant increase in hydrogen consumption. Investment and operating costs were minimized by pilot tests in advance.

  24. 2-4 Conclusions Ultra-Low Sulfur Gasoline and Diesel production started successfully by Jan.2005 with the combination of - maximum utilization of existing units, - the installations of proper process and - best catalyst selection. Catalyst testing is one of the key technologies. IDEMITSU can solve various problems practically and cost-effectively. fin

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