Ultra Low sulfur diesel l Sulfur components n which are present n which are difficult n effect of current diesel HT l How to get to ULSD (~ 15 ppmwt) n Catalyst volume n Pressure levels n Example of revamp l Deer Park example Y:\ashraaa\Diesel HDS\Presentation Heezen

Sulfur Components Boiling point, in degr F 99 (R 1 =R 2 =CH 3 ) (R=C 2 H 5 ) Relative rate constant RSH + H 2  RH + H 2 S Mercaptans R 1 SR H 2  R 1 H + R 2 H + H 2 S Sulfides Thiophenes Benzo-thiophenes Di-benzo-thiophenes Y:\ashraaa\Diesel HDS\Presentation Heezen

Current HDS levels 94% HDS 99% HDS Y:\ashraaa\Diesel HDS\Presentation Heezen

Sulfur distribution of GOHT LSD Y:\ashraaa\Diesel HDS\Presentation Heezen

Sulfur Removal Rate of C-S bond cleavage >> Rate of ring hydrogenation Reaction network ex Houalla et al (1980) Y:\ashraaa\Diesel HDS\Presentation Heezen

Deep HDS levels 20% FCC LGO Feed, 1.6 wt% sulfur 582 ppmwt 4-MDBT 244 ppmwt DMDBT 297 ppmwt TMDBT 257 ppmwt 4,6 DMDBT data ex Grace Davison Y:\ashraaa\Diesel HDS\Presentation Heezen

Conclusion l For ULSD n difference between SR and SR/FCC/DCU u more cracked stock, more substituted di-benzothiophenes u difficult when 4,6 substituted (sterical hindrance) u very difficult cracked stock require more hydrogenation power n concentration on the substituted di-benzothiophenes u boiling range ~ 630 °F u requires different catalyst Y:\ashraaa\Diesel HDS\Presentation Heezen

How to get to ULSD l Extra catalyst volume l Hydrogen partial pressure l Other options, example l Reactor configuration Y:\ashraaa\Diesel HDS\Presentation Heezen

Catalyst volume Y:\ashraaa\Diesel HDS\Presentation Heezen

Effect of Cat volume Deer Park DHT testing Y:\ashraaa\Diesel HDS\Presentation Heezen

Reactor configurations l Add co-current n additional reactor in the loop n same pressure n H 2 S present l Add counter current n same pressure n no H 2 S present in bottom n Synsat technology (CCC,Lummus others) l Add via intermediate stripper n can be different pressure n very little H 2 S Y:\ashraaa\Diesel HDS\Presentation Heezen

Integration with existing unit Potential for: -Reuse existing DHT -Reuse work up section Y:\ashraaa\Diesel HDS\Presentation Heezen

Hydrogen partial pressure l Only for HDS n no cetane improvement n note 15 ppmwt, so different from 50 ppmwt l Desirable to have 800# design pressure n reasonable shape u DP, CR, PS, Norco, LARC n border line u DC n requires extra pressure u PAP Y:\ashraaa\Diesel HDS\Presentation Heezen

Effect of pressure Y:\ashraaa\Diesel HDS\Presentation Heezen

How to get to ULSD UOP study (NPRA March 2000) base case500 ppmwt higher activity catalyst285 H 2 S scrubber180 recycle gas purity140 from CRU gas to 99 vol%) increase EOR WABT120 requires color control reactor new reactor 30 same volume Y:\ashraaa\Diesel HDS\Presentation Heezen

Simplified refinery lay out Y:\ashraaa\Diesel HDS\Presentation Heezen

Diesel production post Crude expansion project l Hydrocracker diesel product u conversion unit, high H 2 partial pressure (pp) u diesel product ~ 30 Mbbl/sd, S ~ 25 ppmwt (pilot plant) l Delayed coker unit HT u DCU product HT, high H 2 pp u diesel product ~ 20 Mbbl/sd, S ~ 450 ppmwt l Diesel HT u SR + FCC LGO, low H 2 pp u product ~ 43 Mbbl/sd, S ~ 450 ppmwt Y:\ashraaa\Diesel HDS\Presentation Heezen

Performance extrapolations as function of reaction order Y:\ashraaa\Diesel HDS\Presentation Heezen

Sulfur extrapolations l From 2 wt% to 450 ppmwt, cat volume X l From 2 wt% to 50 ppmwt, cat volume 3.7 X u same catalyst, same H 2 pp, same reactor temperature etc u can be reduced by capex optimization (2-3, used 2.5 X) l From 2 wt% to 15 ppmwt, cat volume 6 X u same cat, same H 2 pp, same reactor temperature etc u can be reduced by capex optimization (3-5, used 4 X) Y:\ashraaa\Diesel HDS\Presentation Heezen

Performance extrapolations as function of reaction order Y:\ashraaa\Diesel HDS\Presentation Heezen

Pool to 50 ppmwt Sulfur l HCU u No investment l DCU-HT u 2nd draw, LLGO (50 ppm) and HLGO (~2000 ppm) l DHT u entire stream needs additional hydrotreating l Reprocessing u 5 Mbbl/sd (DCU-HT) + 43 Mbbl/sd (DHT) Y:\ashraaa\Diesel HDS\Presentation Heezen

Cost of producing 50 ppmwt l Flowrate48 Mbbl/sd, Sulfur 600 ppmwt u Refractive sulfur u Requires moderate H 2 pp (500+) l Limited stream specific data u general data available (Shell, Catalyst companies, etc) l Integrate within existing DHT unit u revamp with new large reactor, compressor, heat exchangers, separators, pumps u cost ~ 800 $/bbl investment (-30% to +50%) u create extra draw from DCU-HT u Inside battery limit, US Gulf coast : 45 MM$ Y:\ashraaa\Diesel HDS\Presentation Heezen

Integration with existing unit Y:\ashraaa\Diesel HDS\Presentation Heezen

15 ppmwt Sulfur l HCU u H 2 S scrubber, catalyst improvement l DCU-HT u entire stream additional hydrotreating l DHT u entire stream additional hydrotreating l Reprocessing u 20 Mbbl/sd (DCU-HT) + 43 Mbbl/sd (DHT) Y:\ashraaa\Diesel HDS\Presentation Heezen

Cost of producing 15 ppmwt l Flow rate 63 Mbbl/sd, Sulfur 450 ppmwt u Anticipate modest modifications on HCU (~10 MM$) u Refractive sulfur removal required u Requires moderate ppH2 (500+) l No stream specific data u limited general data available (Shell, Cat companies, etc) l Integrate within existing DHT unit u really big new reactor, compressor, HX-ers separators, pumps, work up section u cost ~ 1100 $/bbl investment u ISBL, USGC: 70 MM$ Y:\ashraaa\Diesel HDS\Presentation Heezen

5 ppmwt Sulfur l HCU u entire stream additional hydrotreating l DCU-HT u entire stream additional hydrotreating l DHT u entire stream additional hydrotreating l Reprocessing u 20Mbbl/sd (DCU-HT)+43Mbbl/sd(DHT)+30Mbbl/sd (HCU) Y:\ashraaa\Diesel HDS\Presentation Heezen

Cost of producing 5 ppmwt l Flow rate 93 Mbbl/sd, Sulfur 310 ppmwt u Refractive sulfur removal required u Requires high ppH2 (800+ #) l No stream specific data u Very limited general data available (Shell, Cat companies, etc) u design basis weak l Cost estimate basis new unit (1000#) u cost ~ 2000 $/bbl investment u ISBL, USGC: 200 MM$ Y:\ashraaa\Diesel HDS\Presentation Heezen

Manufacturing cost (*) on total pool Y:\ashraaa\Diesel HDS\Presentation Heezen

Deer Park case l Deer Park advantage n economy of scale n H 2 availability n Gulf Coast, low labor n HCU stream has ‘low’ Sulfur l Deer Park disadvantage n ~30% of refinery output n 3 diesel producing units n no niche market n no No6 fuel production n high S in crude diet n no flexibility in crude diet n no spare capacity Y:\ashraaa\Diesel HDS\Presentation Heezen

Europe versus US I l EU past n 95% point of 700 °F n Cetane No 50 n Space velocity 1 hr-1 l EU future n 95% point of °F n Sulfur <50 ppmwt n Cetane No u no FCC LGO l US current n 90% point 640 ºF u 95% ~660 ºF n Cetane No 42 n Space velocity 2 hr-1 l US future n 90% point of 640 °F n Sulfur <50 ppmwt n Cetane No 42 u FCC, DCU LGO Y:\ashraaa\Diesel HDS\Presentation Heezen

Europe versus US II l EU refinery n bottom conversion u vis-breaker u minimal diesel prod. u produces liquid fuel n FCC unit u gasoline + LGO u reasonable quality LGO n only FCC LGO u now to diesel u future to cutter stock l US refinery n bottom conversion u Delayed coker u Significant diesel prod. u No/little 6-oil production n FCC unit u geared for gasoline u poor quality LGO n two non SR LGO u now to diesel u no cutter outlet Y:\ashraaa\Diesel HDS\Presentation Heezen

Europe versus US III l EU refinery n easier low sulfur implementation u change in 95% point u cut out of LGO n Cetane u use SR u outlet for FCC LGO available l US refinery n sulfur more difficult to implement u No change in end point u diesel units too small n Cetane u No outlet for DCU/FCC LGO available u HCU? 5000 $/bbl Y:\ashraaa\Diesel HDS\Presentation Heezen