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

Ultra Low sulfur diesel

Sulfur components which are present which are difficult effect of current diesel HT

How to get to ULSD (~ 15 ppmwt) Catalyst volume Pressure levels Example of revamp

Deer Park example

Y:\ashraaa\Diesel HDS\Presentation-06202000-Heezen

Sulfur Components

S

R+ 4 H2

CH2 CH3

CHCH3

R

+ 2 H2S

S

R+ 3 H2

CH2

CH3

R

H2S +

S

R R2

+ 2 H2

R R2

H2S+

Boiling point,in degr F

99 (R1=R2=CH3)

184

94 (R=C2H5)

430

630

Relative rateconstant60

20

1

0.59

0.44

RSH + H2 RH + H2S

Mercaptans

R1SR2 + 2 H2 R1 H + R2H + H2SSulfides

Thiophenes

Benzo-thiophenes

Di-benzo-thiophenes


Current HDS levels

94% HDS

99% HDS


Sulfur distribution of GOHT LSD

0.1

1

10

100

1000

10000

0 0.2 0.4 0.6 0.8 1

Volume fraction

Su

lfur

in p

pm

wt

S in fraction Cumm Sulfur Sulfur in cumm fraction


Sulfur Removal

S

S

4.2*1E-8 2.8*1E-5

1.1E-4 4.7E-6

Slow

Rate of C-S bond cleavage >>

Rate of ring hydrogenation

Reaction network ex Houalla et al (1980)


Deep HDS levels

Conversion of individual Sulfur species

0.6

0.7

0.8

0.9

1

625 630 635 640 645 650 655 660 665

WABT

Conv

ersio

n

4-MDBT DMDBT TMDBT 4,6 DMDBT

20% FCC LGOFeed, 1.6 wt% sulfur 582 ppmwt 4-MDBT 244 ppmwt DMDBT 297 ppmwt TMDBT 257 ppmwt 4,6 DMDBTdata ex Grace Davison


Conclusion

For ULSD difference between SR and SR/FCC/DCU

more cracked stock, more substituted di-benzothiophenes difficult when 4,6 substituted (sterical hindrance) very difficult cracked stock require more hydrogenation power

concentration on the substituted di-benzothiophenes boiling range ~ 630 °F requires different catalyst


How to get to ULSD

Extra catalyst volume Hydrogen partial pressure Other options, example Reactor configuration


Catalyst volume

1

10

100

1000

10000

100000

0 1 2 3 4 5 6 7 8 9 10

Catalyst volume (1= 500 ppmwt)

Su

lfu

r in

pro

du

ct

First order Second order 2nd going to 1.25nd order


Effect of Cat volume

HDS at 40 bar ppH2 and 370C IABT

0.0

50.0

100.0

150.0

200.0

250.0

300.0

350.0

400.0

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9

WHSV

S in

pro

duct

, ppm

LGO over C448

FRGO over C448

FRGO+25%LCO over C448

LGO over stab C424

FRGO over C424


Deer Park DHT testing


Reactor configurations

Add co-current additional reactor in the loop same pressure H2S present

Add counter current same pressure no H2S present in bottom Synsat technology (CCC,Lummus others)

Add via intermediate stripper can be different pressure very little H2S


Integration with existing unit

Reactor vo lume requiredto product 500 ppmwt (as

per current design)

New reactor vo lumerequired to go to 50

ppmwt

N EW

H2

H2 +liqu id

H2 +liqu id

liqu id

Aminescrubber

LSD ex DCUHT

Potential for: -Reuse existing DHT -Reuse work up section


Hydrogen partial pressure

Only for HDS no cetane improvement note 15 ppmwt, so different from 50 ppmwt

Desirable to have 800# design pressure reasonable shape

DP, CR, PS, Norco, LARC border line

DC requires extra pressure

PAP


Effect of pressure

HDS at 370C and 1.0 WHSV

0.0

50.0

100.0

150.0

200.0

250.0

300.0

350.0

20 25 30 35 40 45 50

ppH2, bar

S in

pro

duct

, ppm

LGO over C448

FRGO over C448


LGO over stab C424

FRGO over C424



How to get to ULSD

UOP study (NPRA March 2000)base case 500 ppmwt higher activity catalyst 285H2S scrubber 180recycle gas purity 140

from CRU gas to 99 vol%)increase EOR WABT 120

requires color control reactornew reactor 30

same volume


SelectiveHydrogenation

NaphthaHDT

KeroseneHDS

DieselHDS

Vacuumtow er CFH

Catcracker

unit

Reform er

De-isohexaniser

Alkylation

CDU

Delayedcokerunit

DCU HT

HCU

Gasoline

Kerosene

D iesel

Simplified refinery lay out


Diesel production post Crude expansion project

Hydrocracker diesel product conversion unit, high H2 partial pressure (pp) diesel product ~ 30 Mbbl/sd, S ~ 25 ppmwt (pilot plant)

Delayed coker unit HT DCU product HT, high H2pp diesel product ~ 20 Mbbl/sd, S ~ 450 ppmwt

Diesel HT SR + FCC LGO, low H2pp product ~ 43 Mbbl/sd, S ~ 450 ppmwt


1

10

100

1000

10000

100000

0 1 2 3 4 5 6 7 8 9 10


Su

lfu

r in

pro

du

ct


Performance extrapolations as function of reaction order


Sulfur extrapolations

From 2 wt% to 450 ppmwt, cat volume X

From 2 wt% to 50 ppmwt, cat volume 3.7 X same catalyst, same H2pp, same reactor temperature etc can be reduced by capex optimization (2-3, used 2.5 X)

From 2 wt% to 15 ppmwt, cat volume 6 X same cat, same H2pp, same reactor temperature etc can be reduced by capex optimization (3-5, used 4 X)


1

10

100

1000

10000

100000

0 1 2 3 4 5 6 7 8 9 10


Su

lfu

r in

pro

du

ct


Performance extrapolations as function of reaction order


Pool to 50 ppmwt Sulfur

HCU No investment

DCU-HT 2nd draw, LLGO (50 ppm) and HLGO (~2000 ppm)

DHT entire stream needs additional hydrotreating

Reprocessing 5 Mbbl/sd (DCU-HT) + 43 Mbbl/sd (DHT)


Cost of producing 50 ppmwt

Flowrate 48 Mbbl/sd, Sulfur 600 ppmwt Refractive sulfur Requires moderate H2pp (500+)

Limited stream specific data general data available (Shell, Catalyst companies, etc)

Integrate within existing DHT unit revamp with new large reactor, compressor, heat exchangers,

separators, pumps cost ~ 800 $/bbl investment (-30% to +50%) create extra draw from DCU-HT Inside battery limit, US Gulf coast : 45 MM$


Integration with existing unit

Reactor vo lume requiredto product 500 ppmwt (as

per current design)

New reactor vo lumerequired to go to 50

ppmwt

N EW

H2

H2 +liqu id

H2 +liqu id

liqu id

Aminescrubber

LSD ex DCUHT


15 ppmwt Sulfur

HCU H2S scrubber, catalyst improvement

DCU-HT entire stream additional hydrotreating

DHT entire stream additional hydrotreating

Reprocessing 20 Mbbl/sd (DCU-HT) + 43 Mbbl/sd (DHT)



Flow rate 63 Mbbl/sd, Sulfur 450 ppmwt Anticipate modest modifications on HCU (~10 MM$) Refractive sulfur removal required Requires moderate ppH2 (500+)

No stream specific data limited general data available (Shell, Cat companies, etc)

Integrate within existing DHT unit really big new reactor, compressor, HX-ers separators, pumps,

work up section cost ~ 1100 $/bbl investment ISBL, USGC: 70 MM$


5 ppmwt Sulfur

HCU entire stream additional hydrotreating

DCU-HT entire stream additional hydrotreating

DHT entire stream additional hydrotreating

Reprocessing 20Mbbl/sd (DCU-HT)+43Mbbl/sd(DHT)+30Mbbl/sd (HCU)



Flow rate 93 Mbbl/sd, Sulfur 310 ppmwt Refractive sulfur removal required Requires high ppH2 (800+ #)

No stream specific data Very limited general data available (Shell, Cat companies, etc) design basis weak

Cost estimate basis new unit (1000#) cost ~ 2000 $/bbl investment ISBL, USGC: 200 MM$


Manufacturing cost

S in ULSD 50 ppm 15 ppm 5 ppm

Reprocessingvolume Mbbl/sd

48 63 93

Capex MM$ 45 80 200

H2+catalyst costMM$/y 5 13 38

Total c$/gl(*) 1.7 3.0 7.5

Incremental cost for Sremoval, MM$/ton

14 285 1700

(*) on total pool


Deer Park case

Deer Park advantage

economy of scale H2 availability Gulf Coast, low labor HCU stream has ‘low’ Sulfur

Deer Park disadvantage

~30% of refinery output 3 diesel producing units no niche market no No6 fuel production high S in crude diet no flexibility in crude diet no spare capacity


Europe versus US I

EU past 95% point of 700 °F Cetane No 50 Space velocity 1 hr-1

EU future 95% point of 650-680 °F Sulfur <50 ppmwt Cetane No 51-58

no FCC LGO

US current 90% point 640 ºF

95% ~660 ºF Cetane No 42 Space velocity 2 hr-1

US future 90% point of 640 °F Sulfur <50 ppmwt Cetane No 42

FCC, DCU LGO


Europe versus US II

EU refinery bottom conversion

vis-breaker minimal diesel prod. produces liquid fuel

FCC unit gasoline + LGO reasonable quality LGO

only FCC LGO now to diesel future to cutter stock

US refinery bottom conversion

Delayed coker Significant diesel prod. No/little 6-oil production

FCC unit geared for gasoline poor quality LGO

two non SR LGO now to diesel no cutter outlet


Europe versus US III

EU refinery easier low sulfur

implementation change in 95% point cut out of LGO

Cetane use SR outlet for FCC LGO

available

US refinery sulfur more difficult to

implement No change in end point diesel units too small

Cetane No outlet for DCU/FCC

LGO available HCU? 5000 $/bbl


Documents

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