Innovative Catalyst Solutions for (Ultra) Low Sulphur Diesel

The Middle East Fuels Symposium 3rd Annual Meeting Abu Dhabi, March 2009

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Catalyst Development for (Ultra) Low Sulphur

1000 900 800 700 600 500 400 300 200 100 0

Rel Vol Activity

1950

1960

1970

1980

1990

2000

2010

YEAR
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Contents
STARS Catalyst Road to 50 / 10ppm sulphur Commercial experiences

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STARS Technology
STARS -- New catalyst manufacturing technology which maximizes the number of Super Type II Active Reaction Sites with very high intrinsic activity for HDN and HDS What are Type II Sites?
NiMoS (or CoMoS) with weak bond to the support -- more fully sulfided greater access to high activity edge and corner sites very high intrinsic activity per active site

STARS can be sulphided using feed only (i.e without need for spiking agent) achieving maximum activity.
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STARS Catalyst Technology

Performance and benefits demonstrated extensively in pilot plant tests and commercial units. First batches installed early 1998. Activity benefits of up to 20 C confirmed in commercial operations with the latest generation of STARS catalysts.

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STARSTM Catalysts Ketjenfine KF 848, KF 860, KF 868

NiMo STARSTM catalyst for deep HDN, applied in FCC pretreat, MHC and Hydrocracker pretreat service.

Ketjenfine KF 757, KF 767, KF 770

CoMo STARSTM catalyst for (Ultra) Deep Diesel HDS

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HDS Performance of KF-757, CoMo STARS Catalyst

160

140

RVA HDS

120

100

80 KF-752 KF-756 KF-757

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HDS Performance of KF 757 vs KF 756,

KF 756 WABT (oC) +60 +40 KF 757 +20 Base LGO 0 500

T= 8 oC
HGO 1000

T= 10 oC
LGO 1500

Time on stream (hrs)

Figure 4
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STARSTM KF 757 has higher HDN activity RVA-HDN LGO LGO/LCO 80/20 LGO/LCO 50/50 LCO 100 KF-756 100 100 100 100 KF-757 130 125 123 127

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The road to 50/10ppm Effects of 1000 50 10ppm sulfur diesel on:

cycle length catalyst volume hydrogen consumption exotherm

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Case Study Current case

Operating Conditions Reactor Inlet Pressure Cycle Length Product Sulfur Feed Definition Feed Blend Feed Specific Gravity Feed Sulfur Feed Nitrogen ASTM D86 IBP/50%/95%/FBP Total Aromatics kg/l wt-% ppmwt C wt% 15% LCO / 85% SRGO 0.854 1.14 194 184 / 285 / 360 / 374 37 barg months ppmwt 50 > 60 1000

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Effect of 50/10ppm on Cycle Length

Decreasing Product Sulfur Specification Constant Catalyst Volume Upgrading Catalyst Technology
Product Sulfur Catalyst Type Loading Catalyst Vol. WABT Cycle Length m3 C Months ppmwt 1000 KF-756 Sock Base T1 > 60 350 KF-756 Sock Base T1+20 36 50 KF-756 Sock Base T1+55=T2 6 50 KF-757 STARS Dense Base T2-15 13 10 KF-767 STARS Dense Base T2 6

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Effect of 50/10 ppm on Rx Vol Catalyst Volumes and Cycle length for 50/10pm
Product Sulfur Catalyst Type Loading Cycle Length Catalyst Volume Months m3 ppmwt 50 KF 757 STARS Dense 13 Base 50 KF 757 STARS Dense 24 1.6 * Base 50 KF 757 STARS Dense 36 2.2 * Base 10 KF 767 STARS Dense 24 2.5 * Base

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Effect of 50/10ppm on Hydrogen/Exotherm

Product Sulfur Catalyst Type Chem. Hydrogen Consumption Approx. Exotherm Nm3/m ppmwt 1000 KF 756 Base 350 KF 756 1.1 * Base 50 KF 757 STARS 1.15 * Base 10 KF 767 STARS 1.3 * Base

Base

Base + 5

Base +10

Base +15

Higher chemical hydrogen consumption and exotherm caused by higher aromatics saturation at lower product sulphur

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Commercial Experience

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Commercial Experience (1) KF 757 in LSD operation

Installed in May 1998, replacing KF-756, 20,000 BPSD Blocked operation LGO and HGO 30 bars ppH2 Reports 8C better activity with KF-756, as expected from laboratory test Cycle length from 1 year with KF 756 to 2 years with KF-757
400 KF-756 390 KF-757 380 WABT (C)

370

360

350 Deactivation Rate = 0.7 C/month 340 0 50 100 150 200 250 300 350

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Days on stream (Days)

Commercial Experience (2) KF-757

Total pressure Treat gas H2 purity LHSV H2/oil
410 400 390 380 WABT, C 370 360 350 340 330 320 310 0 5 10 15 20 TOS, Months 25 30 35 40 0 - 16 months on stream Deactivation 0.3C/month 16 - 34 months on stream Deactivation 1.1C/month

42 bar 85% 3 300 Nm3/m3

Feed Sulphur Product Sulphur Cycle length

0.2 0.8%wt 35ppm 3 years

WABT, Normalised to 35ppm

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Commercial Experience (3) KF-848 in ULSD

About 30 % CGO in feed Inlet pressure 65 bar LHSV 1.2 1.8 5 Years cycle, 1st year 50 -10 ppm S, last four years 10 ppm S)
1.0000

0.1000

Sulfur, wt%

Sulfur Feed wt% Sulfur Product wt%

0.0100

0.0010

0.0001

0.0000 1-Aug-01

1-Aug-02

1-Aug-03

31-Jul-04

31-Jul-05

31-Jul-06

Date
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Commercial Experience (3) KF-848 in ULSD

WABT, Normalised to 10 ppm
410

400

390

380 WABT, C

370 30 - 60 months on stre am Deactivation 1.4C/month

360

350

340 0 - 30 months on stream Deactivation 0.5C/month 330 0 10 20

Cycle 60 months
30 TOS, Months 40 50 60

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Commercial Experience STARS Catalysts

To date we have sold more than 90,000 tons of STARSTM catalysts world wide Of this 54,000 tons is KF 757 STARSTM
KF 757 60%

Other STARS catalysts

Of the 54,000 tons KF 757, 42,000 tons are for (U)LSD production

77% KF 757 in (U)LSD

KF 757 other applications

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Commercial Experience STARS Catalysts

Via the UOP-Albemarle HPC Alliance, we have designed a large number of grassroots/revamped HDS units for ultra low sulphur units on STARS (KF 757) Among these a number of units in Takreer and 2 other large projects in the Middle East

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Summary
STARSTM is a new concept in catalyst design, maximizing the number of Super Type II Active Reactions Sites. STARSTM catalyst have significantly higher HDS activity (up to 160%) than non-STARS for ultra deep desulfurization of diesels down to 10 ppm. STARSTM catalysts can be sulphided with feed only without the need for a spiking agent for maximum activity Decreasing product sulfur specifications reduces cycle length dramatically STARSTM catalysts can make (ultra) low sulphur diesel in existing units with acceptable cycle length. No CAPEX may be required Excellent commercial experience of STARSTM catalysts with respect to activity and stability
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Innovative Catalyst Solutions for (Ultra) Low Sulphur Diesel

The Middle East Fuels Symposium 3rd Annual Meeting Abu Dhabi, March 2009

Strictly confidential - proprietary information of Albemarle Corporation