Innovative Catalyst Solutions for (Ultra) Low Sulphur Diesel

The Middle East Fuels Symposium – 3rd Annual Meeting

Abu Dhabi, March 2009

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Strictly confidential - proprietary information of Albemarle Corporation
 Catalyst Development for (Ultra) Low Sulphur
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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

RVA HDS 140

120

100

80
KF-752 KF-756 KF-757

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 HDS Performance of KF 757 vs KF 756,

KF 756
+60
WABT (oC)

+40
KF 757
+20
∆T= 8 oC ∆T= 10 oC
Base
LGO HGO LGO

0 500 1000 1500

Time on stream (hrs)

Figure 4
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STARSTM KF 757 has higher HDN activity

RVA-HDN KF-756 KF-757

LGO 100 130

LGO/LCO 80/20 100 125
LGO/LCO 50/50 100 123
LCO 100 100 127

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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 barg 50
Cycle Length months > 60
Product Sulfur ppmwt 1000

Feed Definition
Feed Blend 15% LCO / 85% SRGO
Feed Specific Gravity kg/l 0.854
Feed Sulfur wt-% 1.14
Feed Nitrogen ppmwt 194
ASTM D86 IBP/50%/95%/FBP ºC 184 / 285 / 360 / 374
Total Aromatics wt% 37
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Effect of 50/10ppm on Cycle Length

Decreasing Product Sulfur Specification

Constant Catalyst Volume

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

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Effect of 50/10 ppm on Rx Vol

Catalyst Volumes and Cycle length for 50/10pm

Product Sulfur ppmwt 50 50 50 10

Catalyst Type KF 757 KF 757 KF 757 KF 767
STARS STARS STARS STARS
Loading Dense Dense Dense Dense
Cycle Length Months 13 24 36 24
Catalyst Volume m3 Base 1.6 * Base 2.2 * Base 2.5 * Base

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Effect of 50/10ppm on Hydrogen/Exotherm

Product Sulfur ppmwt 1000 350 50 10

Catalyst Type KF 756 KF 756 KF 757 KF 767
STARS STARS
Chem. Nm3/m Base 1.1 * Base 1.15 * Base 1.3 * Base
3
Hydrogen
Consumption
Approx. °C Base Base + 5 Base +10 Base +15
Exotherm

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 8°C 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 (ºC)

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 42 bar
Feed Sulphur 0.2 – 0.8%wt

Treat gas H2 purity 85%
Product Sulphur 35ppm

LHSV 3
Cycle length 3 years

H2/oil 300 Nm3/m3
WABT, Normalised to 35ppm

410

400

390

380

370
WABT, °C

360
16 - 34 months on stream
350
Deactivation 1.1°C/month
340 0 - 16 months on stream
Deactivation 0.3°C/month
330

320

310
0 5 10 15 20 25 30 35 40
TOS, Months
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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 Feed wt%
Sulfur Product wt%
Sulfur, 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
360
Deactivation 1.4°C/month

350

340
0 - 30 months on stream
Cycle 60 months
Deactivation 0.5°C/month
330
0 10 20 30 40 50 60
TOS, Months

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Commercial Experience STARS Catalysts
KF 757 60%

To date we have sold more
than 90,000 tons of STARSTM
catalysts world wide Other STARS
catalysts

Of this 54,000 tons is KF 757
STARSTM

77% KF 757 in

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