albermarle catalysts

7/22/2019 Albermarle Catalysts

1/24

Strictly confidential - proprietary information of Albemarle Corporation

Innovative Catalyst Solutions for (Ultra) Low Sulphur Diesel

The Middle East Fuels Symposium 3rdAnnual Meeting

Abu Dhabi, March 2009


2/24



3/24


0

100

200

300

400

500

600

700

800

900

1000

1950 1960 1970 1980 1990 2000 2010

YEAR

RelVolActivity

Catalyst Development for (Ultra) Low Sulphur


4/24


Contents

STARS Catalyst

Road to 50 / 10ppm sulphur

Commercial experiences


5/24


STARS -- New catalyst manufacturing technology which

maximizes the number ofSuperType IIActive Reaction Siteswith 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.

STARS Technology


6/24


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 commercialoperations with the latest generation of STARS catalysts.

STARS Catalyst Technology


7/24


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


8/24


HDS Performance of KF-757, CoMo STARS Catalyst

80

100

120

140

160

KF-752 KF-756 KF-757

RVAH

DS


9/24

Strictly confidential - proprietary information of Albemarle CorporationFigure 4

Base

+20

+40

+60

0 500 1000 1500

Time on stream (hrs)

WABT(oC)

KF 756

KF 757

LGO LGOHGO

T= 8 T= 10oC

HDS Performance of KF 757 vs KF 756,

oC


10/24


STARSTM KF 757 has higher HDN activity

RVA-HDN KF-756 KF-757

LGO

LGO/LCO 80/20

LGO/LCO 50/50

LCO 100

100

100

100

100

130

125

123

127


11/24


The road to 50/10ppm

Effects of 1000 50 10ppm sulfur diesel on:

cycle length

catalyst volume

hydrogen consumption

exotherm


12/24


Case Study Current case

0.854kg/lFeed Specific Gravity

1000ppmwtProduct Sulfur

Feed Definition

Operating Conditions

37wt%Total Aromatics

15% LCO / 85% SRGOFeed Blend

C

ppmwt

wt-%

monthsbarg

184 / 285 / 360 / 374ASTM D86 IBP/50%/95%/FBP

194Feed Nitrogen

1.14Feed Sulfur

> 60Cycle Length50Reactor Inlet Pressure


13/24


Effect of 50/10ppm on Cycle Length

Decreasing Product Sulfur Specification

Constant Catalyst VolumeUpgrading Catalyst Technology

BaseBaseBaseBaseBasem3Catalyst Vol.

T2T2-15T1+55=T2T1+20T1CWABT

13

Dense

KF-757STARS

50

DenseSockSockSockLoading

6636> 60MonthsCycle Length

KF-767STARS

KF-756KF-756KF-756Catalyst Type



14/24


Effect of 50/10 ppm on Rx Vol

Catalyst Volumes and Cycle length for 50/10pm

2.5 * Base2.2 * Base1.6 * BaseBasem3Catalyst Volume

36

Dense

KF 757

STARS

50

242413MonthsCycle Length

DenseDenseDenseLoading

KF 767

STARS

KF 757

STARS

KF 757

STARS

Catalyst Type



15/24


Effect of 50/10ppm on Hydrogen/Exotherm

Base +10

1.15 * Base

KF 757

STARS

50

1.3 * Base1.1 * Base

Base +15Base + 5BaseCApprox.

Exotherm

BaseNm3/m3

Chem.

HydrogenConsumption

KF 767

STARS

KF 756KF 756Catalyst Type103501000ppmwtProduct Sulfur

Higher chemical hydrogen consumption and exotherm caused by

higher aromatics saturation at lower product sulphur


16/24


Commercial Experience


17/24


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

Deactivation Rate = 0.7 C/month

340

350

360

370

380

390

400

0 50 100 150 200 250 300 350

Days on stream (Days)

KF-757

KF-756

WABT(C)

Deactivation Rate = 0.7 C/month

340

350

360

370

380

390

400

0 50 100 150 200 250 300 350

Days on stream (Days)

KF-757

KF-756

WABT(C)


18/24


Commercial Experience (2) KF-757

Total pressure 42 bar

Treat gas H2 purity 85%

LHSV 3

H2/oil 300 Nm3/m3

Feed Sulphur 0.2 0.8%wt

Product Sulphur 35ppm

Cycle length 3 years

WABT, Normalised to 35ppm

310

320

330

340

350

360

370

380

390

400

410

0 5 10 15 20 25 30 35 40

TOS, Months

WABT,C

0 - 16 months on stream

Deactivation 0.3C/month

16 - 34 months on stream



19/24


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)

Commercial Experience (3) KF-848 in ULSD

0.0000

0.0001

0.0010

0.0100

0.1000

1.0000

1-Aug-01 1-Aug-02 1-Aug-03 31-Jul-04 31-Jul-05 31-Jul-06

Date

Sulfur,wt%

Sulfur Feed wt%

Sulfur Product wt%


20/24


Commercial Experience (3) KF-848 in ULSD

WABT, Normalised to 10 ppm

330

340

350

360

370

380

390

400

410

0 10 20 30 40 50 60

TOS, Months

WABT,

C

0 - 30 months on strea m


30 - 60 months on strea m


Cycle 60 months


21/24


Commercial Experience STARS Catalysts

To date we have sold more

than 90,000 tons of STARSTMcatalysts world wide

Of this 54,000 tons is KF 757

STARSTM

Of the 54,000 tons KF 757,

42,000 tons are for (U)LSDproduction

KF 757 60%

Other STARS

catalysts

77% KF 757 in

(U)LSD

KF 757 other

applications


22/24


Commercial Experience STARS Catalysts

Via the UOP-Albemarle HPC Alliance, we have designed a large

number of grassroots/revamped HDS units for ultra low sulphurunits on STARS (KF 757)

Among these a number of units in Takreer and 2 other large projects

in the Middle East


23/24


Summary

STARSTM is a new concept in catalyst design, maximizing the number of

SuperType IIActive Reactions Sites.

STARSTM catalyst have significantly higher HDS activity (up to 160%) thannon-STARS for ultra deep desulfurization of diesels down to 10 ppm.

STARSTM catalysts can be sulphided with feed only without the need for aspiking 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 ofSTARSTM catalysts with respect toactivity and stability


24/24


Innovative Catalyst Solutions for (Ultra) Low Sulphur Diesel

The Middle East Fuels Symposium 3rdAnnual Meeting

Abu Dhabi, March 2009

albermarle catalysts

Documents