View
262
Download
1
Category
Preview:
Citation preview
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
7/22/2019 Albermarle Catalysts
2/24
Strictly confidential - proprietary information of Albemarle Corporation
7/22/2019 Albermarle Catalysts
3/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
4/24
Strictly confidential - proprietary information of Albemarle Corporation
Contents
STARS Catalyst
Road to 50 / 10ppm sulphur
Commercial experiences
7/22/2019 Albermarle Catalysts
5/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
6/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
7/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
8/24
Strictly confidential - proprietary information of Albemarle Corporation
HDS Performance of KF-757, CoMo STARS Catalyst
80
100
120
140
160
KF-752 KF-756 KF-757
RVAH
DS
7/22/2019 Albermarle Catalysts
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
7/22/2019 Albermarle Catalysts
10/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
11/24
Strictly confidential - proprietary information of Albemarle Corporation
The road to 50/10ppm
Effects of 1000 50 10ppm sulfur diesel on:
cycle length
catalyst volume
hydrogen consumption
exotherm
7/22/2019 Albermarle Catalysts
12/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
13/24
Strictly confidential - proprietary information of Albemarle Corporation
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
10503501000ppmwtProduct Sulfur
7/22/2019 Albermarle Catalysts
14/24
Strictly confidential - proprietary information of Albemarle Corporation
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
105050ppmwtProduct Sulfur
7/22/2019 Albermarle Catalysts
15/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
16/24
Strictly confidential - proprietary information of Albemarle Corporation
Commercial Experience
7/22/2019 Albermarle Catalysts
17/24
Strictly confidential - proprietary information of Albemarle Corporation
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)
7/22/2019 Albermarle Catalysts
18/24
Strictly confidential - proprietary information of Albemarle Corporation
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
Deactivation 1.1C/month
7/22/2019 Albermarle Catalysts
19/24
Strictly confidential - proprietary information of Albemarle Corporation
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%
7/22/2019 Albermarle Catalysts
20/24
Strictly confidential - proprietary information of Albemarle Corporation
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
Deactivation 0.5C/month
30 - 60 months on strea m
Deactivation 1.4C/month
Cycle 60 months
7/22/2019 Albermarle Catalysts
21/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
22/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
23/24
Strictly confidential - proprietary information of Albemarle Corporation
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
7/22/2019 Albermarle Catalysts
24/24
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
Recommended