Rare Earth Free Catalyst for FCC 16 th – 17 th April, 2012 New Delhi International Conference On “Refining Challenges & Way Forward” Vipan Goel 2 Agenda Rare Earth importance in FCC catalyst RE-free and Low RE Catalyst Technologies - family REMEDY ™ Performance REDUCER ™ Performance Reference List Summary
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Rare Earth Free Catalyst for FCC - World Petroleum Council · Rare Earth Free Catalyst for FCC 16 th – 17 th April, 2012 New Delhi International Conference On “Refining Challenges
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Rare Earth Free Catalyst for FCC
16th – 17th April, 2012
New Delhi
International Conference On“Refining Challenges & Way Forward”
Vipan Goel
2
Agenda
� Rare Earth importance in FCC catalyst
� RE-free and Low RE Catalyst Technologies - family
� REMEDY™ Performance
� REDUCER™ Performance
� Reference List
� Summary
3
Rare Earth Increases the Zeolite Active Site Density
Gasoline Yield and Octane Response to Unit Cell Size
91.0
91.5
92.0
92.5
93.0
93.5
94.0
94.5
95.0
24.2 24.25 24.3 24.35 24.4 24.45
Unit Cell Size, Angstroms
Gas
olin
e O
ctan
e N
umbe
r, R
ON
47.0
47.5
48.0
48.5
49.0G
asol
ine
Yie
ld, w
t%
5
Electron Microprobe Analysis of ResidUltra Ecat
� Microprobe analysis show vanadium to migrate to regions of high RE2O3.
� ResidUltra employs a RE oxide-based vanadium trap. RE oxides do not form stable compounds with silica and sulfate and thus remain available as a vanadium trap.
� ResidUltra is an integral catalyst. It is effective even in units with low vanadium mobility.
REMEDY™ provided similar in-unit Activity and produced low Dry Gas rates
18
Equilibrium Catalyst Shifts with REMEDY™
74
72
70
REMEDY™ 2 GSR®
GENESIS® GSR®
120
115
110
105
100
REMEDY™ 2 GSR®
GENESIS® GSR®
24.29
24.28
24.27
24.26
REMEDY™ 2 GSR®
GENESIS® GSR®
3500
3250
3000
2750
2500
56.0%
54.0%
52.0%
50.0%
Activity, % Zeolite SA, m2/gm Unit Cell Size, Å
V plus Na, ppm ZSA Retention, %
� Similar Activity and Zeolite SA retention
� Additional V+Nalevels
� Lower UCS, but higher than an un-stabilized Zeolite
19
REMEDY™ Commercial Performance – Final Remark
�The performance of REMEDY™ was a successful
– Similar Conversion levels at the same catalyst addition rate
– Low Dry Gas and Slurry Yield
– High Gasoline Selectivity at similar Octane
– Coke Selectivity was maintained– Gasoline Sulfur reduction maintained– No increase in Flue Gas Opacity
�UCS is down from 24.29Å to 24.27Å but confirms the stabilization of zeolite even without rare earth
20
REDUCER™ Performance
21
REDUCER™ for Resid Cracking: Refinery Background
� UOP SBS, partial burn, resid cracking
� Base case : IMPACT® Family
� New REDUCER blend: 50/50 ResidUltra™/Hi-Ni Trap REACTOR™
� Based on the success, have since reformulated the REDUCER™ system to 70% Hi-Ni Trap REACTOR™
22
Ecat Data (100% Turnover)
Activity Remained Similar after Addition of REDUCER ™
Confirming Good Vanadium Tolerance of REDUCER ™
62.0
64.0
66.0
68.0
70.0
72.0
74.0
76.0
78.0
2,00
0.0
2,50
0.0
3,00
0.0
3,50
0.0
4,00
0.0
4,50
0.0
5,00
0.0
5,50
0.0
6,00
0.0
6,50
0.0
MA
T w
t.% F
F
V (mg/kg)
ccc
Resid Catalyst REDUCER™
23
REDUCER™ Demonstrated Good Nickel Tolerance
Ecat Data (100% Turnover)
2.0
3.0
4.0
5.0
6.0
7.0
3000 4000 5000 6000 7000
Gas
Fac
tor
Ni Equivalents [mg/kg]
Gas Factor vs. Ni Equiv.
1.1
1.5
1.9
2.3
3000 4000 5000 6000 7000
Co
ke F
acto
r
Ni Equivalents [mg/kg]
Coke Factor vs. Ni Equiv.
REDUCER™Resid Catalyst REDUCER™Resid Catalyst
24
Reduction in Regen Temp Allowed for an Increase in A tmospheric Resid by 15% abs
FCC Data of REDUCER™ (50/50 Blend)
REDUCER™
100% Turnover
100% Turnover
Catalyst to Oil Ratio Base + 0.4
Hydrogen, wt% Base + 0.02
Dry Gas, wt% Base + 0.2
Propylene, wt% Base + 0.4
Total C4=s, wt% Base + 0.6
LPG, wt% Base + 2.0
Gasoline, wt% Base – 1.6
LCO, wt% Base – 0.2
Bottoms, wt% Base – 0.2
Coke, wt% Base – 0.1
Delta coke Base – 0.09
CAR (mTPD) Base
Regen Temp Base -15°C
25
Conclusions of REDUCER™ Commercial Performance
� Rare earth was reduced from 3.1 to 2.2 wt.% (nearly 0.2m$/annum saving in RES
for refinery CAD @1MTD)
� Despite high Ni+V, the high performance was maintained and even improved
� Base on the yield trends at 50%, refiner increased the concentration to 70% RE free catalyst
� REDUCER™ has been successfully rolled out in EMEA region(18 resid applications)
26
Reference List
27
Low-and-No-RE Commercial Applications
ID Target RE(wt.%)
%RE Free Cat
Unit Type Region Ni(ppm)
V(ppm)
1 0 100 Texaco Design Europe 237 4032 0 100 UOP SBS Europe 444 1,1713 0 100 Shell Mod II Europe 777 9314 0 100 ICI/TPR Europe 409 8365 0 100 Exxon Mod III Europe 108 2476 0 100 UOP SBS Europe na na7 0 100 EXXON III Europe 108 2478 0 100 UOP SBS Europe 597 1,7769 0 100 K OF B Europe 129 16010 0 100 EXXON III Europe 40 12811 0 100 UOP SBS Europe 56 012 0 100 UOP C Europe 169 49013 0 100 UOP SBS Europe na na14 0 100 UOP Stack Europe 356 1,28215 2.2 30 KEL ORTHO Europe 50 12616 0 100 UOP HIGH EFF North America 72 18117 0.6 50 UOP SBS North America 210 55018 0.8 25 KEL MOD III North America 1,036 96619 1.0 50 EXXON MOD IV North America 838 3,01520 3.2 20 UOP HIGH EFF North America 9,085 2,11021 0 100 UOP Stack North America 394 50022 0 100 Texaco Design North America 3,077 1,66623 0 100 UOP Stack North America 50 2,32424 0 100 KEL MOD III 2RIS North America 705 1,23625 0 80 UOP SBS North America 584 1,214
• Demonstrating excellent performance across a wide r ange of metals levels Low metals VGO to high metals Resid applications
• Rare Earth Reduction 100% to 20%
28
Low-and-No-RE Commercial Applications
ID Target RE(wt.%)
%RE Free Cat
Unit Type Region Ni(ppm)
V(ppm)
26 0 100 UOP Stack Asia 1,483 2,26427 0 100 UOP SBS Asia 504 24328 0 100 SHELL DESIGN Asia 36 1,23529 0 100 UOP SBS Asia 1,116 19030 0 100 UOP VSS Europe 62 12031 0 100 UOP VSS Europe 175 56632 1.5 50 UOP Stack North America 492 1,25533 2.4 30 EXXON IV Europe 2,461 3,27334 2.5 ? UOP SBS Europe 1,018 1,05935 1.8 50 EXXON IV Europe 2,060 3,63236 2.5 30 UOP SBS Europe 3,170 5,05937 1.8 50 UOP RFCC Europe 14,806 1,32138 1.6 50 UOP C Europe 1,545 2,47639 2.2 30 SHELL 3 Europe 2,172 5,00340 1.0 70 UOP SBS Europe 3,736 4,52841 2.5 30 UOP C Europe 1,813 2,58942 2.5 30 UOP ST Europe 2,420 3,63743 1.6 50 K OF F Europe 2,550 1,91044 2.5 30 UOP RCC Europe 2,883 4,30045 2.5 30 UOP C Europe 5,321 2,42246 2.2 30 K III Europe 3,796 6,94047 2.5 30 K OF F Europe 2,228 2,81748 2.5 30 UOP SBS Europe 2,301 3,36749 2.5 30 EX FX Europe 6,044 4,93750 1.7 50 UOP ST Europe 3,547 4,747
• Demonstrating excellent performance across a wide r ange of metals levels Low metals VGO to high metals Resid applications
• Rare Earth Reduction 100% to 20%
29
Summary
� Grace has invested in R&D and capital to bring non-RE and low-RE catalysts to the market
� Successful launch of family globally– REACTOR™ - high ZSA, non-RE catalyst – Improve LPG olefinincity– REBEL™ - high MSA, non-RE catalyst– REMEDY™ - low RE catalyst systems for VGO/HT feed applications– REDUCER ™ - low RE catalyst systems for resid feed applications– DeSOX Products with reduced Cerium level to control SOX emission
� Performance is comparable to RE-catalysts� Producing on commercial scale for 50 units� Low to Zero RE product portfolio extended to special functionalities
– Resid Ultra™ designed for resid feed applications special technology with lower RE content metal trap with similar performance to our flagship IMPACT® technology.
– New low/no Super DESOX® formulations, on an equivalent Super DESOX®
performance basis, provide significant cost reductions over Super DESOX®
� Solution for Refiners during economic uncertainty