Advances in FCC Catalyst Development Low/No …akbal.imp.mx/foros-ref/xvii/CIP/CIP1.pdfAdvances in...
Transcript of Advances in FCC Catalyst Development Low/No …akbal.imp.mx/foros-ref/xvii/CIP/CIP1.pdfAdvances in...
Advances in FCC Catalyst Development
Low/No Rare Earth FCC Catalysts
Joanne Deady
Vice President – Global Marketing, RT
2
Outline
Rare-Earth Market: Supply and Demand
Use of Rare Earth in FCC catalyst
Davison‟s Low/No Rare Earth FCC Portfolio
Case Study
– Catalyst options with lower rare earth
– Impacts on operation
Conclusions
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1950 1960 1980 1990P
rod
uc
tio
n K
mT
20001970
0
140
20
100
160
120
80
60
40
Credit: ACS, Du and Graedel.
Major Rare Earth Supplier is China
97% of world output
Dominant supplier since the 90‟s
Export quotas restrict supply
– Decreased 50% since 2009
– Quota needed for every pound
of material
Consolidation reduces suppliers
Environmental compliance
investment adds cost
Limited short term options for supply outside of China
Development of new sources will take 5-10 years
oxid
e
ca
rbo
na
te
nitra
te
oxa
late
ch
lori
de
hyd
roxyca
rbo
na
te
TREO
4
“Green” technologies (hybrid cars, wind turbines, energy-efficient lighting)
Military applications (guidance systems)
Lightweight electronic components (cell phones, music devices, flat panels)
Automotive (catalytic convertors, glass, motors)
FCC catalysts (activity and metals trapping), FCC environmental additives
Substitutes do not exist for many applications
Rare Earth Metals are Key Raw Materials in Many Industries
Credit: ACS, Du and Graedel
5
Future Rare Earth Metals Demand
Source: Lanthanide Resources and Alternatives, Oakdene Hollins Research & Consulting – May, 2010
La and Ce are forecasted to be in oversupply
China could become a net importer by 2015?
End users are actively searching for alternatives which may
ease some demand in the near future.
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Use of Rare Earth in FCC
Rare earth discovered to enhance activity of
zeolites in 1960‟s
– Control the activity, selectivity and hydrogen
transfer of the zeolite
– Protect zeolite from metals deactivation
In the 80‟s and 90‟s, rare earth free catalysts
maximized FCC gasoline octane
Environmental additives rely upon rare earth
for SOx and NOx reduction
In 90‟s, FCC rare earth levels increased
– Improved coke selectivity
– Metals trapping
Rare earth is the primary driver for activity and can provide unique
functionalities to the FCC operation
Grace Davison-A History of FCC Innovation
1942 – 1st FCC catalyst
1948 – Microspheroidal catalyst
1955 – High alumina catalyst
1966 – Awarded patent for USY process
1985 – SOx transfer additives
1987 – Increased use of coke selective REUSY
1990 – RE free zeolites dominate market
1998 – NOx reduction additives
2003 – IMPACT® catalyst platform
2008 – MIDAS ® catalyst for max LCO
2011 – New zero rare earth FCC catalysts &
additives
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low unit cell size 24.25 Å
Si/Al = 27
7 Al atoms/unit cell
Rare Earth Increases the Zeolite Active Site Density
Moderate unit cell size 24.32 Å
Si/Al = 12
15 Al atoms/unit cell
catalyst
wt% Re2O3
on catalyst
Unit Cell Size
(Å)
Conversion, wt%
at constant C/O
A 1.1 24.24 53
B 1.8 24.27 65
C 2.2 24.31 69
D 3.3 24.34 73
E 3.7 24.36 76
F 5.7 24.41 80
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Industry Equilibrium Catalyst Trends 2000-2010
201020082006200420022000
2.8
2.6
2.4
2.2
2.0
E-cat RE2O3, wt %
201020082006200420022000
24.32
24.31
24.30
24.29
24.28
E-cat Unit Cell Size, Å
201020082006200420022000
72
71
70
69
68
E-cat Activity (MAT), wt %
24.24 24.30 24.40 24.48
Histogram of E-cat UCS (2010)
9
“Sweet Spot” Exists for Catalytic Performance
47.0
47.5
48.0
48.5
49.0
49.5
3.0
3.4
3.8
4.2
4.6
24.20 24.25 24.30 24.35 24.40 24.45
Gaso
line, w
t%Co
ke, w
t%
Unit Cell Size, Å
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Olefins and RON Decrease with Increasing UCS
28.0
30.0
32.0
34.0
36.0
38.0
40.0
42.0
44.0
91.0
91.5
92.0
92.5
93.0
93.5
94.0
94.5
24.20 24.25 24.30 24.35 24.40 24.45
Gaso
line O
lefin
s, w
t%G
aso
lin
e R
ON
Unit Cell Size, Å
11
0
1000
2000
3000
4000
5000
6000
1980 1985 1990 1995 2000 2005 2010
FC
C f
ee
d b
arr
els
pro
ce
ss
ed
, k
bp
d
0
20
40
60
80
100
120
140
160
180
#u
nits
in U
SFCC barrels # units
Historical Trends in US FCC Unit Throughput
Capacity grew fastest in the late 80’s, early 90’s, while use of REUSY also increased
12
Davison Low/No Rare Earth FCC Catalyst Solutions
Company Confidential - INTERNAL ONLY
High Zeolite Activity Low Zeolite Activity
MIDAS®
Max Bottoms Reduction
RESID-MX
Max Metals Tolerance
ALCYON M™
High activity high MSA
REBEL®
Z-21 Technology for bottoms reduction
GENESIS®
Ultimate formulationflexibility for resid feeds
GENESIS®-LX
Ultimate formulationflexibility for VGO/HT feeds
REDUCER™
Low RE Technology for resid feeds
GENESIS®-XT
Next generation -flexibility for medium to high metal feeds
REMEDY™
Low RE Technology for VGO/HT feeds
ALCYON™
Ultra High Activity
IMPACT™
Minimum Coke & Gas
ResidUltra™
Next generation metals trap
RESULT™
Next generation low to moderate metals
REACTOR™
Z-22 Technology for higher olefins
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Grace has a long history of RE-free innovation in FCC
1964
Grace invents USY
1976
Introduction of REUSY
1990
Z-14G RE free zeolite
1991
XP-L RE free
catalyst series
1997
Z-21 RE free
zeolite in Nexus
2008 -2010
Significant R&D effort
begins on RE replacement
2010
Z-22 RE free zeolite
Grace launches REpLaCeR, RE free catalysts
The addition of RE for stabilization of USY was revolutionary in cat cracking, delivering
coke selectivity and activity improvement
Several RE free catalysts were available in the 1990‟s, with a primary focus on increasing
gasoline octane
REACTOR™ is one of the new REpLaCeR™ family of RE free catalysts
It is built upon Grace Davison‟s alumina-sol technology platform and incorporates the
new rare-earth free Z-22 zeolite
Investigations continue, combining past experience and current material science to
discover the next innovation for catalyst activity and stability
Future
Grace Davison - Company Confidential
14
Alternate methods are used to stabilize the zeolites in
Grace‟s RE-free catalyst
– Proprietary stabilizing compounds
– Unique manufacturing processes
Alternative materials provide activity and stability similar to
RE containing catalysts
– Similar UCS as RE containing zeolites
– Truly RE-free, without stabilization, would yield a very low
UCS and activity
Non Rare Earth Zeolite Stabilization
24.20
24.24
24.28
24.32
Fully exchanged
Low RE exchange
No stabilization
Z-21 Z-22
Eq
uilib
rate
d U
CS
Proprietary Grace non-RE Stabilization
Z-21 and Z-22 have higher UCS after
deactivation than zeolite without stabilization
Z-2
2 T
ech
no
log
y
REACTOR™
Z-22 technology – new improvement over the Z-14G zeolites used at over 125 refineries in the 1990‟s.
Matches activity and selectivity of RE containing catalysts formulations without rare earth.
Z-2
1 T
ech
no
log
y
REBEL™
Z-21 technology launched in late‟90‟s as Nexus (10 commercial applications)
Matches activity and selectivity of RE containing high matrix MIDAS® catalyst without rare earth.
REACTOR™ - RE-free Catalyst
Catalysts with rare earth alternatives
March, 2011
Grace Davison - Company Confidential
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Catalyst Properties – REACTOR™
Grace Davison - Company Confidential
REACTOR™ Aurora
Fresh Properties
Al2O3, wt.% 42.2 44.2
RE2O3, wt.% 0 1.5
DI 4 5
SA, m2/g 393 418
ZSA, m2/g 323 352
MSA, m2/g 70 66
CPS-1 / No Metals
SA, m2/g 252 262
ZSA, m2/g 194 203
MSA, m2/g 57 59
UCS 24.22 24.25
SA Retention 64% 63%
ZSA Retention 60% 58%
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Performance of REACTOR™ vs. Aurora™
Grace Davison - Company Confidential
Similar activity Improved C4= olefins yield
Slightly lower gasoline yield Similar bottoms conversion
1
3
5
7
50 55 60 65 70 75 80
C/O
Ra
tio
Conversion (wt%)
Aurora™
REACTOR™
4
5
6
7
8
50 55 60 65 70 75 80
To
tal C
4=
s (
wt%
)
Conversion (wt%)
Aurora™
REACTOR™
40
44
48
52
56
60
50 55 60 65 70 75 80
C5
+ G
as
oli
ne
(w
t%)
Conversion (wt%)
Aurora™
REACTOR™
2
6
10
14
18
50 55 60 65 70 75 80
Bo
tto
ms
(w
t%)
Conversion (wt%)
Aurora™
REACTOR™
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Yields at Constant Conversion of 74% - No metals
REACTOR™, has similar
performance to
RE-catalyst (Aurora™)
• Similar activity
• Higher LPG olefins
• Similar bottoms
conversion
• Similar coke selectivity
• Slightly lower gasoline
Designed for low to
moderate metal feeds
Grace Davison - Company Confidential
REACTOR™ Aurora™
Catalyst to Oil Ratio 6.0 6.0
Hydrogen, wt.% 0.05 0.04
Tot C1+C2, wt.% 1.4 1.4
Dry Gas, wt.% 1.5 1.4
C3=„s, wt.% 5.0 4.5
Total C3's, wt.% 5.8 5.2
Total C4=„s, wt.% 7.4 6.8
Total C4‟s, wt.% 11.8 10.9
Gasoline, wt.% 52.1 53.7
RON 91.8 90.9
MON 79.9 79.3
LCO, wt.% 19.1 19.4
Bottoms, wt.% 7.4 7.1
Coke, wt.% 2.4 2.3
REBEL™
Catalysts with rare earth alternatives for
maximum bottoms upgrading
May, 2011
Grace Davison - Company Confidential
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Catalyst Properties – REBEL™ vs. MIDAS®
Grace Davison - Company Confidential
REBEL™ MIDAS®
Fresh Properties
RE2O3, wt.% 0.02 1.38
SA, m2/g 240 250
ZSA, m2/g 120 140
MSA, m2/g 120 110
CPS Deactivation w/ 1000ppm Ni / 2000ppm V
SA, m2/g 145 155
ZSA, m2/g 60 75
MSA, m2/g 85 80
Unit Cell 24.29 24.31
SA Retention, % 61% 62%
ZSA Retention, % 50% 54%
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DCR Testing - REBEL™ vs. MIDAS®
Slightly lower activity Lower Hydrogen yield
Similar bottoms conversion Better coke selectivity
Grace Davison - Company Confidential
4
5
6
7
8
9
60 65 70 75 80
Cat/
Oil
Ratio
Conversion (wt%)
REBEL™
MIDAS®
0.1
0.15
0.2
0.25
0.3
0.35
60 65 70 75 80
Hyd
rogen
(w
t%)
Conversion (wt %)
REBEL™
MIDAS®
4
6
8
10
12
14
16
60 65 70 75 80
Bott
om
s (
wt%
)
Conversion (wt%)
REBEL™
MIDAS®
2
3
4
5
6
60 65 70 75 80
Coke (
wt%
)
Conversion (wt%)
REBEL™
MIDAS®
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Constant Conversion Yields
REBEL™ provides
relative to base:
Slightly less
activity
Lower H2 yield
Similar gasoline
selectivity
Similar bottoms
conversion
Similar coke
Grace Davison - Company Confidential
REBEL™ MIDAS™
Cat-to-Oil 7.2 6.5
Hydrogen, wt% 0.21 0.26
C1 + C2's, wt% 2.0 2.0
Total C3, wt% 4.3 4.2
C3= wt% 3.8 3.7
Total C4, wt% 8.5 8.4
Total C4='s, wt% 6.5 6.4
Gasoline, wt% 51.4 51.6
LCO, wt% 21.1 21.4
Bottoms, wt% 8.9 8.6
Coke, wt% 3.6 3.8
REMEDY™ - Low RE Catalyst System
Catalysts with rare earth alternatives for coke
selective bottoms cracking
March, 2011
Grace Davison - Company Confidential
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Case Study – Reduced Rare Earth vs REMEDY Option
Operating Objectives
Minimize catalyst costs due to rare earth hyperinflation
Maintain or improve total profitability
Total liquid yield and LCO are important
UOP Side by Side
Modern RTD and FIT
Full burn
Fired Feed Heater
Operating constraints
Air Blower
Catalyst Circulation
Wet gas at 98% of volume capacity
Feedstock Properties
Vacuum Gas Oil
24.1 API
11.7 UOP K
1.3 wt% Sulfur
0.2 wt% ConCarbon
Equilibrium Catalyst Properties
74 wt% Activity
110 m2/gm ZSA
2.6 wt% Rare Earth
Unit Cell Size 24.32 Å
470 ppm Nickel
1700 ppm Vanadium
Catalyst Additions 5 tpd
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Fresh Catalyst Properties, Additions and ECAT Activity
Catalyst BASE
Re2O3, Wt.% 2.6
Zeolite SA, m2/gm 220
Total SA, m2/gm 290
Catalyst Additions, tpd 5
ECAT Activity 74
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Base Yield and Operating Conditions
Feed Temp, F 600
Reactor Temp, F 992
Regenerator Temp, F 1325
Cat/Oil 6.2
Air Blower Base
Wet Gas Compressor Base
Dry Gas, scfb 214
C3=, Vol% 6.3
iC4, Vol% 3.1
C4=, Vol% 7.3
Gasoline, Vol% 54.9
RON/MON 92.5/80.5
LCO, Vol% 28.8
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Economics
Moderate LCO incentive
C4= attractive due to volume
expansion
Product Value $/B
Dry Gas 55 ($/FOE)
C3= 85
C4= 105
iC4 80
Gasoline 109
Road Octane
Barrel Credit0.5 (Base 88)
LCO 115
Slurry 65
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Base Fresh Catalyst Properties, Additions and ECAT Activity
Catalyst BASE Low Rare Earth
Re2O3, Wt.% 2.6 0.7
Zeolite SA, m2/gm 220 260
Total SA, m2/gm 290 330
Catalyst Additions, tpd 5 10
ECAT Activity 74 74
ECAT activity must be maintained due to catalyst circulation constraint
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Low Rare Earth Yields and Operating Conditions
Catalyst BASE Low Rare Earth
Reactor Temp, F 992 983
Feed Temp, F 600 590
Regenerator Temp, F 1325 1317
Cat/Oil 6.2 6.2
Air Blower Base Base
Wet Gas Compressor Base 1.02 Base
Dry Gas, scfb 214 216
C3=, Vol% 6.3 7.0
iC4, Vol% 3.1 2.7
C4=, Vol% 7.3 7.7
Gasoline, Vol% 54.9 53.1
RON/MON 92.5/80.5 93.3/80.8
LCO, Vol% 28.8 29.7
Product value , $/B (1) Base -0.2 $/b
(1) Product Value includes total catalyst cost
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Lowering Rare Earth Can Result in Higher Daily Costs
Base Lower RE
Daily Cost Cat adds, tpd
Reduce Re2O3
by 75%
Catalyst $/ton
is lower
Catalyst
additions
double
Daily cost
increases by
30%
+30%
31
REMEDY™ FCC Catalyst
Formulated with new RE free zeolites from
Grace Davison
– Proprietary stabilization process
– Unique treatment step to boost activity
– Foundation for new family of catalysts
Delivers similar activity and stability as
traditional RE based catalysts
Performance verified in multiple commercial
applications around the globe
32
Fresh Catalyst Properties, Additions and ECAT Activity
Catalyst BASE Low Rare Earth REMEDY™
catalyst
Re2O3, Wt.% 2.6 0.7 0.2
Zeolite SA, m2/gm 220 260 250
Total SA, m2/gm 290 330 320
Catalyst Additions, tpd 5 10 5
ECAT Activity 74 74 74
New FCC technology delivers required activity without rare earth
33
RE-Free Innovations Save Cost and Maintain Performance
Reduce Re2O3
by 90%
Maintain
activity and
catalyst
additions
Daily cost
decreases by
30%
Base Lower RE REMEDY™
Daily Cost Cat adds, tpd
-30%
34
Optimized Yields and Operating Conditions
Catalyst BASE Low Rare Earth REMEDY™
catalyst
Reactor Temp, F 992 983 988
Feed Temp, F 600 590 595
Regenerator Temp, F 1325 1317 1321
Cat/Oil 6.2 6.2 6.2
Air Blower Base Base Base
Wet Gas Compressor Base 1.02 Base 1.02 Base
Dry Gas, scfb 214 216 207
C3=, Vol% 6.3 7.0 6.9
iC4, Vol% 3.1 2.7 3.0
C4=, Vol% 7.3 7.7 7.8
Gasoline, Vol% 54.9 53.1 53.6
RON/MON 92.5/80.5 93.3/80.8 93.3/80.9
LCO, Vol% 28.8 29.7 29.2
Product value , $/B (1) Base -0.2 $/b +0.4
(1) Product Value includes total catalyst cost
REMEDY™
ECONOMICS
Reduce
daily costs
by 30%
Increased
profitability
by $7 mm/yr
for a 50,000
bpd FCCU–Lower dry
gas
–Higher C4=
& gasoline
35
Conclusions
Rare earth market prices are likely to remain elevated
– Restricted supply
– High demand
– Few viable alternatives exist for most applications
Activity and stability are critical for economic FCC operations
Consider all shifts when reformulating to lower Re2O3 on
catalyst
– Total daily cost, not just $/ton
– Operational impacts
Technology innovations alleviate the pressure and offer
alternatives for rare-earth based FCC catalyst
36
Thank you
GRACE®, GRACE DAVISON®, ENRICHING LIVES, EVERYWHERE.®, IMPACT® and MIDAS® are trademarks,
registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. ResidUltra™, REACTOR™,
REBEL™, REMEDY™ and REplaceR™ are trademarks of W. R. Grace & Co.-Conn. This trademark list has been
compiled using available published information as of the publication date of this presentation and may not accurately
reflect current trademark ownership or status. © Copyright 2011 W. R. Grace & Co.-Conn. All rights reserved.