Worldwide FCC Equilibrium
Catalyst Trends A Ten-Year Review
Marilyn Moncrief
David Hunt
Kelly Stafford
Grace Davison
Refining Technologies
20 www.e-catalysts.com
race Davison's laboratories test
thousands of equilibrium fluid
cracking catalyst (Ecat) samples each year. These samples provide important insights into FCC unit
operations and are critical for unit optimization and troubleshooting.
G
The purpose of this article is twofold.
First, it will communicate how Ecat
activity, contaminants and other properties have shifted over the past ten
years, both worldwide and by geographic region. Second, it will allow
the individual refiner to rank their own
FCC Ecat properties relative to the
industry in several key categories.
The following data reflects ten years
of Ecat sample analyses from 1997
through 2006. The data represents
over 117,000 individual Ecat samples from approximately 300 FCC
units around the world.
Figures 24 to 32 show a ten-year
trend of average Ecat properties
across all regions of the world: Asia
Pacific (AP), European Union (EU),
Latin America (LA) and North
America (NA). EU includes Europe,
Africa, the Middle East and Russia.
North America includes the United
States, Canada and the U.S. Virgin
Islands. Data reflects Ecat samples
Figure 24
Average MAT Activity by Region 1997-2006
that we have received from 1997
through 2006, both from refiners
using Grace Davison FCC catalyst
as well as competitor products.
73
72
71
MAT, wt.%
70
Region
AP
EU
LA
NA
WW
69
68
67
66
65
64
1997
1998
1999
2000
2001
2002
2003
2004
2006
2005
Year
Figure 25
Average Rare Earth by Region 1997-2006
2.75
RE203, wt.%
2.50
2.25
Region
AP
EU
LA
NA
WW
2.00
1.75
1.50
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
Year
Figure 26
Average Unit Cell Size by Region 1997-2006
24.33
UCS, Angstroms
24.32
24.31
24.30
Region
AP
EU
LA
NA
WW
24.29
24.28
24.27
Figure 24 identifies interesting
trends in MAT activity. All regions
experienced significant increases in
activity from 1997 through 2004, at
which time activity stabilized. On a
worldwide basis, average activity
increased from 67.5 to 70.7 wt.%
over
the
ten-year
period.
Additionally, North America has
consistently reported the highest
activity of the four regions, while
Asia Pacific has seen the greatest
overall gains, from 64.2 to 69.7
wt.%.
Higher activity is consistent with
increases in Ecat rare earth content
(Figure 25) and Ecat Unit Cell Size,
UCS (Figure 26). Worldwide, average rare earth has climbed more
than 65%, from 1.54 to 2.56 wt.%,
over the past ten years. Similar
increases are seen in each geographic region. Consistent with rare
earth, average Ecat UCS data has
seen a steady rise from 24.27 to
24.30Å.
Unit cell size and rare earth data
suggests that the increase in Ecat
activity is largely due to higher levels of rare earth exchanged onto
the catalyst zeolite. Figures 25 and
26 also confirm conditions in the
FCC Ecat that can lead to higher
gasoline selectivity as a result of the
shift to higher UCS Ecat. For many
catalyst systems, this shift in UCS
also suggests improved catalyst
coke selectivity.
FCC catalyst alumina content has
experienced a steady upward trend
from 38.9 to 44.0 wt.%, as seen in
Figure 27. Higher Al2O3 has been
observed in all regions and confirms the industry's acceptance of
the value of alumina content on
FCC catalyst performance. Grace
reported on the value of alumina-sol
catalyst technologies in a recent
Catalagram publication. (1)
24.26
1997 1998
1999
2000
2001
2002
Year
2003
2004
2005
2006
Ecat contaminant trends are seen
on Figures 28 to 32. Nickel in parCatalagram 102 Fall 2007
21
Figure 27
Average Alumina by Region 1997-2006
47.5
Al203, wt.%
45.0
42.5
Region
AP
EU
LA
NA
WW
40.0
37.5
35.0
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
Year
Figure 28
Average Nickel by Region 1997-2006
4500
Increased Ecat activity together
with higher nickel and vanadium
levels suggest that today's catalysts
have improved coke selectivity due
to enhanced metals trapping and
improved zeolite and matrix design.
4000
3500
Ni, ppm
ticular (Figure 28) provides insight
into the differing FCC feedstocks
processed in the Pacific Rim units
as compared to the rest of the
world. Vanadium (Figure 29) has
been on the rise in the Asia Pacific
region, increasing from 1900 to
2400 ppm and reflecting a 26%
increase with a 14% increase in
nickel. This trend is reversed on a
worldwide basis, where vanadium
has increased less than 6% while
nickel is up almost 20% over the
ten-year period, from 1475 to 1750
ppm. Nickel, and to a lesser extent
vanadium, acts as dehydrogenation
catalyst that increases the yields of
the unwanted products hydrogen
and coke.(2) Vanadium is also mobile
under FCC regenerator conditions
and reduces catalyst activity by
destroying zeolite framework.(3)
3000
Region
AP
EU
LA
NA
WW
2500
2000
1500
1000
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
Year
Figure 29
Average Vanadium by Region 1997-2006
3000
Iron presents a mixed picture
(Figure 30).
Iron levels have
dropped by 11% in Europe, 10% in
Asia Pacific, and almost 5% in Latin
America over the last ten years. Iron
in North America, on the other
hand, dropped significantly in the
late 1990's, but has been increasing
steadily since 2000. Today the
FCC's with the highest Ecat iron levels are located in North America.
Organic based iron deposited on
the catalyst during the cracking
reactions can have a serious
adverse effect on activity and bottoms cracking.(4)
2750
V, ppm
2500
Region
AP
EU
LA
NA
WW
2250
2000
1750
1500
1997
1998
1999
2000
2001
2002
Year
22 www.e-catalysts.com
2003
2004
2005
2006
Calcium (Figure 31) had been stable for several years, but has
climbed substantially since 2002.
Worldwide CaO levels have
increased 74% overall from 0.083 to
0.144 wt.%. Asia Pacific has the
highest levels, while North and Latin
America have seen the highest percentage increases. Europe has the
lowest average calcium by weight
percent and has also experienced
the lowest percentage increase
Figure 30
Average Iron by Region 1997-2006
over the time period. Ca is often
found on the surface of the Ecat
together with Fe and may be
involved in the mechanism by which
Fe poisons the Ecat.(4)
Figures 33 through 42 present normal distributions of worldwide 2006
Ecat data. These plots can be used
as a quick reference to determine
where an individual FCC unit falls
versus the industry. The numbers
atop each bar represent the number
of FCC units within that data range.
0.56
Fe, wt.%
0.54
0.50
0.48
0.46
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
Year
Figure 31
Average Calcium by Region 1997-2006
0.20
As can be seen in Figure 33, MAT
activity reflects a range from 57 to
81 with a mean of 70.7 wt.%. Most
FCC units operating at an activity
level greater than 77% likely
process deeply hydrotreated feedstock, while units operating at lower
activity could be processing residual based feedstocks and targeting
lower conversion levels.
0.15
Region
AP
EU
LA
NA
WW
0.10
0.05
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
Year
Figure 32
Average Sodium by Region 1997-2006
0.425
0.400
0.375
Na, wt.%
Figure 34 presents a rare earth
range from 0.02 to 5.48 wt.% with a
mean of 2.56 wt.%. Many units
operating at higher rare earth levels
are taking advantage of Grace
Davison's IMPACT catalyst technology, which incorporates an integral
rare earth vanadium trap. Figure 34
also confirms the limited number of
units using a zero rare earth catalyst.
Region
AP
EU
LA
NA
WW
0.52
CaO, wt.%
Sodium (Figure 32) has been trending downward on a worldwide
basis, decreasing by over 12%
since 1997. Asia Pacific and North
America have contributed to the
overall decrease by dropping
almost 25% and 18%, respectively.
Over the last ten years FCC units in
Europe have the lowest levels of
sodium, while Latin America has the
highest. Sodium on Ecat comes
both from the raw materials used to
manufacture the catalyst as well as
salt contamination in the feedstock.
Sodium can deactivate the catalyst
by poisoning the acid sites on the
matrix and zeolite and by surface
area sintering.(5)
0.58
Region
AP
EU
LA
NA
WW
0.350
0.325
0.300
0.275
0.250
1997
1998
1999
2000
2001
2002
Year
2003
2004
2005
2006
Catalagram 102 Fall 2007
23
Figure 33
MAT Activity Distribution
Alumina has a fairly broad range
from 26.5 to 56.5 wt.%, with a mean
of 44.0 wt.%, as can be seen on
Figure 35.
70
61
60
Figure 38 shows the worldwide iron
distribution. Like nickel, several
units operate with a very high Iron
content. The range is from 0.19 to
2.29 wt.% with a mean of 0.53 wt.%.
Calcium reflects a range of 0.02 to
1.34 wt.% and a mean of 0.14 wt.%,
as can be seen in Figure 39.
Sodium distribution ranges from
0.09 to 0.95 wt.% (Figure 40). The
mean is 0.30 wt.%.
A normal distribution for total surface area is presented in Figure 41.
Surface area indicates a range from
72 to 254 m2/g and a mean of 148
m2/g.
24 www.e-catalysts.com
48
Frequency
40
35
33
30
20
10
17
10
10
6
4
4
1
0
0
56
64
60
68
72
MAT Activity, wt.%
76
80
Figure 34
Rare Earth Distribution
60
58
54
Mean 2.561
50
41
40
33
30
26
22
20
13
10
14
11
7
6
3
2
0
Figure 42 shows the distribution of
the Ecat 0-40 micron content, which
ranges from 0 to 28 wt.% with a
mean of 8 wt.%. The high end of
the range indicates units, which can
hold a tremendous amount of 0-40
material and perhaps generate
additional fines from catalyst attrition. Several units at the low end of
the distribution likely have cyclone
problems, which limit their ability to
hold particles less than 40 microns.
0.0
1.6
0.8
2.4
3.2
RE203, wt.%
4.0
2
1
4.8
5.6
Figure 35
Alumina Distribution
90
80
76
70
66
Mean 44.00
67
60
Frequency
Data presented in this article confirms that the FCC industry values
high activity catalysts for units that
process hydrotreated feedstocks,
are constrained by catalyst circulation and strive to operate at high
conversion levels. Ecat contaminant
levels continue to increase, particularly CaO and Fe. As a result, the
industry will continue to demand
Mean 70.71
50
Frequency
Nickel and vanadium distributions
are shown on Figures 36 and 37.
While average Ecat vanadium levels
are higher than nickel, nickel levels
show a much wider distribution at
the high end. Nickel ranges from a
low of 22 ppm to several units with
nickel levels greater than 12,000
ppm. The average nickel level
worldwide is approximately 1750
ppm. Vanadium ranges from 40 to
7026 ppm, with a mean of about
1880 ppm.
63
50
40
36
30
30
20
10
0
4
8
6
0
32
40
48
Al203, wt.%
56
Figure 36
Nickel Distribution
206
200
Mean 1756
Frequency
150
100
60
50
12
0
2 0 00
0
4 00 0
8
6000
Ni, ppm
6
1
8000
10000
12000>
Figure 37
Vanadium Distribution
60
55
50
Frequency
Mean 1881
40
37
38
38
33
30
26
19
20
10
10
10
10
8
5
2
0
1000
0
2 0 00
3000
4 00 0
5000
1
1
6000
7000
V, ppm
Figure 38
Iron Distribution
117
120
102
100
Mean 0.5305
Frequency
80
60
40
26
26
20
0
11
1
0.20
0.32
0.44
0.56
0.68
Fe, wt.%
0.80
4
6
0.92
1.04>
Catalagram 102 Fall 2007
25
Figure 39
Calcium Distribution
160
152
140
Mean 0.1441
120
Frequency
100
80
59
60
47
40
20
14
0
0.0
0.2
7
6
2
0
0.4
0.6
CaO, wt.%
5
1
0
0.8
1.0>
Figure 40
Sodium Distribution
91
90
79
80
Mean 0.3003
Frequency
70
60
50
47
39
40
30
21
20
10
6
2
0
0.08
0.16
0.24
0.32
0 . 4 0 0.48
0.56
2
3
3
0.64
0.72
0.80
Na, wt.%
Figure 41
Total Surface Area Distribution
80
73
68
70
Mean 147.9
62
Frequency
60
50
46
40
30
18
20
10
0
26 www.e-catalysts.com
0
15
5
4
80
120
160
200
Total Surface Area, m2/g
1
240
1
0
280
Figure 42
0-40 Micron Particle Distribution
70
References
1. Petti, Yaluris and Hunt, “Recent
Commercial Experience in Improving
Refining Profitability with Grace Davison
Alumina-Sol Catalysts,” Catalagram No. 99,
pg. 2-11, 2006
65
60
Mean 8.198
54
52
Frequency
50
2. Petti, Tomczak, Pereira, Cheng,
“Investigation of nickel species on commercial FCC equilibrium catalysts-implications
on catalysts performance and laboratory
evaluation,” Applied Catalysis General 169
(1998), pg. 95-109
40
40
33
30
20
14
14
9
10
3
2
0
0
2
4
6
8
10 12 14
0-40 Micron, wt.%
FCC catalysts that provide excellent
coke selectivity and high liquid
yields through enhanced metals tolerance. This data also confirms that
16
18
3
4
3. Wormsbecher, Cheng, Kim, Harding,
“Deactivation and Testing of Hydrocarbon
Processing Catalysts,” ACS Symposium
Series 634, 1996 American Chemical Society
1996, pg. 283-295
20 22>
there is a wide distribution of contaminant metals and that each catalyst
application must be designed for the
specific application.
4. Yaluris, et al, “The Effects of Fe
Poisoning on FCC Catalysts,” NPRA Annual
Meeting 2001, New Orleans, LA, AM 01-59
5. Zhao, Cheng, “Deactivation and
Testing of
Hydrocarbon Processing
Catalysts,” ACS Symposium Series 634, 1996
American Chemical Society 1996, pg. 159170
Catalagram 102 Fall 2007
27