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Catalytic cracking was pursued as a desirable process over thermal cracking for two
major reasons. The first reason being that catalytic cracking gives more control over the
products by breaking large hydrocarbons more towards the middle minimizing the yield
of light hydrocarbons and maximizing the yield of gasoline. Also, the gasoline produced
in catalytic cracking is of much higher quality, namely a higher octane number. This is
due to the skeletal isomerization, dealkylation of aromatics, and dehydrogenation
reactions that take place in a reactor. Thus, the reason for the development of the catalytic
cracker over thermal units is because of the higher yield and quality of gasoline.
Process Parameters
The FCC unit is very flexible with the ability to crack feedstocks from naphtha to
pretreated residue. The process variables that enable the FCC to be so flexible are catalyst
activity, temperature, catalyst/oil ratio, space velocity, and contact time. Feedstocks to the
FCC unit typically include the heavy vacuum gas oil fraction though, with boiling point
ranges of 640-980 F. The range of feedstocks fed to a FCC is limited by the upper boiling
point because of high metal content in the heavier streams.
Four major influences of feedstock that affect the FCC unit are Conradson Carbon
residue, metals, sulfur, and nitrogen content. Conradson Carbon residue gives a high
yield of coke, which decreases the catalyst activity. Metals and nitrogen in the feed also
reduce catalyst activity. Sulfur is released as SO2, H2S, and sulfur in the distillate.
Modern catalyst technology has helped make catalytic cracking the most used process in
the refining industry today. High yields of high-octane gasoline are obtained in today's
FCC units using a high activity zeolite-based catalyst held in a matrix of amorphous
silica-alumina. The pore diameters of the zeolite catalyst prevent large hydrocarbons
from passing through until cracked giving a high conversion of the feedstock. Thus, pore
size governs the conversion of feedstock to specific fractions.
Typical operations of the FCC unit are given on Table 1, which is adapted from Gary and
Handwerk.
Table 1: Parameters of FCC
Parameters FCC
Reactor Space Velocity (lb/hr/lb) 1.1-13.4
C/O (v/hr/lb) 5-16
Recycle/Fresh Feed 0-.5
Catalyst Requirement, lb/bbl Feed .15-.25
Cat. Crclt. Rate, ton Cat./BBl total feed .9-1.5
On-Steam Efficiency 96-98
Reactor Temp. (F) 885-950
Regenerator Temp. (F) 1200-1500
Reactor Pressure (psig) 8-30
Regenerator Pressure (psig) 15-30
RON 92-99
MON 80-85
In the first experimental run, the staged bed MAT reactor had a lower layer of the
high zeolite, low matrix activity catalyst and an upper layer of the moderately
active amorphous catalyst. With the oil vapors flowing downward through the
reactor, the oil contacted the amorphous catalyst first and the zeolite catalyst
second. In the second run, the catalyst layers were reversed so that the oil
vapors first contacted the zeolite catalyst and then the amorphous catalyst. Both
runs used the same reaction conditions and equal amounts of catalyst. The
results of the staged bed MAT runs are shown in Table 1. They indicate that the
"matrix-first" configuration has a large conversion advantage over the "zeolite
first" run. With the "matrix-first" configuration, a conversion of 69 wt.% was
achieved. With the catalyst beds reversed, the conversion dropped to 51 wt.%.
Compared on an activity basis, the "matrix-first" catalyst arrangement had more
than twice the activity (2.2) of the other arrangement (1.0). Other investigators
have observed similar improvements in MAT conversion when an amorphous
catalyst preceded a zeolite catalyst(Ref. 6).
The results of the staged bed MAT runs demonstrate more clearly the interaction
of matrix cracking and zeolite cracking. With the matrix bed ahead of the zeolite,
conversion improved by 18 wt%, with about 80% of the additional conversion
occurring by the cracking of bottoms. The bottoms molecules that were
unconverted in the "zeolite first" run are upgraded to valuable products (gasoline
and LCO) in the "matrix first" run. The selectivities of converted products are also
better when the matrix contacts the feed first and precracks it. In the "matrix first"
run, dry gas selectivity declined 25%, and coke selectivity declined 36%, relative
to the "zeolite first" run.
Comparing the zeolite catalyst results in Figure 1 and the "zeolite first" staged
bed results in Table 1 shows that the MAT conversions achieved in the two
experiments are nearly equal. The matrix bed of the staged bed experiment does
not enhance cracking of gas oil which has already been cracked by the zeolite.
This suggests that the matrix can promote primary cracking of relatively large
hydrocarbon molecules such as those found in a fresh feed, but it is inactive to
smaller, less reactive hydrocarbons such as those generated from zeolite
cracking.
How matrix acidity and surface area can be manipulated to optimize cracking
selectivity and octane is illustrated in the final set of experiments. In these studies
three catalyst formulations, each with a different tape of matrix and having REY
as the zeolite component, were tested in the MAT unit using the normal single
stage reactor configuration. The matrix types that were used varied in
composition, surface area and acidity of cracking sites. The MAT yields of the
three catalysts at 70 wt.% conversion are shown in Table 4. The term "matrix
activity" used in the table refers to the combined effects of matrix acidity and
surface area.
The test results show that significantly different selectivities result depending on
the type of matrix used. Catalyst A, which has the lowest matrix activity, has the
highest yields of coke and gas and the lowest yields of the most valuable liquid
products (gasoline and LCO). This is because the few matrix sites in Catalyst A
are strongly acidic and promote overcracking of gasoline. Catalyst B, with its
moderately active matrix, has the lowest coke and gas yields. It also provides
much improved yields of valuable products compared to Catalyst A. Catalyst C,
which has the highest matrix activity, produces yields that generally fall between
those of Catalyst A and Catalyst B. These results suggest that there is an
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optimum level of matrix activity for each situation, below which or above which
valuable products will be degraded to less valuable products.
MAT paraffin-to-olefin ratios of the C 4's are included in Table 4 to indicate the
relative octane trend of the three catalysts. Higher gasoline octane is expected
when the iC4/C4= ratio is lower. On this basis Catalyst C would have the highest
gasoline octane, followed by Catalyst B, and then Catalyst A. Because Catalyst A
produced higher yields of coke and gas, lower liquid products, and poorer
octane, we conclude that a low activity matrix offers no performance benefits. In
contrast, the catalysts with higher matrix activity, Catalysts B and C, provide
varying degrees of improvement in selectivities and product quality.
Conclusion
FCC catalyst matrix plays a key role in determining overall activity, selectivity,
and octane trends. Matrix provides primary cracking sites, generating
intermediate feed molecules for further cracking to desirable products by the
internal zeolite sites. The type of matrix used in the cracking catalyst alters
activity and selectivities and can be controlled by the manufacturer to meet
specific refining needs.
References
1. Silverman, L.D.; Winkler, W.S.; Tiethof, J.A. and Witoshkin, A. Paper AM-8662, N.P.R.A. Annual Meeting, March 23-25, 1986.
2. Otterstedt, J.E.; Zhu, Y.M. and Sterte, J. Appl. Catal., 38, 143-55 (1988).
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3. Otterstedt, J.E.; Gevert, S.B.; Jaeraas, S.G. and Menon, P.G. Appl. Catal., 22,
159-79 (1986).
4. Scherzer, J. and McArthur, D.P. Ind. Eng. Chem. Res., 27, 1571-6 (1988).
5. Speronello, B.K. and Reagan, W.R. Oil Gas J., 82, 139 (1984).
6. Ritter, R.E. and Young, G.W. Paper AM-84-57, N.P.R.A. Annual Meeting,
March 25-27, 1984.
7. Parry, E.P., J. Catal., 2, (1963), 371.
8. Gladrow, G.M.; Krebs, R.W. and Kimberlin, C.N. Ind. Eng. Chem. Prod. Res. &
Dev. 45 (1953) 142-147.
[An abbreviated version entitled "FCC Matrix/Zeolite Interactions" was published
in the February 1990 issue of HYDROCARBON PROCESSING, pp 55-56.]
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