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1.0 Introduction
The kinetics modeling of catalytic cracking has been traditionally
based on using a lumping strategy: chemical species with similar
behaviors are grouped together forming a smaller number of pseudo
species (Coxson and Bischoff, 1987).
Commercial
FCC
feedstocks
usually
contain
thousands
of
order and stoichiometry for the different lumps reaction were defined
and examined with experimental data.
Gasoline
k T1
1
Gas oil
k T3
k T2
Light gases&coke
However, since
gasoline
contains
a restricted range of
r g k T1 1 C go k T3 2 C g
These
authors
carried
out
their
work
at
different
temperatures. They concluded that LaY catalyst had higher activity and
better gasoline selectivity than LaX. By referring to their results, it can
be inferred that the gasoline overcracking rate constant was negligible
while compared to the VGO cracking rate constant.
Table 2.1. The three lump model rate constants for different VGO
compositions. kT1, kT2, kT0, kT3 represent the gasoline formation
rate constant, the coke and gases formation rate constant,
the overall VGO cracking rate constant, and the gasoline
overcracking rate constant respectively (Nace et al., 1971).
Charge Stock
P1
231.8
26.3
1.83
0.83
0.06
P2
232.7
26.2
1.09
0.80
0.03
P3
334.0
28.0
1.86
0.82
0.05
N1
139.2
33.5
1.54
0.85
0.04
N2
234.2
29.4
2.35
0.86
0.07
N3
236.2
31.0
2.02
0.85
0.06
PN33
236.4
30.9
1.94
0.85
0.05
PA31
324.7
21.0
2.87
0.85
0.12
PA32
322.9
18.6
1.95
0.81
0.09
PA33
322.1
17.6
1.48
0.80
0.07
PA331
315.5
12.6
2.66
0.81
0.17
PA34
322.1
17.8
1.78
0.81
0.08
PA37
310.3
7.71
2.18
0.75
0.21
PA38
321.1
16.6
1.66
0.79
0.08
AA45
412.3
9.3
2.28
0.76
0.19
PC32
319.3
15.0
1.15
0.78
0.06
conversion.
Reported
kinetic
constants
at
two
different
In 1987, Yen et al. introduced the four lump model splitting the
light gases + coke lump in two separate lumps: a) coke and b) light
gases. These authors used a second order reaction for VGO cracking.
The kinetic parameters were determined from riser pilot plant data and
were
correlated
with
feedstock
characteristics,
and
operating
Table 2.2: Calculated values for the kinetic constants of the triangular
reaction scheme. kT0, kT1, kT2, kT3 represent the overall VGO
cracking rate constant, the gasoline formation rate constant,
the gas and coke formation rate constant and the gasoline
overcracking rate constant respectively (Corma et al., 1984).
480 _C
503 _C
524 _C
2.91
5.14
11.07
2.44
4.21
8.96
0.47
0.93
2.11
16.21
30.71
65.82
Table 2.3: Calculated values for the kinetic constants of the triangular
reaction scheme. kT0, kT1, kT2, kT3 represent the overall VGO
cracking rate constant, the gasoline formation rate constant,
the gas and coke formation rate constant and the gasoline
overcracking rate constant respectively (Kramer and de Lasa,
1988).
T, _C
500
550
kT0
4.11
5.03
kT1
3.04
3.12
kT3
0.00
0.00
kT2
1.07
1.91
In 1994 Gianetto et al. studied the effect of the crystal size of the Yzeolite on gasoline composition. They used the Riser Simulator to carry
out their experimental work. A four lump model was applied as
follows:
Light gases
k 31
VGO
(A)
k 21
k 11
Gasoline (B)
k 22
k 32
Coke
rgo k 11 C 2go
rg k 11 C 2go (k 21 k 22 )C g
rlg k 31 C 2go k 21 C g
rc k 32 C 2go k 22 C g
These authors found that the zeolite catalysts with small crystals
were moderately more active than those with large crystals. Moreover,
they pointed out that the gasoline overcracking was negligible for both
small crystal zeolites and large crystal zeolites, since the calculated
constants were very small.
In 1994, Farag et al. studied the effect of the addition of metal
traps in the FCC catalysts. Experimental runs were performed in a
microcatalytic fixed bed reactor. It was concluded that the addition of
10
the metal traps was beneficial for the gasoline yield and research
octane number. The four lump model was used to evaluate the kinetics
constants. The equations developed from the four lump model were
also reliable to evaluate the adsorption constants for VGO, gasoline,
and light gases. It was also reported that the values for the kinetic
constants for the cracking of gasoline to coke and light gases were
very close to zero.
More recently Ali and Rohani (1997) developed a simple dynamic
model to describe the dynamic behavior of the FCC unit (riserregenerators and their interactions). The four lump model was
employed to simulate the cracking reactions. Their model was able to
simulate the data of an industrial scale unit reasonably well.
Juarez et al., (1997) extended the four lump model to five
lumps. These authors further divided the gases lump into two different
lumps: a) dry gas, b) liquefied petroleum gas (LPG). Note that LPG can
be formed either directly from gas oil or as a secondary product from
gasoline overcracking. On the other hand, dry gas (H 2, C1, C2) can be
formed either directly from gas oil cracking or as a secondary product
from gasoline and LPG cracking. The five lump model can be
schamatically represented as:
11
VGO
Coke
Gasoline
Dry gas
LPG
The five lump model
12
rate
is
independent
of reactant
composition,
extent
of
= t-n
(2.7.4.a)
(2.7.4.b)
13
(2.7.4.c)
(2.7.4.d)
where is the fraction of remaining active sites, t is the catalyst timeon-stream, kd and kd1 catalyst decay constants, n the order of catalyst
activity decay and Cgo is the gas oil feedstock concentration.
Wojciechowski (1974) suggested a more detailed form of the
power law by integrating eq (2.7.4.c) with =1 at t=0. This yields the
following:
= [1+ kdt(n-1)]-N
(2.7.4.e)
cracking
(Campbell
and
Wojciechowski,
1971;
John
and
14
gas oil cracking in a CREC Riser Simulator. Liguras and Allen (1989)
used this equation to describe the cracking of model compounds using
an amorphous silica-alumina-zirconia catalyst. Ali and Rohani (1997)
also used the exponential decay function in the case of a dynamic
model for FCC units.
More recently, a modified exponential function, =exp(-tn) was
considered. This empirical relation was used to represent activity
decay for the cracking of 2-methylpentane on USY zeolite (Babitz et
al., 1997). It was found that the 0.4 value was adequate for the n
parameter. Hopkins et al (1996), used the same equation with n=0.5
and this for the modeling of catalytic activity decay while cracking
hexane.
(2.7.4.f1)
b) =1/(1+Cc)
(2.7.4.f2)
c) =1/(1+Cc)2
(2.7.4.f3)
d) =1-Cc
(2.7.4.f4)
e) =(1-Cc)2
(2.7.4.f5)
15
=1/(1+Ccn)
(2.7.4.g)
(2.7.4.h)
16
(2.7.4.i)
constants
which
are
functions
of
feedstock
composition,
(2.7.4.j)
catalyst.
The use of 2 suggests that the coke concentration, C c, can reach
a limiting level Cmc at the early stages of the reaction. Then coke
formation is halted and a residual activity is available for other
cracking reactions (Pitault et al.,1994).
Corma et al., (1994) studied paraffins catalytic cracking. These
authors suggested that the use of a TOS decay model is not consistent
with a kinetic model in which the product olefins are strongly adsorbed
on the catalyst. To account for this, the following model was
suggested;
17
d/dt = -kmd m X
(2.7.4.k)
where kmd and m are the decay model parameters and X is the
conversion.
In this respect, this model assumed that there is a direct
relationship between coke formation and catalyst deactivation. In fact,
eq (2.7.4.k) can be derived from Froment and co-workers model as
follows;
dCc/dt = r0c
where
(2.7.4.l)
(2.7.4.m)
(2.7.4.n)
18
2.3- Conclusions
In conclusion, while the mechanism of coke formation is not yet
well understood, two types of models have been proposed in the
technical literature for catalyst deactivation. One of these model is
based on the time-on-stream and this represent a rather rudimentary
approach to catalyst decay modeling. A second approach is to relate
catalyst decay to coke content, being this a more sound mechanistic
description of catalyst decay.
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References
Acharya, D.R., Huges, R., and Li, K., Deactivation of Silica-Alumina
Catalyst During the Cumene Cracking Reaction, Applied Catalysis A,
52, pp 115-129, (1989).
Ali, H., and Rohani., S., Dynamic Modeling and Simulation of a RiserType Fluid Catalytic Cracking Unit. Chem. Eng. Technol. 20, pp 118130, (1997).
Babitz, S.M., Kuehne, M.A., Kung, H.H., and Miller, J.T., Role of Lewis
Acidity in the Deactivation of USY Zeolites During 2-Methylpentane
Cracking, Ind. Eng. Chem. Res, 36, pp3027-3031(1997).
Corella, J., Fernandez, A. and Vidal, J.M., Pilot Plant for the Fluid
Catalytic Cracking Process: Determination of the Kinetic Parameters of
Deactivation of the Catalyst, Ind. Eng. Chem. Proc. Des. Dev., 25,
pp554-562 (1986).
Corma, A., and Martinez-Triguero, J. Kintics of Gas Oil Cracking and
Catalyst Decay on SAPO-37 and USY Molecular Sieves, App Catal,
118,pp.153-162 (1994).
Corma, A., and Wojciechowski, B.,W., The Chemistry of Catalytic
Cracking , Catal. Rev.- Sci. Eng., 27 (1), pp. 29-150, (1985).
Coxson, P.G. and Bischoff, K.B., "Lumping strategy. 1. Introductory
techniques and applications of cluster analysis", Ind.Eng.Chem.Res.,
26, 1239-1248, (1987)
Farag, H. Catalytic Cracking of Hydrocarbons With Novel Metal Traps.
PhD Thesis Dissertation, the University of Western Ontario, LondonOntario, Canada, (1993).
Farag, H., Blasetti, A., and de Lasa, H. Catalytic Cracking With FCCT
Loaded With Tin Metal Traps. Adsorption Constants for Gas Oil Gasoline
and Light Gases. Ind. Eng. Chem. Res. Vol. 33, pp. 3331-3140,
(1994).
Farag, H., Ng, S. and de Lasa H. Kinetic Modeling of Catalytic Cracking
of Gas Oil Using in Situ Traps (FCCT) to Prevent Metal Contaminant
Effects. Ind. Eng. Chem. and Res. (1993).
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