Applied Catalysis A: General 258 (2004) 47–53

Coking kinetics on the catalyst during alkylation of fcc
off-gas with benzene to ethylbenzene
Longya Xu

, Jinxiang Liu, Qingxia Wang, Shenglin Liu, Wenjie Xin, Yide Xu
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
P.O. Box 110, Dalian 116023, PR China
Received 28 March 2003; received in revised form 3 July 2003; accepted 11 August 2003
Abstract
The production of ethylbenzene from the alkylation of dilute ethylene in fcc off-gases with benzene has been commercialized in China over
a newly developed catalyst composed of ZSM-5/ZSM-11 co-crystallized zeolite. The duration of an operation cycle of the commercial catalyst
could be as long as 180 days. The conversion of ethylene could attain higher than 95%, while the amount of coke deposited on the catalyst
was only about 10 wt.%. Thermogravimetry (TG) was used to study the coking behavior of the catalyst during the alkylation of fcc off-gas
with benzene to ethylbenzene. Based on effects of reaction time, reaction temperature, reactants and products on coking during the alkylation
process, it is found that the coking rate during the alkylation procedure follows the order: ethylbenzene > ethylene > propylene > benzene
for single component, and benzene–ethylene > benzene–propylene for bi-components under the same reaction condition. Furthermore, the
coking kinetic equations for benzene–ethylene, benzene–propylene and ethylbenzene were established.
© 2003 Elsevier B.V. All rights reserved.
Keywords: ZSM-5/ZSM-11 co-crystallized zeolite; Benzene alkylation; Ethylbenzene; Coking kinetics
1. Introduction
Processes for ethylbenzene production by the alkylation
of benzene with ethylene require a purification of the feed
gas to remove small amounts of impurities such as hydrogen
sulfide, carbon dioxide and water vapor which are harmful to
the catalyst even at a level as low as several hundred or even
thousand ppm [1–3]. Only under such a condition can the
catalyst maintain a relatively long and stable operating life.
Industrial fcc processes have been used to produce gaso-
line and diesel fuels. In these processes, a large amount
of by-products, i.e., fcc off-gases, is yielded, which con-
sist of about 20% of ethylene. In order to make use of the
dilute ethylene in the fcc off-gases, the Dalian Institute of
Chemical Physics of China, together with the Second Re-
finery of Fushun Petrochemical Corporation, a subsidiary
of SINOPEC, have developed a new technology for the di-
rect conversion of the dilute ethylene in fcc off-gases with
benzene to ethylbenzene in the 1990s. For the production

Corresponding author. Tel.: +86-411-4693292;
fax: +86-411-4693292.
E-mail address: lyxu@dicp.ac.cn (L. Xu).
of ethylbenzene by the alkylation of C
6
H
6
with dilute C
2
H
4
in the fcc off-gases, the most important point in our studies
was the development of a sulfur- and water-resistant cat-
alyst with long operation life. With the development of a
ZSM-5/ZSM-11 co-crystallized zeolite catalyst, more than
95% of the ethylene in the fcc off-gases can react with
benzene to form ethylbenzene [4–7].
Owing to coke deposition over the surface of the catalyst
during the reaction, the reactivity of the catalyst deactivates
with the time on stream [8]. Moreover, it has been found
that different reactants, or even different products, will re-
sult in different coking behaviors. So, it is of significance to
conduct investigations on the coking behaviors and coking
kinetics of various types of hydrocarbons, such as alkenes
and aromatics, over the commercial catalysts under their
corresponding reaction conditions. Such studies will give
us some clues for further improvement in the stability of
the catalyst and for optimizing the operation conditions.
In the present study, the catalytic performance of a
ZSM-5/ZSM-11 co-crystallized zeolite catalyst has been
evaluated. The coking behaviors and coking kinetics during
the alkylation of fcc off-gases with benzene to ethylbenzene
have been investigated. Some interesting information was
0926-860X/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2003.08.008
48 L. Xu et al. / Applied Catalysis A: General 258 (2004) 47–53
obtained in these studies, which will guide us to explore
the optimal conditions for technical operations and for
prolonging of the stability of the catalysts.
2. Experimental
2.1. Preparation of the ZSM-5/ZSM-11 co-crystallized
zeolite catalyst
A ZSM-5/ZSM-11 co-crystallized zeolite catalyst was
produced by the Third Refinery of Fushun Petrochemical
Corporation of SINOPEC according to the relevant patents
[6,7].
2.2. Reactant feed
The reactants used for the coking study of the commer-
cial catalyst were pure ethylene (99.99%), pure propylene
(99.99%), pure benzene (99.99%) and pure ethylbenzene
(99.99%). The carrier gas or dilute gas used was high purity
N
2
.
2.3. The catalytic performance of the ZSM-5/ZSM-11
co-crystallized zeolite catalyst
The catalytic performance of the ZSM-5/ZSM-11
co-crystallized zeolite catalyst for the alkylation of ben-
zene with the dilute ethylene in fcc off-gases to produce
ethylbenzene was evaluated in a commercial unit with the
capacity of 30,000 t per year ethylbenzene yield in the
Second Refinery of Fushun Petrochemical Corporation of
SINOPEC. After flushing with N
2
at 793 K, the reactants
comprising C
6
H
6
and fcc off-gas with a C
6
H
6
/C
6
H
4
mole
ratio of 5:1 was introduced into the reactor at a weight
space velocity of 0.5 h
−1
under a pressure of 0.7 MPa. A
gas chromatograph equipped with a thermal conductiv-
ity detector (TCD) and a 4 mm × 6 m Porapak-QS col-
umn was used for separation and analysis of the reaction
products.
2.4. Coking experimental by thermogravimetric
analysis
The coking reactions were carried out at 673 K. All
coke deposition measurements were performed on a
Table 1
The typical composition of the fcc off-gas (vol.%)
H
2
O
2
N
2
CO CO
2
CH
4
C
2
H
4
C
2
H
6
C
3
H
6
C
3
H
8
H
2
O H
2
S
1 14.2 1.0 12.5 1.18 5.9 31.0 19.7 15.9 0.41 0.10 0.31 0.27
2 14.0 1.1 11.0 0.75 1.1 32.1 19.2 19.8 0.59 0.15 0.33 0.30
Ethylene content in fcc off-gas is about 19–21 vol.%, content of C
3
H
6
is 0.5 vol.%, that of CO is 1 vol.%, that of CO
2
is 2–6 vol.%, that of O
2
is 1 vol.%,
content of H
2
S is 700–3000 ppm and that of H
2
O is 3000–4000 ppm.
thermo-balance of a Shimadzu DT-30 thermo-analyzer,
with a range of ±10 mg at a heating rate of 10 Kmin
−1
and
a chart speed of 1.25 mmmin
−1
.
Each catalyst sample was put in a small basket made
of quartz, and this was suspended at the center of the re-
action tube and then balanced with weights. The carrier
gas was divided into two paths: one went into the balance
box as a gas seal and the other went through the reac-
tor. After flushing with He in a temperature-programmed
mode up to 773 K for eliminating any free water on the
catalyst, the catalyst was cooled to the reaction temper-
ature of 653 K. Next, the reactants at atmospheric pres-
sure were brought into the reactor by the N
2
carrier gas
at a total flow rate of 40 ml min
−1
. The coking process
was monitored with a thermo-balance and was recorded
on-line.
3. Results and discussion
3.1. Catalytic performance of the ZSM-5/ZSM-11
co-crystallized zeolite catalyst for the alkylation of benzene
with ethylene in fcc off-gas
The components of the unpurified fcc off-gas consisted
of 19 vol.% of ethylene and other compounds, as listed in
Table 1. The ethylene content of the fcc off-gas was about
19–21 vol.%. Other components were: C
3
H
6
0.5 vol.%, CO
1 vol.%, CO
2
2–6 vol.%, O
2
1 vol.%, H
2
S 700–3000 ppm,
and H
2
O 3000–4000 ppm.
From the catalytic performance over the ZSM-5/ZSM-11
co-crystallized zeolite catalyst, it was found that a C
2
H
4
conversion as high as 99.6% was achieved, with an ethyl-
benzene selectivity of 99.2% under the given reaction condi-
tions, as shown in Table 2. After running the reaction for 150
days, the conversion of ethylene was still higher than 99%.
This shows that the ZSM-5/ZSM-11 co-crystallized zeolite
catalyst possesses a superior alkylation activity and an ex-
cellent catalytic stability. After 215 days time on stream, the
catalyst lost its activity due to coke deposition. An on line
regeneration was then necessary. Although such coke depo-
sition will unavoidably cause a decrease in catalytic activity
for a prolonged time on stream, the catalytic activity and se-
lectivity can be renewed if the deposited coke is burned off
under suitable regeneration conditions, as can be seen from
Table 2.
L. Xu et al. / Applied Catalysis A: General 258 (2004) 47–53 49
Table 2
The catalytic performance of the alkylation of benzene with fcc off-gas
over the ZSM-5/ZSM-11 co-crystallized zeolite catalyst
Reaction time
(days)
C
2
H
4
Conversion (%)
Ethylbenzene
selectivity (%)
10 99.5 99.3
20 99.6 99.2
50 99.6 99.3
100 99.2 99.2
150 99.1 99.3
200 98.6 99.2
3.2. Effect of the coking reaction time on the carbon
deposition over the ZSM-5/ZSM-11 co-crystallized
zeolite catalyst
The effect of reaction time on the coking behavior of
the ZSM-5/ZSM-11 co-crystallized zeolite catalyst for var-
ious reactants at a coking reaction temperature of 673 K
was investigated. As we can see from the isothermal cok-
ing TG curves of the catalyst (Fig. 1), the coking of both
C
3
H
6
and C
2
H
4
on the ZSM-5/ZSM-11 co-crystallized
zeolite catalyst are quite heavy, which increases rapidly
with coking reaction time on stream within 2 h, while that
of benzene maintains a much lower level, and only a very
small increment can be observed with the increase in the
coking reaction time. Meanwhile, for the alkylation re-
actions of benzene with olefins over the ZSM-5/ZSM-11
co-crystallized zeolite catalyst, it is reasonable to expect a
relatively lower coking deposition over the catalyst for dual
components of ethylene–benzene or propylene–benzene
with the coking reaction time. However, for the coking re-
action of ethylbenzene on the commercial catalyst, the coke
deposition is rather heavy, which suggests that the ethylben-
0 20 40 60 80 100 120 140 160
0.0
0.5
1.0
1.5
Propylene
Ethylene
Ethylbenzene
Propylene-benzene
Ethylene-benzene
Benzene
A
m
o
u
n
t
o
f
c
o
k
e
(
%
)
Coking reaction time (min)
Fig. 1. The effect of reaction time on the coking behaviors of various reactants over the ZSM-5/ZSM-11 co-crystallized zeolite catalyst.
zene produced from the alkylation of benzene with ethylene
undergoes cracking under the alkylation reaction condition,
thus causing heavy coke deposition on the catalyst, and
shortening the running life of the catalyst.
3.3. Effect of the coking reaction temperature on the
carbon deposition over the ZSM-5/ZSM-11 co-crystallized
zeolite catalyst
Coke deposition over the catalyst surface during the reac-
tion is a crucial factor leading to the deactivation of a catalyst
[9,10]. The deactivation of a catalyst depends closely on the
reaction temperature and the concentration of the reactants.
Fig. 2 shows the effect of reaction temperature on carbon
deposition when C
2
H
4
and C
3
H
6
were used respectively as
the reactants over the ZSM-5/ZSM-11 co-crystallized zeo-
lite catalyst. In addition, the effect of reaction temperature
on carbon deposition caused respectively by ethylbenzene
and benzene on the catalyst is also shown in Fig. 2. On the
other hand, the effect of reaction temperature on carbon de-
position during the alkylation of C
6
H
6
with C
2
H
4
(C
3
H
6
)
at a C
6
H
6
/C
2
H
4
(C
3
H
6
) ratio of 1 is shown in Fig. 3. After
running the coking reaction for 140 min online, with a ben-
zene concentration of 20% as the reactant, the amount of
deposited coke was much less, and no increase in amount
was observed as the reaction temperature was increased.
This is due to the fact that the stable ␲ bonds of the benzene
molecules made the benzene rings difficult to be broken.
However, with the introduction of the ethyl-groups into the
benzene molecules, the amount of coke deposition tended
to increase with the increase in reaction temperature. This
means that the benzene rings of ethylbenzene molecules
are more easily to be broken than that of the pure benzene
rings. When ethylene or propylene was used as a reactant,
50 L. Xu et al. / Applied Catalysis A: General 258 (2004) 47–53
600 650 700 750
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Propylene
Benzene
Ethylbenzene
Ethylene
A
m
o
u
n
t

o
f

c
o
k
e

(
w
t
%
)
Reaction temperature (K)
Fig. 2. The effect of reaction temperature on the amounts of coke deposition by single reactants on the ZSM-5/ZSM-11 co-crystallized zeolite catalyst.
with the same reactant concentration of 20% and at the
same coking reaction time of 140 min, it was found that
ethylene and propylene deposited large amounts of coke
during the reaction process, even under relatively lower
reaction temperatures. A more interesting phenomenon was
observed, which showed that coke deposition decreased
when the reaction temperature was increased, as shown in
Fig. 2. This can be explained as that, at lower temperatures,
both ethylene and propylene can polymerize easily on the
600 650 700 750
0. 6
0. 8
1. 0
1. 2
1. 4
Benzene-propylene
Benzene-ethylene
A
m
o
u
n
t

o
t

c
o
k
e

(
w
t
%
)
Reaction temperature (K)
Fig. 3. The effect of reaction temperature on the amounts of coke deposition by dual-component reactants on the ZSM-5/ZSM-11 co-crystallized zeolite
catalyst.
acid sites of the catalyst, forming heavy hydrocarbons and
coke deposits on the catalyst. Thus, as the reaction tempera-
ture was increased, the dehydrogenation and hydrogenation
(hydrogen transfer) reactions were accelerated, leading to a
decrease in coke formation and deposition.
Fig. 3 shows the effect of reaction temperature on the
amount of coke deposition by dual component reactants
on the ZSM-5/ZSM-11 co-crystallized zeolite catalyst. For
dual component reactants such as benzene–ethylene and
L. Xu et al. / Applied Catalysis A: General 258 (2004) 47–53 51
benzene–propylene, with a volume concentration ratio of
20:20, similar coking behaviors could be observed during
the coking reaction over the commercial ZSM-5/ZSM-11
co-crystallized zeolite catalyst. With an increase in re-
action temperature, the amount of coke yielded from a
benzene–ethylene or benzene–propylene feed became less
and less, even somewhat lower than that of a single com-
ponent such as ethylene or propylene, but still much higher
than that of benzene or ethylbenzene. Generally, the cok-
ing can be restrained by the addition of benzene into the
reaction feed gas. Thus, an increase in the benzene to ethyl-
benzene ratio is favorable for prohibiting coke formation
and deposition, and for prolonging the reaction life of the
catalyst.
3.4. Effect of reactant concentration on the coking behavior
of the ZSM-5/ZSM-11 co-crystallized zeolite catalyst
In addition to the reaction temperature and the composi-
tion of the reactants as factors influencing the coking behav-
ior of the ZSM-5/ZSM-11 co-crystallized zeolite catalyst,
another important factor is the concentration of the reactant.
A relation between the amount of coke deposition and the
concentration of the reactant or product has been established
after running the coking reaction for 140 min under the re-
action temperature of 673 K, as shown in Figs. 4 and 5.
First, the effect of the concentration of a single component
on coke deposition was investigated. As shown in Fig. 4, a
sharp increase in coke deposition was observed with concen-
trated ethylene or propylene. However, with the increase in
the concentration of the benzene reactant, only a relatively
small increase in the amount of coke was resulted from ben-
zene. This means that ethylene and propylene can crack eas-
ily and cause coke deposition on the catalyst, thus play an
0 10 20 30 40 50
0.0
0.2
0.4
0.6
0.8
1.0
Proylene
Benzene
Ethylene
Ethylbenzene
A
m
o
u
n
t

o
f

c
o
k
e

(
w
t
%
)

Concentration (vol%)
Fig. 4. The effect of reactant concentration on coking deposition by single reactants over the ZSM-5/ZSM-11 co-crystallized zeolite catalyst.
important role on the loss of catalyst activity. Therefore, in
order to improve the catalytic reactivity, it is necessary to
carry out the alkylation reaction at a higher molar ratio of
benzene to ethylene, so as to prohibit coke deposition during
the reaction and to prolong the catalyst life. With regard to
the effect of the concentration of ethylbenzene on coke de-
position, it was found that the coking behavior was almost
the same as that of ethylene and propylene. This means that
ethylbenzene, which is yielded from the alkylation of ben-
zene with ethylene, can crack easily and cause serious coke
deposition on the catalyst. Generally, the amount of coke
formed by ethylene or propylene and ethylbenzene are far
greater than that by benzene, which is illustrated by compar-
ing the results of varying the reactants with that of varying
the concentration.
The effect of the concentration dual-component reac-
tants on coke deposition over the catalyst is shown in
Fig. 5. These results show that at a mole ratio of ben-
zene to ethylene (or propylene) of 4, the amount of coke
deposited by dual-reactants, such as benzene–ethylene or
benzene–propylene, increased linearly with the concentra-
tion of the reactants. Almost the same coking trend resulted
from benzene–ethylene or benzene–propylene, as com-
pared to that from ethylene or propylene, and this implies
that coke deposition is caused more easily by ethylene or
propylene than by benzene.
3.5. Coking kinetics in the alkylation of benzene with
ethylene and propylene
In order to simplify the coking kinetic behaviors of
the alkylation process of benzene with olefins, we in-
vestigated the coking kinetics only for benzene–ethylene,
benzene–propylene and ethylbenzene.
52 L. Xu et al. / Applied Catalysis A: General 258 (2004) 47–53
20/5 30/7.5 40/10 50/12.5
Concentration (vol%)
0. 0
0. 5
1. 0
1. 5
A
m
o
u
n
t

o
f

c
o
k
e

(
w
t
%
)
Benzene-propylene
Benzene-ethylene
Fig. 5. The effect of reactant concentration on coking deposition by dual-component reactants over the ZSM-5/ZSM-11 co-crystallized zeolite catalyst.
Under the condition of constant reaction temperature, the
coking rate can be expressed as follows:
dc
dt
= kC
n
b
C
m
c=
(1)
Here, dc/dt is the coking rate, k is the rate constant, C
b
is the
benzene concentration, C
c= is the ethylene (or propylene)
concentration, and n and m are reaction orders.
C
b
can be treated as a constant, as the benzene concen-
tration has little influence on coking. Thus, Eq. (1) becomes
dc
dt
= kC
m
c=
(2)
The reaction rate constant can then be expressed in the form
of an Arrhenius equation
k = Ae
−E/RT
(3)
By combining Eqs. (2) and (3), we can obtain
dc
dt
= Ae
−E/RT
C
m
c=
(4)
The logarithm form of Eq. (4) can be written as
ln

dc
dt

= ln A +mln C
c= −
E
R
1
T
(5)
It is clear that a plot of ln(dc/dt) virus ln C
c= gives a straight
line. The reaction order m and the reaction rate constant k
can then be obtained from the slope and the intercepts, re-
spectively. The plot of ln(dc/dt) versus 1/T is also a straight
line, and from the slope of which the coking activation en-
ergy can be obtained.
Table 3
The reaction orders and activation energies of coking for different reactants
Kinetics parameter Benzene–
ethylene
Benzene–
propylene
Ethylbenzene
Reaction order 0.5 0.4 0.3
Activation energy
(kJ mol
−1
)
15.6 31.5 11.8
If the effects of reaction temperature and reactant con-
centrations on the coking behavior of the ZSM-5/ZSM-11
co-crystallized zeolite catalyst are studied, the reaction
order and the activation energies of coking for various re-
actants can be calculated, as listed in Table 3. Their coking
rate equations for different reactants can also be obtained,
as shown in Table 4.
The results in Table 3 show that the reaction orders of
dual-component reactants, such as benzene–ethylene and
benzene–propylene, are higher than that of the ethylbenzene
product. This implies that the concentration of the reactants
exerts much greater influence on the alkylation of benzene
with ethylene than with propylene. From the results of the
Table 4
The coking rate equations for various reactants
Benzene–ethylene
dc
dt
= 1.44 ×10
−4
exp

15641.5
RT

C
0.5
c=
Benzene–propylene
dc
dt
= 6.36 ×10
−6
exp

31472.5
RT

C
0.4
c=
Ethylbenzene
dc
dt
= 7.99 ×10
−3
exp

11863.3
RT

C
0.3
c=
L. Xu et al. / Applied Catalysis A: General 258 (2004) 47–53 53
coking activation energies shown in Table 2, the following
sequence can be obtained:
ethylbenzene (11.8 kJ mol
−1
)
> benzene–ethylene (15.6 kJ mol
−1
)
> benzene–propylene (31.5 kJ mol
−1
)
By correlating the coking activation energy with the coking
capacity, it is obvious that the coking rate for the alkyla-
tion of benzene with ethylene is much faster than that with
propylene, and that the coke capacities of dual-component
reactants of benzene–ethylene and benzene–propylene are
lower than that of the ethylbenzene product.
With regard to the coke deposition over the ZSM-5/ZSM-
11 zeolite catalyst, its acid sites are usually considered as
the active centers for coking as well as for alkylation. There-
fore, the coking rate should be directly proportional to the
strength of the acid sites of the zeolite catalyst. Moreover,
coking is greatly affected by the structure of the zeolite,
such as the channels and the pores. The ZSM-5/ZSM-11
zeolite catalyst belongs to the pentasil type zeolite, which
has a three-dimensional structure, with channels of about
0.5–0.6 nm in diameter. These characteristics are favorable
for the selective formation of ethylbenzene and for limiting
the yield of multinuclear aromatic hydrocarbons, which are
precursors of coke formation [7]. In general, this kind of
shape selectivity can lead to decrease in coke deposition on
the catalyst and can prolong the stability of the catalyst.
4. Conclusions
1. The best results of 90% ethylene conversion and 80%
ethylene selectivity to ethylbenzene were obtained under
n(benzene)/n(ethylene) = 5 (mol). The amount of coke
on the catalyst was only about 8.5 wt.% after 50 days of
time-on-stream.
2. Over the commercial ZSM-5/ZSM-11 zeolite catalyst,
all the coke depositions of a single component reac-
tant, such as ethylene, propylene, ethylbenzene and
benzene, as well as of dual component reactants, such
as benzene–ethylene and benzene–propylene, increased
with the time on stream of the reaction. Much serious
coke deposition resulted from C
3
H
6
, C
2
H
4
and ethyl-
benzene, as compared with that from benzene.
3. The amounts of coke formed from both benzene and
ethylbenzene showed little effect by the reaction tem-
perature. The amounts of coke formed from other reac-
tants, such as ethylene, propylene, benzene–ethylene and
benzene–propylene, decreased with the increase in tem-
perature. On the other hand, the amounts of coke de-
position from other reactants and from the ethylbenzene
product increased with the increase of concentration.
4. Coking rate equations for benzene–ethylene and
benzene–propylene and ethylbenzene were deduced.
5. Acid sites on the ZSM-5/ZSM-11 zeolite catalyst are
active centers for coking. The shape selectivity of the
catalyst can lead to decrease in the amount of coke de-
position on the catalysts, and can prolong the stability
of the catalyst.
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