Journal of Natural Gas Chemistry 14(2005)129–139

Hydrogen Ef fect on Coke Removal and Catalytic

Performance in Pre-Carburization and Methane Dehydro-
Aromatization Reaction on Mo/HZSM-5
Hongtao Ma, Ryoichi Kojima, Satoshi Kikuchi, Masaru Ichikawa∗
Catalysis Research Center, Hokkaido University, N-21 W-10, Kita-ku, Sapporo 001-0021, Japan
[Manuscript received June 28, 2005; revised August 19, 2005]

Abstract: In this study, the effects of pre-carburization of catalyst, hydrogen addition to

methane feed and the space velocity of methane on the catalytic performance in methane to
benzene (MTB) reaction were discussed in detail over Mo/HZSM-5 catalyst at 1023 K and 0.3
MPa. Compared with the non- pre-carburized catalyst, the Mo catalyst pre-carburized under the
flow of CH4 +4H2 at 973 K was found to have the higher activity and better stability of the
catalyst. Further 6% H2 addition to the methane feed suppressed the aromatic type of coke
formation effectively, and improved the stability of catalyst markedly, moreover gave a much
longer reaction life of catalyst (53 h at 1023 K and 5400 ml/(g·h)) and much more formation
amounts of benzene and hydrogen. With increase of methane space velocity, both the
naphthalene formation selectivity and the coke formation selectivity were decreased by the
shortened contact time; the benzene formation selectivity and total formation amount before
the complete deactiva- tion of catalyst were increased markedly, while the total naphthalene
and coke formation amounts did not change much. At high methane space velocity (≥5400
ml/(g·h)), a new middle temperature coke derived from the high temperature aromatic coke was
formed on the catalyst; all the coke formed could be burnt off at lower temperature in oxygen,
compared with those obtained at low space velocity. Considering the benzene formation amount
and catalyst stability together, 5400 ml/(g·h) was proved to be the most efficient methane space
velocity for benzene production.
Key words: methane dehydro-aromatization, pre-carburization, space velocity, H2 addition,
benzene formation amount, aromatic coke

1. Introduction aromatics by molecular shape selectivity effect of

As an effective utilization of methane, the
methane dehydro-aromatization was focused in
the last decade [1–28]. Over the Mo/HZSM-
5 bi- functional catalyst at high reaction
temperature, methane can be converted into light
aromatics (ben- zene and naphthalene) and
hydrogen. Mo active species can activate the C—
H bond of methane; and HZSM-5 supplies the
acid sites for the oligomeriza- tion and cyclization
of hydrocarbons to form aromat- ics, and
suppresses the deeper condensation of light
∗ Corresponding author. Tel: +81-11-706-9140; Fax: +81-11-706-9139; E-mail: michi@cat.hokudai.ac.jp.
its proper size channel (channel 5.4 nm×5.6 nm,
the size is close to benzene dynamic diameter)
[9,13,29]. How- ever, the deactivation of the
catalyst caused by serious coke formation is still
one of the major obstacles in its development.
In the last several years, the suppression of
coke formation was focused and a lot of
important pro- gresses were obtained. We have
reported that the addition of CO 2, H2 or steam
into methane feed can remove the carbonaceous
deposit on the catalyst sur- face effectively
[6,22,23,30,31]; and that the addition
130 Hongtao Ma et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005
of noble metals such as Rh or Ru was very
effective to stabilize the catalyst under the
hydrogen added reaction conditions [32]. By
means of a post-steam- treatment of catalyst
before reaction to modify the dispersion of active
Mo species, Wang et al. [33] suc- ceeded to
decrease the number of Brönsted acid sites, and
obtain higher stability of catalyst. Su et al. [34]
used a base treatment to increase the pore volume
of ZSM-5 support and produce the secondary
pore; the reaction life of catalyst was also
prolonged effectively. Bai et al. [35] carried out
100 h reaction experi- ment with 2% CO2
addition at the temperature of 973 K and space
velocity of 1500 ml/(g·h) ; the re- sults revealed
that the coke burnt-off temperature in the TPO
experiments was increased with the increase of the
reaction time. It makes the regeneration of Mo
catalyst difficult because of the much lower sub-
limation temperature of Mo oxides [26].
Moreover, the coke formation can also be reduced
by using sila- nation methods to modify the
surface of HZSM-5 of Mo/HZSM-5 catalyst
[36,37] or by means of dealumi- nation methods to
weaken the acidity of HZSM-5 of Mo/HZSM-5
catalyst [38,39].
For methane dehydro-aromatization reaction,
the
final aim is to obtain higher formation amounts of
products, such as benzene and hydrogen.
Consider- ing repeated regeneration is not good
for the Mo cat- alyst because of the facile
sublimation of Mo oxides species at 823∼1073 K
[13,26,40], it is very important to produce much
more products in single-pass reac- tion on the Mo
catalyst. However, up to now, many studies
focused on the stability of catalyst, not on the
product formation amount per unit catalyst. At
lower space velocity, longer reaction life of
catalyst can be obtained, however, the product
formation amount is not high enough. Thus, it is
important to find the relationship between space
velocity and the product formation amount in
order to understand this reac- tion. Zhang et al.
[41] discussed the effect of space velocity on the
catalytic performance of Mo catalyst, but the
reaction life was less than 4 h, higher space ve-
locity decreased the activity of catalyst too fast.
Xu, Bao and co-workers studied the effect of
contact time on the catalytic performance at initial
reaction stage on a 6%Mo/MCM-22 catalyst, and
reported that at a longer contact time (lower
space velocity) the con- densation reaction
resulted in the formation of coke [42]. Shu et al.
also reported the effect of space ve- locity at 1023
K [43], however, the reaction time was also too
short, and the results did not give us infor- mation
about the effect of space velocity on the for-
mation amounts of products.
Here, in this work, methane dehydro-
aromatization was carried out at 1023 K and
different methane space velocities from 1350 to
8100 ml/(g·h). The effects of pre-carburization by
CH4 /4H2 at 973 K and 6% hydrogen addition to
the methane feed were also investigated to
enhance the stability of catalyst. The used catalyst
was characterized by the TGA- TPO-MS method.
Based on the experimental data, the effects of
pre-carburization, and H 2 addition and methane
space velocity on the benzene formation and coke
formation performance were discussed in detail.
2. Experimental
2.1. Catalyst preparation
The 6%Mo catalyst was prepared by conven-
tional impregnation technique with NH 4-ZSM-5
zeo- lite (SiO2 /Al2 O3 =40, Tosoh Co., Japan) and
an aque- ous solution of ammonium
heptamolybdate (Kanto Chem. Co. of Japan).
After removal of the water solvent by using a
vacuum evaporator below 323 K, the catalyst
sample was calcined in air at 823 K for 8 h.
2.2. Catalytic evaluation
The methane dehydro-aromatization reaction
was conducted in a flow type fixed-bed quartz
reactor con- taining 300 mg of catalyst at 1023 K
under 0.3 MPa, and at four different methane
space velocities varied from 1350 to 8100
ml/(g·h).
In order to obtain much more information
about the effect of space velocity on the coke
formation, three different types of reactions were
compared in this paper. The detailed experimental
procedures are shown in Figure 1. In the case of
reaction A, the cata- lyst was not pre-carburized
and the reaction was car- ried out in pure methane
gas stream (mixed with 10% Ar as internal
standard). In the case of reaction B, the catalyst
was pre-carburized by V (CH4 )/V (4H2 ) at 973 K
for 2 h, and the reaction was carried out in pure
methane. In the case of reaction C, the cat- alyst
was pre-treated by V (CH4 )/V (4H2 ) at 973 K, and
then the reaction was carried out in methane with
6%H2 addition. All products were analyzed by on-
line FID-GC and TCD-GC; and all reactions were
stopped till the benzene concentration in the tail
gas was less than 1% (FID peak area).
 Journal of Natural Gas Chemistry Vol. 14 No. 3 2005
Figure 1. Dif ferent reaction types used in experi-
ment
2.3. Characterization of used catalysts
After the reaction run, the used catalysts were
characterized by the temperature-programmed
oxi- dation (TPO) method. The TPO experiments
were conducted by using a TG-DTA 2000S (Mac
Science Ltd.) combined with a Thermolab Mass
spectrome- ter. The O2 /He stream (flow rate:
O2 =15 ml/min and He=100 ml/min) was fed on
the 30 mg of used Mo/HZSM-5 catalyst in a
fused alumina boat. Then the temperature was
increased at a rate of 10 K/min, while monitoring
H2O, CO and CO2 continuously with a mass
spectrometer (ThermoLab VG Gas) at m/e=18,
28 and 44, respectively. Relative peak heights
of H2O and CO+CO2 were calculated by con-
sidering the relative probability of ionization and
of fragmentation for each compound.
3. Results and discussion
3.1. Catalytic performance for dif ferent
types of reactions
Figure 2 shows the benzene formation perfor-
mance for three different types of reactions at
1023 K
131
and 2700 ml/(g·h) of methane space velocity.
With- out catalyst pre-carburization and without
hydrogen addition to the methane feed (Reaction
A), the ben- zene formation rate was decreased to
almost zero after 17 h; while after the pre-
treatment of catalyst by us- ing mixture gas V
(CH4 )/V (4H2 ) at 973 K for 2 h, the reaction life of
catalyst was prolonged to 23 h (Reac- tion B). But
in fact, the best stable benzene formation was
obtained in reaction C, the further 6% hydrogen
addition to the methane feed enhanced the
catalyst stability markedly. The benzene
formation rate still maintained 30% of the highest
value even after 64 h reaction run.
Figure 2. Benzene formation performances
in dif ferent reactions A (1),
B (2) and C
(3) at methane space velocity of 2700
ml/(g·h)
In order to understand why the pre-
carburization and hydrogen addition affected the
catalytic perfor- mance of Mo/HZSM-5 so
effectively, the initial naph- thalene formation rate
and the selectivity of naphtha- lene in
hydrocarbon products in different types of re-
actions are shown in Figure 3. Since the
naphthalene can be a precursor of coke deposited
on the Brönsted acid site that causes the
deactivation of catalyst, it is important to discuss
the naphthalene formation rate and selectivity in
different reactions. At first, it was found that the
initial naphthalene formation rate and selectivity
to naphthalene were decreased a little af- ter the
pre-treatment of catalyst by V (CH4 )/V (4H2 ); and
then, they were decreased further in the reaction
with 6% hydrogen addition.
Iglesia and co-workers reported that Mo oxide
species was dispersed highly on the surface of
HZSM- 5 and was exchanged with OH groups in
HZSM-5 to form (Mo2O5)2+ dimers anchored at
two cation ex- change sites during the calcination
process after im- pregnation [13]. The reduction
and carburization of
132 Hongtao Ma et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005
Figure 3. Naphthalene formation rate and
selectiv- ity at initial reaction time
(15 min) in dif ferent reactions
(Mo2O5)2+ species during CH4 reactions resulted
in the formation of MoC x clusters and the
concurrent regeneration of the OH groups that
were displaced by the Mo oxo dimers during
catalyst synthesis. Thus, two sites required for the
conversion of CH4 to aro- matics are formed:
MoCx for C—H bond activation and initial C—C
bond formation, and acid sites for oligomerization
and cyclization of hydrocarbons to form stable
aromatics.
In reaction A, Mo oxide was reduced into
MoCx
species by CH4 at the initial reaction time and
1023 K in the pure methane stream. The
converting rate could be high enough, then it was
possible to result in the formation of MoC x
cluster with bigger parti- cle size, and the release
of much more acid sites. On the contrary, in the
reaction under condition B, tem- perature was
increased slowly in V (CH4 )/V (4H2 ) and kept at
973 K for 2 h. The lower methane concentra- tion
in mixture gas and lower pre-carburization tem-
perature led to a slow but complete
transformation of Mo oxide to MoC x cluster.
This pre-treatment by V (CH4 )/V (4H2 ) might
result in a much higher dis- persion of MoC x
clusters with a smaller particle size and a smaller
number of acid sites, compared with those in
reaction A. It was the reason why the catalyst had
higher catalytic activity and showed lower naph-
thalene formation selectivity in reaction B. Since
the
coke deposited on the excess Brönsted acid site,
which was derived from naphthalene adsorption,
was usu- ally responsible for the deactivation
[13,21,22,24,37], the decrease in the number of acid
sites suppressed the coke formation and improved
the reaction life of catalyst.
In the reaction C, the equilibrium balance in
dehydro-aromatization reaction was shifted to the
re- actant side by the addition of hydrogen,
especially the naphthalene formation reaction and
other fur- ther deep-condensation reactions, in
which much more amount of hydrogen was
produced, were suppressed more than the benzene
formation reaction. Thus, the selectivity to
naphthalene and the aromatic coke for- mation on
the Brönsted acid sites were suppressed [24]. As
a result, the catalytic reaction was stabilized by
the addition of hydrogen into the methane feed.
3.2. Ef fect of methane space velocity on
the catalytic activity of catalyst
Table 1 shows the effect of space velocity on
the benzene and naphthalene formation rates at the
initial time of the reactions A, B and C. It was
shown that the ratio of benzene formation rate at
different space velocities was equal to the ratio of
space velocity; al- most 2 or 3 times higher
benzene formation rate was obtained in the
reaction at 5400 or 8100 ml/(g·h) of methane
space velocity, compared with the reaction at 2700
ml/(g·h). These results indicated that the con-
tact time between the catalyst and reactant gas
was enough for benzene formation under all the
reaction conditions used in this study. However,
the ratio of naphthalene formation rate is smaller
than the ratio of space velocity; for example, in
the case of reaction C, only 1.7 or 2.2 times
higher naphthalene forma- tion rate was obtained
in the reaction at 5400 or 8100 ml/(g·h) of
methane space velocity compared with the
reaction at 2700 ml/(g·h). Naphthalene forma-
tion on the surface of Mo/HZSM-5 needs much
longer contact time than benzene formation. On
the other hand, the diffusion coefficient of
naphthalene is much smaller than that of benzene;
naphthalene formation is affected more seriously
by the shape selective abil- ity of ZSM-5 channel
than benzene formation, espe- cially at high space
velocity. Thus, the shorter contact time at higher
methane space velocity decreased the naphthalene
formation rate and selectivity. Moreover, the deep
dehydro-condensation reaction could also be
suppressed, which usually resulted in the decrease
of coke formation selectivity.
 Journal of Natural Gas Chemistry Vol. 14 No. 3 2005 133

Table 1. Ef fect of space velocity on benzene and naphthalene formation activities at

initial reaction time in reactions A, B and C
Space Benzene Naphthalene Selectivity
Reactio velocity formation formation to
n of methane Rate∗ rate∗∗ naphthalene in
(ml/(g·h)) (nmol/(g·s)) (nmol/(g·s)) product∗∗
(%)
A 1350 756 496 24.2
2700 1721 859 21.9
5400 3636 1293 18.8
8100 4989 — —
B 1350 764 289 20.7
2700 1728 710 20.1
5400 3719 1033 15.7
8100 5407 1321 13.8
C 2700 1195 378 15.6
5400 2520 638 14.1
8100 3325 823 12.9

* Data was obtained at 120min of time-on-stream; ** Data was obtained at 15 min of time-on-stream.

The benzene formation performance at

different methane space velocities in reaction B is
shown in Figure 4, and the benzene, hydrogen and
naphthalene formation performance at different
methane space ve- locities in reaction C are
shown in Figure 5. It is clear that the benzene
formation rate was decreased faster and the
reaction life of catalyst was shortened with the
increase of methane space velocity. However, the
ratio of catalyst life was not corresponding to the
ratio of space velocity, and apparently, the
benzene formation amount was increased with
methane space velocity. As shown in Figure 5,
similar to benzene for- mation performance, the
hydrogen formation rate was also decreased faster
with the increase of space veloc- ity, and the
apparent hydrogen formation amount was
increased with space velocity. However, the
naphtha- lene formation performance had
different tendency;

Figure 5. Ef fect of space velocity on benzene,

Figure 4. Ef fect of space velocity on benzene hy- drogen and naphthalene formation
for- mation rate in reaction B rates in reaction C
(1) SV 1350, (2) SV 2700, (3) SV 5400, (4) SV 8100 (1) SV 2700, (2) SV 5400, (3) SV 8100
134 Hongtao Ma et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005
the total naphthalene formation amount did not
change much with the increase of space
velocity.
The calculated amounts of benzene and
hydrogen formed in the reactions at different space
velocities are shown in Figure 6. It is clear that the
benzene and hy- drogen formation amounts were
increased with the in- crease of methane space
velocity up to 5400 ml/(g·h); on the contrary, the
products formation amount was increased slowly
over 5400 ml/(g·h). From this view- point, 5400
ml/(g·h) is the most efficient space veloc- ity for
methane to benzene reaction at 1023 K.
Figure 6. Ef fect of space velocity on the forma-
tion amounts of benzene and hydrogen
in single-pass reactions A (1), B (2)
and C
(3) at 1023 K
It was also revealed that the deactivation
behav- ior of the catalyst was different with or
without hy- drogen addition to methane feed.
Without hydrogen addition, a key time-point was
found in the reaction run, such as 24, 19 and 14 h,
corresponded to the re- action at the space
velocity of 1350, 2700 and 5400 ml/(g·h),
respectively. The activity was stable or de-
creased very slowly before the time-point, while
after the point the catalyst was deactivated much
faster. This time-point should be owing to the
blockage of zeolite channels by coke formation.
Once the open
mouth size of the channels was decreased to the
size through which benzene product could not
pass, the catalyst was deactivated much faster.
However, in reaction C, 6% added hydrogen
can remove partial coke formed in the channels
at any time; probably it can help product benzene
to leave the channel. Thus, the benzene formation
activity was always decreased very slowly, and
there was no time-point found in the reaction run.
3.3. Ef fect of space velocity on the coke
for- mation performance
The coke formation on the surface of catalysts
used in the methane dehydro-aromatization
reactions at different space velocities was
characterized by TG- TPO-MS experiment.
Figure 7 shows the variety of coke formation
amount with space velocity, which was obtained
from the weight loss of used catalyst in TG- TPO
experiments. The total amount of coke formed on
the surface of Mo catalyst did not change much
with space velocity.
Figure 7. Ef fect of space velocity on the coke
for- mation amount in reactions A (1),
B (2) and C (3) at 1023 K
The TPO-COx profiles are shown in Figure 8.
TPO profiles of the catalysts used in the reactions
A and B revealed that the pre-carburization by V
(CH4 )/V (4H2 ) before the reaction did not affect
the forms of the coke on Mo catalysts so much.
The TPO-COx profiles always showed similar
characters with the same space velocity. In both
reaction A and B, the peak-top temperature of the
TPO profiles of the coke formed on Mo catalyst
was decreased with the increase of space velocity,
which was resulted from
 Journal of Natural Gas Chemistry Vol. 14 No. 3 2005
a lower condensation degree of the coke because
of lower selectivity to naphthalene. At lower
space ve- locity (1350 and 2700 ml/(g·h)), usually
there are only two types of coke formed on the
surface of catalyst: one is called low temperature
coke (LC); another is called high temperature
coke (HC). A typical H2O profile in TPO
experiment is shown in Figure 9(a). The peak top
temperature is corresponded to the peak top
temperature of high temperature coke in the CO x
profiles. Very few amount of H2O was formed at
lower temperature during TPO experiment. These
results suggested that the low temperature coke
has a very low ratio of H/C, while the high
temperature coke has a high ratio of H/C, and it
should be an aromatic type of coke, which is
difficult to be burnt off by oxygen at lower
temperature in TPO experiment. In combina- tion
with the reference result [13], this result proved
again that usually there are two major coke
formed on the surface of Mo catalyst in methane
dehydro- aromatization, one is the hydrogen-poor
type of coke
Figure 8. TPO-COx prof iles of the catalysts used in reactions A (a), B (b) and C (c) at dif ferent space
velocities
(1) SV 1350, (2) SV 2700, (3) SV 5400, (4) SV 8100
135
deposited on the MoC x species, and another is the
aromatic type of coke formed on the Brönsted
acid sites.
In the pure methane reaction at higher space
velocity (≥5400 ml/(g·h)) with or without
pre- carburization of catalyst, three types of coke
formed on the surface of catalysts (Figure 8(a)
and (b)). Ex- cept the low temperature coke and
high temperature coke, a new middle temperature
coke (MC) was de- rived from the high
temperature coke. In comparison with the TPO-
COx and TPO-H2O profiles (Figure 9 (b)) of the
catalyst used in the reaction at high space
velocity, it is clear that both the middle
temperature coke and high temperature coke have
high ratio of H/C; they are both aromatic types of
coke deposited on the Brönsted acid sites.
Apparently, with the in- crease of space velocity,
the amount of middle temper- ature coke was
increased whereas the amount of high temperature
coke was decreased (Figure 8(a) and (b) and
Table 2).
136 Hongtao Ma et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

Table 2. Peak temperatures of the TPO prof iles and the amount of coke
formed on the Mo catalysts used in dif ferent reactions
Reactio Space velocity of Peak temperature (K) The amount of coke (mg/g)
n methane LC MC HC LC MC HC Total
(ml/(g·h))
A 1350 811 — 876 17.9 — 73.7 91.6
2700 812 — 881 13.8 — 77.9 91.7
5400 793 850 889 28.0 19.8 40.6 88.4
8100 775 841 898 26.4 42.0 14.9 83.3
B 1350 811 — 877 30.0 — 71.6 101.6
2700 805 — 884 25.4 — 76.3 101.7
5400 782 848 896 33.0 36.9 29.5 99.4
8100 780 851 902 31.2 38.9 27.2 97.3
C 2700 808 — 863 38.1 — 65.2 103.3
5400 796 — 868 40.0 — 61.7 101.7
8100 791 844 that
873 was affected
45.6 mainly
15.9 by
28.6the
dehydro-
90.1
condensation rate and condensation time. At
lower space velocity, the deeper condensation
reaction was promoted by much longer reaction
time and the formation amount of aromatic coke
with high condensation degrees was increased,
while the formation amount of aromatic coke with
low condensation degree was too little to be
found in the TPO experiment. On the contrary, at
high space velocity, much shorter contact time led
to the increase of the percentage of aromatic coke
with low condensation degree, which could be
found in TPO experiment. That was the reason
why the middle temperature coke only could be
found in TPO profiles of the catalysts used at high
space velocity, and the amount of middle
temperature coke was in- creased with the
increase of space velocity. However, in the
reaction with 6% hydrogen addition, catalyst
usually had much longer reaction life, which
decreased the effect of space velocity on the
Figure 9. The comparison of the TPO-H2O and decreasing of the coke dehydro-condensation
TPO- COx (CO+CO 2) prof iles of the degree; thus the middle temperature coke was
catalysts used in the reaction C at space only observed in TPO profile of the catalyst used
velocity of 2700 ml/(g·h) (a) and the
reaction B at space velocity of 8100
at much higher methane space velocity. The burnt-
ml/(g·h) (b) off temperature of the low tem- perature coke was
(1) COx, (2) H2O also decreased with space velocity. These results
are very important for the regeneration of Mo
When compared with the TPO profiles of the catalyst [26].
catalysts used in pure methane reaction, an Detailed data about the coke formation
obvious difference is that only two apparent coke- amount listed in Table 2 were calculated from TG
removing peaks were observed in TPO profiles of and TPO re- sults. In the case of reaction A,
the catalysts used in the reaction with 6% 13.8/77.9 mg LC/HC per unit gram catalyst was
hydrogen addition. Af- ter deconvolution, the formed in the reaction at space velocity of 2700
formation of three types of coke can be observed
only on the catalyst used in the re- action at 8100 ml/(g·h); while in reaction B, the LC/HC
formation amount per unit gram cata- lyst was
ml/(g·h) of methane space velocity. Since the 25.4/76.3 mg. The percentage of aromatic type of
carbonaceous deposit was formed from the coke (HC) in the total coke amount was de-
gradually deep dehydro-condensation reactions, creased in the reaction B, which was attributed to
ac- tually the aromatic coke was a mixture of the
carbona- ceous deposits with different
condensation degrees
 Journal of Natural Gas Chemistry Vol. 14 No. 3 2005
decrease of Brönsted acid sites. It corresponded
to the naphthalene formation results on those
catalysts. In the reaction C, with 6% hydrogen
addition, the LC/HC formation amount was
38.1/65.2 mg per unit gram catalyst used in the
reaction at 2700 ml/(g·h) of methane space
velocity. These results indicated that the aromatic
type of coke (HC) formation was still re- sponsible
for the gradual deactivation of the catalyst,
although the 6% hydrogen addition to the
methane feed suppressed its formation
significantly. To obtain much longer catalyst life,
it is still necessary to de- crease the amount of
undesirable excess Brönsted acid sites on the
catalyst by using other methods, such as
silanation and dealumination, or other modified
pre- carburization treatment.
Based on the data in Table 2 and the reaction
life of the catalyst, the coke formation rates at
different space velocities were calculated and
shown in Figure
10. Obviously, in every reaction used in this study,
Figure 10. Coke formation rates at dif ferent space
velocities in reactions A (a), B (b), C (c)
137
the coke formation rate was increased with the in-
crease of space velocity, although the total coke
for- mation amount did not change much. On the
other hand, both the pre-carburization by V
(CH4 )/V (4H2 ) mixed gas and in particular the
small amount of hy- drogen addition decreased the
coke formation rate sig- nificantly, by which the
reaction life was prolonged (Figure 2).
The possible coke formation routes are listed
in Figure 11. During the reaction, at first methane
is activated on the MoCx to form CHx species; and
then CHx is cyclized to form benzene and
naphthalene. However, the deep dehydrogenation
of CHx causes the hydrogen-poor type of coke
formation, which de- posited on/close to MoC x
species; and the further deep
dehydrocondensation of light aromatics causes
the aromatic type of coke formation, which
mainly deposited on the Brönsted acid sites.
Figure 11. Proposed coke formation routes
Thus, basically, the coke is formed from the
further deep-condensation reactions, in which
larger amount of hydrogen is also formed. From
this view- point, it is easy to understand the effect
of those fac- tors on the coke formation rate listed
in Table 3. The increase of both space velocity
and reaction temper- ature will enhance the
products formation rates, and further increase the
coke formation rate; while the pressure increase
will decrease the coke formation rate effectively by
shifting the balance of coke formation reactions
to the CH x intermediate or light aromat- ics
products side. Hydrogen addition can remove the
coke by reaction and also shift the coke formation
bal- ance. As for the Brönsted acid sites, it is
generally accepted to promote the aromatic type
of coke for- mation.
Table 3. Inf luence of dif ferent factors on the coke
formation rate
Influence factors Coke formation
rate
Space velocity (SV) ր ր
Reaction temperature (T ) ր ր
Reaction pressure (p) ր ց
Hydrogen in feed (H2%) ր ց
Amount of Brösted acid ց ց
site
138 Hongtao Ma et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

4. Conclusions 21: 35
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