Ind. Eng. Chem. Res.

2003, 42, 3203-3209 3203

Kinetics of Methane Nonoxidative Aromatization over Ru-Mo/

HZSM-5 Catalyst
Maria C. Iliuta, Ion Iliuta, Bernard P. A. Grandjean,* and Fa1cal Larachi
Department of Chemical Engineering & CERPIC, Laval University, Quebec, Canada G1K 7P4

Kinetic study of oxygen-free methane dehydrogenation and aromatization over Ru-Mo/HZSM-5

was carried out in a fixed-bed differential reactor under atmospheric pressure. The reaction
temperature was varied between 873 and 973 K, and the methane feed fraction ranged from 50
to 90% v/v. A plausible reaction pathway involved in oxygen-free methane dehydrogenation and
aromatization over Ru-Mo/HZSM-5 was proposed. Different models based on Langmuir-
Hinshelwood-Hougen-Watson reaction mechanisms were tested to correlate the kinetic data.
Among these models, the one postulating that the surface dehydrogenation reaction of adsorbed
methane is rate-determining was successful in terms of physical likeliness (thermodynamic and
kinetic parameters) and statistical goodness of fit. The activation energy, adsorption enthalpy,
and entropy frequency were evaluated by means of Arrhenius or Vant Hoff relationships.

Introduction of coke deposit.15 Other workers, however, questioned

The direct conversion of methane primarily into
hydrogen, and to a certain extent to other commodity
products, such as aromatics (benzene, toluene, naph-
thalene), constitutes an important challenge in hetero-
geneous industrial catalysis. Compared with methane
oxidative coupling and methane partial oxidation, the
advantages of methane nonoxidative conversion lie in
its higher selectivity toward higher hydrocarbon prod-
ucts as well as easy separation of the reaction main
product, i.e., benzene, from the methane feed. In addi-
tion, problems stemming from side reactions such as
methane complete oxidation can be circumvented under
nonoxidative reaction conditions. On the contrary,
severe thermodynamic limitations resulting in low
conversions, especially at lower temperatures, and
sometimes catalyst deactivation, through coke formation
and deposition, have been identified as the main set-
backs for methane nonoxidative dehydrogenation and
aromatization. The underlying mechanisms of methane
aromatization are still not completely well understood,
and further fundamental studies are required on this
important topic.1
Over the years, much of the literature connected to
nonoxidative dehydrogenation and aromatization of
methane focused on improving potential catalytic ma-
terials. Compared to other metal-doped HZSM-5, mo-
lybdenum-containing HZSM-5 materials rank among
the most promising catalytic systems for methane
dehydrogenation and aromatization and have been
under intensive scrutiny for the past 10 years.1-12
However, all these studies show that Mo/HZSM-5
catalyst activity and stability need to be improved.
Modification of Mo/HZSM-5 by adding various transition
metal promoters, e.g., Co, Cs, Cu, Fe, Ir, La, Li, Pd, Pt,
Ru, V, W, and Zr, has been shown to enhance both
stability and activity.13-19 The role of Pt as a promoter
for Mo/HZSM-5 is somewhat controversial. Pt was
reported not to affect the catalytic activity, while it
enhanced the catalyst stability by reducing the amount
* To whom correspondence should be addressed. E-mail:
grandjean@gch.ulaval.ca.
10.1021/ie030044r CCC: $25.00 2003 American Chemical Society
Published on Web 06/11/2003
the validity of the relationship between catalyst stability
and coke, as they observed that addition of Pt prolonged
catalyst stability, while it enhanced coke formation and
slightly decreased methane conversion.16 Promotion
with divalent copper improved to some extent both
stability and catalytic performance.17 Vanadium addi-
tion was shown to be detrimental to both CH4 conver-
sion and aromatics selectivity.18 Conversely, addition of
Zr, W, Fe, or Co to Mo/HZSM-5 was found to favor
higher conversion, and/or selectivity toward aromatics,
often combined with coke reduction.9,19 Properly dis-
persed Ru over Mo/HZSM-5 proved to be a promising
promoter for improving the conversion into benzene as
well as the catalyst stability.12,13,20
In contrast, in the open literature, very little informa-
tion is available about the kinetics of methane dehy-
drogenation and aromatization. Rival et al.21 developed
a simplified phenomenological reaction-permeation
kinetic model describing oxygen-free methane aroma-
tization in a fixed-bed conventional configuration (i.e.,
without hydrogen permeation) as well as with hydrogen
permeation in a membrane catalytic reactor configura-
tion. However, no attempt was made to model the
catalyst activity decline though the authors observed
rapid deactivation of the catalyst under permeation
conditions. Moreover, the model was descriptive of
virtual steady-state conditions around the maximum
methane conversion attained between the induction and
the deactivation steps with the membrane in duty.
Another restriction was that the kinetic model was
validated based on conversion measurements at 873 K
only, wherein benzene conversion was still rather low
(2.5%).
Based on several studies of the interaction between
the Mo species and the zeolite, various modes of
methane activation have been suggested.1 There is a
widespread consensus that the hexavalent molybdenum
initially available in the zeolite channels likely as
MoO3,22 or as (Mo2O5)2+ dimers23-26 is first converted
into active Mo2C carbide species,6 which are believed
to represent the key compound in methane activation.10
These active sites catalyze methane activation into CHx
(x < 4) fragments, which are in turn transformed by
3204 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003
oligomerization into mainly ethylene and ethane on the
acidic sites of the HZSM-5 crystallites.6,7,10,23 Such
products are further converted into aromatics (benzene,
toluene, naphthalene).27
In our previous works,12,20 the oxygen-free methane
aromatization was studied in a membrane catalytic
reactor at temperatures up to 973 K using a Ru-Mo/
HZSM-5 catalyst. Methane aromatization was evaluated
under two sets of conditions: without hydrogen perme-
ation in a conventional fixed-bed catalytic reactor and
with hydrogen permeation in an inert membrane cata-
lytic reactor. The role of hydrogen in the reversibility
of deactivation in the membrane mode, and its effect
on the nature of minor end products and byproducts,
such ethane, ethylene, toluene, and naphthalene, was
discussed.
In this study, a kinetic study of oxygen-free methane
dehydrogenation and aromatization over Ru-Mo/HZ-
SM-5 was carried out using kinetic data obtained in a
conventional fixed-bed reactor under nondeactivating
conditions. The reaction was conducted at atmospheric
pressure. The reaction temperature was varied between
873 and 973 K, while the methane concentration ranged
from 50 to 90% v/v in the feed stream. A detailed
reaction pathway involved in oxygen-free methane
dehydrogenation and aromatization over Ru-Mo/HZ-
SM-5 was proposed. The low conversions allowed as-
sumption of a reasonable differential reactor approxi-
mation.28 Different model scenarios based on Langmuir-
Hinshelwood-Hougen-Watson reaction mechanisms
were tested. The kinetic models were restricted to the
steady-state regime between the induction and the
deactivation steps.
Experimental Section
Synthesis and Pretreatment Method of the Ru-
Mo/HZSM-5 Catalyst. The method is similar to that
described previously.12,20 A 0.5% Ru-3% Mo/HZSM-5
catalyst was prepared by incipient wetness coimpreg-
nation of the ammonium form of the zeolite NH4ZSM-5
(Si/Al ) 15, supplied by Zeolyst) using the required
amount of aqueous ammonium heptamolybdate ((NH4)6-
Mo7O244H2O) and ruthenium chloride both supplied by
Aldrich. Subsequently, the catalyst was air-dried at
ambient temperature for 12 h and then for 2 h at 393
K. It was finally air-calcined for 4 h at 873 K. The solid
samples were pressed, crushed, and sieved to separate
catalyst granules in the size range 20-35 mesh for
subsequent use in aromatization reactions.
Before exposure to reactant, i.e., methane, the catalyst
underwent gradual heating under argon in tempera-
ture-ramped mode up to 873 K. It was maintained at
this temperature for 4 h. Then, temperature was
increased to 973 K and the catalyst was treated in
flowing air for 30 min. The gas flow was then switched
to argon, and the catalyst cooled to 573 K. Finally, pure
hydrogen was used for 30 min for catalyst reduction at
573 K.
Apparatus and Procedure. The experimental setup
consisted of a 17-mm-i.d. fixed-bed reactor. This reactor
assembly could be easily configured for the reaction test
with permeation by a simple replacement of the inner
tube with a membrane.12 The reactor loaded with 3 g
of catalyst was connected to a gas feeding unit and
analytical equipment. Kinetic runs were carried out at
five different temperatures, viz., 873, 898, 923, 948, and
973 K. At each temperature, the methane-to-argon
molar ratio was varied by changing the methane
concentration between 50 and 90% v/v. In all these runs,
the hourly gas space velocity (HGSV) was kept at 270
mL(STP)h-1g-1. The flow rates were regulated with a
mass flow controller. All methane aromatization tests
were run at atmospheric pressure.
Analysis. The gaseous reaction products were ana-
lyzed on-line by means of a Perkin-Elmer gas chromato-
graph equipped with a flame ionization detector con-
nected to a GS-Q capillary megabore column (30 m long
and 530 m i.d.) supplied by J&W Scientific and a
thermal conductivity detector connected to a Carboxen
1010 capillary column (30 m long and 530 m i.d.)
supplied by Supelco. All detected gaseous products in
the reactor exit stream were quantified: benzene,
toluene, ethylene, and ethane. Benzene was the domi-
nant hydrocarbon product; the selectivity to benzene
exceeded 90% in all kinetic tests. The coke deposition
was found to depend strongly on the temperature,
methane flow rate, and reaction time. In the reaction
conditions used in this work (methane flow rate, HGSV
) 270 mL(STP)h-1g-1; temperature, T ) 873-973 K),
the kinetic measurements were performed when the
catalyst activity stabilized to a constant level (800-1400
min of reaction on stream). In these conditions, the
carbon contributed by the coke deposits was found to
be negligible and was discounted in the carbon balance.
For instance, after 4000 min of reaction on stream,
the increase in catalyst weight represented less than
0.1% of the carbon contained in the total amount of
methane consumed at 873 K and 0.2% at 973 K.
Taking into account that benzene was the major reac-
tion product, methane conversion into benzene was
calculated based on benzene concentration.
Experimental Results
Assessment of Mass-Transfer Effects. In any
kinetic model, the resistance due to film (external) and
pore (internal) diffusion must be minimized in order to
propose an intrinsic rate. Usually, in the submillimeter
particle size range, internal mass-transfer retardation
does not affect gas-phase catalytic reactions.28 Here it
is considered that the oxygen-free methane dehydroge-
nation and aromatization reaction is internal diffusion
free because the catalyst particle sizes range between
400 and 800 m.
For estimation of the external diffusion effects, two
series of runs were undertaken at 873 K and 1 atm with
different amounts of catalyst and a feed stream consist-
ing of a 90:10 v/v% methane-to-argon mixture. In one
series, the amount of catalyst introduced in the reactor
was 3 g, and in the other, it was 1.5 g. The feed flow
rate was correspondingly adjusted to yield constant
HGSV for methane, FCH4/W, for the two amounts of
catalyst. These resulted in HGSV evolving in the range
130-770 mL(STP)h-1g-1. The results showed that the
conversions for both series at constant FCH4/W are feed
flow rate independent, thus precluding the presence of
any external mass-transfer resistance in the conditions
tested in this work. Similar results also indicated that
the external mass-transfer limitations can be considered
negligible.29 To achieve meaningful conversion levels
unaltered by diffusion, the following kinetic investiga-
tion was carried out at a methane hourly space velocity
of 270 mL(STP)h-1g-1 for different temperatures and
methane feed compositions.
Catalyst Stability. The current Ru-Mo/HZSM-5
catalyst exhibited remarkable stability in the reaction

Figure 1. Time evolution of methane conversion to benzene over
Ru-Mo/HZSM-5 catalyst at different temperatures (873-973 K)
and 270 mL(STP)g-1h-1.
Figure 2. Effect of temperature on methane conversion under
different methane concentrations.
conditions used. As a matter of fact, no significant
activity decline was detected during continuous opera-
tions that lasted for as long as 1400 min (Figure 1). In
addition, the experimental tests showed that at the
hourly gas space velocity used in this work coke forma-
tion can be practically ignored in the steady-state
conditions of reaction for which the proposed kinetic
model was validated.
As reported in previous work, methane aromatization
in an oxygen-free environment proceeds via an induction
period prior to the formation of hydrocarbon products:
ethylene, ethane, benzene, toluene, and naphthalene.
Figure 1 shows that the induction period is not affected
by temperature. However, the induction period is strongly
dependent on methane space velocity (not shown here).
The lower the methane hourly space velocity, the longer
the induction period, in agreement with literature
findings.7,21
Kinetic Data. The effect of temperature on methane
conversion under different methane to argon molar
ratios is depicted in Figure 2. An increase of tempera-
ture from 873 to 973 K brought about a significant effect
on oxygen-free methane dehydrogenation and aroma-
tization over Ru-Mo/HZSM-5. The figure also reveals
that methane conversion is more pronounced the more
diluted the feed stream.
Figure 3 shows the experimental reaction rates versus
methane concentrations at different temperatures. In-
Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3205
Figure 3. Experimental reaction rate as a function of methane
concentration at different temperatures.
creased temperatures,r methane inlet concentrations,
or both have a significant effect on oxygen-free methane
dehydrogenation and aromatization.
For each temperature, the space-time conversion
data have been analyzed and the rates of reaction were
obtained by differential analysis of the plug-flow reactor
equation:28
rexp ) dXCH4/d(W/FCH4) (1)
Kinetic Modeling
Mechanism and Rate Equations. The process of
methane activation is still the focus of debate in the
literature, and consequently, many kinds of reaction
mechanisms have been proposed. Some works suggested
that the reaction intermediate is ethylenesthe sole
primary product, which is further converted to benzene.
Other works suggested that the key intermediate in the
formation of benzene is ethane, which is dehydrogenated
to ethylene, and ethylene is further converted to ben-
zene. All elementary reaction pathways in the actual
proposed mechanisms are speculative, but it seems
however that there is an almost common agreement
that ethylene is the sole reactant in benzene formation.
Therefore, in the proposed mechanism, the coupling
of CH2 species was considered the main reaction path-
way in ethylene formation and this was the intermedi-
ate in benzene production. Possible steps related to the
ethane transformation into ethylene, CH3 decomposition
to CH2, or both have not been considered for the sake
of simplicity.
As shown in the Introduction, the complicated mecha-
nistic picture of this nontrivial bifunctionally catalyzed
reaction is one of the reasons why so little information
about the reaction kinetics has been published. It was
demonstrated that the active Mo2C carbide species
catalyze the methane activation into CHx (x < 4)
fragments, while the HZSM-5 acidic sites catalyze their
oligomerization first toward ethylene (ethane), which
are further converted into aromatics (benzene, toluene,
naphthalene). To take into account the role played by
both the Mo active sites and the zeolite acid sites in the
reaction, a double-site mechanism might be beneficial
for consideration in the model derivation. Considering
S1 the active Mo sites and S2 the acid sites of the zeolite,
3206 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003

the following series of elementary steps can be proposed: the kinetic model:

1. CH4 + S1 T CH4S1 (2) K5 1

3. CH2S 798 CHS (12)
2 2 4
2. CH4S1 T CH2S1 + H2 (3)
1 K6 1
3. C2H4S 798 C2H4 + S (13)
3. CH2S1 T CH2 + S1 (4) 2 2
Many possible rate equations can be written for the
4. CH2 + S2 T CH2S2 (5) oxygen-free methane dehydrogenation and aromatiza-
tion over Ru-Mo/HZSM-5 catalyst based on single-site
mechanism. In the absence of any experimental evi-
1
5. CH2S2 T C2H4 + S2 (6) dence allowing capture on line of the true intermediate
2 species during this reaction, a reaction pathway such
as the one depicted by steps 1-3 is considered as a good
1 1 1 starting point for the conceptualization of this reaction.
6. CH T CH + H (7) A series of submodels can be derived from this reaction
2 2 4 6 6 6 2 2
pathway depending on the rate-limiting step to assume
However, it was noticed that assuming the surface the physical likeliness of the resulting kinetic and
reaction 3 as the rate-determining step (as will be thermodynamic parameters and also the statistical
demonstrated later) led to a rate equation expression goodness of fit (least-squares criterion). After several
similar to the one obtained considering a single-site attempts, three plausible models have been screened out
mechanism. Moreover, in the case of a double-site and will be discussed in what follows.
mechanism, it was not possible to determine all equi-
librium constants associated to the proposed model. model 1: rate-determining step is assumed to be
Also, considering steps 3-5 (eqs 4-6) as the rate- the methane adsorption (8)
determining steps is a much more difficult task, espe- 1 1/6
cially due to the lack of information related to the PCH4 - P P3/2
quantitative relation between the S1 and S2 catalytic K P C 6H 6 H 2
r 1 ) k1 (14)
sites. Because the actual experimental data do not allow K3 1/6 3/2
K3 1/6 1/2
proving or disproving which one of these mechanisms 1+ P P + P P
K2K4 C6H6 H2 K4 C6H6 H2
is the more plausible, we decided to choose the simplest
one, i.e., the single-site mechanism. model 2: rate-determining step is assumed to be
The kinetic model was validated in the steady-state the surface reaction 9
conditions, when no evident deactivation of the catalyst
was observed. In the absence of gas-film or pore diffu- 1 1/6
sional resistance, a mechanism involving adsorption/ PCH4 - P P3/2
K P C 6H 6 H 2
desorption steps and surface reactions will control the r2 ) k2 (15)
rate of catalytic reaction. Different models based on K3 1/6
1 + K1PCH4 + P P1/2
Langmuir-Hinshelwood mechanisms were used to cor- K 4 C 6H 6 H 2
relate the kinetic data using the approach suggested by
Hougen and Watson.30 The following assumptions were model 3: rate-determining step is assumed to be
made to establish the model equations: (i) all active the CH2 dimerization and desorption (10)
sites (S) whereon surface reaction occurs are identical;
(ii) all elementary steps involve partial first order with 1 1/6
respect to every respective reactant; (iii) external mass PCH4 - P P3/2
K P C 6H 6 H 2
transfer and intraparticle resistances are negligible; (iv) r3 ) k 3 (16)
no irreversible loss of active sites occurs; (v) the rate PH2 + K1PCH4PH2 + K1K2PCH4
equations for the reaction steps were derived on the
basis of the mass action law.31 where

( )
The final reaction rate expressions were obtained by
manipulation of the following series of elementary steps:
G4
K4 ) exp - (17)
RT
K1
1. CH4 + S 798 CH4S (8) PC1/66H6,e PH
3/2
G
K2
Kp )
PCH4,e
2,e
) exp -( )
RT
(18)
2. CH4S 798 CH2S + H2 (9)
Estimation of Kinetic Parameters. The above rate
1
K3 equations contain three unknown parameters: (k1, K2,
3. CH2S 798 C2H4 + S K3 ) K6/K5 (10) K3) or (k2, K1, K3) or (k3, K1, K2). These parameters were
2 estimated by treating the rate data for each temperature
separately. The amounts of methane, benzene, and
1 K4 1 1 hydrogen were used in the parameter estimation. The
4. C2H4 798 C6H6 + H2 (11)
2 6 2 molar amounts of methane and benzene were deter-
mined from chromatographic analysis, and the amount
Step 3 was obtained by merging CH2 dimerization and of hydrogen was stoichiometrically calculated from the
C2H4 desorption steps for the sake of simplification of global reaction (CH4 T 1/6C6H6 + 3/2H2). As the rate
 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003 3207

equation is nonlinear with respect to these unknown

parameters, a nonlinear regression program based on
Marquardts algorithm was used to obtain a mathemati-
cal fit for the above rate equations by minimizing the
objective function for the residual sum of squares:32
n
F) k (rcalc
k - rexp
k )
2
(19)

The equilibrium constant Kp for the global reaction

was calculated using the following expression for the
Gibbs free energy (NIST thermodynamic tables33):

G ) - (575 - 0.427T ) 1000/6 (20)

The equilibrium constant K4 was calculated using the
following relationships for the Gibbs free energy, heat,
and entropy for ethylene to benzene equilibrium reac-
tion 4 (eq 11): Figure 4. Vant Hoff and Arrhenius plots for equilibrium and
rate constants.
G4 ) H4 - TS4 (21)
Table 1. Estimated Kinetic and Equilibrium Constants
Associated to Model 2
where
temp, K k2, mol/gcathatm K1, atm-1 K3, atm-1/2
H4 ) - 12296 + 5.456(T - 298) + 1.516 873 0.00717 2.877 2.359
-3 2 2 -5 3 3 898 0.0102 2.197 2.870
10 (T - 298 ) - 0.36725 10 (T - 298 ) (22) 923 0.014 1.675 3.020
948 0.019 1.280 3.185
S4 ) 0.434 + 5.456 ln(T/298) + 3.033 973 0.025 1.029 3.300
10-3(T - 298) -0.55087 10-5(T 2 - 2982) (23)
creases. The adsorption constant K1 exhibits, as ex-
Discussion pected, a decreasing trend with an increase in temper-
ature. The equilibrium constant of CH2 dimerization
The magnitude of the objective function for the and C2H4 desorption merged steps (K3) increases with
residual sum of squares (19) had almost the same value the increase of temperature. Taking into account the
for all proposed models. The kinetic models were definition expression of this constant, K3 ) K6/K5, it is
therefore tested by two different methods: (i) physico- clear that this trend is in agreement with expectation.
chemical constraints and (ii) residual analysis. The ratio between K6 and K5 increases with tempera-
Analysis of the experimental data was performed on ture, even though the adsorption constant (K6) decreases
a mathematical basis, and therefore, it did not account with the increase of temperature, and this is due to the
for the thermodynamic significance of the kinetic pa- fact that the equilibrium constant of the CH2 dimeriza-
rameters. From thermodynamic considerations, the rate tion step decreases with temperature, CH2 dimerization
constant, the activation energy, and the adsorption being an exothermic process.
constants should have positive values. Models 1 and 3 The kinetic and adsorption constants are tempera-
were therefore disqualified on the basis of improper ture-dependent parameters. These constants evaluated
trends with the temperature of the kinetic and adsorp- and tabulated at various temperatures were used to
tions constants. determine the activation energy, the frequency factor,
The fitting results were further analyzed using the the adsorption enthalpy, and entropy using Arrhenius
statistical criteria suggested by Froment and Bischoff34 and Vant Hoff relationships:
in order to evaluate the adequacy of model 2 and the
accuracy of the kinetic constants. The residual analysis k2 ) k0,2 exp(- Ea/RT) (25)
was based on the following expression of the relative
residuals: Sads,i Hads,i
ln Ki ) - (26)
R RT
RR ) (rexp - rcal)/rexp (24)
Arrhenius and Vant Hoff plots are shown in Figure
The representation of the relative residuals as a 4. The activation energy was calculated to be 88.2 kJ/
function of methane concentration showed that the mol, and the frequency factor k0,2 was 1.368 103 kmol/
values of RR were normally distributed with almost zero kgcath. The adsorption enthalpy for K1 was -73.4 kJ/
mean and exhibited no trend. We can conclude that the mol, and the corresponding adsorption entropy was
rate-determining step for the oxygen-free methane -75.3 J/molK. This entropy value is coherent with the
dehydrogenation and aromatization over Ru-Mo/HZ- Boudart et al.35 chemical-kinetic criteria:
SM-5 is the surface reaction of dehydrogenation of
adsorbed methane, and model 2 can represent the Sads < 0 (27)
kinetic data well.
The kinetic and equilibrium constants associated with 10 < -Sads < 12.2 - 0.0014Hads (28)
model 2, estimated by nonlinear regression, are tabu-
lated in Table 1. It is evident from this table that with A very good correlation is obtained between the
an increase in temperature the rate constant k2 in- observed and predicted rates (MARE ) 4.5%) and
3208 Ind. Eng. Chem. Res., Vol. 42, No. 14, 2003
Figure 5. Experimental versus calculated reaction rate.
between observed and predicted methane conversion
(MARE ) 1.6%). The experimentally observed rate of
reaction and the theoretically predicted rate values at
the five temperatures are plotted in Figure 5. Hence,
the proposed kinetic model fits very well with our
experimental observations.
Conclusion
Kinetic behavior for the oxygen-free methane dehy-
drogenation and aromatization over Ru-Mo/HZSM-5
was studied experimentally in a fixed-bed differential
reactor under nondeactivating conditions, at atmos-
pheric pressure, reaction temperature varying between
873 and 973 K and methane feed fraction ranging from
50 to 90% v/v. A detailed reaction pathway was pro-
posed, and different models based on Langmuir-Hin-
shelwood-Hougen-Watson reaction mechanisms were
applied to correlate the kinetic data. The results of
kinetic modeling suggest that the rate-determining step
for oxygen-free methane dehydrogenation and aroma-
tization over Ru-Mo/HZSM-5 is the surface reaction of
dehydrogenation of adsorbed methane. The proposed
model was found to be in conformity with the trend
shown by the kinetic and adsorption constants in the
temperature range 873-973 K. A value of 88.2 kJ/mol
was calculated for the reaction activation energy. The
calculated enthalpy of methane adsorption on the Mo
active sites was -73.4 kJ/mol and the corresponding
adsorption entropy was -75.3 J/mol K. The kinetic
model based on the proposed reaction mechanism
predicts very well the measured conversion and reaction
rate values.
Acknowledgment
Financial support from the Natural Sciences and
Engineering Research Council of Canada (NSERC) and
the Fonds pour la formation de chercheurs et daide a Catalysts of Mo/HZSM-5 in the Dehydroaromatization of Methane
la recherche (Quebec) is gratefully acknowledged.
Nomenclature
Ea ) activation energy, J/mol
F ) objective function
FCH4 ) molar flow rate of methane, kmol/h
G ) Gibbs free energy, J/mol
Hads ) adsorption enthalpy, J/mol
Hi ) heat of reaction i, J/mol
ki ) controlling-step rate constant, kmol/kgcathatm (i )
1, 2) or kmol/kgcath (i ) 3)
Ki ) equilibrium constant
Kp ) equilibrium constant for global reaction, atm2/3
MARE ) mean absolute relative error, MARE ) N - 1|1
- ycalc,i/yexp,i|
Pj ) partial pressure of component j, atm
ri ) reaction rate, kmol/kgcath
R ) constant of ideal gas, 8.314 J/mol K
Sads ) adsorption entropy, J/molK
Si ) entropy of reaction i, J/molK
T ) temperature, K
W ) mass of catalyst, kg
XCH4 ) methane conversion
y ) kinetic parameter (as introduced in the expression of
MARE)
Subscripts
e ) equilibrium
Superscripts
calc ) calculated
exp ) experimental
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Received for review January 17, 2003
Revised manuscript received April 28, 2003
Accepted May 6, 2003
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