Ind. Eng. Chem. Res.

2007, 46, 5265-5270 5265

KINETICS, CATALYSIS, AND REACTION ENGINEERING

Kinetic Analysis of Rate Data for Dry Reforming of Methane

Marı́a Martha Barroso Quiroga and Adolfo Eduardo Castro Luna*
Facultad de Ingenierı́a y Ciencias Económico-Sociales, INTEQUI-CONICET-UNSL, AV. 25 de Mayo 384,
5730 Villa Mercedes (S.L.), Argentina

The kinetics of the CO2 reforming of methane was investigated on a Ni-Rh-Al2O3 catalyst. Twenty-seven
mechanistic models were considered and fitted to the experimental data by numerically integrating the rate
equation of the dry reforming of methane reaction. A thermodynamic analysis showed that the reverse water
gas shift reaction operates in or very close to thermodynamic equilibrium. A strategy of model discrimination
and parameter estimation led to a model that considers CO2 molecular adsorption, CH4 dissociative adsorption,
and its surface chemical reaction as the rate-determining step. The parameter estimates in the resulting model
are statistically significant and thermodynamically consistent.

Introduction reaction 1 is highly dependent on feed composition and

Carbon dioxide reforming of methane or dry reforming of
methane (DRM) to synthesis gas has lately attracted renewed
interest. An advantage of producing synthesis gas1 by this route,
instead of using steam reforming or partial oxidation, is the low
H2/CO ratio obtained, which is of particular interest in the
synthesis of valuable oxygenated products, such as alcohols and
aldehydes. A large number of supported catalysts with promis-
sory catalytic activity have been proposed for methane reform-
ing.
The deposition of carbonaceous species on the catalyst active
sites represents an important limitation to the reaction, producing
deactivation and pressure rise due to blocking of the catalyst
pores and voids, which causes pressure increases in the reformer
furnace tubes.2
Because of their low cost, Ni based catalysts are often
preferred.3 Also, it has been reported in the literature that group
VIII metals are catalytically active and selective for this
reaction.4,5 Particularly, Rh-based catalysts exhibited very low
carbon formation. Several studies involving the development
of bimetallic Ni-Rh catalysts suggested the formation of Ni-
Rh alloys.6-9
While the thermodynamics of the reaction is well under-
stood,10 knowledge about the reaction mechanism and kinetics
is still highly controversial.12-14 Methane reforming belongs to
a rather complex reaction network:
CH4 + CO2 T 2CO + 2H2 (1)
CO2 + H2 T CO + H2O (2)
CO2 + 4H2 T CH4 + 2H2O (3)
CH4 + H2O T CO + 3H2 (4)
CH4 T C + 2H2 (5)
2CO T C + CO2 (6)
As can be deduced readily from the equations, the importance
of the reactions 2-6 for the overall product composition of
* To whom correspondence should be addressed. E-mail: cstrln@
fices.unsl.edu.ar.
10.1021/ie061645w CCC: $37.00 © 2007 American Chemical Society
Published on Web 07/03/2007
conversion. For supported Pt, Ni, and Ru catalysts, Bradford
and Vannice12,15 have proposed that the CH4-CO2 reaction
proceeds via reversible dissociation of CH4 to form CHx and H
species, followed by quasi-equilibrated steps, where CO2
adsorbs, dissociates, and reacts with CHx and hydroxyl groups
to form CHxO species. In this proposal, CHxO dissociates to
form adsorbed CO and H, which then desorb to form CO and
H2. Other authors16 have reported the absence of CHx species
on the catalyst surfaces, suggesting that the interaction of CHx
with surface oxygen is fast, to form CHxO via
CHx + O f CHxO (7)
Another recently proposed mechanism14 indicates that CH4
decomposes to chemisorbed C in a series of elementary
H-abstraction steps, which become increasingly fast as H atoms
are withdrawn from CH4, the first H-abstraction being the
kinetically relevant step. CO2 is dissociatively adsorbed on the
catalyst surface as CO and O.
Previous work on the kinetics of the DRM reaction has
reported an apparent activation energy range between 29 and
306 kJ/mol.11
The aim of this work is to find a rate equation that describes
the system behavior in operating conditions, to use it later in
the design and/or simulation of an industrial reactor.
We undertook this work because in spite of the importance
of and interest in the reaction the mechanism of the reaction is
not yet understood, and there are no expressions that reasonably
describe the kinetics of the process.
Experimental Section
Equipment and Materials. The experiments were carried
out in a conventional continuous-flow reactor.
Feed Section. Gaseous CH4, H2, N2, and CO2 are fed to the
system by automatic mass flow meters.
Reactor. The reactor is a quartz tube, 850 mm long, with an
inner diameter of 16 mm. The catalyst sample (diluted with
inert R-Al2O3) is loaded into the reactor, with a 1:10 ratio to
avoid axial and radial temperature profiles.
5266 Ind. Eng. Chem. Res., Vol. 46, No. 16, 2007
Analysis Section. Effluent gases are analyzed in a Shimadzu
GC-3A gas chromatograph, which uses Ar as the carrier and a
Carbosphere 80/100 column. The results are then evaluated
automatically by a DeskJet Spectra-Physics 4600 integrator. The
gas chromatograph was capable of separating the four reaction
gases, as far as water was condensed before the analysis.
Catalyst Preparation. Our group has been studying the
behavior of catalysts obtained by Ni impregnation or inclusion
in γ-alumina, which are obtained by different preparation
procedures that include new technologies such as sol-gel
methods. In this case, a nickel-rhodium-alumina catalyst was
prepared by thermal decomposition and subsequent hydrother-
mal treatment, according to the following procedure: 162.37
mmol of aluminum sec-butoxide was added to 70.8 g of a
solution of Ni 1-metoxi 2-propoxide in 1-metoxi 2-propanol
(0.0697 mmol of Ni/g of solution or 4.936 mmol of total Ni).
The noble metal precursor, Rh(NO3)3·2H2O (Johnson & Mat-
they; 0.4926 mmol of total Rh), was also added to the alcoholic
solution made from aluminum and nickel alcoxides. This
solution was exposed to ambient humidity and was left until it
was completely dry (T ) 308 K). Afterward, it was dried at
423 K for 12 h. The sample, diluted in water, was placed in a
reactor under pressure at 293 K for 13 h. Finally, it was calcined
at 1123 K for 100 h.
A typical test consists of the in situ reduction of the catalyst
under hydrogen flow at 1123 K for 14 h. Then, the H2 flow is
replaced by an equimolar mixture of CH4-CO2, and the
temperature is set to 1073 K until stationary conditions are
reached (4-6 h, approximately). The reaction temperature is
lowered, and the composition of the reactor effluent is periodi-
cally measured until the minimum temperature is achieved. By
changing the reactant flow rate, the space time, W/FCH40, is
changed from 0.2 to 0.7 g h mol-1. CH4 and CO2 conversions
are calculated using methane as the reference component, to
which all the conversions are related.
The catalyst contains 14% of Ni and 1.4% of Rh. Its BET
surface area is 173 m2/g, the pore volume is 0.57 cm3/g, and its
mean pore radius is 119 Å. Catalyst loadings were grounded to
a particle size of 0.16-0.25 mm and loaded into the reactor
mixed with inert R-alumina of the same size. The reactor was
warmed up with H2 flow until 1123 K was reached, during a
period between 12 and 15 h. The study begins with a reference
test to check the catalyst activity (T ) 1053 K, P ) 1.0 atm,
feed ratio CO2/CH4 (F) ) 1, W/FCH40 ) 0.5 gcat h mol-1).
Possible deactivation is checked by a periodic repetition of the
reference test.
The temperature profile along the catalyst bed was experi-
mentally determined as isothermal, and the pressure drop was
negligible.
To investigate the absence of external and internal diffusional
influences, a number of experimental tests were carried out,
concluding that their influence is negligible. Furthermore,
calculations also proved that external mass and heat transfer
resistances were nonsignificant. Intraparticle diffusional limita-
tions were ruled out using the Weisz-Prater criterion. The
equations and results are shown in the following.
External Mass and Heat Transfer Effects. The partial
pressure and temperature gradients between the flowing fluid
and the exterior surface of the catalyst were evaluated through
the following equations and conditions from Froment and
Bischoff.17
rCH4MmPtSc2/3
∆PCH4 ) (8)
amGJD
[ ]
-∆H ln(1 + δpCH4/Pt)
(∆T)max ≈ 0.7 (9)
Mmcp δ
The conditions are as follows: T, 898 K; Pt, 1.1 atm; W, 0.1 g;
XCH4, 0.2935; γ, 1; pCH4, 0.1675 atm; Ft, 4 × 10-4 kmol/h; rCH4,
0.4193 kmol/(kgcat h); pCH4, 1.4351 atm; Sc, 0.0473; Mm, 19.58
kg/kmol; am, 33.47 m2/kgcat; G, 77.91 kg/(m2 h); Re, 0.121; JD,
4.879; ∆H, 259.53 kJ/mol; and cp, 6.107 kJ/(kg K). The results
are as follows: ∆PCH4 ) 1.21 × 10-4 atm and (∆T)max ≈ 0.128
K.
Internal Mass-Transfer Effect. For spherical particles and
first-order reactions with respect to the CH4 component, the
Weisz-Prater modulus can be written as18
rCH4Fsrp2RT
D) e1 (10)
pCH4De
The conditions are as follows: Fs, 956 kg/m3; rp, 9.4 × 10-5
m; and De, 0.015 m2/h. The results is D ) 0.105.
Experimental Results
The operation variables were studied at atmospheric pressure
in the following ranges: reaction temperature, 778-898 K;
space-time, W/FCH40 (catalyst weight to CH4 molar feed rate
ratio at the reactor inlet), 0.2-0.7 g h mol-1; and feed ratio
CO2/CH4, (F), 1.0 molCO2/molCH4. The catalyst reached a
constant activity level after 4-6 h on-stream, without showing
signs of deactivation after 1 week of continuous operation.
Exploratory tests varying the feed ratio of CO2/CH4 produced
deactivation, obtaining reproducible results only at stoichio-
metric composition. Mark et al.,19 Bodrov et al.,20 and Erdöhelyi
et al.21 obtained also reproducible results only at stoichiometric
feed ratios or with excess of CO2. Because of the reaction
network described above and its dependence on feed composi-
tion, the kinetics of the reforming reaction (eq 1) reported here
have been studied only at stoichiometric feed composition under
integral conditions.
Kinetic Analysis. The reaction equilibrium for the production
of synthesis gas from CH4 reforming with CO2 (eq 1) is strongly
influenced by the simultaneous occurrence of the reverse water
gas shift (RWGS) reaction (eq 2). Some authors have shown
that the reverse water gas shift reaction operates very close to
thermodynamic equilibrium during CH4-CO2 reforming,11,15,22
while others have assumed that this reaction is at equilibrium
in the kinetic treatment to facilitate the analysis. Bradford and
Vannice11 have reported that the RWGS reaction is very close
to thermodynamic equilibrium over a wide temperature range.
Our experimental results show CO2 conversions higher than
the corresponding CH4 conversions as a consequence of the
RWGS equilibrium.
The measured H2/CO ratios were always less than unity (see
Table 1) and showed good agreement with those calculated by
the stoichiometric demand given by eq 11, which means that
the reaction of dry reforming is influenced by the simultaneous
occurrence of the RWGS reaction.12
H2/CO ) (3 - rCO2/rCH4)/(1 + rCO2/rCH4) (11)
where rCH4 and rCO2 are the experimental rates of CH4 and CO2
conversions, respectively.
The converted CO/CO2 ratio ranges from 2 (i.e., the stoi-
chiometric value of DRM reaction) to 1 (i.e., the stoichiometric
value of RWGS reaction). In the absence of carbon deposition,
a CO/CO2 ratio ) 2 is possible only if the RWGS reaction does
 Ind. Eng. Chem. Res., Vol. 46, No. 16, 2007 5267

Table 1. Catalytic Activity of the Catalyst

CH4 conversion CO2 conversion H2/CO H2/CO
T (K) (%) (%) (eq 11) (measured) CO/CO2 rCH4 (mol g-1 h-1) rCO2 (mol g-1 h-1)
848 12.8 21.6 0.49 0.49 1.59 0.64 1.72
826 8.2 15.4 0.39 0.41 1.53 0.41 1.18
798 6.0 10.6 0.44 0.38 1.57 0.20 0.55

not occur. In Table 1 our results show CO/CO2 ratios between
1 and 2 suggesting the influence of the RWGS reaction.
Thermodynamic Analysis. The RWGS pressure ratio was
determined to ascertain the extent of the RWGS equilibrium.
Figure 1 shows this ratio as a function of temperature as well
as the corresponding thermodynamic equilibrium constant.
Despite the fact that the uncertainty in the calculation of the
water composition, as it was estimated from an overall material
balance, produces large confidence limits in the estimated
RWGS pressure ratio, it can be concluded that the experimental
data are at or very close to equilibrium, over the entire
temperature range investigated. The same concept applied to
the DRM reaction showed that the DRM is significantly shifted
toward the reaction products.
Reaction Schemes. Elementary steps were considered, where
CH4, CO2, CO, and H2 were associatively or dissociatively
adsorbed on the catalyst surface. Only one type of site was
assumed where reactants compete for adsorption.6,9
Certain considerations were made for the proposed reaction
elementary steps, to limit the number and steps of the reaction
mechanisms down to a reasonable value. These considerations
are based on elementary steps that were considered to be
possible in the literature.11,14,23-26
1. Carbon dioxide is adsorbed on the catalyst surface as CO2L
or liberates CO, leaving an adsorbed oxygen atom.
2. Methane is adsorbed on the catalyst surface. Adsorbed CH4
reacts with the adsorbed oxygen or dissociates to form chemi-
sorbed radicals, such as CH3L, CH2L, CHL, and CL, liberating
hydrogen or forming HL.
3. The concentration of the carbon-containing radicals, CH3L,
CH2L, CHL, and CL, is less than the total concentration of the
active sites.
4. Adsorbed oxygen reacts with the carbon-containing radicals
to form COL or to liberate CO.
5. Adsorbed hydrogen, HL, reacts with the other ones at
adjacent sites to liberate H2.
The combination of these elementary steps led to the proposal
of 27 different mechanisms, considering the surface chemical
reaction as the rate-determining step. The proposed kinetic
scheme, Figure 2, shows two different forms of the parallel
formation of CO: from the reaction of radicals that contain
carbon with CO2L and with OL. The selected models are by
no means a complete survey of all possible kinetic equations.
Twenty-seven rate equations were formulated according to
the Langmuir-Hinshelwood-Hougen-Watson formalism for
the DRM reaction.
Model Discrimination and Parameter Estimation. The
kinetic analysis of experimental results was carried out on the
basis of the integral method. Estimated CH4 conversions were
obtained through integration of the continuity equation for the
reference component in a plug flow tubular reactor.
So, for CH4
dXCH4
) rref (12)
d(W/FCH40)
where rref ) f(Pj,θ) is the reaction rate of the DRM reaction; Pj
represents the partial pressure vector, and θ is the parameter
vector.
Parameter estimation was obtained by minimizing the objec-
tive function
n
Φ) ∑ (xCH4,exp - xCH4,calc)2 (13)
I)1
where n represents the number of tests carried out, xCH4,exp are
the experimental methane conversion values, and xCH4,calc are
the methane conversion values estimated according to the model
in each test and obtained through integration of the continuity
equation for the reference component. A fourth-order Runge-
Kutta routine was applied.
Minimized values were estimated through a single response
routine applying Marquardt’s algorithm.27
The parameter estimation was implemented with all the data
at all temperatures. To speed up the convergence of the
minimization procedure, the rate and adsorption parameters were
reparameterized to increase the parameter search rate and
minimize the statistical correlation between the pre-exponential
factor and the activation energy (or, for adsorption constants,
the heat of adsorption); the temperature-dependent constants
were reparametrized by

Figure 1. Extent of the RWGS equilibrium as a function of temperature.

9: calculated RWGS pressure ratio. Solid line: RWGS thermodynamic
equilibrium constant. Figure 2. Kinetic scheme.
5268 Ind. Eng. Chem. Res., Vol. 46, No. 16, 2007

( (
k ) kTm exp -
Ea 1
-
R T Tm
1
)) (14)
Table 2. Reaction Scheme and Corresponding Steps in Figure 2
CO2 + L
CH4 + L
) CO2L
) CH4L
step 1
step 3

[ ( )]
CH4L ) CH3L + H2 step 4
∆Hi 1 1 CH3L + CO2L ) 2 CO + 2 H2 + 2 L step 18 r.d.s.
Ki ) Ki,Tm exp - - i ) CH4,CO2, etc.
R T Tm
(15) Table 3. Optimized Parameters for the Selected Modela
parameter activation energy or adsorption
where Tm is the average temperature for all the tests. parameter estimate enthalpy
The preexponential factors A(k) and A(Ki) can be calculated k1,Tm 14.13 A(k1) 3.59 × 1021 mol bar-2 g-1 h-1
from the kTm and Ea and Ki,Tm and ∆Hi values by the Arrhenius (t) (2.2)
E1 46.98 E1 3.32 × 105 J/mol
equation and van’t Hoff equation, respectively. (t) (12.7)
2.89 × 10-8 mol bar-2 g-1 h-1

( )
KCH4,Tm 0.16 A(KCH4)
Ea (t) (3.7)
A(k) ) kT exp (16) ∆HCH4 -15.52 ∆HCH4 -1.09 × 105 J/mol
RT (t) (-3.8)

( )
KCO2,Tm 1.79 A(KCO2) 3.52 × 10-8 mol bar-2 g-1 h-1
∆Hi (t) (2.3)
A(Ki) ) Ki,T exp (17) ∆HCO2 -177.44 ∆HCO2 -1.25 × 105 J/mol
RT (t) (-6.4)

The adequacy of the fit of each set of rate equations was

a Tm ) 850 K.
tested by means of the F value, and the significance of the Table 4. Activation Energy and Reaction Enthalpy Changes
parameters was tested by means of the t value and 95%
activation energy (kJ/mol)
confidence interval of the parameter estimates. The F value is
calculated by dividing the mean squares due to regression (the Ea ) 332.04
sum of the squares of the predicted responses divided by the reaction enthalpy change (kJ/mol)
number of parameters) by the mean residual squares (the sum
298 K 850 K
of residual squares divided by the degree of freedom of residuals,
which is the number of experiments minus the number of ∆H0 ) 247.30 ∆H0 ) 259.89
parameters). The t value of a parameter estimate is the ratio of
the parameter estimate minus zero and the standard deviation In reference to the model fitting, the value F obtained from
of that parameter. If a parameter is found to have a very small 9954.78 is 3 orders of magnitude larger than the tabulated 99%
t or a large confidence interval including zero, it is considered value, which is 3.186. The model exhibits parameters that are
to have no significant contribution to the rate equation. statistically and physicochemically consistent. The adsorption
Consequently, it may be deleted from the latter. The adequacy constants must satisfy certain thermodynamic criteria proposed
of the models was tested by analyzing their residuals. Discrimi- by Boudart et al.28
nation between rival models was based on this statistical testing Thermodynamic Consistency of the Parameter Estimates.
and on their compatibility with the physicochemical constraints. Thermodynamics imposes the relation E1 - E-1 ) ∆H. Because
the activation energies for the forward and reverse reactions
are positive
Results and Discussion
After a reasonable number of trials, seven of the proposed E > ∆H (18)
models were considered as nonconvergent. Fourteen models
For the selected model, the activation energy satisfies this
were ruled out because their parameter estimates were statisti-
concept, as shown in Table 4. It is also in the activation energy
cally meaningless.
range reported in the literature for the DRM.11 Some authors,
In spite of the fact that three models had good statistical
such as Mark et al.19 and Bradford and Vannice,15 have obtained
fitting, they were discarded for presenting positive adsorption
activation energies lower than 247.3 kJ/mol, the minimum value
enthalpies. Finally, from the retained set of equations, three
of the enthalpy changes of the DRM reaction, which is in
models were found to fit the experimental data well, and the
contradiction with eq 18.
significant parameter estimates satisfied the Arrhenius and the
The adsorption constants, KCH4 and KCO2, have to satisfy a
van’t Hoff equations. Physicochemical criteria allowed arriving
number of thermodynamic criteria according to Boudart et al.28
at the best model that fits the experimental data and provides a
(1) ∆S0j,a < 0. The preexponential factors of the adsorption
mechanistic description of the reaction. Results are shown in
constants satisfy the following rule, A(KCH4) and A(KCO2):
Table 3.
The selected model has the following characteristics: the first
step of the reaction (steps 3 and 4 in Figure 2) implies adsorption ∆S0CH4,a and ∆S0CO2,a < 0 (19)
and decomposition of CH4 and nondissociative adsorption of
J
CO2 (step 1 in Figure 2) on the active sites of the catalyst or ∆S0CH4,a ) R ln[A(KCH4)] ) -144.31 (20)
probably on the support, and a subsequent surface reaction of mol‚K
both adsorbed species that constitutes the rate-determining step
J
(r.d.s, step 18 in Figure 2). This model shows an activation ∆S0CO2,a ) R ln[A(KCO2)] ) -142.66 (21)
energy with a positive sign and negative adsorption enthalpies mol‚K
(see Table 3).
The reaction scheme leading to the retained set of rate (2) ∆S0j,a in absolute value must be lower than Sj,g
0
.
equations and generated out of the detailed scheme of Figure 2
is shown in Table 2. |∆Sj,a
0
| < Sj,g
0
(22)
 Ind. Eng. Chem. Res., Vol. 46, No. 16, 2007 5269

Table 5. Boudart’s Third Rule Applied to the Selected Model

0
∆Sj,a -12.2 + 0.0014∆H0CH4,a
component (J mol-1 K-1) (J mol-1 K-1)
CH4 -144.31 -203.77
CO2 -142.66 -225.75

The ∆S0j,a values obtained from ref 29 at T ) 298.15 K for

CH4 and CO2 are 186.27 kJ kmol-1 K-1 and 213.68 kJ kmol-1
K-1, respectively.
Thus,

|∆S0CH4,a| < S0CH4,g (23)

144.31 < 186.27

|∆S0CO2,a| < S0CO2,g (24)

142.66 < 213.68

Figure 3. Methane conversion, XCH4, as a function of space time, W/FCH40.
(3) The third criterion, -∆S0j,a < 12.2 - 0.0014∆H0j,a, is Dots represent experimental values of XCH4 vs W/FCH40; full lines are the
estimated XCH4 of the selected model vs W/FCH40, at different temperatures.
shown in Table 5.
(4) Usually, the absolute value of the entropy change is higher
than 42 kJ/(mol K). Because ∆S0CH4,a is 144.31 kJ mol-1 K-1
and ∆S0CO2,a is 142.66 kJ mol-1 K-1, this rule is also satisfied.
The final model exhibits enough thermodynamically consis-
tent parameters to allow a solid model justification.
The rate equation and its parameter values, with a 95%
confidence value, are

k1KCH4KCO2(pCH4pCO4/pH20.5 - pH21.5pCO2/Kref)
rref )
(1 + pCH4/pH20.5KCH4 + pCO2KCO2)2
(25)
where

k1 ) 3.59 × 1021 exp (332.04RT( 52.40) (26)

-109.68 ( 57.53
KCH4 ) 2.89 × 10-8 exp( ) (27)
RT
-125.39 ( 39.11
KCO2 ) 3.53 × 10-8 exp( ) (28)
RT
The agreement between the model predictions and the
experimentally measured conversions is shown in Figures 3 and
4.
Conclusions
The kinetics of the CO2 reforming of methane was investi-
gated at undiluted stoichiometric feed composition on a Ni-
Rh-Al2O3 catalyst, free of external and internal diffusional
limitations, in the temperature range 778-898 K, at atmospheric
pressure.
No evidence of coke formation or deactivation was found
during the kinetic study.
On the basis of the kinetic and thermodynamic treatment of
the experimental data it was concluded that the RWGS reaction
influences the global system and that it should be considered
at equilibrium, under the test conditions of this work, in
agreement with other authors.
Twenty-seven different reaction mechanisms were proposed,
combining elementary steps where CH4, CO2, CO, and H2
species were adsorbed on the catalyst surface, in a dissociative
or nondissociative way. The corresponding rate equations were
Figure 4. Carbon dioxide conversion, XCO2, as a function of space time,
W/FCH40. Dots represent experimental values of XCO2 vs W/FCH40; full lines
are the estimated XCO2 of the selected model vs W/FCH40, at different
temperatures.
formulated according to the Langmuir-Hinshelwood-Hougen-
Watson formalism.
When a strategy of model discrimination and parameter
estimation was applied, a model, which considers CH4 dissocia-
tive adsorption, CO2 molecular adsorption, and their surface
chemical reaction, as the rate-determining step, was selected.
The CO2 conversion values were calculated directly from CH4
conversion values of the selected model.
The selected model describes the system behavior under
operating conditions, and its parameter values are statistically,
physicochemically, and thermodynamically consistent. The
obtained rate expression could be used in the design or
simulation of an industrial reactor.
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ReceiVed for reView December 20, 2006
ReVised manuscript receiVed May 2, 2007
Accepted May 15, 2007
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