Chemical Engineering Journal 215–216 (2013) 542–549

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Chemical Engineering Journal

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A comparative study on the kinetics of carbon dioxide reforming of methane over

Pt–Ni/Al2O3 catalyst: Effect of Pt/Ni Ratio
Sß eyma Özkara-Aydınoğlu a,b, A. Erhan Aksoylu a,⇑
a
Department of Chemical Engineering, Boğaziçi University, 34342 Bebek, Istanbul, Turkey
b
Beykent University, Faculty of Engineering & Architecture, Department of Chemical Engineering, Ayazağa, 34396 Sßisßli, Istanbul, Turkey

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" Power-law type rate expression 0.7

0.2Pt-15Ni
0.7
0.6 0.6 0.2Pt-15Ni
obtained for 0.3%Pt-10% Ni/Al2O3 0.3Pt-10Ni
0.3Pt-10Ni
r(CH4 ) (mmol/gcat.s)
r(CH4 ) (mmol/gcat.s)

0.5 0.5

have reaction orders of 1 CH4 and 0.4

0.3
0.4

0.3

0.87 for CO2. 0.2 0.2

0.1 0.1
" Power-law type rate expression 0 0
0 0.02 0.04 0.06 0.08 0.1 0 0.02 0.04 0.06 0.08 0.1
obtained for 0.2%Pt-15% Ni/Al2O3 P (CH4 ) (atm) P (CO2 ) (atm)

have reaction orders of 1.09 CH4 and 0.5

0.3Pt-10Ni
0.5

1.40 for CO2.

r(CH4) (mmol/gcat.s)

0.4
0.2Pt-15Ni 0.4
r(CH4 ) (mmol/gcat.s)

" Surface reaction mechanisms are

0.3
0.3

0.2
completely different for both 0.2

0.1 0.1 02.Pt-15Ni

samples. 0
0.3Pt-10Ni
0
" CO inhibition effect is stronger and 0 0.01 0.02 0.03 0.04

P(CO) (atm)
0.05 0.06 0.07
0 0.02 0.04 0.06 0.08
P(H2 ) (atm)
CO2 utilization is suppressedon the
catalyst with high Ni:Pt loading
ratio.

a r t i c l e i n f o a b s t r a c t

Article history: Kinetics and surface reaction mechanism of CO2 reforming of methane (CDRM) was studied over 0.2%Pt–
Received 20 July 2012 15%Ni/Al2O3 and 0.3%Pt–10%Ni/Al2O3 catalysts in order to determine the effect of Ni/Pt loading ratio on
Received in revised form 5 November 2012 kinetic behavior. The simple power-law type rate expressions obtained for 0.3%Pt–10%Ni/Al2O3 and
Accepted 6 November 2012
0.2%Pt–15%Ni/Al2O3 have reaction orders of 1 and 1.09 for CH4 and 0.87 and 1.40 for CO2, respectively, con-
Available online 17 November 2012
firming methane consumption rate for 0.2%Pt–15%Ni/Al2O3 sample is more sensitive to the increase in par-
tial pressure of CO. The comparative analysis of meaningful surface reaction models for the catalysts and the
Keywords:
optimized model parameters obtained revealed that the surface reaction mechanisms are completely dif-
Pt–Ni catalysts
Dry reforming of methane
ferent. CO inhibition effect is stronger and CO2 utilization is suppressed on the catalyst with high Ni:Pt load-
Kinetics ing ratio. On the other hand, with a decrease in Ni:Pt loading ratio, CH4 adsorption becomes weaker, ability
CO2 reforming of methane of utilizing CO2 as the oxygen source gets stronger and CO inhibition effect is practically eliminated.
Synthesis gas Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction studied over numerous supported metals catalysts, especially on

the Ni-based catalysts, owing to the low cost and abundance of
In recent years; many studies have been carried out utilizing Ni. Many research groups have focused on developing Ni-based
methane, CH4 to produce synthesis (syngas), a mixture of CO and catalysts, particularly Ni modified with small amounts of noble
H2 [1–5]. However; CO2 reforming of methane has received consid- metals, like Pd [8,9], Rh [10–12], Ru [9,13], or Pt [14–18], aiming
erable interest as the low H2/CO ratio in the syngas produced to achieve high levels conversions with minimized carbonaceous
makes its further use highly advantageous in the production of deposits.
long chain hydrocarbons [2,3,6,7]. The DR reaction has been In our previous work [18], we developed a set of d-Al2O3sup-
ported Pt–Ni bimetallic catalysts, and tested their DR activity as
⇑ Corresponding author. Tel.: +90 212 359 7336; fax: +90 212 287 2460.
well as combined reforming performances. Among all the catalysts
E-mail addresses: seyma.aydinoglu@gmail.com (S
ß . Özkara-Aydınoğlu), aksoylu@
tested, 0.2 wt.%Pt–15 wt.%Ni/d-Al2O3 and 0.3 wt.%Pt–10 wt.%Ni/d-
boun.edu.tr (A. Erhan Aksoylu). Al2O3 catalysts having the lowest and highest Ni/Pt molar ratios,

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.11.034
 Sß. Özkara-Aydınoğlu, A. Erhan Aksoylu / Chemical Engineering Journal 215–216 (2013) 542–549
respectively, showed distinct and extreme differences both in their
DR activity and stability profiles and in their responses to the
changes in reactant stream composition during activity tests,
which indicated the mechanistic differences of the surface reaction
over those catalysts.
Although the kinetic and mechanistic studies for CO2 reforming
of methane have been extensively performed over Ni-based cata-
lysts, there are debates about the accurate mechanism details.
Generally, it is argued that the dry reforming reaction has one sin-
gle rate determining step (RDS) or two RDS’s. In single RDS view-
point, Wei and Iglesia [19] reported CH4 decomposition as the
RDS of the reforming reaction, whereas Luo et al. [20] and Osaki
and Mori [21] concluded the decomposition of CHxO as the RDS.
The other opinion is that two RDS’s are involved in the reforming
reaction. Bradford and Vannice [22] and Nandini et al. [23] sug-
gested a mechanism which involves dissociative CH4 adsorption
and CHxO decomposition as RDS’s. However; Aparicio [24] re-
ported further dissociation of CH4 and desorption of CO as the
RDS’s in the reforming reaction. Tsipouriari and Verykios [25] con-
cluded that CH4 dissociation and the reaction of surface carbon
species with La2O2CO3 were RDSs in the reforming reaction over
Ni/La2O3 catalyst.
Cui et al. [26] believed the reason of differences in the reported
reforming mechanisms is the fact that mechanism investigations
were conducted at different temperatures, which may have
affected the reforming mechanism and the RDS remarkably. Hence,
they studied the dry reforming reaction over typical Ni/a-Al2O3
catalyst in a temperature range of 823–1023 K in order to investi-
gate the effect of temperature on reforming mechanism and RDS.
According to their study the CH4 dissociation was the RDS and
CO desorption also restrained the dry reforming in 823–848 K
while the reaction between CHx and CO2 became the RDS in
923–1023 K.
In the present work, the kinetic behavior of the 0.2 wt.%Pt–
15 wt.%Ni/d-Al2O3 and 0.3 wt.%Pt–10 wt.%Ni/d-Al2O3 catalysts in
DR was investigated as a function of temperature and partial pres-
sures of CH4, CO2, CO and H2. The aim was to investigate the kinet-
ics of DR over those two catalysts in order to determine the
changes both in the parameters of power type rate expression,
and in the types and parameters of possible mechanistic expres-
sions resulting from the change in Ni/Pt loading ratio. The conclu-
sions and detailed information had been obtained from the
characterization and performance test results in our previous
study [18] are combined with the present kinetic data to propose
plausible kinetic models for DR reaction.
2. Experimental
The thermally stable d-Al2O3 support was obtained by drying
c-Al2O3 (Alcoa) at 423 K for 2 h and then by calcining it at
1173 K for 4 h. The two bimetallic 0.2 wt.%Pt–15 wt.%Ni/d-Al2O3
(0.2Pt–15Ni) and 0.3 wt.%Pt–10 wt.%Ni/d-Al2O3 (0.3Pt–10Ni) were
prepared by sequential impregnation, in which impregnation of
aqueous nickel nitrate solution was followed by heat treatment
at 873 K for 4 h in muffle furnace and then by impregnation of
aqueous tetraammineplatinum nitrate solution. The resulting
slurries were dried overnight at 388 K and finally calcined at
773 K for 4 h [18].
The catalytic DR of methane was carried out in a fixed-bed
down-flow tubular quartz reactor under atmospheric pressure. In
these experiments, 5 mg of 250–425 lm fresh catalyst particles
were fixed at the center of the 6 mm-ID microreactor. The details
of the reaction system and the analytical method have been
reported elsewhere [7,18]. Blank tests showed that the reactor
543
material and the support alone were not catalytically active under
the reaction conditions used.
Before each reaction experiment, the catalyst samples were re-
duced in situ in a stream of 50 ml/min of pure hydrogen at 773 K
for 2 h and then flushed under 30 ml/min of Ar flow at the same
temperature. The partial pressure dependencies were determined
at 873 K by maintaining a constant partial pressure of 0.08 atm
of one reactant and varying the pressure of the other reactant be-
tween 0.02 and 0.08 atm. A balance of argon was adjusted to main-
tain atmospheric pressure and to keep the total flow constant. The
space velocity was varied between 1,200,000, 1,440,000 and
1,800,000 ml/h gcat, for guaranteeing both low conversion levels
and the absence of transport effects, which are necessary for
obtaining intrinsic kinetic information. It should be noted that
our preliminary tests confirmed the current study was conducted
in the kinetic region free from any diffusion effect. The effect of
H2 and CO addition was also studied at 873 K using 5 mg of catalyst
and a total flow of 100 ml/min with constant partial pressures of
the two reactants 0.08 atm, while the inlet partial pressures of H2
or CO were changed between 0 and 0.075 atm. To determine the
apparent activation energies, the reforming reaction was carried
out with a feed composition of CH4:CO2 = 1:1 over a temperature
range of 853–893 K.
3. Results and discussion
The kinetic behavior of the 0.2Pt–15Ni and 0.3Pt–10Ni catalysts
in DR was investigated as a function of temperature and partial
pressures of CH4, CO2, CO and H2.
The catalyst mass-based reaction rates in the kinetic measure-
ments, ðr CH4 Þ, are calculated from the conversion versus residence
time ðW cat =F CH4 Þ data as follows (Eq. (1)):
xCH4 F CH4
r CH4 ¼ ð1Þ
W cat
where xCH4 is CH4 conversion, F CH4 is CH4 flow rate in the feed in
ml min1 converted to mmol s1, W cat is catalyst weight in g and
ðr CH4 Þ is the reaction rate in mmol g1 s1.
CH4 consumption rates were obtained from intrinsic kinetic
data in the initial rate region by using differential method of data
analysis, through which a wide range of conversions can be ob-
tained by varying the ratio of W cat =F CH4 . In the kinetic tests, a set
of experiments were carried out at different initial reactant con-
centrations, and the initial rates were calculated by differentiating
the data and extrapolating it to zero times.
3.1. Apparent activation energies
The apparent activation energies were calculated over temper-
ature range of 853–893 K, based on the consumption rates of CH4
and CO2 as well as on the production rates of CO and H2. The exper-
imental data were taken after 90 min. time-on-stream (TOS) to en-
sure stable performance of the catalyst. The Arrhenius plots,
through which activation energies (Eapp) were calculated, are given
in Fig. 1. The activation energies calculated from the slopes of these
plots are shown in Table 1 and compared with similar data re-
ported in the literature.
It is remarkable that the activation barrier for CH4 consumption
is higher than that for CO2 consumption, which is in agreement
with reported values in literature [22,27–30]. The apparent activa-
tion energies for H2 production are greater than those correspond-
ing to the CO formation, which is probably due to the occurrence of
reverse water gas shift reaction consuming H2 to produce
additional CO. The difference in the activation energies of the
544 Sß. Özkara-Aydınoğlu, A. Erhan Aksoylu / Chemical Engineering Journal 215–216 (2013) 542–549

rate (micromol/g.s)
5

2 CH4
CO2
1 CO
H2
0
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
-1
1000/T (K )

Fig. 1. Arrhenius plots over temperatures ranging between 853 and 893 K. Catalyst: 0.3Pt–10Ni. Reaction conditions: CH4/CO2 = 1/1. Space velocity = 1,200,000 ml/h g-cat.

Table 1 at constant feed composition and different space times were used
Apparent activation energies (Eapp) in the current work and in the related literature. to verify linear behavior in the initial rates region. Seven different
Catalyst Eapp (kcal/mol) References CH4/CO2 ratios were used, and experimental runs were conducted
CH4 CO2 CO H2
at three different space times for each feed composition. Initial
rates of CH4 consumption were extracted from intrinsic kinetic
0.3Pt–10Ni 26.9 23.6 24.9 35.8 This work
data taken at 873 K in 21 duplicate experiments for each catalyst
0.2Pt–15Ni 26.6 16.9 21.0 35.2 This work
Ni/SiO2 23.0 19.0 20.0 27.0 [19] sample. The reaction rates were calculated from slopes of the con-
Ni/MgO 22.0 21.0 21.0 35.0 [19] version versus residence time plots and are given in Table 2 for
Ni/TiO2 26.0 21.0 23.0 32.0 [19] both 0.3Pt–10Ni and 0.2Pt–15Ni catalysts.
Ni/Al2O3 16.9 16.5 17.7 23.5 [24]
The empirical power-law type rate expression used for DR reac-
Ni/Al2O3 12.2 13.4 19.2 - [25]
Ni/SiO2 14.9 16.7 16.5 22.4 [24]
tion is given in (Eq. (2)):
Ni/CaO–Al2O3 25.5 23.6 24.6 35.2 [26]
Ni–K/CeO2–Al2O3 11.0 11.0 11.3 12.9 [20]
Pt(0.86%)/Al2O3 22.5 20.2 18.5 19.3 [27]
ðrCH4 Þ ¼ kðPCH4 Þa ðPCO2 Þb ð2Þ
Pt(0.31%)/ZrO2 24.0 20.0 21.6 34.0 [19]
The reaction orders (a and b) and the apparent rate constant (k)
Pt(0.82%)/TiO2 23.0 19.0 20.5 32.0 [19]
were estimated by non-linear regression analysis minimizing the
sum of the squared differences of calculated and experimental
two catalysts, 0.3Pt–10Ni and 0.2Pt–15Ni, most probably stems CH4 reforming rates using the Levenberg–Marquardt algorithm
from different Ni/Pt loading ratio of those catalysts and the conse- provided in the computer software POLYMATH 5.1 environment.
quent change in the surface mechanism. The activation energies of The resulting rate versus partial pressure data obtained at 873 K
Ni/CaO–Al2O3 catalyst obtained by Lemonidou and Vasalos [29] are were used to estimate the reaction orders shown in (Eq. (2)) via
in reasonable agreement with the activation energies calculated for utilizing non-linear regression analysis. The results of the regres-
0.3Pt–10Ni in this study (Table 1). sion analysis are given in Table 3.
It is observed that the reaction order for CH4 was close to first-
3.2. Effect of CH4 and CO2 partial pressures on intrinsic rate order for both catalysts. The reaction order for CO2 was 0.87 for
0.3Pt–10Ni sample, lower than the order for CH4, which is typical
The influence of the partial pressures of CH4 and CO2 on the DR for DR reaction. The orders with respect to CH4 and CO2 suggest
rate was studied over both 0.2Pt–15Ni and 0.3Pt–10Ni catalysts at that CO2 adsorbs more strongly than CH4 and that methane surface
atmospheric pressure under differential conditions at 873 K. coverage is relatively lower for 0.3Pt–10Ni sample. This result is in
In the tests, a constant CH4 partial pressure of 0.08 atm was good agreement with the findings of Tsipouriari and Verykios [25].
used as the CO2 partial pressure was varied between 0.02 and However, the order for CO2 was 1.40 for 0.2Pt–15Ni sample and
0.08 atm, and vice versa (Table 2). Methane conversion data taken this suggests us that the reaction rate is more sensitive to CO2 par-

Table 2
Initial rates of DR of methane at 873 K over 0.3Pt–10Ni & 0.2Pt–15Ni Catalysts. (SV = 1,200,000–1,800,000 mL/h g-cat; TOS = 90 min).

Experiment no. Partial pressures (atm) CH4/CO2 Reaction rate (mmol g1 s1)
CH4 CO2 0.3Pt–10Ni 0.2Pt–15Ni
1–3 0.02 0.08 0.25 0.0551 0.0917
4–6 0.04 0.08 0.50 0.1108 0.1941
7–9 0.06 0.08 0.75 0.1668 0.3074
10–12 0.08 0.08 1.00 0.2230 0.4183
13–15 0.08 0.06 1.33 0.1735 0.2821
16–18 0.08 0.04 2.00 0.1217 0.1581
19–21 0.08 0.02 4.00 0.0675 0.0613
 Sß. Özkara-Aydınoğlu, A. Erhan Aksoylu / Chemical Engineering Journal 215–216 (2013) 542–549 545

Table 3
Estimated reaction rate parameters.

Catalyst Reaction orders k r2 (mmol g1 s1)2

a b
0.3Pt–10Ni 1.00 0.87 25.4 (mmol g1 s1 atm1.87) 2.7  107
0.2Pt–15Ni 1.09 1.40 230.0 (mmol g1 s1 atm2.49) 2.1  106

tial pressure, than to CH4 partial pressure. It is also observed that
higher rate values obtained over 0.2Pt–15Ni sample led to a dras-
tically higher k value compared to that obtained from 0.3Pt–10Ni.
In the study of Wang and Lu [28]; the reaction orders based on
power rate law for both CH4 and CO2 was found as 1.00 and 1.11,
respectively, for Ni/c-Al2O3 catalyst at 873 K.
The results indicate that the performance of the 0.2Pt–15Ni
sample strongly depends on the CO2 partial pressures; most prob-
ably, the utilization of oxygen coming from CO2 in cleaning depos-
ited carbon has comparably high sensitivity to CO2 partial pressure
due to both relatively lower Pt content of the catalyst as well as its
higher Ni/Pt ratio. Due to its relatively higher content of Pt, which
enhances the oxygen utilization in cleaning of the deposited car-
bon, the CO2 dependence is rather limited for the 0.3Pt–10Ni sam-
ple; instead the reaction rate is a stronger function of methane
concentration in the reactant feed.
As shown in Fig. 2A, a linear relationship between the CH4 con-
sumption rate and CH4 partial pressure for both catalysts was ob-
served. It is also observed that rate of reaction increases with
increasing partial pressure of carbon dioxide in a pressure range
of 0.02–0.08 atm for both catalysts (Fig. 2B). This result is in good
agreement with that of Zhang and Verykios [31]; they stated that
increasing partial pressure of CO2 resulted in a rapid increase of
0.7
(A)
0.6
0.5
r(CH4) (mmol/gcat.s)
the reaction rates at low partial pressures (less than 0.13 atm) over
Ni/c-Al2O3 and Ni/CaO/c-Al2O3 catalysts. Wang and Lu [28] also re-
ported a similar result for Ni/c-Al2O3 catalyst in DR reaction at
873 K for pressures of less than 0.06 atm. Tsipouriari and Verykios
[25] found similar results over Ni/La2O3 catalyst in this reaction. It
is shown that the reaction rate is strongly affected by the partial
pressure of methane for CH4 partial pressures lower than
0.2 atm. A very strong influence is observed as the CO2 partial pres-
sure is varied in the range 0–0.1 atm. Qualitatively the trends in
dependencies agree with those reported by Lemonidou and Vasa-
los [29].
The reaction rates for the consumption of methane as a function
of methane and carbon dioxide are shown in Fig. 2. The points in
these figures show the experimental results; the lines were fitted
the experimental data and have the equations given by the power
type rate-law (Eq. (2)). It is observed that experimental results and
the proposed power type rate laws for both catalysts are in good
agreement (Table 3).
3.3. Effect of CO addition on DR of CH4
In order to understand the effect of products on the kinetic
expression, carbon monoxide with inlet partial pressure varying
between 0.015 and 0.060 atm was added to the feed stream with
constant partial pressures of the two reactants CO2 and CH4 as
0.2Pt-15Ni 0.08 atm at 873 K first (Table 4).
0.3Pt-10Ni The rate values obtained show that there is a CO inhibition ef-
fect on methane consumption and incorporation of CO into the rate

expression is a necessity. It should be noted that the orders with

0.4
respect to CH4 and CO2 were assumed same as in ‘DR without
0.3 CO’ case, and the product inhibition of CO was lumped both in
the order with respect to CO and in the value of k. The same meth-
0.2
odology was also employed in the kinetic study by Gülyüz et al.
0.1 [32]. Thus, the power-function rate expression for dry reforming
reaction becomes:
0
0 0.02 0.04 0.06 0.08 0.1
ðrCH4 Þ ¼ kðPCH4 Þa ðP CO2 Þb ðPCO Þd ð3Þ
P (CH 4 ) (atm)
Partial pressures of CH4, CO2 and CO in the feed and the calcu-
0.7 lated initial reaction rate data used in the evaluation of CO reaction
(B) order are presented in Table 4. CH4 consumption rates in the pres-
0.6 0.2Pt-15Ni
ence of CO were also plotted as a function of partial pressure of car-
0.3Pt-10Ni
r(CH4 ) (mmol/gcat.s)

0.5 bon monoxide in Fig. 3A. The reaction rate parameters, k and d of
(Eq. (3)) were determined by POLYMATH software using nonlinear
0.4 regression technique and their values are given in Table 5 for each
0.3 catalyst.

0.2
Table 4
0.1
Effect of CO partial pressure on DR rates. (SV = 1,200,000 mL/h g-cat; TOS = 90 min).
0 Experiment no. Partial pressures (atm) ðr CH4 Þ (mmol g1 s1)
0 0.02 0.04 0.06 0.08 0.1
CH4 CO2 CO 0.3Pt–10Ni 0.2Pt–15Ni
P (CO 2 ) (atm) 22 0.08 0.08 0.015 0.2183 0.2619
23 0.08 0.08 0.030 0.1856 0.2158
Fig. 2. Variation of the reaction rates for the consumption of methane ðr CH4 Þ as a 24 0.08 0.08 0.045 0.1638 0.1705
function of the partial pressures: (A) methane ðP CH4 Þ; and (B) carbon dioxide ðP CO2 Þ. 25 0.08 0.08 0.060 0.1517 0.1419
The points are experimental data. The lines are the fitting using Eq. (2).
546 Sß. Özkara-Aydınoğlu, A. Erhan Aksoylu / Chemical Engineering Journal 215–216 (2013) 542–549

0.5 Table 6
Effect of H2 partial pressure on DR rates. (SV = 1,200,000 mL/h g-cat; TOS = 90 min).
(A) 0.3Pt-10Ni
Experiment no. Partial pressures (atm) ðr CH4 Þ (mmol g1 s1)
r(CH4 ) (mmol/gcat.s)

0.4
0.2Pt-15Ni CH4 CO2 H2 0.3Pt–10Ni 0.2Pt–15Ni

0.3 26 0.08 0.08 0.015 0.2867 0.2731

27 0.08 0.08 0.03 0.2910 0.2826
28 0.08 0.08 0.045 0.2955 0.2800
0.2 29 0.08 0.08 0.06 0.2961 0.2729
30 0.08 0.08 0.075 0.2942 0.2806

0.1

the reforming reaction. However, the present experimental results

0
can still not disclose whether the desorption of CO is a rate deter-
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
mining step in the reforming reaction 873 K.
P(CO) (atm)

0.5 3.4. Effect of H2 addition on intrinsic rate

(B)
The disappearance of methane is also affected by the increased
0.4
partial pressures of H2 in the feed stream. The effect of H2 addition
r(CH4) (mmol/gcat.s)

0.3
0.2
0.1
0 initially declined for 0.2Pt–15Ni sample whereas it was slightly en-
0 0.02 0.04
P(H2 ) (atm)
Fig. 3. Variation of the reaction rates for the consumption of methane ðr CH4 Þ as a
function of the partial pressures: (A) carbon monoxide ðP CO Þ; and (B) hydrogen
ðP H2 Þ.
It is observed that the presence of CO for both catalysts have
negative effect on the consumption of methane in DR. However;
the rate of methane consumption for 0.2Pt–15Ni sample was found
more sensitive to the increase in partial pressure of CO as the reac-
tion order with respect to CO for this sample is 1.6 times the value
of that for the 0.3Pt–10Ni catalyst.
The inhibition effect of CO on reaction rate is explained by the
adsorption of CO on active sites where it dissociates into activated
surface carbon and O. This type of activated surface carbon formed
from CO reacts more slowly compared to that of C (or CH) species
formed by activation of CH4 [29]. This explanation can also clarify
the rapid deactivation of the 0.2Pt–15Ni catalyst as it is more sen-
sitive to the presence of CO than the 0.3Pt–10Ni sample. Olsbye
et al. [33] and Cui et al. [26] also observed inhibiting effect of CO
in dry reforming of CH4 using Ni/La-Al2O3 and Ni/a-Al2O3 catalysts,
respectively.
It has been reported that both CH4 dissociation and CO adsorp-
tion occurs on Ni active sites [26]. Some kinetic models suggested
that most of the species adsorbed on the Ni active sites were CO
and CH species [26,34,35]. Parallel to the literature, the inhibition
effect of CO increases from (0.26) to (0.41) as the Ni content in-
creases from 10 wt.% for 0.3Pt–10Ni catalyst to 15 wt.% for 0.2Pt–
15Ni sample. The adsorption of CO on the Ni active sites inhibited
the adsorption and dissociation of CH4, which further restrained
was also studied through mixed feed tests for which hydrogen inlet
partial pressure varying between 0.015 and 0.075 atm in the feed
stream while the partial pressures of CH4 and CO2 were kept fixed
at 0.08 atm at 873 K (Table 6).
CH4 consumption rates in the presence of H2 were plotted as a
02.Pt-15Ni function of partial pressure of hydrogen in Fig. 3B. Upon the addi-
0.3Pt-10Ni tion of hydrogen to the feed, the rate of methane conversion was
0.06 0.08 hanced for 0.3Pt–10Ni sample. However; increasing H2 partial
pressure further had essentially no effect on the CH4 reforming
activity of the both Ni catalysts, as evidenced by the invariance
of the rate of methane consumption with increasing H2 partial
pressure (Fig. 3b and Table 6). This result is also consistent with
other Ni-based catalysts in literature [25,26]. We can conclude that
Ni–H can be produced on the nickel catalysts and it can reach equi-
librium state with the product hydrogen formed in DR [26,36].
Therefore, the reaction steps involving the hydrogen species on
the catalyst surface were the rapid or equilibrium steps. Munera
et al. [37] also reported that rate of methane consumption is not
affected by the partial pressure of H2 (0–0.08 atm) over Rh/La2O3
catalyst.
3.5. Surface reaction models
There have been various reports where the kinetics of methane
dry reforming with carbon dioxide has been expressed as a simple
power-law model due to its simplicity in application. However,
over a wide range of partial-pressure data, these models may be
inadequate. Hence, it becomes necessary to understand the mech-
anistic aspects of the reforming reaction. In the related literature,
researchers have proposed Langmuir–Hinshelwood (LH), Eley-
Rideal (ER) and Hougen-Watson (HW) type of reaction models
[25,28,31,33,37–40].
In this study, DR kinetics data obtained were fitted to LH and
ER-type rate expressions. The rate expressions whose validities
were tested for both Pt–Ni catalysts are presented in Table 7. In
the models, the Ki values stand for the adsorption coefficients for
each species. In order to analyze whether there is a change in reac-
tion kinetics depending on composition of Pt–Ni systems, experi-

Table 5
Estimated reaction rate parameters in the presence of CO.

Catalyst Reaction order of CO (d) k Power-type rate law

0.3Pt–10Ni 0.26 8.2 mmol g1 s1 atm1.61 ðr CH4 Þ ¼ kðP CH4 ÞðP CO2 Þ0:87 ðP CO Þ0:26
0.2Pt–15Ni 0.41 25.7 mmol g1 s1 atm2.08 ðr CH4 Þ ¼ kðP CH4 Þ1:09 ðP CO Þ1:40 ðP CO Þ0:41
 Sß. Özkara-Aydınoğlu, A. Erhan Aksoylu / Chemical Engineering Journal 215–216 (2013) 542–549 547

Table 7 effect of CO is not included within the rate expressions proposed

Langmuir–Hinshelwood (LH) type rate expressions. up to now. But, the negative influence of CO addition on CH4 con-
Model no. Proposed rate equations sumption rate should also be represented in the model equations.
1 kK CO2 PCH4 PCO Hence; Model 6 was derived from Model 1 simply by adding the
ðr CH4 Þ ¼ ð1þK CO2 PCO2 Þ
inhibiting effect of CO in the denominator. Considering that the or-
2 k1 PCH4 P CO2
r CH4 ¼ ð1þK 1 PCH
4
Þð1þK 2 PCO2 Þ ders for the reactants are greater than unity, the exponents of the
3
r¼
aPCH4 P2CO
2
components occurring in the numerator of the LH type rate expres-
2
ðP CO2 þbPCO þcP CH4 Þ2
2 sions are left as variables. Model 7 assumes an Eley–Rideal (ER)
4 ðr CH4 Þ ¼
kK CO2 K CH4 PCH4 PCO2
ð1þK CO2 PCO2 þK CH4 P CH4 Þ2 type of heterogeneous model in which the reaction between CHx
5 ðr CH4 Þ ¼ ð1þK 1 PCH
kP CH4 PCO2 and CO2,g is rate-limiting at low pressures of carbon dioxide. CH4
þK 2 PCO Þð1þK 3 PCO2 Þ

6
4
kK CO2 PCH4 PCO2
is adsorbed on the catalyst surface and dissociates to CHx and H.
ðr CH4 Þ ¼ ð1þK CO P
2 CO2
þK CO PCO Þ The slow and the rate-determining step is the reaction of adsorbed
7 kK CH4 PCH4 P m
ðr CH4 Þ ¼
CO
ð1þK CH4 P CH4 Þ
2
CHx with CO2 from the gas phase. This type of model has been pre-
8 m
kPCH PnCO viously reported by Olsbye et al. [33] and Mark et al. [39]. The
ðr CH4 Þ ¼ ð1þK CO 4 2
PCO2 þK CO PCO þK CH4 PCH4 Þ
2 inhibiting effect of both CO and CH4 is considered in Model 8.
The nonlinear regression analysis performed clearly showed
that the surface reaction mechanisms are completely different for
mental CH4 consumption rate data for both 0.3Pt–10Ni and 0.2Pt– 0.3Pt–10Ni and 0.2Pt–15Ni samples. The first six models gave
15Ni samples were fitted to eight different kinetic models listed in physically meaningful values for DR over 0.3Pt–10Ni catalyst,
Table 7 through utilizing nonlinear regression analysis with Leven- while only models 5, 7 and 8 worked for DR over 0.2Pt–15Ni (Ta-
berg–Marquardt algorithm provided in the POLYMATH 5.1 soft- bles 8 and 9). For 0.3Pt–10 Ni, Model 1 gives the lowest squared er-
ware for estimating kinetic parameters. ror meaning that CH4 is weakly adsorbed and the surface coverage
The model discrimination was made on the basis of the variance of methane is relatively low for 0.3Pt–10Ni sample at the pressures
value and/or physical meaningfulness of the constants present in studied; hence, this model is the best one to describe the behavior
the model. Models giving either poor correlation coefficients or 0.3Pt–10Ni sample. The values obtained from the nonlinear analy-
negative parameter values were ruled out. In some models, the sis over Model 2, which gives the error margin close to that of
95% confidence interval was greater than the parameters itself,
yielding negative values of the parameters, which is physically
Table 8
impossible; these models were also excluded. The equation that
Model parameters obtained for 0.3Pt–10Ni catalyst.
best fits the experimental data was determined by comparing the
variance of the experimental error (r2) for each model and select- Model no. Rate parameters r2 (mmol g1 s1)2
1 1 1
ing the equation with a smaller variance. 1 k = 14.34 mmol g s atm 2.29  106
Some of the groups who performed kinetic studies on the CO2- K CO2 ¼ 2:99 atm1
reforming reaction have proposed a LH-type mechanism with an 2 k1 = 68.18 mmol g1 s1 atm2 2.86  106
undefined number of H atoms in the intermediate CHx species K1 = 1.55 atm1
and with dissociative adsorption of CO2 [28,38]. Zhang and Veryk- K2 = 10.57 atm1

ios [31] have derived a rate expression in a Langmuirian model 3 a = 6.2 mmol g1 s1 atm3 4.75  104
assuming that methane dissociation was the rate determining step. b = 1.7 atm2
c = 0.45 atm1
The results reported by Olsbye et al. [33] showed that the experi-
mental data were consistent with LH mechanism, in which the sur- 4 k = 49.9 mmol g1 s1 9.98  106
1
K CO2 ¼ 1:74 atm
face reaction is the rate-determining step, or an ER-type
K CH4 ¼ 0:55 atm1
mechanism, in which the reaction between CHx and CO2,g is rate-
limiting at low carbon dioxide pressures. The models considered 5 k = 84.6 mmol g1 s1 atm2 2.95  104
K1 = 1.71 atm1
in this study and their main assumptions can be summarized as
K2 = 6.00 atm1
follows; Model 1 was proposed by Mark et al. [39], who investi- K3 = 15.88 atm1
gated the kinetics of CO2/CH4 reforming with Ir/Al2O3. The model
6 k = 18.6 mmol g1 s1 atm1 3.98  105
based on (ER) type of heterogeneous model assumes that CO2 is ad- K CO2 ¼ 2:25 atm1
sorbed on the catalyst surface in adsorption equilibrium. The slow K CO ¼ 9:03 atm1
and the rate-determining step is the reaction of adsorbed CO2 with
CH4 from the gas phase leading directly to products. Model 2 was
proposed by Wang and Lu [28] for Ni/Al2O3 catalyst. In this model;
the authors proposed a rate model based on the stepwise mecha- Table 9
Model parameters obtained for 0.2Pt–15Ni catalyst.
nism, where in methane is decomposed to hydrogen and active
carbon followed by the conversion of this active carbon with CO2 Model no. Rate parameters r2 (mmol g1 s1)2
to 2CO. The rate-determining step was determined as the CO for- 5 k = 71.0 mmol g 1
s 1
atm 2
7.73  104
mation step. Zhang and Verykios [31] proposed a rate expression K1 = 1.00 atm1
(Model 3) derived from a LH-type model, assuming methane disso- K2 = 30.0 atm1
ciation is the rate-determining step. Mark et al. [39] also proposed K3 = 1.20 atm1

a LH model type rate expression (Model 4) over Rh/c-Al2O3, which 7 k = 2020 mmol g1 s1 8.88  105
assumes that both reactants are adsorbed and the rate determining K CH4 ¼ 0:078 atm1
m = 1.36 atm1
step is the surface reaction between the adsorbed reactants to form
products H2 and CO. The resulting equation was also proposed by 8 k = 428 mmol g1 s1 atm2 6.76  105
Richardson and Paripatyadar [40]. Olsbye et al. [33] have reported K CH4 ¼ 1:49 atm1
K CO2 ¼ 2:49 atm1
the kinetic studies of DR reaction over a highly active Ni/La/Al2O3
K CO ¼ 43:7 atm1
catalyst in a micro-catalytic fixed-bed reactor; the proposed LH
m = 1.14, n = 1.49
type rate expression is given by Model 5. The observed inhibiting
548 Sß. Özkara-Aydınoğlu, A. Erhan Aksoylu / Chemical Engineering Journal 215–216 (2013) 542–549
Model 1 for 0.3 Pt–10 Ni, designates that equilibrium constant of
CO2 (K2) is higher than equilibrium constant of CH4 (K1). This sug-
gests that the catalyst has ability to utilize CO2, the reactant acting
as the oxygen source, easily. Wang and Lu have also reported a
similar relation between the equilibrium constants of CO2 and
CH4 for this model (25). Model 3 proposed by Zhang and Verykios
[31] fitted the observed data with a very high squared error in non-
linear estimation. Relatively high squared error obtained from
Model 6, which was derived from Model 1 simply by adding the
inhibiting effect of CO in the denominator, indicates that 0.3Pt–
10Ni does not significantly suffer from CO inhibition.
Though it yields relatively high squared error values, Model 5 is
the only common kinetic model which yields physically meaning-
ful kinetic parameters for both 0.3Pt–10Ni and 0.2Pt–15Ni. The
negative influence of CO addition on the reaction rate is included
in this model. This model predicts that CH4 and CO adsorb on the
same type of active site whereas CO2 adsorbs on a different site.
In the present work; the adsorption coefficients for 0.3Pt–10Ni
sample increase in the following sequence: K1 < K2 < K3. This hints
us the fact that CO2 is more strongly adsorbed than CH4, which is
consistent with the K values found for Model 2 for 0.3Pt–10Ni.
The same conclusion has also been made based upon power rate
type results. These results are also in good agreement with the re-
sults of Olsbye et al. [33]. It should be noted that the inhibition ef-
fect of CO, which is reflected by K2, is five times greater for 0.2Pt–
15 Ni, which is a clear indication that the sample with higher Ni:Pt
molar ratio severely affected by CO inhibition.
The inhibiting effect of CO over 0.2Pt–15Ni is very strong and it
should also be included in the model equation. Model 8 also takes
into account the effect of CO on the reaction rates and gives the
best result with the smallest variance among the three rate expres-
sions in Table 9.
In our previous work [18]; the DR catalytic performances of
0.3Pt–10Ni and 0.2Pt–15Ni samples have been studied and it was
observed that 0.3Pt–10Ni sample (low Ni/Pt ratio) showed highly
stable and active profile whereas 0.2Pt–15Ni sample (high Ni/Pt ra-
tio) rapidly deactivated due to the blocking of active sites by car-
bon deposits. In the present study; strong inhibition effect of CO
on reaction rate for 0.2Pt–15Ni through the adsorption of CO on ac-
tive sites, where it dissociates to activated surface carbon and O,
was confirmed. This type of activated surface carbon formed from
CO reacts more slowly compared to that of C (or CH) species
formed by activation of CH4 [29]. This explanation also strongly
clarifies the change in surface reaction mechanism depending on
the Pt load and Ni/Pt ratio of the catalysts.
4. Conclusions
The results show that
 The kinetics of CO2 reforming of methane within the parameter
range investigated over 0.3Pt–10Ni and 02.Pt–15Ni can be
expressed by a simple power-law rate equation, with reaction
orders of 1 and 1.09 for CH4 and 0.87 and 1.40 for CO2, respec-
tively, confirming methane consumption rate for 0.2%Pt–15%Ni/
Al2O3 sample is more sensitive to the increase in partial pres-
sure of CO.
 The comparative analysis of meaningful surface reaction models
for the catalysts and their optimized model parameters revealed
that the surface reaction mechanisms are completely different.
CO inhibition effect is stronger and CO2 utilization is suppressed
on the catalyst with high Ni:Pt loading ratio. On the other hand,
with a decrease in Ni:Pt loading ratio, CH4 adsorption become
weaker, ability of utilizing CO2 as the oxygen source gets stron-
ger and CO inhibition effect is practically eliminated.
Acknowledgements
This study has been supported by Bogazici University through
Project BAP 6755, by State Planning Organization of Turkey
through Project DPT 07K120630 and by TUBITAK through project
111M144.
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