Ind. Eng. Chem. Res.

2002, 41, 4681-4685 4681

RESEARCH NOTES

Coke Formation on Pt/ZrO2/Al2O3 Catalysts during CH4 Reforming

with CO2
Mariana M. V. M. Souza, Donato A. G. Aranda,, and Martin Schmal*,,
NUCAT/PEQ/COPPE, Universidade Federal do Rio de Janeiro, C.P. 68502,
21945-970 Rio de Janeiro, Brazil, and Escola de Quimica, Universidade Federal do Rio de Janeiro,
C.P. 68542, 21940-900 Rio de Janeiro, Brazil

The CO2 reforming of methane was studied over Pt supported on Al2O3, ZrO2, and x % ZrO2/
Al2O3 (1 e x e 20 wt %). The Pt/Al2O3 deactivated very quickly during 20 h onstream at 1073
K and a CH4/CO2 ratio of 1:1, while the catalysts with a ZrO2 content above 5 wt % presented
improved stability during 60 h. Temperature-programmed oxidation studies showed that the
amount of carbon on Pt/Al2O3 is much larger than that on zirconia-containing catalysts.
Deactivation is attributed to carbon formation surrounding the metal-support perimeter. The
high stability of zirconia-based catalysts is probably due to strong Pt-Zrn+ interactions, which
reduce carbon formation during the reaction by promoting CO2 dissociation. High ratios of CH4/
CO2 were also used in an attempt to accelerate deactivation, but even under these severe
deactivation conditions, the catalyst with 10 wt % ZrO2 exhibited excellent stability.

1. Introduction surface.11 Therefore, the reforming reaction proceeds

The catalytic reforming of CH4 with CO2, rather than
H2O, for the production of synthesis gas, i.e., a mixture
of CO and H2, has attracted substantial interest.1-4 The
reaction is well suited to a lower H2/CO product ratio,
which is preferable as feed for Fischer-Tropsch plants5
and for the synthesis of acetic acid, dimethyl ether, and
oxoalcohols.6 Moreover, dry reforming is of interest for
environmental reasons because it reduces both CO2 and
CH4 emissions, which are so-called greenhouse gases.7
The major obstacle for larger diffusion of this process
in industry is the high thermodynamic potential to form
coke under elevated temperatures.5 Temperatures around
1073 K are required to reach high conversions because
of the high endothermic nature of the process. Thus, the
catalyst deactivation is a serious challenge and must
be overcome by effective catalysts.
CH4 + CO2 T 2CO + 2H2 H298K ) 247.3 kJ/mol
(I)
Although the most commonly used support for CO2/
CH4 reforming is alumina,2,8,9 it has been found that
Pt reaches much higher conversions and better stability
when supported on ZrO2.10-12 Van Keulen et al.13
showed that Pt/ZrO2 is very stable for a period of over
1000 h, at 923-973 K and a feed ratio of CO2/CH4 ) 2.
The coking resistivity of Pt/ZrO2 is associated with
strong Pt-Zrn+ interactions, which result in the forma-
tion of ZrOx species in close contact with the Pt
* To whom correspondence should be addressed. E-mail:
schmal@peq.coppe.ufij.br. Fax: (5521) 2562-8300.
NUCAT/PEQ/COPPE.
Escola de Quimica.
10.1021/ie010970a CCC: $22.00 2002 American Chemical Society
Published on Web 08/06/2002
basically on the metal-support perimeter.14
When zirconia is dispersed on alumina, it provides a
better dispersion for Pt particles because these systems
combine the unique chemical properties of ZrO2 with
the high surface area and mechanical stability of Al2O3.
We showed earlier that Pt/ZrO2/Al2O3 catalysts exhibit
high activity and suffer less deactivation than Pt/Al2O3
or even Pt/ZrO2.15 In the present work we tried to
develop a better understanding of the nature of coking
in CO2 reforming of CH4, by doing temperature-
programmed oxidation (TPO) analysis of carbon deposits
and varying the CH4/CO2 ratio in the feed. We inves-
tigated the relation between coking and catalyst per-
formance at a temperature typically used for commercial
operations (1073 K).
2. Experimental Section
2.1. Catalyst Preparation and Characterization.
Al2O3 (Harshaw) and ZrO2 were used as supports. Al2O3
was calcined in air at 823 K for 16 h (BET area ) 200
m2/g), and ZrO2 was prepared by calcination of zirco-
nium hydroxide (MEL Products) in air at 823 K for 2 h
(BET area ) 62 m2/g).
ZrO2/Al2O3 samples were prepared by impregnation
over an alumina powder with a nitric acid solution (50%)
of zirconium hydroxide, as described elsewhere.15 Zir-
conia loading was varied between 1 and 20 wt %. The
catalysts were prepared by an incipient wetness tech-
nique, using an aqueous solution of H2PtCl66H2O
(Aldrich), followed by drying at 393 K for 16 h and
calcination in air at 823 K for 2 h. For all catalysts, the
platinum content was around 1 wt %. The prepared
catalysts will be referred to as PtAl for Pt/Al2O3, PtZr
for Pt/ZrO2, and PtxZr for Pt/x % ZrO2/Al2O3.
4682 Ind. Eng. Chem. Res., Vol. 41, No. 18, 2002
H2 and CO chemisorptions were measured on all
catalysts at room temperature after reduction by 10%
H2/Ar at 773 K using an ASAP 2000 apparatus (Mi-
cromeritics). Because of the metal-support interac-
tion,14 chemisorption on the PtZr catalyst was also
carried out after reduction at 573 K to better estimate
the Pt dispersions.15
2.2. Catalytic Test. The reaction was carried out in
a fixed-bed flow-type quartz reactor, loaded with 20 mg
of catalyst. A thermocouple was placed on top of the
catalyst bed to measure the catalyst temperature. The
catalysts were dried in situ with flowing nitrogen at 423
K, before reduction with 10% H2/N2 for 1 h at 773 K.
After reduction, the sample was purged with nitrogen
for 30 min at the same temperature. All catalytic tests
were performed under atmospheric pressure, and the
total feed flow rate was 200 cm3/min (WHSV ) 160 h-1),
over the temperature range 723-1173 K. Stability tests
were carried out at 1073 K with stoichiometric condi-
tions (CH4:CO2 ) 1:1) as well as with an excess of CO2
for PtAl and an excess of CH4 for the Pt10Zr catalyst,
maintaining the total feed flow rate of 200 cm3/min with
helium. The reaction products were analyzed by an
online gas chromatograph (CHROMPACK CP9001),
equipped with a Hayesep D column and a thermal
conductivity detector.
Temperature-programmed surface reaction (TPSR)
was also performed to investigate CO2 reforming of CH4
over platinum catalysts, using a dynamic mode ap-
paratus. After reduction at 773 K, the catalyst was
purged with He at this same temperature during 1 h
and cooled to room temperature. The amount of catalyst
and total feed flow rate were the same as those used in
stability tests, with a CH4/CO2/He ratio of 1:1:18. TPSR
was performed by heating the catalyst at 10 K/min up
to 823 K, maintained for 30 min, and subsequently
ramped to 973 K, remaining at this temperature for 1
h. The effluent gas composition was monitored online
by a quadrupole mass spectrometer (Dycor MA100M
Ametek).
TPO of carbonaceous deposits was carried out in the
same dynamic mode apparatus as that used for TPSR.
After reaction, the samples were cooled to room tem-
perature under a helium flow and then heated to 1073
K at a rate of 10 K/min in a 5% O2/He mixture (30 cm3/
min). Integration of the CO2 evolution spectra allowed
the quantification of carbon deposition.
3. Results and Discussion
The amounts of irreversibly adsorbed H2 and CO, at
room temperature, were reported in a previous paper.15
Alumina-supported catalysts with zirconia loading up
to 10% presented high H/Pt values (around 0.85). The
lower dispersion of the Pt20Zr catalyst (H/Pt ) 0.60)
can be attributed to the presence of large ZrO2 crystal-
lites on the support. After high-temperature reduction,
the H2 chemisorption on PtZr was markedly decreased
compared to that on PtZr reduced at 573 K (H/Pt varied
from 0.34 to 0.57). This type of behavior suggests the
migration of partially reduced zirconia onto the plati-
num surface (a SMSI type state). However, the presence
of ZrOx moieties did not cause any decrease in CO
chemisorption on the PtZr catalyst. The high values of
the CO/H2 ratio on zirconia-containing catalysts and in
particular on the PtZr catalyst reduced at 773 K (CO/
H2 ) 6.9) predict an interaction of CO with the Pt-ZrOx
interface, shown by IR of CO adsorbed on PtZr systems,
as reported in ref 15.
Figure 1. CO formation during TPSR over Pt catalysts. Reaction
conditions: CH4:CO2:He ) 1:1:18, total feed flow rate ) 200 cm3/
min.
The activity of the catalysts was evaluated under
reforming conditions, with a CH4/CO2 ratio of 1:1, over
a temperature range of 723-1173 K. The activity is
influenced by the nature of the support.15 At higher
temperatures, PtAl and Pt1Zr catalysts are less active
than Pt10Zr, the most active catalyst over the whole
temperature range investigated: the CH4 conversion
ranged from 5.5% at 723 K to 93.5% at 1173 K.
TPSR measurements were carried out under similar
conditions. Figure 1 presents the TPSR profiles of CO
production on PtAl, PtZr, and Pt10Zr catalysts. As
shown, the PtZr catalyst exhibits higher initial activity,
mainly at lower temperatures, but deactivates very fast,
while PtAl and Pt10Zr catalysts present good stability
at 823 K during the first 30 min onstream. On the other
hand, the Pt10Zr catalyst showed the best performance
at 973 K.
The support influences strongly the stability of the
catalysts, as reported previously.15 The order of activity
maintenance at 1073 K was Pt10Zr > Pt5Zr > Pt20Zr
and PtZr . PtlZr > PtAl. As reported, PtAl and Pt1Zr
catalysts exhibited high linear deactivation rates of 4.0
+ 0.5%/h and 3.3 + 0.4%/h, respectively, during the first
20 h onstream at 1073 K because of the rapid deposition
of inactive carbon, which will be discussed later. The
Pt10Zr catalyst deactivated only at a rate of 0.1%/h
during 60 h onstream at this temperature.15
There are two potential causes of deactivation: coke
deposition and sintering of metal particles. Most authors
agree that the coke formation is the main source of
deactivation.10,16-18 Bitter et al.10,17 showed that sinter-
ing of Pt particles during reforming conditions can be
excluded based on EXAFS results of fresh and used Pt/
Al2O3 and Pt/ZrO2. Thus, the fast deactivation of PtAl
should be associated with carbon deposition.
Figure 2 shows the oxidation profiles of carbon
deposited on the PtAl, PtZr, and Pt10Zr catalysts after
21 h of reaction at 1073 K and a CH4/CO2 ratio of 1:1.
For the PtAl catalyst, the oxidation started at 520 K,
exhibiting a major peak around 700 K and a smaller
one at 830 K. For zirconia-containing catalysts, the
onset of the oxidation was at lower temperature, around
373 K. The amount of carbon deposited at 1073 K, as
quantified by integration of the CO2 formation during
TPO runs, was normalized to surface Pt, and the results
are displayed in Table 1. It shows that after 21 h
onstream the Pt surface is not entirely covered by
carbon; thus, the high values of C/Pt, mainly for the PtAl
catalyst, must be due to accumulation of carbon on the
support.

Figure 2. TPO profiles for PtAl, PtZr, and Pt10Zr catalysts, after
exposure to a CH4:CO2:He ) 1:1:18 mixture at 1073 K for 21 h.
Table 1. Amount of Coke As Quantified by TPO
mg of coke/ mg of coke/
catalyst (g of catalyst)h C/Pt catalyst (g of catalyst)h C/Pt
PtAl 6.3 10.2 Pt10Zr 0.3 0.5
PtZr 0.6 0.9
Noronha et al.19 have suggested that the various TPO
peaks are not due to different forms of carbon but rather
to different locations on the catalyst surface, for Pt/Al2O3
and Pt/ZrO2. The low-temperature peaks observed in
TPO of coked Pt/Al2O3 have been typically ascribed to
carbon surrounding the metal particles, while those at
high temperatures are ascribed to the carbon deposition
over the support.20 Deactivation is attributed to carbon
formation surrounding the metal-support perimeter.
On zirconia-containing catalysts, coke has a higher
reactivity and does not cause any blockage of Pt-ZrOx
interfacial sites.
The higher stability and coking resistivity of Pt/ZrO2
have been related to strong Pt-Zrn+ interactions, which
result in the formation of ZrOx species on the Pt
surface.11 Indeed, our TPR results15 indicated that
zirconia can be reduced at lower temperatures than 500
K, resulting in ZrOx species that may decorate the Pt
surface, diminishing the hydrogen chemisorption capac-
ity. The interfacial sites on Pt-ZrOx are active for CO
adsorption and CO2 dissociation, providing active spe-
cies of oxygen that may react with carbon formed by
CH4 decomposition on the metal particle, suppressing
carbon accumulation.11,15,16 Moreover, zirconia is a well-
known oxygen supplier, and its oxygen mobility is about
3 times higher than that of alumina,21 which helps to
keep the metal surface free of carbon. When zirconia is
dispersed over alumina, the Pt surface is not extensively
recovered by ZrOx, as shown by chemisorption measure-
ments.15 Thus, the Pt-ZrOx interface in ZrO2/Al2O3
systems appears to be more active and stable for CO2
reforming of methane.
Carbon deposition during methane reforming can be
originated from either methane decomposition (reaction
II) or CO disproportionation (Boudouard reaction III),
which are thermodynamically favorable below 1173
K.5,22
CH4 T C + 2H2 H298K ) 75 kJ/mol (II)
2CO T C + CO2 H298K ) -172 kJ/mol
(III)
Ind. Eng. Chem. Res., Vol. 41, No. 18, 2002 4683
Figure 3. Effect of the ratio CO2/CH4 on the stability of PtAl at
1073 K. Reaction conditions: flow rates of CO2 ) 10 cm3/min and
CH4 + He ) 190 cm3/min.
Kinetically, both the methane decomposition reaction
and the Boudouard reaction, which give undesirable
carbon, are known to be exceptionally slow in the
absence of a catalyst, but both can be readily catalyzed
by many transition metals.23 Thermodynamic calcula-
tions5 showed that the extent of carbon deposition
during reforming decreases at higher reaction temper-
atures, in agreement with several experimental obser-
vations.2,13,24 These results suggest that CO dispropor-
tionation is the main contributor to carbon deposition
because it is exothermic and the equilibrium constant
decreases with increasing temperature. Despite these
evidences, there are disagreements concerning the
source of carbon deposition. Swaan et al.25 and Ef-
stathiou et al.26 showed by TPO with isotopic mixtures
that most of the carbon accumulated during reforming
reaction over Ni/SiO2 and Rh/Al2O3, respectively, is
derived from a CO2 molecule. Other authors claimed
that carbon is formed from methane, over a large variety
of catalysts, including Pt/Al2O3 and Pt/ZrO2.17,18,27,28 So,
there is not a consensus in the literature about the
origin of the coke formation during reforming conditions.
We tried to elucidate this question by investigating
the PtAl catalyst, which exhibited the fastest deactiva-
tion under stoichiometric conditions, in a more detailed
way. Stability tests were performed with an excess of
CO2 in the feed, as shown in Figure 3. It shows that a
surplus of CO2 improves the performance of the catalyst
and an excess of 50% is enough to reach good stability.
On the other hand, when methane flowed alone over
the catalyst at 1073 K, the maximum conversion was
only 0.8%, which suggests that PtAl is not active for CH4
decomposition. Therefore, it is possible to ascribe the
coke deposition to CO disproportionation because an
excess of CO2 favors the reverse reaction, which mini-
mizes carbon formation.
We also examined the behavior of Pt10Zr, which
showed the best stability under stoichiometric condi-
tions,15 with higher ratios of CH4/CO2, to accelerate the
catalyst deactivation. Stability tests under severe condi-
tions were carried out with CH4/CO2 ratios of 2:1 and
3:1, and the results are shown in Figures 4 and 5,
respectively. The Pt10Zr catalyst exhibited excellent
stability even under severe deactivation conditions.
With the CH4/CO2 ratio of 2:1, the rate of deactivation
was 0.15%/h, and with the ratio of 3:l, this rate
increased to 0.4%/h, based on CO2 consumption. These
deactivation rates are much lower than those reported
by Stagg-Williams et al.29 for Pt/ZrO2. In this case the
4684 Ind. Eng. Chem. Res., Vol. 41, No. 18, 2002
Figure 4. Stability test with Pt10Zr at 1073 K and a feed ratio
of CH4:CO2 ) 2:1. Reaction conditions: flow rates of CH4 ) 10
cm3/min, CO2 ) 5 cm3/min, and He ) 185 cm3/min.
Figure 5. Stability test with Pt10Zr at 1073 K and a feed ratio
of CH4:CO2 ) 3:1. Reaction conditions: flow rates of CH4 ) 10
cm3/min, CO2 ) 3.3 cm3/min, and He ) 187 cm3/min.
rate of deactivation was 1.5%/h during 23 h of reforming
reaction at 1073 K and the CH4/CO2 ratio of 2:1, when
the X(CH4)/X(CO2) conversion ratio was greater than
0.5. On the basis of the conversion rate, Stagg et al.16
proposed that the CH4 decomposition rate is initially
greater than the CO2 dissociation rate and that the CH4
decomposition is responsible for the deactivation of the
catalyst. In the present study, the X(CH4)/X(CO2) con-
version ratio was 0.47, only slightly lower than 0.5 due
to the reverse water gas shift reaction, whose influence
is small at high temperatures. It reinforces our previous
statement that CO disproportionation is determinant
for coke deposition because the presence of CO2 below
the stoichiometric value favors this reaction (2CO T C
+ CO2).
4. Conclusions
CO2 reforming of methane is strongly affected by the
nature of support oxides. The Pt/ZrO2/Al2O3 and Pt/ZrO2
catalysts presented very high stability compared to the
Pt/Al2O3 at 1073 K. The deactivation is primarily caused
by coke deposition surrounding the metal-support
perimeter, although carbon deposits are located basi-
cally on the support. The principal route of carbon
deposition is the CO disproportionation. The catalyst
with 10 wt % ZrO2 exhibited excellent stability even
under severe deactivation conditions.
Acknowledgment
M.M.V.M.S. and D.A.G.A. are grateful to FAPERJ
(Fundacao de Amparo a Pesquisa do Estado do Rio de Advances in the Conversion of Methane to Synthesis Gas. Catal.
Janeiro) and CNPq (Conselho Nacional de Pesquisa e
Desenvolvimento Cientifico, Brazil) for financial support
during this work.
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Received for review November 30, 2001
Revised manuscript received May 29, 2002
Accepted June 13, 2002
IE010970A