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I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 991 999

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journal homepage: www.elsevier.com/locate/ijhydene

Synthesis gas production from dry reforming of methane

over Ni/Al2O3 stabilized by ZrO2

Supaporn Therdthianwonga,, Apichai Therdthianwongb, Chairut Siangchina,

Sarayut Yongprapatc
a
Department of Chemical Engineering, Faculty of Engineering, King Mongkuts University of Technology Thonburi (KMUTT),
126 Pracha-Uthit Rd., Bangmod, Tungkru, Bangkok 10140, Thailand
b
Fuel Cells and Hydrogen Research and Engineering Center, King Mongkuts University of Technology Thonburi (KMUTT),
126 Pracha-Uthit Rd., Bangmod, Tungkru, Bangkok 10140, Thailand
c
The Joint Graduate School of Energy and Environment (JGSEE), King Mongkuts University of Technology Thonburi (KMUTT),
126 Pracha-Uthit Rd., Bangmod, Tungkru, Bangkok 10140, Thailand

art i cle info ab st rac t

Article history: The effect of zirconia as a promoter and catalyst preparation method for Ni/Al2O3 on
Received 20 December 2006 catalyst activity and coke inhibition was investigated for the reforming of CH4 by CO2. The
Received in revised form performance of the promoted catalyst prepared by co-impregnation and sequential
29 November 2007 impregnation methods with different loadings of ZrO2 was compared. The addition of
Accepted 30 November 2007 ZrO2 greatly improved the stability of Ni/Al2O3 catalyst in terms of coke inhibition by
Available online 8 January 2008 enhancing the dissociation of oxygen intermediates, which then react with carbonaceous
species formed over the metal. The rate of catalyst deactivation due to coke deposition
Keywords:
for the sequential impregnated catalyst was lower compared to the co-impregnated
CH4/CO2 reforming
catalyst at the same promoter loading. For the co-impregnated catalyst, ZrO2 loading did
Synthesis gas
not substantially affect the catalyst stability, while the low promoter loading in
Ni/ZrO2/Al2O3
sequentially impregnated catalyst was much more stable than the high loading. The 7%
Co-impregnation
ZrO2 loaded in Ni/Al2O3 by sequential impregnation yielded the most stable catalyst for a
Sequential impregnation
dry reforming reaction.
& 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction have been studied. Carbon deposition can be suppressed by

During the past decade, reforming of methane with carbon
dioxide to produce synthesis gas (H2 and CO) has received
much attention. The research effort has focused on catalyst
development to improve catalyst activity and resistance to
carbon formation so as to achieve stable long-term operation.
Among catalysts that have been studied, an inexpensive
nickel-based catalyst possesses high activity at the beginning
of the reaction but deactivates rapidly due to carbon
deposition [1,2]. To inhibit coke formation, several approaches
using noble metal-based catalyst, such as iridium, rhodium,
rhenium, palladium, and platinum [38]. However, in view of
their limited availability and high cost, it is more practical to
develop a stable anti-carbon nickel-based catalyst. This can
be done by using different types of supports or promoters.
The effects of the support phase on catalytic activity and
carbon deposition have been investigated by many research
groups [916]. Many promoters have been tested with Ni
catalysts decreasing carbon deposition and prolonging the life
of the catalyst [1720].

Corresponding author. Tel.: +66 2 470 9222x403; fax: +66 2 470 9325.
E-mail address: supaporn.the@kmutt.ac.th (S. Therdthianwong).
0360-3199/$ - see front matter & 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.11.029
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992 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y
The method of catalyst preparation is an alternative way to
achieve the carbon inhibition purpose. The effects of catalyst
preparation on catalyst activity and stability have been
observed by many researchers [11,2025]. Catalyst prepara-
tion includes both the preparation sequence and the reduc-
tion step. For example, the Pt/Ni/Al2O3 prepared by a
sequential impregnation method exhibited a better perfor-
mance in dry reforming of methane than that prepared by a
co-impregnation method [22]. Chen et al. [24] have indicated
that the Ni/CeO2Al2O3 catalyst derived from aerogel showed
higher catalytic activity and stability than that derived from
xerogel. For Ni/ZrO2, the catalyst prepared by impregnating
ultra-fine Zr(OH)4 particles with nickel nitrate showed higher
activity and stability for dry reforming than that prepared
using larger particles [25].
Zirconia has been recently used as either a promoter or a
support for Ni and Pt active components in many reactions
such as steam reforming, partial oxidation, and dry reforming
of methane [2530]. Its high coke resistance for catalyst
deactivation is the main reason for its use. Our earlier work of
dry reforming over Ni/ZrO2/Al2O3 has shown that the ZrO2
promoter addition produces a high anti-carbon nickel cata-
lyst. Nevertheless, the effect of ZrO2 loading sequence, co-
impregnation vs. sequential impregnation, was not clearly
observed when 10% ZrO2 was loaded and used in a short time
operation [31].
Here we report our continuing study to thoroughly inves-
tigate the effect of the ZrO2 loading sequence and amount in
long-run-time tested stability. The amount of ZrO2 at 5 and
15 wt% was used in the comparison between catalysts
prepared by co-impregnation and sequential impregnation
methods. For the purpose of finding a suitable ZrO2 amount, a
suitable preparation method was selected from the prelimin-
ary results in this investigation.
2. Experimental
2.1. Catalyst preparation
The unpromoted and ZrO2-promoted 15% Ni/Al2O3 catalysts
were prepared by a conventional impregnation method. The
NiNO3 2  6H2 O (supplied by Carlo Erba) and ZrONO3 2  xH2 O
(supplied by Aldrich) were used as active metal and promoter
precursors. The Al2O3 powder (JRC ALO 6, product of Japan
Chemical Co. Ltd.) was used as the support. Loading of each
precursor was conducted in two ways. One method is a so-
called co-impregnation method in which the aqueous
solutions of both precursors were mixed together before
adding the Al2O3 support. After the addition, water was
removed from the catalyst suspension by evaporation and
then air dried at 110 1C. This catalyst is denoted as xZrAlCI
where x is the percentage of ZrO2. Another loading method is
a sequential impregnation, where the zirconia precursor
was first impregnated into Al2O3, then the paste of the
promoter-support was dried and calcined in air at 110 and
500 1C for 3 h, respectively. Next, the zirconiaalumina (ZrO2/
Al2O3) powder was impregnated with nickel nitrate solution
followed by drying and calcining under the same conditions
outlined above. This catalyst is denoted as xZrAlSI. The
33 (2008) 991 999
15% Ni/Al2O3 obtained is designated as Ni/Al. Catalyst
powder samples were pressed into a disk, then crushed and
sieved into granules with a size of 1:0  0:1 mm.
The 15% Ni/ZrO2, denoted as Ni/Zr, was prepared by
decomposing ZrONO3 2  xH2 O in air at 500 1C for 3 h to obtain
the ZrO2 support. Then the support was impregnated with
nickel nitrate solution following the same procedure used
above.
2.2. Catalyst characterization
The BET surface areas of the catalysts were determined by
nitrogen physisorption at 77 K using an Autosorb I (Quanta-
chrome). The metal dispersion of the catalysts was obtained
by an H2 chemisorption technique in a Chembet 3000
apparatus (Quantachrome) at 298 K. All promoted and un-
promoted catalysts were characterized for their structures
before and after the dry reforming reaction using an X-ray
diffractometer (XRD, Phillips PW 1830) equipped with a CuKa
source having a scanning range of 201001 Braggs angle. The
XRD pattern obtained was further analyzed to estimate the
mean nickel metal crystallite diameter using the Scherrer
equation. The carbon form deposited on spent catalyst was
characterized using a JEOL 2010 transmission electron micro-
scope (TEM), and was obtained by temperature-programmed
oxidation (TPO/TGA) by passing O2 gas over a 0.01 g sample at
20 ml/min with a heating rate of 10 1C/min. The temperature
was increased from room temperature to 110 1C and main-
tained for 10 min before heating it to 900 1C.
2.3. Catalyst activity test
The experiment is divided into two parts. First we studied the
ZrO2 loading sequence. The 5 and 15 wt% ZrO2 were used to
obtain a good preparation method by comparing catalyst
stability. After that, we performed the necessary methods to
investigate the proper amount of ZrO2 loading in the pre-
paration technique chosen. The reaction over 15% Ni/ZrO2
catalyst was also performed for comparison.
The CH4/CO2 reforming reaction was conducted at atmo-
spheric pressure in a fixed bed reactor made from a 316-
stainless steel tube with an inner diameter of 1.27 cm. The
reactor tube was placed in a vertical tube furnace and
connected to the reaction gas mixture. The reactor temperature
was measured and controlled by a thermocouple positioned at
the middle of catalyst bed and a temperature controller.
The dry reforming of methane can be written as follows:
CH4 g CO2 g ! 2CO g 2H2 g
DG0298 170:74 kJ=mol.
Prior to conducting the catalytic reaction, the catalyst was
reduced in situ at 500 1C with 60% H2 in He flowing at a rate of
30 cm3/min for 3 h. Then the bed temperature was raised to
700 1C under flowing He. The catalyst performance was
measured by feeding the reactant gas mixture of CH4
(99.99%) and CO2 (99.999%) over the catalyst bed at a GHSV
of 18,000 cm3/g h. The CH4:CO2 mole ratio studied was kept
constant at 1:1.25 in all experiments. The reforming reaction
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was conducted until the catalyst was mostly deactivated, as promoted Ni/Al2O3 catalysts prepared by both co-impregnation
observed by the drop of pressure across the bed or by the flow and sequential impregnation methods. As the zirconia content
rate of the outlet stream. The reaction gas product was was increased, the BET surface areas of the promoted catalysts
analyzed using a Hewlett Packard 6890 gas chromatography decreased. The influence of low-surface area-ZrO2 on the
equipped with a thermal conductivity detector (TCD) and a reduction of surface area is more dominant in the case of the
Carbosieve SII column for the H2, CO, CO2, and CH4 gas promoted catalyst prepared by the sequential impregnation
composition analysis. method (xZrAlSI series) than that prepared by the co-impreg-
The conversion of methane and carbon dioxide in the nation method (xZrAlCI series). This is because in the xZrAlSI
reforming reaction was calculated as moles of reactant series, alumina pores are partially covered with zirconia prior to
reacted divided by mole of reactant fed, and the product Ni deposition, consequently reducing the penetration of nickel
yields were defined as into alumina pores, whereas zirconia and nickel were deposited
yH concurrently on the Al2O3 surface in the xZrAlCI series.
2 ;out
H2 yield %  100 The XRD patterns of the reduced xZrAlCI and xZrAlSI
2  yCH
4 ;in
catalysts examined are displayed in Fig. 1. The influence of
and the ZrO2 loading sequence on the phases present in the
yCO;out catalysts was not observed in all loadings. In both catalyst
CO yield %  100, series, two major phases of Al2O3 and crystalline Ni were
yCH yCO
4 ;in 2 ;in
detected, and none of the crystalline ZrO2 plane was observed
where yCH ;in and yCO ;in are inlet moles of CH4 and CO2, in the XRD patterns. As explained in our previous work [31],
4 2
respectively, and yCH ;out and yCO ;out are outlet moles of CH4 the ZrO2 may interact with Al2O3 and form a ZrO2Al2O3
4 2
and CO2, respectively. In addition, the molar H2:CO ratio was composite layer, which is an amorphous phase or a crystal-
obtained from the product gas composition: line phase with crystallite sizes smaller than the detection
limit of XRD.
mole of H2 produced The Ni particle sizes determined from the XRD spectra are
H2 : CO ratio .
mole of CO produced summarized in Table 1. The metal particle sizes correspond

The carbon deposited on the catalyst is indicated by coke

yield, which was calculated as the total mole of carbon
formed per total mole of carbon fed. The total moles of carbon
deposited were determined from the TPO/TGA weight change +
+ Ni Al2O3
of the spent catalyst described earlier. The coke yield is
defined as +
+ (f) +
Intensity (a.u)

Total mole of carbon formed

Coke yield %  100.
Total mole of CH4 and CO2 fed (e)
(d)

(c)
3. Results and discussion (b)
(a)
3.1. Characterization of catalyst before reaction
20 30 40 50 60 70 80 90 100
2 Theta (degree)
Table 1 summarizes the BET surface area, XRD-metal crystallite
size, and metal dispersion of the unpromoted and ZrO2- Fig. 1 XRD patterns of the reduced catalysts: (a) Al2O3,
(b) Ni/Al, (c) 5ZrAl(CI), (d) 15ZrAl(CI), (e) 5ZrAl(SI), and
(f) 15ZrAl(SI).

Table 1 Physico-chemical characteristics of the catalysts studied

Catalyst SBET cm2 =g XRD Ni crystal size (nm) Dispersion (%) Total hour of TOS

Reduced Spent

Ni/Al 189 7.5 8.2 7.7 7

5ZrAl(CI) 181 7.7 7.1 6.5 18
15ZrAl(CI) 167 8.4 7.9 5.8 22
5ZrAl(SI) 176 8.2 10.2 9.9 95
15ZrAl(SI). 137 9.6 9.1 6.7 23
Ni/Zr 47 19.8 26.4 1.6 55
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994 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 991 999

with the BET surface area results. The higher the surface area 3.2. Comparison of Ni/ZrO2/Al2O3 preparation method
of the support, the smaller the Ni crystal size. The particle
size of nickel on a ZrO2 support is the largest since the ZrO2 3.2.1. Reaction testing
has the lowest surface area. From the H2 chemisorption In order to follow the activity and stability of catalyst, gas
results, the %dispersion of Ni can be calculated as displayed production rate and feed conversions, as well as the average
in Table 1. It can be observed that the Ni dispersion is quite product yields, are plotted against time on stream (TOS) as
poor for the Ni/Zr catalyst. In addition, the metal dispersion shown in Figs. 2 and 3, respectively. The ZrO2 addition did not
of the sequential impregnated catalyst is higher than that seem to have an influence on catalyst activity, but did affect
of the co-impregnated catalyst. For both preparation catalyst stability. As clearly seen in the gas production rate
methods, the dispersion decreases as the ZrO2 loading and the average feed conversion curves, Ni/Al shows high
increases. The high amount of ZrO2 (15%) could greatly catalytic activity in the first 6 h, although later its perfor-
reduce the surface area of the support leading to low mance drops drastically. For the promoted catalysts at the
dispersion of nickel particles. In the co-impregnation method, same ZrO2 loading, the co-impregnated catalysts showed
nickel precursors and zirconia randomly adsorb on the higher CH4 conversion than the sequential-impregnated
surface, thereby the nickel particle size could be either large ones, while the CO2 conversion was less affected. These
or small. On the other hand, the nickel precursor adsorbs results are similar to our previous work where we performed
more uniformly on the ZrO2/Al2O3 support in the sequential an activity test for 5 h of TOS [31]. Both the H2 and the CO
impregnated catalysts containing 5% ZrO2 resulting in higher yields for all catalysts decreased as the degree of catalyst
metal dispersion. deactivation increased, corresponding to the activity results.

450
Gas production rate (ml/min)

400
350
300
250
200 Ni/Al
150 5ZrAl(CI)
15ZrAl(CI)
100 5ZrAl(SI)
50 15ZrAl(SI)
Ni/Zr
0

80
CH4 conversion (%)

60

40

20

80
CO2 conversion (%)

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100
Time on Stream (hr)

Fig. 2 Time on stream of (a) gas production rate, (b) CH4 conversion, and (c) CO2 conversion over the unpromoted and
promoted catalysts in CH4/CO2 dry reforming at 700 1C and CH4 : CO2 1: 1:25.
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The CO yield, however, was higher than the H2 yield in all reforming. All promoted catalysts resulted in a higher H2:CO
catalysts. This reflects the usual reverse watergas shift ratio than the unpromoted catalyst. The effect of ZrO2 on
reaction CO H2 CO2 H2 O taking place during CH4/CO2 catalyst stability, however, was more pronounced for the
catalyst prepared by the sequential impregnation than for the
catalyst prepared by the co-impregnation.
Considering the catalyst stability, it improves 210 times
that of the unpromoted catalyst depending on the loading
80
method and amount of ZrO2 promoter. For example, the
Ni/Al
5ZrAl(CI) lifetime of the co-impregnated 5ZrAl(CI) and 15ZrAl(CI)
60 15ZrAl(CI)
H2 Yield (%)

5ZrAl(SI) catalysts and the sequentially impregnated 5ZrAl(SI) and

15ZrAl(SI) 15ZrAl(SI) catalysts were extended to approximately 2095 h.
40 Ni/Zr
The stability improvement of the promoted catalyst was
20 confirmed by determining the coke formation rates during
the reaction period as depicted in Fig. 4. It was observed that
0 all ZrO2-promoted catalysts produced at least 2.5 times less
coke than the unpromoted catalyst. This stability enhance-
80 ment could be the result of ZrO2s ability in enhancing CO2
dissociation giving oxygen intermediates that facilitate the
60
CO Yield (%)

40

C Al2O3 + Ni o NiO
20

0
Intensity (a.u)

1.0 + + (e)
0.8 (d)
0.6 (c)
H2:CO

0.4 (b)
0.2
(a)
0.0
0 10 20 30 40 50 60 70 80 90 100 20 30 40 50 60 70 80 90 100
Time on Stream (hr) 2 Theta (degree)

Fig. 3 Time on stream of (a) H2 yield, (b) CO yield, and Fig. 5 XRD patterns of the spent catalysts: (a) Ni/Al,
(c) H2/CO ratio over the unpromoted and promoted catalysts (b) 5ZrAl(CI), and (c) 15ZrAl(CI), (d) 5ZrAl(SI), and
in the CH4/CO2 dry reforming reaction. (e) 15ZrAl(SI) after the CH4/CO2 dry reforming reaction.

0.1
0.089

0.08
Coke (g Coke/g cat. hr)

0.06

0.04 0.036
0.033 0.032

0.02

0.006
0.001
0
Ni/Al 5ZrAl(CI) 15ZrAl(CI) 5ZrAl(SI) 15ZrAl(SI) Ni/Zr

Fig. 4 Coke yield on the Ni/Al, xZrAlCI and xZrAlSI catalysts after the CH4/CO2 dry reforming reaction.
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996 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y 33 (2008) 991 999

400 nm 400 nm

400 nm 400 nm

400 nm 400 nm

Fig. 6 TEM images of the spent catalysts: (a) Ni/Al, (b) 5ZrAl(CI), (c) 15ZrAl(CI), (d) 5ZrAl(SI), (e) 15ZrAl(SI), and (f) Ni/Zr.

Table 2 Characteristic and coke formation rate over the

removal of carbon formed from CH4 decomposition and the
sequential impregnated catalysts after CH4/CO2 reform-
ing Boudouard reaction on the metal. The oxygen intermediates
could inhibit the coke formation in a way similar to the
mechanism proposed [28,30]:
Catalyst Metal Coke rate Total hour
dispersion g C=gcat h of TOS
CO2 2S 2S ! CO2S 2O2S,
(%)
CHx 2S O2S x  1S ! CO2S xH2S.
3ZrAl(SI) 7.5 0.012 49
7ZrAl(SI) 8.5 0.0026 130 Additionally the high Ni dispersion also contributes to the
high stability of the 5ZrAl(SI) catalyst.
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The deactivation rate of the three groups of catalysts was in 3.3. Investigation of ZrO2 loading in sequential
the following order: Ni=Al4xZrAlCI4xZrAlSI. The catalysts impregnated catalysts
prepared by the co-impregnation method were less
resistant to coke formation than those prepared by the Since sequential impregnation could produce more stable
sequential method. Using the sequential impregnation, Ni is catalysts than co-impregnation at 5% ZrO2, the more prom-
located near the ZrO2 where dissociation of oxygen ising ZrO2 loading at lower (3%, 3ZrAl(SI)) and higher
intermediates is promoted; the reaction between these
intermediates and the carbon species deposited is thus
enhanced. On the other hand, Ni is positioned near both
the ZrO2 and the Al2O3 surfaces. This result is also found in 80
the preparation of Pt/Ni/Al2O3 by Tomishige et al. [22]. 3ZrAl(SI)

CH4 conversion (%)

7ZrAl(SI)
Increasing the ZrO2, however, reduces the surface area of 60
the support, lowering the dispersion and stability of the
catalyst. 40
The activity and stability tests of Ni/Zr were also performed
20
in comparison and their results are shown in Figs. 2 and 3.
The stability of the catalyst is poorer than the promoted 0
catalyst but much better than the Ni/Al with inferior activity,
which could be attributed to the substantially low surface
80
area of Ni/Zr (see Table 1). This result is similar to findings
from previous studies [21,32]. The lowest catalytic activity 60
and stability of the Ni/Zr catalyst are due to its lowest Ni H2 yield (%)
dispersion and largest Ni particle size. 40

20
3.2.2. Characterization of catalyst after reaction
Coke deposition is the main cause of catalyst deactivation, as 0
can be seen by the XRD spectra and TEM images of spent
catalysts displayed in Figs. 5 and 6, respectively. The XRD 80
peaks of all spent catalysts mainly matched with carbon (at 2y
60
CO yield (%)

of 26.51), Al2O3 crystalline Ni (at 44.51, 521, 761, 931) and some
NiO (at 37.21, 43.51), which is similar to what was observed 40
with short operation time [31]. Comparing the nickel metal
crystal size of the promoted catalysts before and after the 20
reaction, it seems to be influenced by the reaction exposure
0
time. The metal crystal sizes of the unpromoted catalysts
0 20 40 60 80 100 120 140
exposed to the reaction for fewer than 25 h were insignif-
Time on Stream (hr)
icantly increased. This is in contrast to the 5ZrAl(SI) exposed
to the reaction for 95 h, which led to a slight increase in Fig. 7 (a) CH4 conversion, (b) H2 yield, and (c) CO yield as a
crystal size (see Table 1). The TEM images of both Ni/Al2O3 function of TOS over 3ZrAl(SI) and 7ZrAl(SI) catalysts in the
and promoted catalysts illustrate a number of graphitic fibers dry reforming reaction.
and deposits. Graphitic fibers and deposits in Ni catalysts
after dry reforming at the same temperature were previously
reported [33]. Furthermore, we observed that some of the Al2O3
C Ni NiO
large nickel particles detached from the support due to
segregation of metal particles. For the used Ni/ZrO2 catalyst,
a low amount of carbon was observed, resulting from the +
Intensity (a.u)

o
poor activity of the catalyst, corresponding to the activity and
+ + (d) +
coke rate results (see Fig. 4). The major cause of deactivation
in the Ni/Zr catalyst arises from sintering of nickel observed
from a number of large metal particle sizes, as confirmed by (c)
XRD and TEM results. This could be explained by the (b)
observation that in a low porous support (low BET surface
area), the metal particles can distribute less than in a high (a)
porous support.
20 30 40 50 60 70 80 90 100
As a result, the catalyst prepared by the sequential method
2 Theta (degree)
showed more potential to improve catalyst stability of coke
formation than the one prepared by co-impregnation. The Fig. 8 XRD patterns of the reduced catalysts: (a) 3ZrAl(SI)
sequential impregnation was further investigated to deter- and (b) 7ZrAl(SI), and spent catalysts: (c) 3ZrAl(SI) and
mine the suitable ZrO2 loading. (d) 7ZrAl(SI).
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998 I N T E R N AT I O N A L J O U R N A L O F H Y D R O G E N E N E R G Y
400 nm
Fig. 9 TEM images of the spent catalysts: (a) 3ZrAl(SI) and (b) 7ZrAl(SI).
(7%, 7ZrAl(SI)) values by sequential impregnation was further
examined. Both catalysts could improve catalyst stability,
although the 3% ZrO2 addition to the 15% Ni/Al2O3 did not
improve the metal dispersion, while the 7% promoter led to
better nickel metal dispersion than the unpromoted catalyst,
as shown in Table 2. The CH4 conversion and product yields of
both catalysts compared in Fig. 7 show that the 3ZrAl(SI)
catalyst was more active but much less stable than the
7ZrAl(SI) catalyst. The 3ZrAl(SI) was stable for up to 49 h
before completely deactivating, while the 7ZrAl(SI) was
maintained for more than 130 h without a sign of serious
deactivation. Comparing between the 5ZrAl(SI) and 7ZrAl(SI)
catalysts, the TOS of the 7ZrAl(SI) was higher than that of the
5ZrAl(SI), though the metal dispersion of 7ZrAl(SI) was
slightly lower. As a result, the dispersion of nickel metal
was not a decisive factor influencing the stability of the
promoted nickel catalyst as also previously discussed by
Wei et al. [25].
The reduction of coke formation on the sequential im-
pregnated catalyst (7ZrAl(SI)) was confirmed by the XRD
results and coke formation rate demonstrated in Fig. 8 and
Table 2, respectively. The XRD features associated with Ni and
Al2O3 were observed in both the reduced and the spent
catalysts, while carbon and NiO phases derived from CH4
decomposition and CO2 dissociation, and the oxidation of Ni
particles, respectively, were additionally detected. Similar to
the previous results, the coke filaments and deposits were
detected on the spent catalysts but to a lower extent for the
7ZrAl(SI) catalyst as presented by the TEM images in Fig. 9.
The 7% ZrO2 was suitable to inhibit coke formation to
stabilize the Ni/Al2O3 in CH4/CO2 reforming.
4. Conclusion
From this investigation ZrO2 was found to improve the stability
of the 15% Ni/Al2O3 catalyst deactivated by carbon formation.
The Ni/Al2O3 promoted with ZrO2 was much more stable than
the unpromoted catalyst, although its activity decreased. The
catalysts prepared using the co-impregnation method were
33 (2008) 991 999
400 nm
less resistant to coke formation than those prepared by the
sequential method. It is expected that Ni is more uniformly
distributed and positioned close to the ZrO2, where oxygen
intermediates are dissociated and react with carbon species
afterwards in the sequential impregnated catalyst. In contrast,
Ni is randomly dispersed and can be attached to both ZrO2 and
Al2O3 in the co-impregnated catalyst. Thereby, the dissociated
oxygen intermediates as well as the gasification of coke
species were less enhanced. Increasing the ZrO2 further,
however, led to a reduced surface area and dispersion of the
catalyst and a lowering in the stability of the catalyst. Based on
the stability results, 7% ZrO2 was the optimal amount for
stabilizing the 15% Ni/Al2O3 catalyst in CH4/CO2 reforming
reaction under these conditions.
Acknowledgments
The authors gratefully acknowledge the Energy Planning and
Policy Office (EPPO) of Thailand and the National Research
Council of Thailand (NRCT) for the financial support of this
research. We would like to thank the National Metal and
Material Technology Center of Thailand (MTEC) for the TEM
service provided.
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