Applied Catalysis A: General 343 (2008) 10–15

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Applied Catalysis A: General

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Carbon dioxide reforming of methane over a metal modified Ni-Al2O3 catalyst

Adolfo E. Castro Luna *, Marı́a E. Iriarte
Facultad de Ingenierı´a y Ciencias Económico-Sociales INTEQUI-CONICET-UNSL, Av. 25 de Mayo 384, (5730) Villa Mercedes (S.L.), Argentina

A R T I C L E I N F O A B S T R A C T

Article history: CO2 reforming of methane over modified Ni-Al2O3 was studied. The influence of K, Sn, Mn and Ca on the
Received 21 September 2007 behavior of a Ni-Al2O3 catalyst, prepared by a sol–gel method, was studied. For this purpose, catalytic
Received in revised form 21 November 2007 activity and its resistance to coking were measured. The unmodified catalyst showed its effectiveness in
Accepted 23 November 2007
the dry reforming reaction of methane with low carbon deposition and high and constant catalytic
Available online 27 March 2008
activity during over 30 h of operation. The introduction of 0.5 wt.% of the above mentioned metals
showed, for the case of the K-modified catalyst, compared to the original catalyst, constant but slightly
Keywords:
less activity, and a lower carbon deposition after the same operation period. In the case of Ca, Mn and Sn, a
Methane dry reforming
Nickel-alumina catalyst
dramatic reduction of catalytic activity and a significant increase in carbon deposition were observed
K-modified Ni-Al2O3 catalyst during the period of time under study.
ß 2008 Elsevier B.V. All rights reserved.

1. Introduction or reduce the formation of carbon, through research into the

The CO2 reforming of methane (dry reforming) to produce
synthesis gas, reaction (1), has gained renewed interest in recent
years.
CH4 þ CO2 ! 2CO þ 2H2
This reaction plays a potentially important role in the industry
as well as the steam reforming reaction, especially due to the
generation of synthesis gas with a low H2/CO ratio that can be
preferentially used for the production of liquid hydrocarbons in the
Fischer Tropsch synthesis network.
The dry reforming reaction is accompanied by several side
reactions, of which the reverse water–gas shift reaction (2), the
methane cracking reaction (3) and the Boudouard reaction (4)
appears to be the most important:
CO2 þ H2 ! CO þ H2 O
CH4 ! C þ 2H2
2CO ! C þ CO2
Due to its availability and low cost, nickel is the most
appropriate catalyst for the reaction. However, the Ni-based
catalysts are readily deactivated by the deposition of carbon on the
active centers. This situation leads to the need of developing Ni
catalysts with improved activity and selectivity in order to prevent
* Corresponding author. Tel.: +54 2657 430980; fax: +54 2657 430980.
E-mail address: cstrln@fices.unsl.edu.ar (A.E. Castro Luna).
following aspects: (i) the nature of the support [1–7], (ii) the
support and catalyst preparation method [3,8–11], and (iii)
the addition of promoters [2,9,12,13]. In relation to the latter
variable, it can be mentioned that interesting points are the nature
of the promoter, and the amount used.
(1)
Hou et al. [3] studied the influence of Ca on the performance of
Ni/a-Al2O3 catalysts in the dry reforming reaction, reporting that it
depends upon the properties of the support and the amount of
added Ca. Small amounts of Ca increase the catalyst activity and
stability. Ca improves Ni diffusion, strengthens Ni-Al2O3 interac-
tion and delays Ni sintering. However, an excess of Ca promotes
carbon deposition, readily deactivating the catalyst.
The effect of alkali promoters (Na, Li, K) on Ni/MgO was studied
by Arena et al. [14], who reported that alkali promoters affect
the reducibility, the morphology, the active surface area and the
electronic properties of the catalyst. Choi et al. [15] studied the
(2) performance of Ni/Al2O3 catalysts modified by the addition of Co,
Cu, Zr, Mn, Mo, Ti, Ag and Sn. Compared to the unmodified catalyst,
(3) only Co, Cu and Zr showed a slight improvement in activity, while
the rest of the additives reduced the activity in dry reforming. The
(4) addition of Mn produced a noticeable reduction in carbon
deposition, with a small decrease in catalytic activity. Catalysts
calcined at high temperature showed a higher activity than those
calcined at a lower temperature. Stagg et al. [16] report the
promoting effect of Sn on Pt catalysts if special preparation
methods are used, resulting in the controlled placement of Sn on
the Pt particle, minimizing the promoter–support interaction. In
this paper, the effect of the addition of the metals K, Ca, Mn, and Sn
to a Ni-Al2O3 catalyst obtained via sol–gel is studied. The
preparation method and the pretreatment of the unmodified

0926-860X/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2007.11.041
 A.E. Castro Luna, M.E. Iriarte / Applied Catalysis A: General 343 (2008) 10–15
catalyst were selected to obtain small and homogeneous nickel
particle size, high metallic dispersion in the catalyst and high
resistance to sintering. The unmodified catalyst proved to be very
active, selective and stable in the methane dry reforming reaction
[17].
2. Experimental
2.1. Catalyst preparation
The unmodified catalyst was prepared by a sol–gel method.
Aluminum sec-butoxide and nickel 1-methoxy-2-propoxide were
used as precursors. Both reactants are hydrolyzed adding drop by
drop under mild stirring, on distilled water at 87 8C (molar ratio H2O/
total alkoxides = 97), to assure the formation of peptizable species
(boehmite), obtaining a pale greenish white suspension. Subse-
quently, an acid peptization with HNO3 (0.14 mol/mol total
alkoxides) at 87 8C, was developed. The colloidal solution obtained
is concentrated and vacuum-dried in rotary evaporator, and left to
gel in air, obtaining green plates of boehmite. The resulting material
was dried overnight at 100 8C and calcined in air at 850 8C for 10 h, to
enhance the NiO–Al2O3 interaction to form NiAl2O4. This constitutes
the catalyst precursor and has a nominal 14 wt.% nickel content. It
has been suggested that carbon deposition is closely related to the
catalyst structure. Chen and Ren [18] studied methane dry reforming
over Ni/Al2O3 and showed that carbon deposition is markedly
suppressed if NiAl2O4 is formed during the pretreatment procedure.
The modified catalysts were obtained by the method of
incipient wetness impregnation of the catalyst precursor with
the corresponding metallic precursor. KNO3, Ca(NO3)24H2O,
Mn(NO3)24H2O, and SnCl22H2O were used. In all cases, a metal
charge of 0.5 wt.% was used. The impregnated samples were dried
overnight at 110 8C and calcined in air at 850 8C for 12 h, as well as
the unmodified catalyst.
2.2. Catalyst characterization
2.2.1. Specific area and X-ray diffraction (XRD)
In order to determine the surface area of fresh and used catalysts,
a ChemBet 3000 model Quantachrome sorptometer was used. The
X-ray diffraction spectra were obtained with a Rigaku Geigerflex
diffractometer operated at 40 kV and 30 mA, employing Cu K
(l1 = 1.5405 nm) radiation and NaCl and quartz as external cali-
bration standards, velocity was 38/min and the range was 10–708.
2.2.2. Temperature-programmed reduction (TPR)
For the determination of the catalyst reduction behavior,
temperature-programmed reduction (TPR) experiments were
carried out. A conventional TPR–temperature-programmed hydro-
genation (TPH) set-up with a quartz tubular reactor with an inside
diameter of 6 mm was used. The samples (30 mg) were heated
from room temperature to 350 8C in a N2 flow until no desorption
gases were detected, the samples were then cooled to room
temperature and the carrier gas was replaced by the reaction
mixture (5% H2/N2) at a flow rate of 30 ml min1. A linear increase
in temperature from room temperature to 850 8C at a rate of
10 8C min1 was adopted. The amount of consumed H2 was
detected using a gas chromatograph (Shimadzu GC-14A) equipped
with a thermal conductivity detector and connected to a data
processor (Shimadzu C-R4A).
2.2.3. Temperature-programmed hydrogenation
Carbon deposition was characterized by the temperature-
programmed hydrogenation method, using the same device used
for TPR analysis. The used catalyst was placed in a fixed-bed quartz
11
tube (6-mm ID). The samples (20 mg) were heated from room
temperature to 850 8C at a rate of 10 8C min1 using pure H2
(30 ml min1). The signal corresponding to CH4 formation was
recorded by an FID detector in the same GC and data processor
mentioned above.
2.2.4. Temperature-programmed oxidation
The used catalysts were submitted to temperature-pro-
grammed oxidation (TPO) experiments to determine the amount
of carbon deposited on the catalysts. These experiments were
carried out in a Shimadzu TGA-51 thermobalance in an air
atmosphere at a heating rate of 10 8C min1 from room tempera-
ture to 1000 8C.
2.2.5. Transmission electronic microscopy (TEM)
Transmission electronic micrographs were taken with a JEOL
100 CX system, with a high tension voltage of 100 kV and a
magnification of 80 000, to investigate the surface morphology
and crystallinity of the reduced and used catalysts. The resolution
of this instrument is 6 Å. Moreover, particle size distribution was
obtained to calculate the mean particle sizes.
2.3 Catalytic activity
Methane–CO2 reforming was carried out in a fixed-bed flow
reactor. In the feed section, the reactants were passed through a set
of Brooks 5876A mass flow controllers. An undiluted gaseous
mixture was used. A quartz reactor (12 mm ID) heated by a furnace
with three independent heating zones was used, each with its own
proportional-integral-derivative (PID) temperature controller,
facilitating isothermal operation. The temperature profile along
the bed was measured by a sliding K-type thermocouple placed in a
thermowell located at the central axis of the reactor. The reaction
zone consisting of a mixture of catalyst and alumina serving as a
diluent has a length of 5 cm. Methane (99.99% purity) and
hydrogen (99.9%) were supplied by L’Air Liquide and carbon
dioxide (99.9%) by Argon. Typically 0.1 g of catalyst powder
(ground to 0.12–0.25 mm) diluted with inert alpha alumina of the
same particle size and in a dilution ratio of 1:20, was reduced in
situ in flowing H2 (30 ml min1) at 850 8C for 14 h prior to reaction.
Once the selected operation conditions were obtained, samples
were taken at 30 min intervals and analyzed by on-line gas
chromatography (Shimadzu GC3BT) using a thermal conductivity
detector and a gas sampling valve. A 2 m Carbosphere column and
argon as carrier gas were used to achieve the separation of
hydrogen, carbon monoxide, methane and carbon dioxide. The
data were processed with a Spectra-Physics 4600 Integrator. The
reforming of methane with CO2 was carried out at 750 8C, CH4/
1
CO2 = 1, W=F  CH4 ¼ 0:5 g h mol and 0.1 MPa.
3. Results and discussion
3.1. Surface area
The results of catalysts surface area are shown in Table 1. The
addition of modifiers produces a certain reduction in the area,
possibly not due to the low content of the modifier used, but to the
additional aqueous impregnation method developed. The used
catalysts, after 30 h of operation, show a decrease in the surface
area.
3.2. X-ray diffraction (XRD)
XRD patterns of the unmodified fresh catalyst, (Ni), and the
modified fresh catalysts obtained through impregnation with
12 A.E. Castro Luna, M.E. Iriarte / Applied Catalysis A: General 343 (2008) 10–15

Table 1
Catalyst surface area

Catalyst Catalyst designation Surface area (m2 g1)

Fresh catalyst Used catalyst

14%Ni-Al2O3 Ni 209 139

14%Ni-0.5%K-Al2O3 Ni-K 175 110
14%Ni-0.5%Ca-Al2O3 Ni-Ca 192 142
14%Ni-0.5%Mn-Al2O3 Ni-Mn 170 145
14%Ni-0.5%Sn-Al2O3 Ni-Sn 179 149

Fig. 2. XRD patterns of reduced catalysts. Ni8: metallic Ni.

used Ni, Ni-K and Ni-Ca catalysts, the carbon characteristic line is
not observed, although carbon was indeed detected by TPO.

3.3. Temperature-programmed reduction

Fig. 4 shows the TPR curves of the fresh catalysts (nomenclature

as indicated in Table 1). For the Ni catalyst, a unique band between
590 and 900 8C with a maximum located at about 825 8C is
observed.
In potassium and manganese-modified catalysts, Ni-K and Ni-
Mn, an extended band in the range between 760–905 8C and 690–
Fig. 1. XRD patterns of the fresh catalysts. A: NiAl2O4, O: NiO, g: g-Al2O3. 870 8C, respectively, is observed, with a maximum at about 820 8C.
Apart from this, a shoulder in a range between 590 and 689 8C is
calcium, manganese, tin and potassium, and calcined at 850 8C, are also observed in the potassium-modified catalyst, and between
shown in Fig. 1. From the diffractograms, it is hard to discriminate 660 and 760 8C in the manganese-impregnated catalyst.
between NiAl2O4 and g-Al2O3 as the reflections of these phases In the TPR experiments presented in Fig. 4 for the Ni-Sn and Ni-Ca
overlap. Both phases are amorphous, as evidenced by the extended catalysts, a unique band between 580–910 8C and 620–905 8C,
reflections observed. The following lines are observed at 2u = 31.2–
31.58; 2u = 45–45.78; 2u = 59–608; 2u = 65–668, which would
correspond to g-Al2O3 and NiAl2O4, and the line 2u = 37–37.38
would correspond to NiO, g-Al2O3 and NiAl2O4. The characteristic
peak of NiO (I/I0 = 100%) 2u = 43.178 (2, 0, 0) is not observed as can
be expected given the high calcination temperature used. This
would indicate that the highest nickel proportion is found in the
form of nickel aluminate spinel, as suggested by the peak
magnitude at 2u = 378, 458, 608 and 668, compared to the same
peaks in reduced catalyst diffractograms.
These observations match the results obtained from the TPR
experiments. The lines corresponding to Ca, Mn, K and Sn oxides
are not observed either, probably because they are found in very
low proportions.
Fig. 2 shows the XRD patterns of catalysts reduced ex situ at
850 8C. For reduced samples, the characteristic lines of metallic
nickel at 2u = 44–44.58 (1, 1, 1) and 2u = 51–51.58 (2, 0, 0) appear
and, at the same time, a decrease in the intensity of the lines at
2u = 37–37.48; 45–468; 59–608 and 65–678 is observed, indicating
the reduction of NiAl2O4.
In the XRD patterns of the used catalysts, Fig. 3, apart from the
characteristic lines of g-Al2O3 and Ni8, the line corresponding to
carbon at 2u = 25.7–25.88 is observed, which is considerably higher
for the Mn-modified catalyst, Ni-Mn, than for the Sn-modified one,
Ni-Sn, in accordance with the results of TPO measurements. For the Fig. 3. XRD patterns of used catalysts. C: carbon.
 A.E. Castro Luna, M.E. Iriarte / Applied Catalysis A: General 343 (2008) 10–15
Fig. 4. TPR curves (5% H2 in N2, 30 ml min1, 10 8C min1).
respectively, with a maximum of about 827 8C can be distinguished.
The broad reduction feature corresponds to nickel compounds
resulting from a very strong metal–support interaction. The
shoulder in Ni-Mn and Ni-K catalysts can also be associated with
metal–support interactions, although in a lower proportion.
A sample of pure NiO reduced under the same conditions shows
a unique peak with a maximum at about 390 8C, while a NiAl2O4
sample, also reduced under the same conditions, shows a unique
peak with a maximum at about 820 8C. It is also possible to observe
that the Ni-K catalyst, compared with Ni catalyst, shows an
improvement in the reducibility through a displacement of the
reduction curve maximum of about 25 8C. It seems, in this case,
that potassium modifies the interaction of nickel with the alumina
and consequently the reducibility of nickel species.
3.4. Temperature-programmed hydrogenation
Carbon deposition is a strong limitation in the carbon dioxide
reforming reaction [19–21]. The origin of the inactive carbon can
Fig. 5. TPH profiles of the catalysts after 30 h of CO2 reforming at 750 8C, CH4/
1
CO2 = 1, 0.1 Mpa, W=F  CH4 ¼ 0:5 g h mol .
13
be methane decomposition and/or CO disproportion. The structure
and energy of the carbon formed in a catalyst usually deviates from
ideal graphite. Several types of carbon formation, including
encapsulating carbon, pyrolytic carbon, and carbon whiskers
consisting of long filaments of carbon have been reported. Only
the two latter types of carbon lead to deactivation of the catalyst.
The reactivity of deposited carbon was also investigated by TPH.
Fig. 5 shows TPH profiles after CH4–CO2 reaction (30 h on stream).
Curves corresponding to the K and Ni-K catalysts do not show
carbon deposition. However, it was shown in the SEM micrographs
and in the TPO studies. Curves corresponding to the Ni-Mn, Ni-Sn
and Ni-Ca catalysts show the formation of large amounts of
carbonaceous material with the appearance of only one peak at
about 800 8C in the range of temperature studied. The SEM
micrographs (not shown) show the abundant formation of
filaments. On the other hand, carbon accumulation caused the
destruction of the catalyst, which was crushed to a particle size
smaller than 200 mesh.
3.5. Transmission electronic microscopy (TEM)
The TEM images of the metal-free catalyst and of the
potassium-containing sample (Ni and Ni-K, respectively), after
30 h on stream in the reforming reaction, are shown in Fig. 6. A
comparison between them confirms that a lower amount of carbon
is deposited on the sample with 0.5 wt.% potassium (Fig. 6B). In
addition, the same filamentous nature of the deposited carbon as
that of the potassium-free sample (Fig. 6A) can be observed. It was
also determined that, in both cases, the mean size of nickel
particles is between 5 and 7 nm. These facts indicate that the
modifier, under our experimental conditions, decreases neither the
amount of carbon deposited without modification in the size nor
the structure of the nickel particles, [22]. In conclusion, by adding a
Fig. 6. TEM images of used catalysts (after 30 h on stream) (A) Ni and (B) Ni-K.
14 A.E. Castro Luna, M.E. Iriarte / Applied Catalysis A: General 343 (2008) 10–15

Fig. 7. CH4 and CO2 conversion with time on stream, at 750 8C (30 h of reaction) for
Ni: (*) X CH4 , (*) X CO2 , for Ni-K: (&) X CH4 , (&) X CO2 .
low amount of potassium, it is possible to obtain a catalyst with a
small decrease in activity but with very low carbon deposition.
3.6. Catalytic activity
Figs. 7 and 8 show the data on catalytic activity for all catalysts,
expressed as methane and carbon dioxide conversion at 750 8C
versus the time on stream. In all cases, CH4 conversions were lower
than the corresponding CO2 conversion, probably due to the
influence of the secondary reverse water–gas shift reaction (2)
since water was found deposited in the condenser after long term
runs.
The catalysts denoted as Ni and Ni-K showed an initial step of
about 5 h increase in both conversions, reaching significant
stability (near to the thermodynamic equilibrium at the reaction
conditions) up to 30 h of operation. No deactivation has been
observed during this long reaction period. This means that the
deposited carbon does not deactivate the nickel active sites. This is
the case when the carbon deposited has a filamentous structure,
which can be observed in the TEM micrographs of Fig. 6. The
growth of carbon filaments occurs on a metal surface where the
active metal is carried on the top of the carbon filament and, as a
consequence, the catalytic activity remains constant since the
active metal is still accessible to the reactants.
Ni-Ca, Ni-Sn and Ni-Mn catalysts showed an initial stage of
conversion increase and, after reaching a maximum, a significant
deactivation period started.
Table 2 shows numerical data of catalytic activity at 750 8C for
the catalysts under study. Maximum conversion data and
conversion data obtained after 30 h of operation are included. In
the case of Ni and Ni-K catalysts, they correspond to stable data. In
Fig. 8. CH4 and CO2 conversion with time on stream, at 750 8C (30 h of reaction) for
Ni-Ca: (&) X CH4 , (&) X CO2 , for Ni-Mn: (*) X CH4 , (*) X CO2 , and for Ni-Sn: (~) X CH4 ,
(~) X CO2 .
the rest of modified catalysts, Ni-Ca, Ni-Sn and Ni-Mn, data
correspond to a stage of marked deactivation. This table also shows
data for the H2/CO ratio, where values lower than one can be
explained by the occurrence of the reverse water–gas shift reaction
(2).
Finally, the results obtained by TPO about the total amount of
carbon formed after 30 h of operation are shown. For the sake of
comparison, a normalized activity term (N.A.) was established. It
can be observed that carbon deposition was low for the unmodified
catalyst, Ni. For the Ni-K catalyst, carbon deposition was even
lower than for the unmodified catalyst, but with a decrease in the
conversion values shown.
On the contrary, carbon deposition increases in all the other
modified catalysts, which would account for the dramatic activity
decline, except for the Ni-K catalyst, for which carbon deposition
was even lower than for the unmodified catalyst, but with a
decrease in the conversion values shown.
Snoeck and Froment [23] mentioned that potassium can
migrate from the support to nickel particles, and be predominately
placed on their surface. Also they proposed that potassium, added
as a promoter, decreases the value of the lumped forward rate
coefficient for methane cracking. This effect was explained by a
reduction of the number of sites available for methane decom-
position as a consequence of the presence of potassium on the
metal surface.
By performing large-scale density functional theory (DFT)
calculations, Bengaard et al. [24] demonstrated that a stepped
nickel surface is more active than a surface with close-packed
terraces for hydrocarbon reforming reaction and, also, for carbon

Table 2
Catalyst activity for CH4–CO2 reforming

Catalyst Timea (h) Maximum conver- Final conversionc (%) H2/COc (mol/mol) Carbonc (mg/g cat) N.A.d
sionb (%)

CH4 CO2 CH4 CO2

Ni 5 84.7 90.8 84.7 90.8 0.97 60 1

Ni-K 5 81.3 86.6 81.3 86.6 0.4 <10 1
Ni-Ca 15 83.6 90.0 71.0 75.0 0.88 150 0.84
Ni-Mn 5 60.9 76.8 25.0 42.0 0.28 250 0.41
Ni-Sn 5 73.9 80.4 19.0 36.0 0.44 215 0.26

Reaction conditions: 750 8C, CO2/CH4: 1.0, W=F  CH4 : 0.5 g h mol1.
a
Time to reach maximum conversion.
b
Maximum conversion.
c
After 30 h operation.
d
Normalized activity: ratio of final CH4 conversion to maximum CH4 conversion.
 A.E. Castro Luna, M.E. Iriarte / Applied Catalysis A: General 343 (2008) 10–15
formation. Potassium and other additives are selectively located on
the step edges of the nickel surface. To prevent the nucleation of
carbon, a small fraction of active sites have to be blocked on the
stepped nickel surface. This blockage, however, does not stop the
reforming reaction because it can still take place on the unblocked,
less active sites of the nickel surface (close-packed terraces). Also,
it is well known [25,26] that potassium is a good catalyst for carbon
gasification.
The results obtained in this work with the K-containing
catalysts can be explained on the basis of these conclusions. A
fraction of potassium migrates from the support to the nickel
surface and it is located first on the step sites that are the most
active sites for the reforming reaction. Consequently, a low
potassium content produces a decrease in methane conversion.
The analysis of the reaction products (H2 and CO) reveals that
the presence of the modifier produces a decrease of the H2/CO ratio
(from 0.97 with Ni-Al2O3 to 0.4 with Ni-K-Al2O3). This result is a
consequence of the two effects of potassium mentioned above: the
blockage of Ni active sites for methane cracking (CH4 = C + 2H2)
and the enhancement of carbon gasification (2CO = CO2 + C).
In relation to carbon accumulation, Table 2 and TEM images
show that the addition of a small amount of potassium has an
important effect in reducing the amount of carbon deposited (from
60 mg C/g cat. for the unmodified catalyst to less than 10 mg C/g
cat. for the sample with 0.5 wt.% potassium).
In the case of the Ni-Ca, Ni-Mn and Ni-Sn-modified catalysts,
the situation seems different since after 30 h on stream they show
a significant reduction in activity and also important accumulation
of deactivating carbon. Dias and Assaf [9], studying dry reforming
of methane on a Ca-modified Ni/g-Al2O3 catalyst, explained the
lowering in the experimentally measured H2/CO ratio emphasizing
the role of the RWGS reaction, which becomes important at high
abundance of CO2 producing consumption of H2 and an increase in
CO. They also proposed that carbon deposition occurs through the
deposition of a paraffin polymeric –CH2– chain, which is slowly
transformed into a less reactive polyaromatic deposit, which tends
to form graphite [27], so the carbon accumulation occurs together
with hydrogen, decreasing the quantity of hydrogen in the product
in relation to CO. Also, the high temperature peak shown in our
TPH experiments can be assigned to amorphous and/or graphite
forms of carbon, not to filamentous carbon [28]. On the basis of
these observations, the results obtained in this work with the Ca-,
Mn-, and Sn-containing catalysts can be explained.
4. Conclusions
A Ni-Al2O3 catalyst obtained via a sol–gel method showed an
excellent performance in the reaction of methane dry reforming,
with high and stable catalytic activity. Small amounts of
carbonaceous residues were formed after 30 h on stream at
750 8C. The preparation method allowed obtaining a massive
catalyst with a small and homogeneous nickel particle size (TEM:
5–7 nm) and no effect of sintering. The severe pretreating
condition (calcination: 22 h at 850 8C) produced a high metal–
alumina interaction forming a spinel of nickel aluminate, which
15
after reduction (14 h at 850 8C) has been suggested to markedly
suppress carbon deposition [18].
The effect of the introduction of a 0.5 wt.% of the metals K, Ca, Sn
and Mn, compared with the original catalyst, was studied. In the
case of the Ca, Mn and Sn-modified catalysts, a dramatic reduction
of catalytic activity and a significant increase in carbon deposition
were observed during the period of time under study. The K-
modified catalyst showed low carbon and high stability of its
catalytic activity during 30 h of operation. Compared with the
unmodified catalyst, it showed a slight activity decrease of less
than 4% in methane conversion and more than 17% reduction in
carbon deposition. The activity remains practically constant for the
unmodified and the K-modified catalyst indicating than the carbon
deposits are mostly graphite filaments carrying the nickel particles
on the top. Our data confirm that the incorporation of potassium
hinders the accumulation of carbon on the catalyst surface,
increases the reducibility, probably modifying the metal–support
interaction, and modifies neither the size nor the structure of the
nickel particles. It has been proposed that potassium migrates from
the support to the surface of nickel and neutralizes a fraction of the
most active sites for the reforming reaction producing, as a
consequence, a decrease in methane conversion.
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