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Article history: Ce-promoted Ni/MgAl catalysts were synthesized by means of a methodology that involves the doping
Received 4 March 2009 of NiMgAl mixed oxides derived from hydrotalcites with [Ce(EDTA)] and subsequent thermal decom-
Received in revised form 12 October 2009 position. The effect of the nominal load of Ce in the catalytic performance of the materials was studied.
Accepted 13 October 2009
The solids were characterized by means of XRD, BET area, TPR-H2, TPD-CO2, chemical analysis by ICPs,
Available online 31 October 2009
TGA, SEM and TEM and were evaluated in CO2 reforming of methane at 700 C. The results indicate
the partial reconstruction of the periclase phase during the doping with [Ce(EDTA)] and the formation
Keywords:
of a mixture of crystalline periclase and uorite phases after the calcination. Catalysts with particle sizes
Hydrotalcites
Mixed oxide
of Ni0 between 5 and 9 nm were obtained. Ce presents a promote effect in the degree of reduction of Ni
Ce and the amount and strength of the basic sites. It was evident a benecial effect of cerium in the catalytic
Methane activity and selectivity of the doped materials. The increase of the nominal Ce load between 1 and 10%
Dry reforming causes no considerable effect in the catalytic activity and selectivity or in the size of crystallite in these
materials but in the inhibition of the coke formation. The catalysts show excellent catalytic performance
under drastic conditions of reaction and long operation times. The Ce-doped Ni/MgAl catalyst is stable
up to 100 h of reaction using a feed mixture of CH4/CO2/He 10/10/80 at 24 L g1 h1, up to 20 h of reaction
using CO2/CH4 20/20 at 48 L g1 h1 and up to 15 h of reaction using CO2/CH4 40/40 at 96 L g1 h1. The
lamentous coke formation is demonstrated on the surface of the catalyst when gas of dilution in the
reactants is not used. The developed method of synthesis becomes an interesting methodology for
obtaining catalysts for CO2 reforming of methane.
2009 Published by Elsevier Ltd.
1. Introduction for CO2 reforming, due to the low cost and availability of Ni metal
[517].
Syngas (H2/CO) is an important feed for oxygenated com- However, the major obstacle preventing commercialization of
pounds, FischerTropsch synthesis and it is a vital step in several this process is that, due to the endothermic nature of the process,
processes including gas-to-liquids and hydrogen production for a high operating temperature is required to obtain high conver-
reneries and fuel cells [1]. Three processes are generally used to sions [14]. In this way, the great problem for Ni catalysts is that
convert natural gas-to-syngas: steam reforming, CO2 reforming they suffer severe catalyst deactivation due to sintering, metal oxi-
and partial oxidation of methane [14]. Actually, much attention dation, and especially signicant coke formation [517]. Neverthe-
has been paid to the reaction of carbon dioxide and methane, less, it has been shown that a high dispersion of the metal species
known as dry reforming of methane because of a need for utiliza- over the support can limit the coke formation [1].
tion of methane from natural gas. Additionally, dry reforming of A great number of papers have shown that Ni promoted cata-
methane has suitable H2/CO ratio, which is favorable to Fischer lysts exhibit better activity and coking resistance [1,5,18,19].
Tropsch synthesis [14]. Among them, the addition of CeO2 has been studied extensively
Catalysts play important roles in this reaction and a lot of at- as an effective promoter. Its presence has other benecial effects
tempts have been made to develop active and stable catalysts on the catalyst performance, such as improving the dispersion of
[511]. Supported Ni catalysts are the preferred choice as catalysts the active phase [1821].
Ce-promoted catalysts with the presence of transition metals
have attracted increasing attention in recent years due to their
* Corresponding author. Fax: +57 1 316 5220. high oxygen storage capability [22]. It is well known that in Ce
E-mail address: ramolinag@unal.edu.co (R. Molina). oxide the elimination of lattice oxygen under reducing conditions
leads to the creation of anionic vacancies (CeO2x) correlated to BET surface areas were measured by nitrogen adsorption at
high lattice oxygen mobility, and such oxygen vacancy defects 195 C using a MICROMERITICS ASAP 2000 apparatus.
are proposed to be the reactive sites on the surfaces of metal oxides Chemical analysis of the solids was carried out by means of ICP
[23]. spectroscopy with an equipment TJA IRIS 1000 Radial ICP-AES.
Synthetic layered double hydroxide materials (also known as TPR-H2 proles were taken by means of a CHEMBET 3000
hydrotalcites) have found many applications due to their unique (QUANTACHROME) equipment tted with a thermal conductivity
physicochemical properties [24,25]. By additional modication, detector, following already reported methodologies [32,33]. The
such materials can be converted to catalyst precursors or directly samples (<250 lm) were previously degasied at 400 C for 1 h
to catalysts of many useful reactions [24]. in Ar and reduced at 10 C min1 using 10% (v/v) H2/Ar at
The conventional way to prepare Ni-containing MgAl mixed 0.38 mL s1. Tests were carried out under conditions granting re-
oxide catalysts via hydrotalcite precursors includes co-precipita- sults which are free from the effects of operation variables in the
tion of Ni2+, Mg2+, and Al3+ with a carbonate at basic pH (close to form and at maximal temperature (TM) for reduction proles.
11). Due to their nearly equal cation size, Ni2+ isomorphously re- Basicity measurements were performed by temperature pro-
places Mg2+ within brucite-like layers of hydrotalcites [24]. grammed desorption of CO2 (TPD-CO2) using CHEMBET 3000
Tsyganok et al. [2629] have reported that Ni or noble metals (QUANTACHROME). 100 mg of catalyst was pretreated in owing
could be introduced into MgAl LDH by co-precipitation, recon- He at 500 C for 1 h and cooled to room temperature. CO2 uptake
struction or anion exchange techniques using a pre-synthesized was measured by means 100 lL pulses of CO2 pure (99.9%). The
complex of Ni2+ with EDTA. Calcination of the resulting materials desorbed CO2 was measured in owing He gas with the ow rate
produced the mixed metal oxides which upon reductive pre-treat- of 50 ml/min at 10 C min1.
ment with hydrogen exhibited high, durable, and reusable catalytic Catalysts pre-treatment was carried out at 700 C (10 C min1)
activity in CO2 reforming of methane. for 1 h, with a ow of pure H2 at 40 mL min1 and then, cooled
We have recently reported the synthesis of hydrotalcites con- down under an Ar ow at 40 mL min1. TPR-H2 and TPD-CO2 tests
taining Ce by several co-precipitation methods [30]. The catalysts were performed at the conditions previously described.
showed high activity and selectivity, and good stability. Ce had a Thermogravimetric analysis of the catalysts after the reforming
catalytic activity promoting effect in these solids. reactions was carried out by means of a TA-INSTRUMENT 2950
In this paper, we report a novel method to synthesize Ce-pro- equipment, with 0.001 mg accuracy. The temperature was in-
moted Ni/MgAl catalysts from hydrotalcite-type precursors. We creased at 10 C min1 up to 800 C in nitrogen ow. After
will study the effect of the Ce nominal loads in the catalytic perfor- 10 min at 800 C pure oxygen was injected.
mance of the solids. Scanning electron microscopy (SEM) analyses were performed
by means of a FEI QUANTA 200 equipment, which features an en-
ergy dispersive X-ray microanalysis system (EDX).
2. Experimental part Transmission electron microscopy (TEM) analyses were per-
formed by means of a CARL ZEIZZ LEO-922 equipment. Specimens
2.1. Catalysts synthesis for TEM were prepared by standard techniques. The mean particle
P 3 P 2
diameter was calculated using equation d ni di = ni di , where
NiMgAl hydrotalcite was synthesized from the nitrates of ni is the number of particles and di is the characteristic particle
Mg2+, Al3+ and Ni2+ with Ni/Mg = 2 and (Ni + Mg)/Al = 3 ratios like diameter.
reported elsewhere [26,31]. The nitrate solution was added drop
wise to an aqueous solution of sodium carbonate, which was pre- 2.3. Catalytic tests
heated to 60 C. During co-precipitation, the slurry was vigorously
stirred while keeping pH at 10.5 by slow addition of a diluted solu- Catalytic tests were performed using 50 mg of the mixed oxide
tion of NaOH. After complete addition of the metal nitrate solution, in powder form (<250 lm) similar to a previously reported meth-
the suspension was stirred at 60 C for 1 h, followed by ageing at odology [16,34]. Catalyst was loaded into a tubular quartz reactor
the same temperature for 24 h without stirring. The solid was (6 mm of diameter) and the catalyst bed temperature was mea-
rinsed with deionized water and dried in air at 60 C for 24 h. sured by a thermocouple. The temperature increased up to
The dried solid was ground into a ne powder (<250 lm) that 700 C at 10 C min1 and the samples were reduced in situ with
was further calcined in air at 500 C (10 C min1) for 16 h to pro- pure H2 at 30 mL min1 for 1 h. After reduction the catalyst was
duce the mixed oxide. purged with He for 30 min at the same temperature and reagents
Aqueous solution of [Ce(EDTA)] was prepared at room temper- were injected. All activity tests were carried out under atmospheric
ature by drop wise addition of Ce3+ nitrate solution to tetrasodium pressure with variables feed composition of CO2/CH4/He and total
salt of EDTA dissolved in water at pH 10.5. Equimolar amount of feed ow rate. The reaction products were analyzed with a mass
sodium edetate was taken for Ce chelate formation. The mixed spectrometer connected on line (ThermoONIX).
oxide was suspended in the [Ce(EDTA)] solution with vigorous
stirring at room temperature. The metal load amounted to 0, 1, 3,
5 and 10 wt.% with relation to the weight of mixed oxide. After stir- 3. Results and discussion
ring during 24 h, the solid was separated by centrifugation, rinsed
with the deionized water, dried in air at 60 C for 24 h, and calcined In Fig. 1 the XRD of the hydrotalcite-type precursors (Fig. 1A)
in air at 500 C (10 C min1) for 16 h to produce the mixed oxide. and of mixed oxides obtained after the thermal decomposition of
The hydrotalcites were named HTX and the mixed oxides OMX, those precursors (Fig. 1B) are showed. It was possible to conrm
where X is the nominal load of Ce. the formation of the precursor layered double hydroxide con-
formed by Ni, Mg and Al since the diffraction prole showed the
typical signals of the carbonated phase of the hydrotalcite [25].
2.2. Characterization The diffractogram of the mixed oxide derived from the thermal
decomposition at 500 C of the initial hydrotalcite showed the for-
X-ray diffractograms were taken with a PHILLIPS PW1710 de- mation of an oxide with a periclase-type structure [2629]. Forma-
vice with a copper anode. tion of other types of segregated crystalline phases was not
594 C.E. Daza et al. / Fuel 89 (2010) 592603
Fig. 1. XRD for: (A) precursor hydrotalcites, (B) mixed oxides. .: hydrotalcite, N: CeO2, and d: periclase.
Table 1
proposed in this work, the reconstruction of the mixed oxide Ni,
Molar ratios of mixed oxides by ICPS. Mg and Al was obtained in the presence of the metallic complex
[Ce(EDTA)]. Wang and Lu [18] indicated that in Ni/cAl2O3, cata-
Catalyst Mg/Ni (Ni + Mg)/Al Ce/Ni Ce/Al
lysts, the CeO2 has a positive effect in the activity, stability and
OM0 2.0 3.3 suppression of the coke formation during CO2 reforming of meth-
OM1 2.0 2.9 0.015 0.015
OM3 1.9 3.0 0.031 0.032
ane, and that nominal loads between 1 and 5 wt.% are the suitable
OM5 1.9 2.8 0.048 0.046 ones. In this research nominal loads between 1 and 10 wt.% of Ce
OM10 2.5 3.0 0.075 0.063 are used which correspond to values lower than the anionic ex-
change capacity of hydrotalcites with the molar ratios used [25].
Fig. 1A shows the patterns of XRD of the hydrotalcites obtained
after the treatment with different loads of [Ce(EDTA)], which con-
observed suggesting that the mixed oxide made up of Ni, Mg and rms the reconstruction of the hydrotalcite structure, obtaining in
Al. this way low crystallinity hydrotalcites (meixnerite-type). Never-
Rives [25] indicated that the hydrotalcite-type compounds theless, reections corresponding to the initial oxide are still dem-
when calcined at moderate temperatures (300500 C) formed onstrated, suggesting the partial reconstruction of the material. In
mixed oxides that have the ability to reconstruct the layered struc- the same way, it is possible to observe the signals corresponding to
ture when they are exposed to solutions that contain anions. This CeO2 with uorite structure. Additionally, the absence of a shift in
method has been used to enrich the total metal composition since the reection at 11.4 2h is demonstrated indicating the non-inclu-
they are introduced like anions in the interlayer space, being par- sion of the complex (greater size) in the interlayer space of the
ticularly useful in the case of non-compatible cations with layers, reconstructed hydrotalcite. These results probably suggest that
due to their greater ionic size (example: cations from rare earths). the reconstruction takes place only in the outer edges of the grains
Nevertheless, the inclusion of metallic complexes as the only inter- of the mixed oxide.
layer species is difcult due to the necessity to remove and to avoid Likewise, the inclusion of species of [Ce(EDTA)] does not occur
the contamination with carbonates. In the method of synthesis in the interlayer spaces of the hydrotalcite where CO2 3 y OH
Table 2
Characterization of mixed oxides obtained.
Catalyst BET area (m2 g1) CO2 uptake (lmol/g)a (10) CO2 uptake (lmol/g)b (10) Reduction TM (C) Degree of reduction (%)c
OM0 128 106 57 870 86
OM1 78 134 78 850 97
OM3 76 129 85 850 98
OM5 65 144 90 845 95
OM10 60 143 82 865 98
a
T = 20 C 2.
b
After reduction at 700 C with pure H2.
c
Degree of reduction H2 consumption after pre-treatment
H2 consumption in TPR 100.
C.E. Daza et al. / Fuel 89 (2010) 592603 595
Fig. 2. TPR-H2 for mixed oxides: (A) without pre-treatment, (B) after reduction at 700 C with pure H2.
Fig. 3. TPD-CO2 for the mixed oxides. (A) Without pre-treatment and (B) after reduction at 700 C with pure H2.
anions are located, but it occurs preferentially in the external sur- In Fig. 1B the proles of XRD of doped mixed oxides with differ-
face of layers as suggested by Tsyganok et al. [27]. This result is ent loads of Ce can be observed. The analysis of the results shows
probably obtained because the amount of [Ce(EDTA)] used in that after the thermal decomposition of the reconstructed hydro-
the synthesis is less than the stoichiometric one, and/or to the dif- talcites the oxides thus obtained are made up of periclase phases
culty to remove CO2
3 and OH anions. (MgO type) and uorite phase (CeO2).
596 C.E. Daza et al. / Fuel 89 (2010) 592603
The decrease in the ratio (Mg + Ni)/Al after reconstruction is the re-
sult of variation in the calculation basis due to the incorporation of
Ce in the solid which was conrmed. Ce incorporation in the mixed
oxide increases with the nominal amount used. However, the
incorporation efciency drops. Thus, for a nominal value of
10 wt.% only 2.89% is incorporated (28.9% of efciency) whereas
for a nominal value of 1 wt.% only 0.68% is incorporated (68% of
efciency).
In Table 2 BET areas for synthesized mixed oxides are observed.
Materials with supercial areas between 60 and 80 m2 g1 were
obtained which are typical for this type of oxides produced by
co-precipitation and reconstruction [24]. It was noticed that after
the reconstruction process the supercial areas of the materials
doped with Ce decreased which can be due to the location of the
species of CeO2 in the pores of the particles.
In Fig. 2 the proles of TPR-H2 for mixed oxides with different
Ce loads are shown. The proles show a peak of asymmetric form
whose maximum corresponds to the reduction of Ni2+ to Ni0. It is
probable that the asymmetry of the peak towards lower tempera-
tures is due to the reduction of Ni3+ to Ni2+ whose existence is fea-
sible, given the conditions of synthesis and calcination. The highest
reduction temperatures were between 845 and 870 C indicating
the existence of species of NiO with strong interaction resulting
from the formation of the NiOMgO solid solution, characterized
by its high stability [15]. The proles of reduction of doped mixed
oxides with Ce show that there is a displacement of the tempera-
ture of maximum reduction towards smaller values with respect
to the mixed oxide without Ce (Fig. 1A).
Because the high temperatures of reduction of mixed oxides are
Fig. 4. Thermal stability for OM3. N: NiAl2O4, j: CeO2, and d: periclase.
greater than 840 C in all cases, it is feasible that the reduction of
In Table 1 the chemical analysis of the mixed oxides by ICP the catalysts, at 700 C with pure hydrogen for 1 h, is not complete
spectroscopy are observed. It is possible to see that the Mg/Ni after this pre-treatment. In order to determine in a semi-quantita-
and M2+/M3+ molar ratios are very similar to the nominal ones. tive way the degree of reduction of the catalyst, TPR-H2 tests were
Fig. 5. SEM images for (a) OM1, (b) OM3, (c) OM1Ce reduced and (d) OM3 reduced.
C.E. Daza et al. / Fuel 89 (2010) 592603 597
Fig. 6. TEM images for reduced catalysts, (a) OM0, (b) OM3 and (c) OM10.
Table 3
Dry reforming of methane at 700 C over Ce-promoted Ni/MgAl catalysts.
Weight of catalyst: 50 mg, WHSV = 48 L g1 h1, 20/20/60 CO2/CH4/He, ow: 100 mL/min. Reduction at 700 C for 1 h with pure.
598 C.E. Daza et al. / Fuel 89 (2010) 592603
carried out after the materials underwent the pre-treatment pro- facilitates the electron transfer, playing a transcendental role in
cess under the activation conditions used in this work. Fig. 2B oxide-reductive processes [20,23].
shows the proles of reduction obtained. Fig. 3 shows the proles of TPD-CO2 for mixed oxides doped
Indeed, the results show that the reduction of the catalyst is not with Ce (Fig. 3A) and for the catalysts reduced at 700 C with pure
complete under the conditions used in this work, which indicates H2 (Fig. 3B). In CO2 reforming of methane, the chemical nature of
that only part of the reducible Ni of the material will be active in the support plays a fundamental role in the catalytic performance
the reaction. The degree of reduction of mixed oxides when doped of the system; the supports with strong basic characteristics, favor
with Ce increases from 86 to 9598% demonstrating a benecial ef- the CO2 adsorption (molecule with acid characteristics), facilitating
fect (Table 2). In this way, it is possible to afrm that Ce promotes therefore the gasication of the obtained carbonaceous deposits
the reduction of Ni. Different authors have pointed out the role of during the reaction, whereas those with strong acidity favor the
the coexistence of the Ce3+/Ce4+ redox pair which promotes and growth of carbonaceous deposits [1]. Thus, the support becomes
Fig. 8. SEM images after reaction for: (a) OM1 20/20/60 CH4/CO2/He and (b) OM3 20/20/60 CH4/CO2/He. In gure (a), carbon lamentous is showed by circles.
C.E. Daza et al. / Fuel 89 (2010) 592603 599
and strong sites over the 700 C. The mixed oxide without Ce
shows three distinguishable signals between 100 and 300 C. An
intense signal close to 100 C is observed that corresponds to
weakly adsorbed CO2. In the case of solids with different Ce loads,
different proles characterized by a broad signal between 100 and
400 C are observed. The signals of desorption between 500 and
600 C and over 700 C, shift to higher temperatures after the dop-
ing with Ce, suggesting that it increases the strength of the basic
sites of the material.
Fig. 3B shows the proles of TPD-CO2 of the mixed oxides after
the reduction process with pure H2 at 700 C. A decrease of the
desorption signals is observed, this result is probably due to the
formation of Ni0 nanoparticles on the catalyst surface that blocks
the access towards the basic sites and also, to the possible change
induced in the porosity of the material after the thermal treatment.
The results show the disappearance of the signals at temperatures
higher than 700 C. It is also possible to appreciate that in the
materials doped with Ce the weak basic sites (100250 C) were
stable after the reduction, whereas in the case of the material with-
out Ce these basic sites are unstable. These results suggest that Ce
promotes the thermal stability of the basic sites of the catalyst. At
the same time, the information shown in Table 2 indicates that the
total basicity of mixed oxides and reduced mixed oxides is greater
when they are doped with Ce.
Xu et al. [20] state that the coexistence of Ce2O3 and CeO2 im-
plies electron transfer reactions that increase the inhibition po-
tential towards the carbon formation in the catalyst. The
authors afrm that during CO2 reforming process, CO2 is adsorbed
on the basic or redox centers and there it produces CO and CeO2
in a redox cycle. Afterwards, the CeO2 reacts with the carbon
deposited by dehydrogenization of the CH bond and oxidation
to produce Ce2O3 and CO2 again. That mechanism can explain
the increase in the total basicity of mixed oxides doped with
Ce, given the adsorption of CO2 that can occur in the anionic
vacancies of CeO2.
Fig. 9. Catalytic stability for OM3 catalyst. WHSV = 24 L g1 h1 and 10/10/80 CO2/ However, the variation in the load of Ce did not show a propor-
CH4/He, T = 700 C. tional increase in the basicity which suggests that Ce by itself does
not confer basicity to the material but acts in a synergic effect with
a source of active oxygen species with high reactivity that leads Mg to facilitate transport of the CO2 molecule to the basic site and
to a route by which the carbon formation is inhibited on the cata- this in turn to the metal support interface [35,36].
lyst surface [1,4]. Concerning this matter, the hydrotalcites are pre- Fig. 4 shows the XRD patterns for the mixed oxide doped with
cursors of the mixed metallic oxide synthesis with strong basic 3 wt.% of Ce calcined at different temperatures, during different
characteristics, especially, those hydrotalcites that contain Mg times and in the presence of static air (a representative material
[4,2429]. of the synthesized series was chosen in order to determine its ther-
Fig. 3A shows the existence of different types of basic sites in mal stability under different heating conditions). The mixed oxide
the mixed oxides. Thus, there are weak basic sites between 100 maintains its structural composition (periclase and uorite) up to
and 300 C, sites of average strength between 500 and 700 C, 900 C (5 h). When the material is calcined for 2 h at 1000 C, the
Fig. 10. TEM images and particle size distribution for OM3 oxide after 100 h of reaction. WHSV = 24 L g1 h1 and 10/10/80 CO2/CH4/He, T = 700 C.
600 C.E. Daza et al. / Fuel 89 (2010) 592603
Fig. 12. SEM images after reaction for: (a) OM3 CH4/CO2/He 10/10/80 for 100 h, (b) OM3Ce CH4/CO2 20/20 for 20 h and (c) OM3 40/40 CH4/CO2 for 20 h.
The stability in the dry reforming of methane of the catalysts size distribution between 6 and 14 nm and average particle diam-
doped with Ce was evaluated in a catalytic Test that was carried eter of 12.9 nm, a result that allows to suggest that the sintering of
out for 100 h. The catalytic test was carried out on the catalyst with the active phase of the catalyst during the reaction is very low and
3 wt.% of Ce (that was considered representative of the synthesized that is probably one of the reasons for the high activity. Addition-
series), and with a CO2/CH4/He 10/10/80 mixture at 24 L g1 h1. ally, the micrograph does not show the formation of amorphous
The results are shown in Fig. 9. It was observed a nearly complete carbon or carbon laments on the surface of the catalyst.
CH4 conversion while that for CO2 was greater than 95%, without The stability of the catalysts under drastic reaction conditions
loss of activity of the catalyst during the 100 h of reaction. The was evaluated on the solid with 3 wt.% of Ce in two catalytic tests
selectivities towards CO were between 80% and 90% and towards in which the space velocity of the reactants was changed without
H2 between 70% and 85%, obtaining a syngas with a H2/CO molar dilution gas. Test 1 was carried out with a 20/20 CO2/CH4 feed at
ratio between 0.65 and 1. The high catalytic conversions, which 48 L g1 h1 and test 2 was carried out with a 40/40 CO2/CH4 feed
were even greater than the ones determined by the thermody- at 96 L g1 h1. The results are shown in Fig. 11. The results of test
namic balance of the reaction under these conditions (92% of con- 1 demonstrated the excellent performance of the catalyst with CH4
version), can be the result of parallel reactions that can take place conversions 90 and CO2 8590% and selectivities towards CO
simultaneously in the process (RWGS and reaction of methane and H2 close to 100% for the production of a gas of synthesis with
polymerization) [1]. The larger values in the selectivities towards H2/CO molar ratios greater than 1 with values between 1.1 and 1.4.
CO, can be the product of RWGS process whereas the greater values The increase in the space velocity caused a slight reduction in the
in the CH4 conversions probably were due to the production of catalytic conversions; on the other hand, the production of a syn-
light hydrocarbons and carbon residues via decomposition of thesis gas with a H2/CO molar ratio less than 1 was observed (val-
methane. ues between 0.7 and 1).
Fig. 10 shows the distribution of particle size for the catalyst In test 1 no deactivation of the material was observed for 20 h of
with 1 wt.% of Ce after the catalytic test for 100 h. The catalyst pre- reaction. Probably the conversions of CH4 and H2/CO ratios greater
sented an homogenous distribution of Ni0 particles with a particle than one were the result of the formation of light hydrocarbons
602 C.E. Daza et al. / Fuel 89 (2010) 592603
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reforming of CH4 over LaNi based perovskite precursors. Appl Catal A NiCe catalysts supported on a modied mineral clay. Appl Catal A
2006;311:16471. 2009;364:6574.
[35] Daza C, Kiennemann A, Moreno S, Molina R. Stability of NiCe catalysts [37] Guo J, Lou H, Zhao H, Chai D, Zheng X. Dry reforming of methane over nickel
supported over Al-PVA modied mineral clay in dry reforming of methane. catalysts supported on magnesium aluminate spinels. Appl Catal A
Energy Fuels 2009;23:3497509. 2004;273:7582.