Journal of Natural Gas Chemistry 12(2003)1722

CO2 Reforming of CH4 over Nickel and Cobalt Catalysts Prepared from La-Based Perovskite Precursors
Jianjun Guo, Hui Lou , Yinghong Zhu, Xiaoming Zheng
Institute of Catalysis, Zhejiang University, Hangzhou 310028, China [Manuscript received January 24, 2003; revised March 11, 2003]

Abstract: Four perovskite-type complex oxides (LaNiO3 , La2 NiO4 , LaCoO3 and La2 CoO4 ) were successfully prepared using two sol-gel methods, the Pechini method (PC) and the citric acid complexing method (CC). The catalysts were characterized by XRD and TPR. After reduction, the activity of the catalysts in the CO2 reforming of methane was tested. Ni-based catalysts from La2 NiO4 precursors were the most active and stable catalyst after calcination above 850 , which gave a methane conversion of 0.025 mmol/(gs) for those prepared by the PC method and 0.020 mmol/(gs) by the CC method. It was proposed that the well-dened structure and lower reducibility is responsible for the unusual catalytic behavior observed over the pre-reduced La2 NiO4 catalyst. Key words: carbon dioxide reforming, methane, syngas, perovskite oxide, sol-gel preparation, nickel catalyst, cobalt catalyst

1. Introduction Carbon dioxide reforming of methane has received considerable attention because both CH4 and CO2 , greenhouse gases contributing to global warming, can simultaneously be converted to syngas for the FischerTropsch synthesis of long-chain hydrocarbons [1,2]. The major drawback of this reaction, however, is the catalyst deactivation caused by carbon deposition arising from methane decomposition and the disproportionation of carbon monoxide. Noble metal-based catalysts have been found to be less sensitive to carbon deposition [24]. Considering the high cost and limited availability of noble metals, it is more practical to develop an eective base metal catalyst with high activity and carbon resistance. It has been suggested that a high dispersion of the metal species over the support can reduce the coke formation [5]. One promising method for controlling the metal particle sizes is using the oxide support itself as a source of small metal particles [6]. Shiozaki et al. recently used CaTiO3 or BaTiO3 perovskites

containing a small amount of Ni in the Ti sites as the precursor to obtain highly dispersed and stable Ni metals in situ, which results in high activity during the partial oxidation of CH4 to syngas and sustainability against coke formation [7,8]. Choudhary et al. reported that complex oxides, such as LaNiO3 , La0.8 Ca(or Sr)0.2 NiO3 and LaNi1x Cox O3 (x=0.2 1.0), with a perovskite structure were resistant to coking [9]. Hayakawa et al. [10] also reported that the reaction was accelerated when CO3+ or Ni3+ in the perovskite-type oxide Ca1x Srx Ti1y My O3 (M=Co, Ni) was reduced to the metallic state by the reaction of methane with carbon dioxide . In addition, the carbon deposition can be suppressed by the addition of a basic metal oxide (e.g. MgO or CaO) [6,11]. Recent results claimed that Ni/La2 O3 [12] and Ni/La-Al2 O3 [13,14] exhibited good activity and stability. Meanwhile, Wu et al. examined the LaBO3 (B=Co, Ni, Fe and Cr) as catalysts for CO2 reforming of methane to syngas, which produced a high level of activity [15]. To date, few papers have studied perovskite La2 BO4 and LaBO3 (B=Co,

Corresponding author.

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2. Experimental 2.1. Catalyst preparation The perovskite oxides, LaBO3 and La2 BO4 (B=Co, Ni), were prepared by the sol-gel method, namely Pechini method (PC) [16] and citrate acid complexing method (CC) [17]. In the PC method, a stoichiometric amount of nitrates was dissolved into de-ionized water. 90/10 mole ratio of citric acid/ethylene glycol was rst dissolved in de-ionized water and then mixed with the nitrate solution. The solution was heated at 90 while stirring until it turned into a gel. The gel was then dried at 350 , and the resulting resin was pulverized and pelleted prior to calcination at dierent temperatures (i.e. 440 , 520 , 850 or 1,000 ). In the CC method, the nitrate solution was mixed with appropriate stoichiometry, and the excess citric acid was added after heating the solution to 80 . The temperature was held constant until the solution was very dense and a resin formed. The resulting polymer was calcined in the same way as in the PC method. All precursors were reduced at the given temperature before being used in catalytic performance testing.
Table 1. Precursor LaNiO3 LaNiO3 La2 NiO4 La2 NiO4 LaCoO3 LaCoO3 La2 CoO4 La2 CoO4

2.3. Catalyst characterization The crystal structure of the catalysts before and after the reaction was determined by X-ray powder diraction (XRD) in a Rigaku D/max-IIIB apparatus using Cu K radiation at 30 kV and 20 MA. Diraction peaks recorded between 20o and 70o have been used to identify the structure obtained. The reducibility of the precursors was characterized by the temperature-programmed reduction technique (TPR). The reactor was heated from room temat a linear heating rate of 20 perature to 800 /min in 10%H2 /N2 (30 ml/min). 3. Results and discussion Before being used as catalysts in the CO2 reforming of methane, four perovskite-type precursors (LaNiO3 , LaCoO3 , La2 NiO4 and La2 CoO4 ) were prereduced at 500 in an H2 ow for 1 h. Table 1 shows the activity and stability of the catalysts. Co-based catalysts were less active than the Ni-based catalysts as also observed over supported catalysts [1]. The

Catalytic performance of dierent catalysts after calcination at 850 Preparation method PC CC PC CC PC CC PC CC Conversion (%) CH4 68.48 57.30 65.62 64.13 12.82 12.45 9.89 9.90 CO2 75.96 65.76 73.83 64.65 25.24 21.27 18.10 17.21 Selectivity (%) H2 97.89 94.32 92.67 87.65 65.73 66.81 56.21 55.42 CO 98.45 94.78 99.98 91.71 98.28 97.52 98.97 98.66

* The results were obtained after ca. 15 min of reaction. The relative activity at /a0 , where a110 , a360 and a0 are CH4 conversion rate at 110, 360 and 15 min, respectively.

Ni) used as catalyst precursors and their correlation to CO2 reforming of methane. This paper further investigated CO2 reforming of methane catalyzed by reduced LaBO3 and La2 BO4 (B=Co, Ni) compounds prepared by two sol-gel methods. Among them, the Ni catalyst from K2 NiF4 -type perovskite oxides, La2 NiO4 , exhibits a high activity and rather high stability.

2.2. Catalyst test The CO2 reforming of methane was carried out at 700 and atmospheric pressure using about 20 mg of catalyst (if not mentioned specically) in a xedbed quartz reactor (ca. 4 mm i.d.). The ow rate of the reactants was 30 ml/min, and the products were analyzed by an on-line gas chromatograph equipped with a TCD using a Porapak-Q column.

and reduction at 500 a110 /a 0 1.18 0.98 1.09 0.93 0.54 0.46 0.51 0.52

a360 /a 0 1.13 0.50

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Figure 1. The CO2 reforming of methane on nickel catalysts using La2 NiO4 as precursors prepared by the PC method (a) and the CC method (b) Catalyst weight: 0.02 g, gas ow rate: CH4 /CO2 =10:10(ml/min) (1) H2 , (2) CO, (3) CH4 , (4) CO2

The activity of the CO2 reforming of CH4 over pre-reduced La2 NiO4 catalysts was sensitive to the calcination temperature of the precursors, and that inuence of calcination temperatures is shown in Figure 2. Upon increasing the calcination temperature, the reaction activity and stability increased accordingly. As can be seen in the XRD and TPR exper-

activity and selectivity in the steady state were found to decrease in the order: LaNiO3 >La2 NiO4 LaCoO3 >La2 CoO4 . This may be due to the low reducibility of the Co-based perovskites under pretreated conditions (Figure 5). In the reaction on pre-reduced LaNiO3 catalysts, the conversion of CH4 and CO2 increased with the time on stream, but the rate of coke formation over prereduced LaNiO3 catalyst was so high that the reactor was completely plugged after 110 min. The situation was similar over the pre-reduced LaCoO3 catalyst, on which the reactor was plugged after 112 min. However, no carbon was detected on the pre-reduced K2 NiF4 -type perovskite catalysts, namely La2 NiO4 and La2 CoO4 . This may be attributed to the large number of active sites available on pre-reduced LaBO3 -type catalysts compared to pre-reduced La2 BO4 -type catalysts. The NiO6 octahedron in the LaNiO3 structure is in a threedimensional arrangement, while it is two-dimensional in La2 NiO4 because it is separated by a La-O rock-salt layer along the c-axis [17]. So the eect of preventing Nio from agglomerating by LaOx varies as illustrated by Li et al. [18], and this maybe the main cause of the large amount of carbon deposited on LaBO3 -type

catalysts because carbon tends to accumulate on large Nio and Coo particles [2]. Figure 1 shows the conversion and selectivity on pre-reduced La2 NiO4 prepared by the PC and CC methods. Consequently, after pre-reduction at 500 with pure hydrogen, the catalysts prepared by the PC method showed a higher activity than those prepared by the CC method. The reaction rates of CH4 and CO2 on the former were 0.025 and 0.021 mmol/(gs), respectively, while they were 0.02 and 0.018 mmol/(gs) on the latter. The formation of H2 and CO followed the same sequence as CH4 and CO2 consumption. Furthermore, the reforming reaction on the catalyst prepared by the CC method stopped after about 250 min on stream due to coke accumulation, while the reaction on that from the PC method remained stable even after 500 min. As illustrated by XRD (Table 2), the catalysts prepared by the CC method contained a small amount of NiO and LaNiO3 apart from the La2 NiO4 phase that may cause large nickel cluster formation because NiO will be completely reduced at below the pre-reduction temperature applied. This contributes to the large amount of coke deposition on the catalysts prepared by the CC method.

iments (Table 2 and Figure 3), the rise of the calcination temperature led to better-arranged structures and less amorphous NiO phases. Catalysts reduced from single phase La2 NiO4 with well dened perfor 10 ovskite structures upon calcination at 1,100 hours showed the lowest reducibility, highest reforming activity and remained constant during the 500 min

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test. In contrast, catalysts reduced from those calcined at 440 and 520 showed the lowest stability, and the reaction was stopped after approximately 3 hours due to coke accumulation on catalyst surface.

Table 2. XRD results for perovskite catalysts prepared by PC and CC method Material LaNiO3 LaNiO3 La2 NiO4 La2 NiO4 LaCoO3 LaCoO3 La2 CoO4 La2 CoO4 * Weak XRD peaks Calcination temperature PC

Preparation methods CC LaNiO3 , NiO LaNiO3 , NiO, La2 O3 La2 NiO4 , NiO , LaNiO 3 La2 NiO4 , NiO , LaNiO 3 LaCoO3 , Co3 O4 LaCoO3 , Co3 O4 La2 CoO4 , LaCoO , La2 O 3 3 La2 CoO4 , LaCoO , La2 O 3 3 LaNiO3 LaNiO3 , NiO, La2 O3 La2 NiO4 La2 NiO4 LaCoO3 , Co3 O 4 LaCoO3 , Co3 O 4 La2 CoO4 La2 CoO4

850 1,100 850 1,100 850 1,100 850 1,100

XRD patterns of the four precursor powders indicate that the phase formed depends on the preparation method and calcination temperature (Table 2). LaNiO3 and La2 NiO4 prepared by the PC method and calcined below 520 show a small perovskite phase. In contrast, single perovskite can be obtained by the PC method after calcination at above 850 . When the calcination temperature reached 1,100 , LaNiO3 and La2 NiO4 behave dierently towards temperature. La2 NiO4 shows only a single phase of perovskite structure where Ni exists as Ni2+ , while LaNiO3 is composed of the mixed phases of LaNiO3 , La2 O3 and NiO where Ni exists both as Ni2+ and

Ni3+ . This is consistent with results published by Nakamura [19]. Dierent from LaNiO3 , LaCoO3 and traces of Co3 O4 was identied in LaCoO3 after calcination at 850 and 1,100 (Table 2). The catalysts prepared by the CC method were also characterized by XRD, and all the catalysts showed multiple phases even after calcination at 1,100 for 10 h. This indicates that the PC method is better than the CC method for preparing single-phase perovskite. The catalysts after reaction show similar patterns (Figure 4) as those reported by Zhang [20] and Nam [21]. La2 O2 CO3 (hexagonal and tetragonal) phase are formed at the steady state due to the adsorp-

Figure 2. Inuence of the calcination temperature on the activity of La2 NiO4 as precursors prepared by the PC method Catalyst weight: 0.15 g; gas ow rate: CH4 /CO2 =10:10 (ml/min); calcination temperature: (1) 440 , (2) 520 , (3) 850 , (4) 1,100

Figure 3. XRD spectra of La2 NiO4 Calcination temperature: (1) 440 1,100 , (2) 520 , (3) 850 , (4)

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Figure 5. TPR curves of dierent catalysts prepared by the PC method and calcined at 850 (1) LaNiO3 , (2) La2 NiO4 , (3) LaCoO3 , (4) La2 CoO4

Since the active site of the reforming catalyst is the metallic particles, a study on the reducibility of Ni and Co in catalysts is necessary. The TPR curves of the perovskite precursors obtained by the PC method are given in Figure 5. The perovskites are reduced in and 500700 . two temperature ranges: 350500 According to Ruckenstein, the low temperature peaks

Figure 4. XRD spectra of La2 NiO4 (1) before reduction, (2) after reduction at 500 (PC), (3) after reaction of (2) at 700 for 120 min, (4) after reaction of catalyst from the CC method for 120 min

A TPR experiment at up to 800 (Figure 6) conrmed the XRD results (Table 2 and Figure 4) that single perovskite La2 NiO4 was formed after calcination above 850 . When the calcination temperature increased to 1,100 , the number of low temperature peaks in the TPR proles for La2 NiO4 did not change, but the height of the lower temperature peak abruptly decreased (Figure 6). For the precursors calcined at 440 and 520 , two overlapping peaks were found above 500 . In contrast, there is only one peak above 500 after calcination at 850 and 1,100 . The second peak shifted to a higher temperature region after increasing the calcination temperature from 850 to 1,100 . This suggests that a more dened perovskite structure formed after calcination at higher temperatures, which in turn results in higher activity and stability (Figure 2).

tion of CO2 on La2 O3 . The La2 O2 CO3 that exists in La2 NiO4 prepared by the PC method is mainly hexagonal phase (type Ia [20]), while those prepared by the CC method are both hexagonal and tetragonal phases. Zhang et al. have noted that the carbon species formed on the Ni sites are favorably removed by the oxygen species originating from La2 O2 CO3 and thus oer an active and stable performance due to the existence of synergetic sites which consist of Ni and La elements [20]. It should be noted that the La2 O3 phase that existed in the reduced catalysts disappeared and a new phase, La2 O2 CO3 , formed after 120 min on stream. It seems that, under the reaction conditions, the La2 O2 CO3 also participates in the activation of CO2 and the formation of CO[22].

do not belong to LaBO3 and La2 BO4 (B=Ni and Co) but to the reduction of amorphous Ni or Co oxides [23], and the high temperature peaks are due to the reduction of perovskite phases. Co-based perovskite is more stable under reducing atmosphere than Nibased perovskite because the second reduction peak of LaCoO3 and La2 CoO4 (at 626 and 631 , respectively) is higher than that of LaNiO3 and La2 NiO4 (at 564 and 587 , respectively). This may be the reason for the low reforming activity over Co-based catalysts (Table 1).

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Figure 6. TPR curves of La2 NiO4 prepared by the PC Method Calcination temperature: (1) 440 , (2) 520 , (3) 850 , (4) 1,100

4. Conclusions A preliminary study on the preparation of LaBO3 and La2 BO4 (B=Co, Ni) type perovskite precursors and catalytic activity for the CO2 reforming of CH4 was performed to investigate the eect of B-site metals and preparation methods. All the perovskite catalysts were successfully prepared by the sol-gel method, namely the Pechini method and Citrate acid complexing method. Pre-reduced La2 NiO4 catalyst obtained by the PC method exhibits a rather high activity and the highest stability. XRD and TPR experiment conrmed that the well-dened La2 NiO4 precursor structure and K2 NiF4 -type perovskite play an important role in the CO2 reforming of methane performance. References
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