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CHINESE JOURNAL OF CATALYSIS Volume 30, Issue 11, November 2009 Online English edition of the Chinese language

journal Cite this article as: Chin J Catal, 2009, 30(11): 10761084. RESEARCH PAPER

Characterization and Analysis of Carbon Deposited during the Dry Reforming of Methane over Ni/La2O3/Al2O3 Catalysts
XU Junke1,2, ZHOU Wei2,3, WANG Jihui4, LI Zhaojing4, MA Jianxin2,3,*
1 2 3 4

School of Environmental Science and Engineering, Tongji University, Shanghai, 200092, China Clean Energy Automotive Engineering Center, Tongji University, Shanghai, 201804, China School of Automotive Studies, Tongji University, Shanghai, 201804, China School of Resource and Environmental Engineering, East China University of Science and Technology, Shanghai, 200237, China

Abstract: Ni/La2O3/-Al2O3 and Ni/La2O3/-Al2O3 catalysts were prepared by the incipient wetness impregnation and evaporation methods. Their catalytic properties for the dry reforming of methane without a diluting gas were studied. The fresh and used catalysts and deposited carbon were characterized by H2 temperature-programmed reduction, N2 adsorption-desorption, X-ray diffraction, transmission electron microscopy, thermogravimetry coupled to differential scanning calorimetry, and temperature-programmed hydrogenation. The results showed that there were four carbon species that existed as three types, namely, amorphous (polymeric), filamentous, and graphitic carbon. The amount and type of carbon species on the catalysts depended on the size of Ni particles and texture of the support. The formation and morphology of filamentous carbon were clearly related to the size of Ni particles. Ni particles less than 15 nm suppressed the formation and deposition of filamentous carbons, decreased the amount of carbon deposition, and had more active C species, resulting in a better activity and higher stability of the catalysts. Key words: nickel; lanthanum oxide; alumina; supported catalyst; dry reforming; methane; carbon deposition

Global climate changes associated with the emission of greenhouse gases are of concern around the world. It is urgent to decrease the emission of greenhouse gases for environmental protection. The dry reforming of methane, that is, carbon dioxide reforming of methane, can take advantage of methane and carbon dioxide, both of which are main greenhouse gases, to produce synthesis gas. This process is also of great industrial interest for the lower H2/CO ratio close to or less than 1 that is produced, which is suitable for the synthesis of oxygenated derivatives [1,2]. The dry reforming of methane is particularly important for a gas field containing a significant amount of methane and carbon dioxide, such as CO2-rich natural gas and biogas including landfill gas formed in domestic waste landfills and digester gas produced in bioreactors or digesters [3]. Ni-based catalysts with a high activity and better stability

for the dry reforming of methane have been investigated extensively in recent years [430]. From the industrial standpoint, it is more practical to develop Ni-based catalysts because of their low price and wide availability [16]. However, one of the major problems in the dry reforming of methane is the high thermodynamic potential for coke formation [1,10]. Ding et al. [17] suggested that carbon deposition was inevitable in the temperature range from 573 to 1273 K from a thermodynamics analysis. In the dry reforming of methane, methane decomposition (Reaction (1)) and CO disproportionation (i.e., Boudouard reaction, Reaction (2)) are two major side reactions that contribute to carbon deposition on the catalyst surface, which lead to deactivation or destruction of the catalysts and a plugged catalyst bed [1,7,1619]. CH4 C + 2H2 H0 (1) 298 = 75 kJ/mol

Received date: 4 May 2009. *Corresponding author. Tel: +86-21-69589480; E-mail: jxma@tongji.edu.cn Foundation item: Supported by the Canada-China Scientific and Technological Cooperation Project (2007DFC61690) and Henkel Professorship of Tongji University (081591). Copyright 2009, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier BV. All rights reserved. DOI: 10.1016/S1872-2067(08)60139-4

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

2CO C + CO2 H0 (2) 298 = 172 kJ/mol The deposited carbon can have different structural order, morphology, and reactivity, depending on the specific reaction condition and structure of the catalyst [7]. There are three types of carbon that can be formed on the surface of Ni-based catalysts during the dry reforming of methane [7,9,2022]. Many efforts have been made to improve the carbon deposition resistance of Ni-based catalysts. Adding alkali and alkaline earth metals, such as K [23] and Ca [1,24], and rare earth metals, such as La [6,18,25], Ce [10,26], and Zr [27], can improve carbon deposition resistance. The reaction temperature and pressure also have significant effects on the resistance to carbon deposition [17,19]. In addition, the metalsupport interaction [28] and the metal particle size [5,11,16, 20,22] play important roles in carbon deposition over supported metal catalysts during the reforming reaction. Many reports indicated that bimetallic catalysts can greatly promote the resistance to carbon deposition in methane reforming [11,12,15,2932]. Many literature studies on the dry reforming of methane were performed at high gas hourly space velocity (GHSV) with a diluted gas flow and small size particle catalyst for reducing or avoiding carbon deposition and thus are not directly relevant to industrially significant conditions. In the present work, the carbon deposited on the surface of Ni/Al2O3 catalysts modified by La2O3 during the dry reforming of methane at a moderate flow rate without reactant dilution was characterized and analyzed using H2 temperature-programmed reduction (H2-TPR), BET surface area and porosity analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry coupled to differential scanning calorimetry (TG-DSC), and temperature-programmed hydrogenation (TPH). The main species and types of carbon deposited on the Ni/La2O3/Al2O3 catalysts with different types of Al2O3 were investigated.

The Ni/La2O3/Al2O3 catalyst was prepared by the evaporation method. An aqueous solution of Ni(NO3)26H2O, La(NO3)36H2O, and Al(NO3)36H2O (Sinopharm Chemical Reagent Co., Ltd.) was heated in an electric furnace to evaporate the water in the solution and crystallize the nitrates. The mixed nitrate crystals were dried overnight at 120 oC. The remaining steps were the same as the preparation of the Ni/La2O3/-Al2O3 catalyst. The Ni and La2O3 weight percent content in all the catalysts were 10% and 6%, respectively. 1.2 Catalyst characterization The reducibility of the catalysts was studied by H2-TPR in a Micromeritics AutoChem II-2920 apparatus. Catalyst (0.1 g) was loaded into a quartz tube and heated to 120 oC in an argon flow of 30 ml/min and purged for 30 min. After cooling to room temperature, the carrier gas was replaced by 10% H2/Ar at a flow rate of 30 ml/min. The temperature of the sample was increased from ambient temperature to 900 oC at a rate of 10 oC/min. The H2 consumed in TPR was monitored with a thermal conductivity detector (TCD). The BET surface area, porous volume, and average pore diameter of the catalysts were measured by N2 adsorption at 196 oC using a Micromeritics ASAP 2020 surface and porosity analyzer. A 0.1 g of catalyst was used for each analysis. The sample degassing was performed at 250 oC to remove the moisture and other adsorbed gases from the catalyst surface. The pore size distribution was calculated from the desorption branch of the isotherm by the Barrett, Joyner, and Halenda (BJH) method. XRD analysis was conducted with a Rigaku D/max 2550 diffractometer using Cu K radiation ( = 0.154056 nm) operated at 40 kV and 100 mA. The scanning step of 2 was 0.02o. TEM analysis was carried out on a Hitachi H 800/JEOL JEM-2010 microscope operated at 200 kV. The morphology of the carbon deposited on the reduced or used catalysts and the metal particle size and distribution could be identified. TG-DSC analysis with a Netzsch STA449C thermoanalyzer was also used to investigate carbon deposition. The used catalyst (10 mg) was held in an alumina crucible using an empty alumina crucible as a reference and heated from room temperature to 1000 oC at a rate of 10 oC/min in a mixture of 5% O2/N2 with a flow rate of 120 ml/min. The TPH of the spent catalysts was performed in the same apparatus as described for H2-TPR, and the analysis process was identical to the H2-TPR. 1.3 Catalyst testing The evaluation of catalyst activity was carried out at atmospheric pressure in a fixed-bed flow reactor (stainless steel tube, i.d. 15 mm) packed with 1.0 g of catalyst. The average catalyst particle size was 1.5 mm. The catalyst was reduced at

1 Experimental
1.1 Catalyst preparation The Ni/La2O3/-Al2O3 catalyst was prepared by incipient wetness impregnation with an aqueous solution of Ni(NO3)2 6H2O (Shanghai Hengxin Chemical Reagent Co., Ltd.) and La(NO3)36H2O (Sinopharm Chemical Reagent Co., Ltd.) of commercial -Al2O3 (Wenzhou Jingjing Alumina Co., Ltd., 200400 mesh). These samples were dried overnight at 120 o C and then calcined at 750 oC for 2 h in air. The powder catalysts were pressed into flakes, crushed, and sieved to obtain grains with diameters 12 mm (1020 mesh). The Ni/La2O3/-Al2O3 catalyst was prepared with the same procedure as used for the Ni/La2O3/-Al2O3 catalyst described above. The -Al2O3 support was obtained by calcination of -Al2O3 for 5 h at 1200 oC in air [33].

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

700 oC for 3 h in hydrogen at a flow rate of 30 ml/min before the measurement. The catalytic reforming reaction was carried out at 800 oC. The feed gas was a mixture of methane and CO2 with a molar ratio of 1 without a diluting gas. The feed flow rate was 100 ml/min, which was controlled by mass flowmeters (Alicat), and corresponded to a GHSV of 6000 ml/(gh). The reaction temperature was measured at the center of the catalyst bed using a K-type thermocouple. The gaseous products from the outlet of the reactor were passed through an ice trap to condense water in the products and metered using a soap bubble flow calibrator (Gillian). The compositions of the reactants and products were determined using an online gas chromatograph (Techcomp GC7890 II) equipped with a TDX-01 column (3 m length, 3 mm o.d.) and a TCD. Argon was used as carrier gas. The temperatures of the GC oven and TCD were set at 150 and 180 o C, respectively.

2 Results and discussion


2.1 Catalytic performance In order to understand carbon deposition on the catalysts and provide meaningful reference data for industrialization, the stability tests for the catalysts were performed without a diluting gas. The results are shown in Fig. 1. The CH4 initial conversion of the catalysts decreased in the order Ni/La2O3/ -Al2O3 > Ni/La2O3/Al2O3 > Ni/La2O3/-Al2O3 (Fig. 1(a)).
100 95 CH4 conversion (%) 90 85 80 75 70 CO2 conversion (%) 95 90 85 80 75 70 0 10 20 30 40 50 60 70 Time on stream (h) 80 90 100 (2) (3) (1) (b) (3) (1) (a) (2)

CH4 conversion over the Ni/La2O3/-Al2O3 catalyst was stable after 100 h on stream and was higher than that over the other two catalysts. However, the CH4 conversion over the Ni/La2O3/Al2O3 catalyst continually decreased in the reaction period of 55 h. The amount of carbon deposited on the inner wall of the reactor around the catalyst bed clogged the reactor, which caused the experiment to be terminated. The CH4 conversion due to the Ni/La2O3/-Al2O3 catalyst decreased in the first 13 h and then increased gradually until it was basically stable. This behavior was ascribed to the formation of new active sites when the catalyst was exposed to the reaction mixture that contained the reducing gases hydrogen and carbon monoxide [11,34,35]. La2O3 doped in the catalysts can adsorb strongly the reactant CO2 and react with it to form oxy-carbonate La2O2CO3 [34]. From Fig. 1(b), it can be seen that the CO2 conversion of the catalysts showed an increasing trend at the beginning of the experiments, which suggested a slow process where an equilibrium between La2O2CO3 and other carbonaceous species on the surface Ni crystallites was established [36]. The lowest CO2 conversion was observed on Ni/La2O3/Al2O3, and the CO2 conversion on Ni/La2O3/-Al2O3 was lower than that on Ni/La2O3/-Al2O3 in the later stage of the tests. A higher CO2 conversion favored the reducing of carbon deposition on the catalyst surface by the reverse Boudouard reaction (Reaction (2)). 2.2 H2-TPR characterization and analysis Figure 2 presents the results from H2-TPR. For the Ni/La2O3/-Al2O3 sample, only two major peaks were observed. The first reduction peak at 537 oC was attributed to the reduction of high dispersion NiO particles, and the second peak at 751 oC was due to the reduction of NiAl2O4 spinel [25,3738]. Three reduction peaks appeared in the profile from the Ni/La2O3/Al2O3 catalyst at 373, 465, and 669 oC, which were attributed to the reduction of bulk NiO particles

H2 consumption

(1) (2)

(3) 100 200 300 400 500 600 700 800 900

Fig. 1. Conversion of CH4 (a) and CO2 (b) versus time on stream over the different catalysts. (1) Ni/La2O3/-Al2O3; (2) Ni/La2O3/Al2O3; (3) Ni/ La2O3/-Al2O3. Reaction conditions: t = 800 oC, p = 101.3 kPa, GHSV = 6000 ml/(gh), V(CH4)/V(CO2) = 1.

Temperature (oC)
Fig. 2. TPR profiles of the different catalysts. (1) Ni/La2O3/-Al2O3; (2) Ni/La2O3/Al2O3; (3) Ni/La2O3/-Al2O3.

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

that did not interact with Al2O3, NiO that interacted strongly with Al2O3, and NiAl2O4 spinel, respectively [22]. With the Ni/La2O3/-Al2O3 catalyst, there were four clear reduction peaks at 398, 632, 764, and 844 oC, which indicated that four types of Ni species with different reducibility existed on the catalyst. The first two peaks were attributed to the reduction of bulk NiO particles and NiO in intimate contact with -Al2O3 [1]. The peak at 764 oC was attributed to the reduction of non-stoichiometric nickel aluminate in the catalyst [39], and the peak above 800 oC was attributed to the reduction of stoichiometric NiAl2O4 spinel [1,39,40]. Comparing the H2-TPR profiles of the three catalysts, it can be observed that almost all the Ni species in the Ni/La2O3/Al2O3 catalyst was reduced below 700 oC. This will cause the migration, aggregation, and growth of the metallic Ni particles leading to the decrease of Ni dispersion, which is one of the main reasons why the supported Ni-based catalyst was easily deactivated [41]. However, it was different for the Ni/La2O3/-Al2O3 and Ni/La2O3/-Al2O3 catalysts where some Ni species were reduced above 700 oC. This could improve the dispersion of metallic Ni particles on the catalyst. The results of the activity tests (Fig. 1) and H2-TPR indicated that the right interaction between the metal and support strongly affected not only the coke formation but also the activity of the reforming catalysts, which is in agreement with Goldwasse et al. [42]. 2.3 N2 adsorption-desorption results Figure 3 shows the N2 adsorption-desorption isotherms and pore size distribution of the catalysts. The catalysts had a typical mesoporous structure. The N2 isotherms were IV type and showed a hysteresis loop of the H2 type associated with the presence of mesoporous pores. The textural properties of the catalysts are listed in Table 1. From Fig. 3(b) and Table 1, it can be seen that the Ni/La2O3/-Al2O3 catalyst exhibited a higher surface area, larger pore volume, and more pronounced mesoporosity. These catalytically favorable textural properties can enhance the dispersion of metal particles, improve the catalyst activity, reduce the carbon deposition, and increase the catalyst stability. Compared with Ni/La2O3/-Al2O3, the Ni/ La2O3/Al2O3 catalyst had a higher BET surface area but lower pore volume and pore diameter, and lower activity and stability as shown in Fig. 1. This indicated that good textural properties (pore size and dispersion) are very important for the catalyst to have a good catalytic performance in the dry reforming of methane. 2.4 XRD characterization and analysis The XRD patterns of the fresh and used catalysts are shown in Fig. 4. For the fresh Ni/La2O3/Al2O3 and Ni/La2O3/-Al2O3 catalysts (Fig. 4(a)), the diffraction peaks of -Al2O3 can be observed. The -Al2O3 diffraction peaks and some other peaks

Adsorbed volume (cm3/g STP)

500 400 300 200 100 0 0.0 0.07 0.2 0.4 p/p0 0.6

(a)

(1) (3) (2) 0.8 1.0

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0.06 0.05 0.04 0.03 0.02 0.01 0.00 0 (2)

(b) (1)

(3) 20 40 60 Pore diameter (nm) 80 100

Fig. 3. N2 adsorption-desorption isotherms (a) and pore diameter distribution (b) of the catalysts. (1) Ni/La2O3/-Al2O3; (2) Ni/La2O3/Al2O3; (3) Ni/La2O3/-Al2O3. Table 1 Catalyst -Al2O3 (powder) Ni/La2O3/-Al2O3 Ni/La2O3/Al2O3 Ni/La2O3/-Al2O3 (4V/A by BET). Textural properties of -Al2O3 and the catalysts ABET/(m2/g) 365.45 233.43 76.67 38.09 Vp/(cm3/g) 0.8950 0.6278 0.0659 0.1165 Dp/nm 9.80 10.76 3.44 12.23

ABET: BET surface area; Vp: total pore volume; Dp: average pore diameter

can be seen in the fresh Ni/La2O3/-Al2O3 catalyst. When the catalysts were calcined at 750 oC for 2 h, the spinel compound NiAl2O4 was formed in the catalysts, but in the XRD patterns, it was hard to distinguish this from Al2O3 due to their similar morphology and characteristic peaks. The diffraction peaks of NiO were obvious in the Ni/La2O3/Al2O3 and Ni/La2O3/ -Al2O3 catalysts, but no such diffraction peaks were found for the Ni/La2O3/-Al2O3 catalyst. This means that there was a higher dispersion of metallic Ni in the latter. It is worthwhile to note that in all these three catalysts, no La2O3 diffraction peak was detected, indicating a high dispersion of La2O3 in the catalysts. The diffraction peak assigned to graphitic carbon at 2 = 26.5o (PDF 26-1080) was observed in the XRD patterns of the three spent catalysts, which showed that graphitic carbon was produced and deposited on the catalyst surface. However, the intensity of the diffraction peak of graphitic carbon for the catalysts was different, and the order of diffraction intensity

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

J-Al2O3 NiAl2O4 NiO

(a)

(3) (2) (1) Graphite Ni0 (b)

Ni/La2O3/-Al2O3, and Ni/La2O3/-Al2O3, respectively. This is the same order as that of the crystallinity of the graphitic carbon in the corresponding catalysts. Therefore, it could be concluded that the particle size of metallic Ni was significant for the deposition of graphitic carbon and the bigger metallic Ni crystallites gave a larger amount of deposited graphitic carbon. It is interesting to note that the carbon formed on the catalyst did not seriously deactivate the catalyst. This implied that such deposited carbon had a porous structure and did not fully cover the metallic Ni sites [7,14]. 2.5 TEM characterization and analysis Figure 5 shows the TEM images of the used and reduced catalysts. Compared with the catalysts before reaction, the particle sizes of metallic Ni particles after reaction had increased to some extent. Fig. 5(e) and (f) show that some metallic Ni particles on Ni/La2O3/Al2O3 and Ni/La2O3/-Al2O3 catalysts had already aggregated after reduction. However, on the Ni/La2O3/-Al2O3 catalyst, metallic Ni particles had excellent dispersion and their size was very small (Fig. 5(d)). The carbon deposited on the Ni/La2O3/Al2O3 and Ni/La2O3/ -Al2O3 catalysts was mainly in the form of whisker (filamentous/fibrous) carbon during the dry reforming of methane (Fig. 5(b) and (c)). The filamentous carbon was in the form of carbon nanotubes (CNTs) according to their morphology. However, the image of Fig. 5(a) showed that no filamentous carbon existed on the Ni/La2O3/-Al2O3 catalyst with a uniform dispersion of metallic Ni particles, which can improve the activity and stability of the catalyst. The Ni particles were located basically over the Al2O3 carrier in catalysts Ni/La2O3/-Al2O3 and Ni/La2O3/-Al2O3 and

Intensity

Intensity

(3)

(2) (1) 10 20 30 40 50 60 2T/( o ) 70 80 90 100

Fig. 4. XRD patterns for the fresh (a) and used (b) catalysts. (1) Ni/La2O3/-Al2O3; (2) Ni/La2O3/Al2O3; (3) Ni/La2O3/-Al2O3. Reaction time was 100, 55, and 25 h for Ni/La2O3/-Al2O3, Ni/La2O3/Al2O3, and Ni/La2O3/-Al2O3, respectively.

was Ni/La2O3/Al2O3 > Ni/La2O3/-Al2O3 > Ni/La2O3/-Al2O3, which indicated the different crystallinity of the graphitic carbon deposited on the catalysts. The crystallite sizes of metallic Ni estimated from XRD line broadening by the Scherrers equation were 10.2, 10.0, and 7.6 nm for Ni/La2O3/Al2O3,

Fig. 5. TEM images of the used ((a), (b), and (c)) and reduced ((d), (e), and (f)) catalysts. (a) and (d) Ni/La2O3/-Al2O3; (b) and (e) Ni/La2O3/Al2O3; (c) and (f) Ni/La2O3/-Al2O3.

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

isolated from one another. This resulted in the better CH4 conversion of the two catalysts (Fig. 1). The decrease in CO2 conversion on the Ni/La2O3/-Al2O3 catalyst could be due to the deposited graphitic carbon, which mainly covered the active sites. However, for the Ni/La2O3/Al2O3 catalyst, many small Ni particles were located at the top of the CNTs, which can also be used as active sites for methane reforming. The sintering of metallic Ni particles (Fig. 1(b)) and gradual accumulation of graphitic carbon (Fig. 4(b)) were the main reason for the activity decrease of the Ni/La2O3/Al2O3 catalyst. Many studies have shown that the formation of carbon filaments on the catalysts is influenced by the metal particle size [5,7,11,16,20,21]. Zhang et al. [11] reported that smaller ensembles were able to suppress carbon formation, but large Ni clusters showed carbon formation. A minimum diameter was required for Ni particles to generate carbon filaments [16,43]. Kim et al. [16] concluded that the average particle size has to be no less than 7 nm to form filamentous carbon. Kroll et al. [43] considered that the minimum metal particle diameter was 6 nm. Chen et al. [20] reported that the ensemble sizes of 3, 4, and 6 nm were responsible for the reforming reaction, water gas shift reaction, and encapsulating carbon forming reactions, respectively. Tang et al. [5] reported that the small size of metallic Ni particles was a key factor in preventing coke formation and the critical size of Ni particles to inhibit carbon deposition was suggested to be 10 nm. Figure 6 presents the Ni particle size distribution of the used catalysts from the results of TEM. The images of the metallic Ni particles were close to round as shown in Fig. 5. The size of most metallic Ni particles on the Ni/La2O3/-Al2O3 catalyst was less than 15 nm. Small particles can improve the activity and stability of catalyst. The Ni particle size on the Ni/La2O3/-Al2O3 catalyst was between 10 and 45 nm. However, the distribution of metallic Ni particle size on the Ni/La2O3/Al2O3 catalyst was very broad, and a few particles had aggregated and sintered to a size more than 100 nm. The aggregation and sintering of the metal will accelerate carbon deposition [44]. From Fig. 5 and Fig. 6, it can be reasonably concluded that the production and growth of carbon filaments can be effectively suppressed on the catalyst when the particle size of metallic Ni is not more than 15 nm. This is in agreement with our previous study [22]. Precipitated carbon atoms can diffuse through Ni particles or along a given crystallographic plane [45]. The diffusion of carbon atoms through Ni particles leads to the formation of filamentous carbon [46]. Based on the growth mechanism of filamentous carbon, the diameter of the tube is dependent on the size of the metallic Ni particles [44]. The diameters of the carbon tubes on the Ni/La2O3/Al2O3 catalyst were from 20 to 110 nm, which was consistent with the size of the metallic Ni particles (Fig. 5(b)). The diameters of the carbon filaments on the Ni/La2O3/-Al2O3 catalyst were uniform with the value of 2537 nm, and the thickness of carbon tubes was thinner than

24 Frequency (%) 20 16 12 8 4 0 12 Frequency (%) 8 4 0 12 8 4 0 (b) (a)

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(c)

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90 100 110

Size of Ni particles (nm)


Fig. 6. Ni particle size distribution of the used catalysts derived from TEM. (a) Ni/La2O3/-Al2O3; (b) Ni/La2O3/Al2O3; (c) Ni/La2O3/-Al2O3.

that on the Ni/La2O3/Al2O3 catalyst (Fig. 5(b) and (c)), which was related to the smaller metallic particle and narrower distribution of particle size for the former. These results suggested that the formation and morphology of filamentous carbon depend on the size of the metallic Ni particles. 2.6 TG-DSC characterization and analysis Figure 7 shows the TG-DSC results for carbon deposited on the used catalysts and their amounts are listed in Table 2. The amounts of carbon deposited on the Ni/La2O3/Al2O3 and Ni/La2O3/-Al2O3 catalysts were 17.46% and 12.41%, respectively. According to Fig. 4 and Fig. 5, most carbon species were in the forms of fibrous and graphitic carbon on these two catalysts. These carbon species are inactive and can cover the active sites, leading to the decrease in catalytic activity (Fig. 1). For the Ni/La2O3/-Al2O3 catalyst, the amount of deposited carbon was 6.73%, which is much lower than those on the other two catalysts. This result was consistent with the XRD and TEM observations. These three catalysts had the same chemical components, so the difference in carbon deposition resistance was due to the different size of the metallic Ni particles and textural properties. From the present experimental and characteristic results, the size of metallic Ni particles less than 40 nm did not affect the CH4 cracking but affected the methane reforming of CO2. The catalyst with the size of metallic Ni particles less than 15 nm had a better activity and stability, suppressed effectively the formation of fibrous carbon, and decreased the deposition of carbon. Therefore, the

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

Mass loss (mg)

-0.4 -0.8 -1.2 -1.6 -2.0 -2.4 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 (c)

3 2 1 0 -1 -2 2.4 1.8 1.2 0.6 0.0 -0.6 0 200 400 600 Temperature (oC) 800 1000

Mass loss (mg)

Fig. 7. TG-DSC profiles of the used catalysts. (a) Ni/La2O3/-Al2O3 after reaction for 100 h; (b) Ni/La2O3/Al2O3 after reaction for 55 h; (c) Ni/La2O3/ -Al2O3 after reaction for 100 h. Table 2 Catalyst Ni/La2O3/-Al2O3 Ni/La2O3/Al2O3 Ni/La2O3/-Al2O3 Analysis of carbon deposited on the spent catalysts Reaction time (h) 100 55 100 Deposited carbon (%) 6.73 17.46 12.41 Average coking rate (mg/(gh)) 0.674 3.174 1.241

better size of the metallic Ni particle for methane reforming of CO2 over the Ni/La2O3/Al2O3 catalyst was less than 15 nm. A mass loss of only one strong exothermic peak from 500 to 750 oC was observed for all samples in the TG-DSC profiles as shown in Fig. 7. This was due to the oxidation of carbon deposited on the catalysts and implied that there was only one kind of main carbon species for each catalyst. In the DSC profiles, the maximum peak temperatures of the Ni/La2O3/ -Al2O3, Ni/La2O3/Al2O3, and Ni/La2O3/-Al2O3 catalysts were 717, 665, and 656 oC, respectively. Zhang et al. [47] suggested that the peak at 616 oC was the exothermic peak of inert carbon or graphitic carbon over a La2NiO4/ZSM-5 catalyst. Luo et al. [48] and Zhang et al. [49] reported a similar result and suggested that the mass loss at/above 650 oC was associated with the removal of filamentous or graphitic carbon deposited on the Al2O3 supports. Based on the XRD and TEM results, the exothermic peaks in the profiles in Fig. 7 can be attributed to the oxidation of filamentous and graphitic carbon species. The exothermic peaks between 300 to 500 oC and above 800 oC

DSC (mW/mg)

DSC (mW/mg)

0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 0.0

1.5 (a) DSC (mW/mg) 1.0 0.5 0.0 -0.5 -1.0 (b) 5 4

Mass loss (mg)

were due to the oxidation of metallic Ni and the crystalline change of Al2O3, respectively. The mass loss below 200 oC can be assigned to the degassing of water contained in the catalysts. 2.7 TPH characterization and analysis Figure 8 shows the TPH profiles of the three used catalysts. It can be clearly seen that there are at least three kinds of carbon species on the catalysts during the dry reforming of methane. Many studies [7,17,4850] reported that three carbonaceous species exist on supported metal catalysts when CH4 decomposed on metal surfaces and designated these carbonaceous species as C, C, and C. The completely dehydrogenated carbidic carbon C is a very active and important intermediate in the carbon dioxide reforming with methane. The C species was responsible for CO formation [48]. The partially dehydrogenated C species can react with H2 or CO2 to form CH4 or CO [51]. C species can be produced by the interactions between C and C species and between C and C themselves [17]. The carbidic cluster C species had the lowest activity and would be the precursor of surface carbon deposition [17,51]. Guo et al. [7] reported that C can be completely removed by hydrogenation below 800 oC, and about half of C and one third of C on Ni/MgAl2O4 can be removed by hydrogenation. Rezaei et al. [14] identified the peak at above 600 oC as due to carbon nanotubes. However, if the inactive carbon species (filamentous or graphitic) can be hydrogenated below 800 oC, they would not be deposited on the surface of the catalysts because of the existence of the large amount of H2 during the reaction at 800 oC. As a result, the inactive carbon species cannot be hydrogenated at all. The peaks at 200 oC and 300400 oC in the TPH profiles would be due to the C and C species, respectively, that were active for the dry reforming of methane. This is the reason why the catalysts kept relatively

CD H2 consumption

CE

CJ (1)

(2)

(3)

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900

Temperature (oC)
Fig. 8. TPH profiles of the used catalysts. (1) Ni/La2O3/-Al2O3 after reaction for 100 h; (2) Ni/La2O3/Al2O3 after reaction for 55 h; (3) Ni/La2O3/ -Al2O3 after reaction for 100 h.

XU Junke et al. / Chinese Journal of Catalysis, 2009, 30(11): 10761084

stable even though a large amount of carbon was deposited on the catalysts. The C and C can be assigned to the amorphous carbon or polyaromatic type species [7]. The peak between 400 and 800 oC should be attributed to the C species that is amorphous carbon as well. From the discussion above, it can be concluded that during the dry reforming of methane, four carbon species (C, C, C, and inactive carbon) were deposited on the catalysts and existed as three general types of carbon, amorphous (polymeric), filamentous, and graphitic, as has been described in other references [7,9,20,21]. The C and C species can be transformed to CO, with the activity of the former being better than the later [7,51]. Compared with the Ni/La2O3/-Al2O3 and Ni/La2O3/-Al2O3 catalysts, the amount of C and C species on the Ni/La2O3/Al2O3 catalyst was smaller, as shown in Fig. 8. This may be the reason for its lower reforming activity. The CO2 conversion on the Ni/La2O3/-Al2O3 catalyst was higher than that on the Ni/La2O3/-Al2O3 catalyst during the post-phase of the reaction (Fig. 1). This was due to the larger amount of C species on the Ni/La2O3/-Al2O3 catalyst.

3 Conclusions
Ni/Al2O3 catalysts modified by La2O3 were prepared by incipient wetness impregnation and the evaporation method and were used for methane reforming of CO2 without a diluting gas. The species and amounts of carbon deposited on the catalysts depended on the size of the metallic Ni particles and the texture of the support. Metallic Ni particles less than 15 nm can effectively suppress the formation of carbon filaments, decrease the amount of carbon deposition, and produce a larger amount of active C species, resulting in a better activity and higher stability of the catalyst.

Acknowledgements
The authors thank Prof. LI Ping, Miss XU Yan, and Mr. YIN Junlin for their work in analysis of TPR, XRD, and TEM, respectively.

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