CO2 Reforming of Methane

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e8
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CO2 reforming of methane on Ni/g-Al2O3 catalyst prepared by dielectric barrier discharge hydrogen plasma
Lijun Jin, Yang Li, Ping Lin, Haoquan Hu*
State Key Laboratory of Fine Chemicals, Institute of Coal Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
article info
Article history: Received 28 September 2013 Received in revised form 27 December 2013 Accepted 26 January 2014 Available online xxx Keywords: CO2 reforming of methane Ni/g-Al2O3 Hydrogen Dielectric barrier discharge Plasma
abstract
Ni/g-Al2O3 catalyst was prepared by direct treatment of Ni(NO3)2/g-Al2O3 precursor with dielectric barrier discharge (DBD) hydrogen plasma at different input powers, characterized by XRD, H2-TPR, CO2-TPD, N2 adsorption and TEM, respectively, and used as the catalyst for CO2 reforming of methane (CRM). The results showed that the input power obviously affected the reduction degree and catalytic performances of catalysts. Low input power under 40 W mainly resulted in the decomposition of nickel nitrate into Ni oxides. The reduction degree, catalytic activity and stability increase with the input power. Similar catalytic performances in CRM reaction can be obtained when the power exceeds 80 W. Compared with the Ni/Al2O3 catalyst prepared by traditional method, Ni/g-Al2O3 samples prepared by H2 DBD plasma exhibit better activities, stability and anti-carbon deposit performances. It is mainly ascribed to smaller Ni particle size, more basic sites and weaker basicity. The increase of Ni particle sizes due to the sintering at high temperature results in the decrease of catalytic activities and coke formation. Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
1.
Introduction
CO2 reforming of methane (CRM) has attracted more attention in the last few decades due to the effective utilization of two greenhouse gases and its low H2/CO ratio of nearly unit in the products [1,2]. Especially considering the reaction stoichiometry, it is more protable to make use of the gases with similar amounts of CH4 and CO2 like biogas or some natural gas streams with high CO2 content [3,4].
Nowadays, tremendous effects have focused on the development of catalysts with high activity and stability for CRM. Nickel-based and noble metal supported catalysts (Rh, Ru, Pd, Pt, etc.) seem to be the promising catalysts [5,6]. Although the noble metal catalysts are proved to be less sensitive to coking, it is more practical to develop improved Ni-based catalysts considering high catalytic activity, products selectivity and low cost [7,8]. However, faster carbon deposit on nickel than noble metals makes it very necessary to develop the coking-resistant Ni-based catalyst for the future application.
* Corresponding author. Tel./fax: 86 411 84986157. E-mail address: hhu@dlut.edu.cn (H. Hu). 0360-3199/$ e see front matter Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.ijhydene.2014.01.171
Please cite this article in press as: Jin L, et al., CO2 reforming of methane on Ni/g-Al2O3 catalyst prepared by dielectric barrier discharge hydrogen plasma, International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.01.171
Recently, many studies found that the catalysts prepared by use of plasma technologies, especially reduced by the plasma, exhibited better lower temperature activity and stability than the conventional catalyst [9e15], which is mainly ascribed to the enhanced metal dispersion and smaller Ni crystal size. Various kinds of non-equilibrium plasmas with features of low temperature and many highenergy electrons are used for the reduction of supported metal catalysts. Halverson and Cocke prepared the Al2O3supported Ru catalyst with highly dispersed metallic particles as well as large metal aggregates by using the capacitively coupled radio-frequency plasma of oxygen/water [10]. Phillips et al. studied the supported Pd/C and Pd/Al2O3 catalysts prepared by plasma torch [11]. Lius group investigated many plasma-assisted catalysts, including Ni/Al2O3, Ir/Al2O3, Ni/SiO2, Pd/HZSM-5 by vacuum glow discharge with/without the following thermal calcination, and found the remarkable enhancement in dispersion and low-temperature activity of the catalysts [12e15]. But they also found that not all supported metal catalysts can be reduced by Ar glow discharge plasma. Some supported Fe(NO3)3, Ni(NO3)2, and Co(NO3)2 matters are just decomposed to the corresponding metal oxides by non-hydrogen plasma, which is attributed to the negative standard electrode potential of the Mn/M ions pair [16]. Hu et al. observed that NiO supported Al2O3 cannot be reduced by cold plasma jet under Ar atmosphere although the discharged gas temperature is 467 C at the discharge voltage of 600 V, but quickly reduced at 10%H2/Ar atmosphere [17]. Li et al. even found that the catalytic stability in partial oxidation of methane was improved by preventing carbon deposit on Ni catalyst when the reduced Ni/Al2O3 catalyst by traditional method was further treated by using plateeplate discharge model via a corona discharge [18]. Chu et al. used the frequency plasma to prepare several glow discharge plasma-assisted catalysts, such as FischereTropsch cobalt catalyst, Ni/a-Al2O3, Pd/a-Al2O3, and developed a novel plasma-assisted calcination and reduction method to prepare novel Ni/SiO2 or Ni/Al2O3 catalysts for methane reforming reaction [19,20]. The results showed that the Ni/gAl2O3 catalyst prepared by directly decomposed and reduced by atmospheric pressure glow discharge plasma jet exhibited high catalytic activity and good anti-carbon deposit performance in CRM reaction. Although the temperature of catalyst bed in discharge zone is 527 C when 20 KHz AC voltage is utilized for 10 min, the Ni particle size on the catalyst surface is about 5 nm. They attributed the excellent low-temperature activity and structure of the catalyst to short treatment time of 10 min in plasma process instead of several hours in conventionally decomposing and reducing the catalyst precursor of Ni(NO3)2/g-Al2O3, which effectively avoided the sintering and aggregation of Ni particles. Dielectric barrier discharge (DBD) plasma can be also used to reduce the supported metal catalysts, such as Pt/g-Al2O3, Co/g-Al2O3, Ni/MgO [21,22]. In this paper, the impregnated gAl2O3 with Ni(NO3)2 was directly treated by H2 DBD at different input powers. The prepared samples were characterized by XRD, H2-TPR, CO2-TPD, TEM, N2 adsorption/desorption and TG techniques, respectively. Their catalytic performances in CO2 reforming of methane were examined and compared with the catalyst prepared by conventional method.
2.
2.1.
Experimental
Catalyst preparation
Ni(NO3)2/g-Al2O3 with 10 wt.% Ni was prepared by incipient wetness impregnation. The support g-Al2O3 with surface area of 260 m2/g (from Dalian Haixin Chemical industrial Co., Ltd.) was crushed, sieved to 20e40 mesh and dried at 120 C for 12 h before use. The desired aqueous solution of Ni(NO3)2 was added and impregnated for 12 h at room temperature, then the mixture was dried at 105 C for another 12 h. The obtained samples were divided into two parts and treated by conventional method or DBD plasma of H2, respectively.
2.1.1.
H2 plasma method
Fig. 1 shows the schematic diagram of the atmospheric pressure DBD reactor used in our experiments. An inside stainless steel rod with a diameter of 3 mm was used as high voltage (HV) electrode. The coaxial stainless steel mesh, which was wrapped around the corundum tube, served as the ground electrode. The discharge gap of the DBD reactor is 2.5 mm. Before discharge, about 1.0 g Ni(NO3)2/g-Al2O3 without decomposition at elevated temperature was loaded into discharge zone and fed with a 100 ml/min ow rate of H2 to remove air for 10 min. Then different discharge voltage with a sine wave was regulated by plasma generator (CTP-2000K, Nanjing Suman Electronics Corp.) with the maximum voltage 40 kV and an adjustable frequency between 10 and 40 kHz to treat the sample for 20 min. The total AC input power was calculated by multiplying the input voltage by the corresponding current. The temperature in the discharge zone was measured quickly by a K-type thermocouple when the discharge was stopped. The prepared catalysts were expressed as P-x (x represents input power).
2.1.2.
Conventional method
For comparison, the Ni(NO3)2/g-Al2O3 sample was calcined at 700 C for 6 h and reduced at 700 C for 2 h with a 20%H2/N2 ow rate of 250 ml/min according to H2-TPR prole. The resultant sample was denoted as C-700.
2.2.
Characterizations
X-ray diffraction (XRD) patterns of the samples were obtained on a D/Max2400 diffractor (Rigaku) with a Cu Ka radiation at 40 kV and 40 mA. The mean size of nickel crystallites was calculated from the broadening of Ni(111) peak, according to ScherrereWarren equation [23]. Temperature-programmed reduction of hydrogen (H2-TPR) measurement was performed in a conventional apparatus equipped with a TCD detector. About 0.10 g catalyst was pretreated at 300 C for 30 min with a N2 ow rate of 60 ml/min before cooling down to 120 C, then heated to 900 C at a heating rate of 10 C/min with a H2 ow rate of 60 ml/min. The basic properties of the catalysts were measured by temperature-programmed desorption of CO2 (CO2-TPD) on the same apparatus as H2-TPR. The sample (0.10 g) was rst pretreated at 300 C for 2 h in a N2 stream of 60 ml/min. After cooling down to 120 C, the sample was
Conversion of CO2 %
FCO2 ; in FCO2 ; out 100% FCO2 ; in
(2)
H2 =CO ratio
Mol of H2 produced Mol of CO produced
(3)
where FCH4 ; in, FCH4 ; out, FCO2 ; in and FCO2 ; out represent the volume of CH4 and CO2 of the inlet and outlet, respectively.
3.
3.1.
Results and discussion

XRD and H2-TPR proles of catalysts
Fig. 1 e Schematic diagram of the apparatus for catalyst preparation by H2 DBD (1. gas inlet; 2. gas outlet; 3. high voltage electrode; 4. ground electrode; 5. catalyst sample).
exposed in CO2 atmosphere for 30 min. Then the sample was purged with N2 until the baseline was steady. Finally, the CO2-TPD was carried out with a ramp of 10 C/min from 120 C to 900 C under the N2 ow rate of 60 ml/min. The specic surface area and pore volume of the catalysts were measured by N2 adsorption/desorption using ASAP 2010 Micromeritics instrument at 196 C. The samples were outgassed at 300 C for 4 h prior to adsorption. Transmission electron microscopy (TEM) images of the fresh and used catalysts were acquired with FEI Tecnai G2 20 instrument. The amount of carbon deposit on the spent catalysts was measured by TG/DTG analysis on a Mettler Toledo TGA/ SDTA851e. About 20 mg of the sample was placed in a ceramic crucible and heated from room temperature to 800 C with a heating rate of 10 C/min under air ow rate of 60 ml/min.
2.3.
Catalytic performance
The CRM reaction was carried out in a stainless steel xed-bed reactor with an inner diameter of 8 mm at atmospheric pressure. 0.40 g catalyst placed in the center of the reactor was rst heated to 700 C under N2 of 200 ml/min, then the gaseous mixture of CO2 (80 ml/min), CH4 (80 ml/min) and N2 (200 ml/ min) with a volume ratio of 2/2/5 instead of N2 was fed into the reactor, along with a total volumetric hourly space velocity (VHSV) of 54,000 ml/(h gcat). The products were analyzed by gas chromatograph (GC 7890) equipped with a thermal conductivity detector (5 A molecular sieve packed column) and a ame ionization detector (GDX 502 packed column). The conversions of CH4 and CO2, and H2/CO ratio were calculated according to the following equations: Conversion of CH4 % FCH4 ; in FCH4 ; out 100% FCH4 ; in (1)
The effect of input power on the structure and properties of Px catalysts prepared by H2 plasma treatment of Ni(NO3)2/gAl2O3 precursor was examined. The results showed that the input power obviously affected the appearance color of the samples (not shown in the paper). When the input power increases from 20 W to 40 W, the sample changes from greenish of P-20 to gray, which means that Ni(NO3)2 supported on the Al2O3 has been partly decomposed to NiO under the effect of plasma [24]. It can be seen from Table 1 that the temperature of discharge region is about 270 C, which is benecial to the decomposition of Ni(NO3)2. With further increasing input power, the powder became black, meaning that parts of Ni oxides were reduced to Ni metal by H2 plasma, which is further conrmed by the XRD results in Fig. 2(a). From the XRD patterns of P-x samples treated at different input powers in Fig. 2(a), it can be seen that the P-20 sample has obvious characteristic peaks of Al2O3 with 2q being 37.4 and 67.3 , and small patterns ascribed to NiO species at 37.2 , 43.5 and 62.9 . No metal Ni phases (44.5 , 51.8 and 76.4 ) were identied, indicating that NiO was not reduced at low input power. Additionally, weak peaks at 32.0 and 39.0 ascribed to Ni2O3 species were also detected. With increasing the input power, the peak of NiO at 37.2 becomes weaker and weaker, while the intensity of Ni(111) peak at 44.5 gradually increases. When the power increases to 120 W, the peak of Ni metal at 51.8 is also detected on P-120 catalyst, which means that more Ni metals are reduced and the reduction degree of sample increases with the input power. H2-TPR proles shown in Fig. 2(b) further verify the reduction of nickel oxides on Al2O3 support. Sample P-20 has two obvious peaks of H2 consumption. One is at 240 C ascribed to the reduction of Ni2O3 species and another is at 560 C due to NiO reduction [25]. With the increase of input power, the peak at 240 C disappears and the peak intensities at high temperature gradually decrease, suggesting the increase of input power leads to the enhancement of reducibility by H2 plasma, and many Ni oxides have been reduced.
Table 1 e Temperatures in the discharge region under different input power.a

Input Power (W) Temperature ( C)
a
20 150
40 270
60 380
80 430
100 480
Quickly measured by a K-type thermocouple when the discharge is stopped.
Fig. 2 e XRD patterns (a) and H2-TPR proles (b) of P-x catalysts treated by H2 DBD at different input power.
Shang et al. thought that higher input power can supply many high-energy electrons to activate the hydrogen molecules and promote the action between catalyst precursor and large amount of H atoms in plasma process, further improving the reduction degree [26]. Compared with the C-700 catalyst prepared by traditional calcination and reduction of H2 at 700 C, the P-120 sample demonstrates similar hydrogen consumption peak below 500 C. However, slightly more hydrogen consumption at above 600 C than that of C-700 suggests that some NiO species are difcultly reduced owing to the interaction of NieO with the aluminum ions of the support. The characterization results of XRD and H2-TPR suggest that Ni(NO3)2/g-Al2O3 precursor can be directly decomposed and further reduced to Ni/g-Al2O3 catalyst by use of H2 DBD plasma at the appropriate input power.
the P-100 and P-120 catalysts have similar but lower methane conversion than P-80 sample despite high reduction degree. From the conversion of CO2 in Fig. 3(b), the P-80 catalyst has high conversion and good stability. It is analyzed that, at high input power (e.g.100 W), the temperature of the electrons themselves is far away from 480 C (see Table 1) of discharge region measured by thermocouple, which not only results in the enhancement of reduction degree, but also accelerates the sintering of active metallic Ni. Considering catalytic performances and economy aspects, in the following studies, 80 W was chosen as the input power for the preparation of catalyst.
3.3. Comparison of catalytic performances on P-80 and C-700 sample

To compare the catalytic performances of the catalysts prepared by H2 DBD plasma and traditional method, P-80 and C700 samples were chosen and used in the CRM reaction at different temperature. The results in Fig. 4 show that the conversions of CH4 and CO2 increase with the reaction temperature because CO2 reforming of methane is an endothermic reaction. The conversion of CO2 is always higher than that of CH4, suggesting that the reverse wateregas shift reaction occurs [22,27]. However, at the same reaction temperature, the P-80 catalyst treated by H2 plasma at 80 W always exhibited higher catalytic activities and better stability (see Fig. 5) than C-700 catalyst. It can be seen from Fig. 5(c) that H2/
3.2.
Catalytic performance of P-x catalysts
CO2 reforming of methane on the P-x catalysts prepared with different input powers was investigated and the results are shown in Fig. 3. It can be seen from Fig. 3(a) that P-20 and P-40 catalysts have low and similar methane conversions, which is mainly related with lower reduction degree. When increasing the input power to 80 W, the initial methane conversion of the catalyst increases although it is lower than the thermodynamic conversion (80.6%) and the stabilities are also enhanced. However, when further increasing the input power,
Fig. 3 e Catalytic activity of catalysts prepared by H2 plasma at different input power (700 C; CH4:CO2:N2 [ 2:2:5(vol.); space velocity: 54,000 ml/h gcat). Please cite this article in press as: Jin L, et al., CO2 reforming of methane on Ni/g-Al2O3 catalyst prepared by dielectric barrier discharge hydrogen plasma, International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.01.171
Fig. 4 e Conversions of CH4 (a) and CO2 (b) of C-700 and P-80 samples at different temperature (CH4/CO2/N2 [ 2/2/5(vol.); space velocity [ 54,000 ml/h gcat; Ni loading 10%).
Fig. 5 e Conversions of CH4 (a) and CO2 (b) and H2/CO ratio (c) of C-700 and P-80 catalysts at 700 C (CH4:CO2:N2 [ 2:2:5(vol.); space velocity [ 54,000 ml/h gcat; Ni loading 10%).
CO ratio on two catalysts is less than the theoretic value of unit, further conrming the occurrence of reverse wateregas shift reaction in CRM. Compared with C-700, the P-80 exhibited higher H2/CO ratio. To explore the reasons for different catalytic performances, two catalysts were characterized by N2 adsorption, XRD, CO2-TPD and TEM analyses. The results by N2 adsorption in Table 2 show that P-80 sample has slight larger surface area and similar pore volume than C-700 catalyst. From the XRD patterns in Fig. 6(a), it can be seen that P-80 catalyst exhibits broader and weaker characteristic peaks ascribed to the metal Ni phase with 2q being 44.5 , 51.8 and 76.4 than C-700 sample
in the XRD patterns, indicating smaller Ni size and better dispersion on P-80 catalyst [22,25]. Table 2 shows that the mean Ni particle size of the P-80 catalyst treated by H2 DBD is 4.4 nm, which is near to the size about 5 nm of Ni/g-Al2O3 prepared by plasma-assisted calcination and reduction method with atmospheric high frequency cold plasma jet [20,26], but obviously smaller than 10.3 nm of C-700 reduced by traditional method, which is well accordant with the results by TEM images in Fig. 7. Compared with C-700 sample, the fresh P-80 catalyst shows smaller size of nickel particle and higher Ni dispersion (see Fig. 7(a) and (b)). Shang et al. [26] thought that small Ni metal size was ascribed to short
Table 2 e eTextural properties and Ni particle sizes of P-80 and C-700 catalysts. Catalysts Textural properties SBET (m2 g1)
P-80 C-700
a b c d e
Ni particle size (nm)a Reduced

4.4 10.3
Vtot (cm3 g1)

0.397 0.396
Usedb
5.3 13.4
Usedc
5.5 12.2
Usedd
5.2 13.6
Usede
9.3 14.2
179 141
Calculated from the Ni(111) peak of XRD patterns according to ScherrereWarren equation. Reaction at 600 C for 6 h. 650 C for 6 h. 700 C for 6 h. 700 C for 32 h.
Fig. 6 e XRD patterns (a) and CO2-TPD proles (b) of C-700 and P-80 samples.
treatment time in plasma process instead of several hours in conventional decomposing and reducing the catalyst precursor of Ni(NO3)2/g-Al2O3, which effectively avoided sintering and aggregation of Ni particles. However, it can be seen from Table 2 that the active Ni metal size increases with the reaction time even at low reaction temperature of 600 C. After reaction of 32 h, the mean particle sizes of P-80 and C-700 samples increased from 4.4 nm to 9.3 nm and 10.3 to 14.2 nm, respectively, which can also be conrmed by the TEM images
in Fig. 7(c)e(d). After 6 h, the Ni size of spent P-80 sample almost has no obvious increase, and well dispersed on the Al2O3 support. However, the particle size increased to near 10 nm after 32 h, although it is still smaller than that of fresh C-700 catalyst. Therefore, it can be concluded that the decrease of catalytic activities is mainly attributed to the sintering of metallic Ni to form larger Ni particles. Higher catalytic activities and better stability of P-80 are mainly related with smaller Ni sizes.
Fig. 7 e TEM images of fresh C-700 (a), fresh P-80 (b) and spent P-80 catalysts after 6 h (c) and 32 h (d). Please cite this article in press as: Jin L, et al., CO2 reforming of methane on Ni/g-Al2O3 catalyst prepared by dielectric barrier discharge hydrogen plasma, International Journal of Hydrogen Energy (2014), http://dx.doi.org/10.1016/j.ijhydene.2014.01.171
Fig. 8 e TG-DTG curves of C-700 and P-80 catalysts after reaction time of 6 h (a) and 32 h (b) at 700 C.
The basic properties of the Ni-based catalysts are also one of the important factors for different catalytic performances. Fig. 6(b) shows the CO2-TPD proles of two catalysts. Generally, it is considered that the proles can be differentiated both in the integral area of the proles and the shift of peak temperature. The former corresponds to the amount of basic sites and the latter indicates the strength of the basic sites. CO2 molecules adsorbed on weaker basic sites are easily desorbed at low temperature and those adsorbed on strong basic sites require high desorbed temperature. It can be found from Fig. 6(b) that both catalysts show three desorption peaks, indicating that there are three kinds of basic sites. Comparing with C-700 sample, P-80 catalyst has more total basic amount. Moreover, the peak temperature of C-700 catalyst prepared by traditional method is above the reaction temperature of 700 C, meaning that the reactant CO2 adsorbed on these sites is relative difcultly desorbed in the reaction. However, the temperature of 660 C attributed to strong basic sites on P-80 catalyst is below 700 C, which indicates that CO2 molecules absorbed on the catalyst can be desorbed in the reaction process, facilitating the CO2 reforming of methane. In addition, the adsorption of methane and carbon monoxide can be also hindered for the competitive adsorption with CO2, and will reduce the carbon deposit via carbon monoxide disproportionation and methane decomposition. Thus, the carbon deposit can be restrained, which can be conrmed by the TG analysis in Fig. 8. Fig. 8 shows the TG/DTG curves of C-700 and P-80 catalysts after reaction for 6 h and 32 h at temperature of 700 C. The weight loss at the temperature region of 200e800 C is ascribed to combustion of deposited carbon [24]. It can be seen from Fig. 8(a) that the P-80 catalyst has better anti-carbon deposit performance in the rst 6 h reaction. The amount of coke is just 2.6%, obviously less than 16.2% of C-700 sample. However, the P-80 exhibits quick increase of carbon deposit rate in the following 26 h, which is from 2.6% to 12.5%, higher than that from 16.2% to 21.2% of C-700 sample. What results in the difference of carbon deposit rate? It is thought that the increase of Ni particle sizes is maybe the main reason. Osaki et al. [28] thought that the carbon formation proceeded mainly on larger Ni ensemble than 9.1 nm in CRM. From Table 2 and Fig. 7(c), it is found that the Ni size of P-80 is obviously smaller than the required ensemble of 9.1 nm after the reaction of 6 h despite slight increase to 5.2 nm, so the amount of carbon deposit is quite little. However, after 32 h of reaction, the Ni
particle increases to near 10 nm (see Fig. 7(d)) due to the sintering at high temperature, which is benecial to the carbon formation and results in the quick increase of carbon deposit on P-80 catalyst. As to the fresh C-700 catalyst, the average Ni size of 10.3 nm makes it higher carbon deposit even in the rst 6 h. Nevertheless, the total amount of coke on P-80 sample is still less than that on C-700 catalyst after 32 h. More basic sites and weaker basicity of P-80 catalyst than C-700 sample are probably another reason for better anti-carbon deposit performance.
4.
Conclusions
The Ni/g-Al2O3 catalyst for CRM reaction was prepared by direct treatment of Ni(NO3)2/g-Al2O3 with DBD H2 plasma at atmospheric pressure. The input power has an obvious effect on the reduction degree and catalytic activities of Ni/g-Al2O3 catalysts. When the power is below 40 W, nickel nitrate was just decomposed into Ni oxides without obvious reduction. The reduction degree increases and the catalytic activities and stability can be improved with increasing input power. But the catalyst prepared at input power of above 80 W has the similar catalytic performance. Compared than C-700 catalyst prepared by traditional calcination and reduction method, the Ni/ g-Al2O3 sample prepared by H2 DBD plasma exhibits better activity, stability and anti-carbon deposit performances, which are mainly ascribed to smaller Ni particle size, more basic sites and weaker basicity of P-80 catalyst. The increase of Ni particle size at high temperature results in the decrease of catalytic activities and the carbon deposit.
Acknowledgments
This work was supported by the Natural Science Foundation of China (No. 20906009, 21176042), the National Basic Research Program of China (973 Program), the Ministry of Science and Technology, China (No. 2011CB201301), International S&T cooperation and exchange programs of Ministry of S&T (No.2013DFG60060), Liaoning Province Education Administration Fund (No. L2013028) and the Fundamental Research Funds for the Central Universities (No. DUT12JN05).
8
references
[1] Liu CJ, Ye JY, Jiang JJ, Pan YX. Progresses in the preparation of coke resistant Ni-based catalyst for steam and CO2 reforming of methane. ChemCatChem 2011;3:529e41. [2] Fan MS, Abdullah AZ, Bhatia S. Catalytic technology for carbon dioxide reforming of methane to synthesis gas. ChemCatChem 2009;1:192e208. [3] Muradov N, Smith F, T-Raissi A. Hydrogen production by catalytic processing of renewable methane-rich gases. Int J Hydrogen Energy 2008;33:2023e35. [4] Ross JRH. Natural gas reforming and CO2 mitigation. Catal Today 2005;100:151e8. guez M, Pieta IS, Herrera MC, Larrubia MA, [5] Garc a-Die Alemany LJ. Nanostructured Pt- and Ni-based catalysts for CO2-reforming of methane. J Catal 2010;270:136e45. [6] Richardson JT, Garrait M, Hung JK. Carbon dioxide reforming with Rh and Pt-Re catalysts dispersed on ceramic foam supports. Appl Catal A-Gen 2003;28:69e82. [7] Jang WJ, Jeong DW, Shim JO, Roh HS, Son IH, Lee SJ. H2 and CO production over a stable NieMgOeCe0.8Zr0.2O2 catalyst from CO2 reforming of CH4. Int J Hydrogen Energy 2013;38:4508e12. [8] Daza CE, Moreno S, Molina R. Co-precipitated Ni-Mg-Al catalysts containing Ce for CO2 reforming of methane. Int J Hydrogen Energy 2011;36:3886e94. [9] Liu CJ, Zou JJ, Yu KL, Cheng DG, Han Y, Zhan J, et al. Plasma application for more environmentally friendly catalyst preparation. Pure Appl Chem 2006;78:1227e38. [10] Halverson DE, Cocke DL. Ruthenium impregnation of plasma grown alumina lms. J Vac Sci Technol 1989;7:40e8. [11] Phillips J. Plasma generation of supported metal catalysts. US 5989648, 1999. [12] Zou JJ, Zhang YP, Liu CJ. Reduction of supported noble-metal ions using glow discharge plasma. Langmuir 2006;22:11388e94. [13] Pan YX, Liu CJ, Shi P. Preparation and characterization of coke resistant Ni/SiO2 catalyst for carbon dioxide reforming of methane. J Power Sources 2008;176:46e53. [14] Zhu XL, Huo PP, Zhang YP, Cheng DG, Liu CJ. Structure and reactivity of plasma treated Ni/Al2O3 catalyst for CO2 reforming of methane. Appl Catal B-Gen 2008;81:132e40. [15] Zhao Y, Pan YX, Xie YB, Liu CJ. Carbon dioxide reforming of methane over glow discharge plasma-reduced Ir/Al2O3 catalyst. Catal Commun 2008;9:1558e62.
[16] Wang ZJ, Zhao Y, Cui L, Du HY, Yao P, Liu CJ. CO2 reforming of methane over argon plasma reduced Rh/Al2O3 catalyst: a case study of alternative catalyst reduction via nonhydrogen plasmas. Green Chem 2007;9:554e9. [17] Hu SJ, Long HL, Xu Y, Shang SY, Yin YX. Reduction mechanism of Ni/Al2O3 catalyst reduced by cold plasma jet for carbon dioxide reforming of methane. Chin J Catal 2011;32:340e4. [18] Li ZH, Tian SX, Wang HT, Tian HB. Plasma treatment of Ni catalyst via a corona discharge. J Mol Catal A-Chem 2004;211:149e53. [19] Liu GH, Li YL, Chu W, Shi XY, Dai XY, Yin YX. Plasmaassisted preparation of Ni/SiO2 catalyst using atmospheric high frequency cold plasma jet. Catal Commu 2008;9:1087e91. [20] Chai XY, Shang SY, Liu GH, Tao XM, Li X, Bai MG, et al. Characterization of Ni/g-A1203 catalyst prepared by atmospheric high frequency cold plasma jet for CO2 reforming of CH4. Chin J Catal 2010;31:353e9. [21] Kim SS, Lee H, Na BK, Song HK. Plasma-assisted reduction of supported metal catalyst using atmospheric dielectricbarrier discharge. Catal Today 2004;89:193e200. [22] Hua W, Jin LJ, He XF, Liu JH, Hu HQ. Preparation of Ni/MgO catalyst for CO2 reforming of methane by dielectric-barrier discharge plasma. Catal Commun 2010;11:968e72. [23] Hou ZY, Yashima T. Small amounts of Rh-promoted Ni catalysts for methane reforming with CO2. Catal Lett 2003;89:193e7. [24] Cheng DG, Zhu XL, Ben YH, He F, Cui L, Liu CJ. Carbon dioxide reforming of methane over Ni/Al2O3 treated with glow discharge plasma. Catal Today 2006;115:205e10. [25] Zhang Y, Chu W, Cao WM, Luo CR, Wen XG, Zhou KL. A plasma-activated Ni/a-Al2O3 catalyst for the conversion of CH4 to syngas. Plasma Chem Plasma P 2000;20:137e44. [26] Shang SY, Liu GH, Chai XY, Tao XM, Li X, Bai MG, et al. Research on Ni/g-Al2O3 catalyst for CO2 reforming of CH4 prepared by atmospheric pressure glow discharge plasma jet. Catal Today 2009;148:268e74. [27] Meshkani F, Rezaei M. Ni catalysts supported on nanocrystalline magnesium oxide for syngas production by CO2 reforming of CH4. J Nat Gas Chem 2011;20:198e203. [28] Osaki T, Mori T. Role of potassium in carbon-free CO2 reforming of methane on K-promoted Ni/Al2O3 catalyst. J Catal 2001;204:89e97.

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 4 ) 1 e8

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FCO2 ; in FCO2 ; out 100% FCO2 ; in

Mol of H2 produced Mol of CO produced

Results and discussion

Table 1 e Temperatures in the discharge region under different input power.a

Quickly measured by a K-type thermocouple when the discharge is stopped.

3.3. Comparison of catalytic performances on P-80 and C-700 sample

Catalytic performance of P-x catalysts

Ni particle size (nm)a Reduced

Vtot (cm3 g1)

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