Chinese Journal of Catalysis

Chinese Journal of Catalysis ›› 2013, Vol. 34 ›› Issue (6): 1242-1249.DOI: 10.1016/S1872-2067(12)60563-4

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Synthesis of three-dimensionally ordered macroporous LaFeO3 perovskites and their performance for chemical-looping reforming of methane

HE Fanga, ZHAO Kuna,b, HUANG Zhena, LI Xin’aia, WEI Guoqianga,b, LI Haibina   

  1. a The Key Laboratory of Renewable Energy and Gas Hydrate of Chinese Academy of Sciences, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China;
    b University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2013-01-14 Revised:2013-03-07 Online:2013-06-07 Published:2013-06-09
  • Supported by:

    This work was support by the National Natural Science Foundation of China (51076154), the National Key Technology R&D Program of the 12th Five-Year Plan of China (2011BAD15B05), and the Science & Technology Research Project of Guangdong Province (2010B010900047).

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Abstract:

Three-dimensionally ordered macroporous (3DOM) LaFeO3 perovskite-type oxides were synthesized using a polystyrene colloidal crystal templating method. The obtained 3DOM LaFeO3 was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The reactivity of the perovskite-type oxides was evaluated using temperature-programmed reduction and multicyclic redox reactions by exposing them to an alternating methane and air atmosphere. The methane oxidation performance of the oxides was investigated in a fixed-bed reactor. The effect of the self-assembly method on the structure of the polystyrene template was also studied. A vertical deposition method yielded a more uniform and orderly polystyrene template than those obtained by centrifugation and evaporation techniques. The solvent and concentration of the precursor solution were the major factors to affect the prepared 3DOM perovskite. SEM analysis showed that samples synthesized with ethanol precursor solvent exhibited a better 3DOM structure than those produced with ethylene glycol, and that 1.0 mol/L may be an optimal precursor solution concentration. XRD and FTIR results suggested that the obtained 3DOM LaFeO3 was pure crystalline perovskite. Two kinds of oxygen species were found to exist on the 3DOM perovskites: surface adsorbed oxygen and bulk lattice oxygen. The surface oxygen contributed to the complete oxidization of methane to CO2 and H2O because of its higher reactivity, while the bulk lattice oxygen tended towards partial methane oxidation to H2 and CO. The available oxygen in the 3DOM LaFeO3 was higher than that of the same mass of non-3DOM LaFeO3 during the partial oxidation of methane. Methane was partially oxidized into syngas with a H2/CO ratio of around 2:1 in a wide time range of the reactions. The generated H2/CO = 2 syngas was suitable for subsequent gas-to-liquids processes, such as Fischer-Tropsch and/or methanol synthesis.

Key words: Three-dimensionally ordered macroporous LaFeO3 perovskite, Oxygen carrier, Synthesis gas, Chemical-looping reforming, Methane