Chemical Research in Chinese Universities ›› 2022, Vol. 38 ›› Issue (4): 1032-1040.doi: 10.1007/s40242-021-1281-5

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Improving Catalytic Stability and Coke Resistance of Ni/Al2O3 Catalysts with Ce Promoter for Relatively Low Temperature Dry Reforming of Methane Reaction

HE Lulu1, CHEN Xin1, REN Yuanhang1, YUE Bin1, TSANG Shik Chi Edman2, HE Heyong1   

  1. 1. Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, P. R. China;
    2. Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford OX1 3QR, UK
  • Received:2021-07-21 Revised:2021-08-31 Online:2022-08-01 Published:2021-09-24
  • Contact: HE Heyong;YUE Bin E-mail:heyonghe@fudan.edu.cn;yuebin@fudan.edu.cn
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (No.22088101) and the Fund of China Petroleum&Chemical Corporation (No.420068-2).

Abstract: Aseries of Ni catalysts supported on alumina with different Ce contents(1.0%-6.0%, mass fraction) was prepared by the impregnation method and used for dry reforming of methane(DRM) at a relatively low temperature of 650 oC. The promotion effect of Ce with different loading amounts on the physicochemical properties of the catalysts was systematically characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), N2 adsorption-desorption, thermo elemental IRIS Intrepid inductively coupled plasma atomic emission spectrometer (ICP-AES), UV-visible diffuse reflectance spectroscopy(UV-Vis DRS), Fourier transformation infrared(FTIR) spectra, H2-temperature programmed reduction(H2-TPR) analysis, H2-temperature programmed desorption(H2-TPD), and the X-ray photoelectron spectroscopy(XPS) techniques. The results indicate that all the catalysts mainly exist in the NiAl2O4 phase after being calcined at 750 oC with small Ni particle sizes due to the strong metal-support interaction derived from the reduction of the NiAl2O4 phase. The Ce-promoted catalysts show better catalytic performance as well as the resistance against sintering of Ni particles and deposition of carbon compared to the Ni/Al2O3 catalyst. The Ni-6Ce/Al2O3 exhibits the best catalytic stability and coke resistance among the four catalysts studied, which is due to its small Ni nanoparticles sizes, excellent reducibility as well as high amount of active oxygen species. In a 400 h stability test for DRM reaction at 650 oC, Ni-6Ce/Al2O3 exhibits less coke deposition and small growth of Ni nanoparticles. This work provides a simple way to preparing the Ni-Ce/Al2O3 catalyst with enhanced catalytic performance in DRM. The Ni-6Ce/Al2O3 catalyst has great potential for industrial application due to its anti-sintering ability and resistance to carbon deposition.

Key words: Dry reforming of methane(DRM), Cerium oxide, Ni-based catalyst, Coke resistance