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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2016, Vol. 10 Issue (2) : 273-280    https://doi.org/10.1007/s11705-016-1563-5
RESEARCH ARTICLE
CO2 methanation and co-methanation of CO and CO2 over Mn-promoted Ni/Al2O3 catalysts
Kechao Zhao1,Zhenhua Li1,*(),Li Bian1,2
1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2. College of Science, Hebei University of Engineering, Handan 056038, China
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Abstract

A series of Mn-promoted 15 wt-% Ni/Al2O3 catalysts were prepared by an incipient wetness impregnation method. The effect of the Mn content on the activity of the Ni/Al2O3 catalysts for CO2 methanation and the co-methanation of CO and CO2 in a fixed-bed reactor was investigated. The catalysts were characterized by N2 physisorption, hydrogen temperature-programmed reduction and desorption, carbon dioxide temperature-programmed desorption, X-ray diffraction and high-resolution transmission electron microscopy. The presence of Mn increased the number of CO2 adsorption sites and inhibited Ni particle agglomeration due to improved Ni dispersion and weakened interactions between the nickel species and the support. The Mn-promoted 15 wt-% Ni/Al2O3 catalysts had improved CO2 methanation activity especially at low temperatures (250 to 400 °C). The Mn content was varied from 0.86% to 2.54% and the best CO2 conversion was achieved with the 1.71Mn-Ni/Al2O3 catalyst. The co-methanation tests on the 1.71Mn-Ni/Al2O3 catalyst indicated that adding Mn markedly enhanced the CO2 methanation activity especially at low temperatures but it had little influence on the CO methanation performance. CO2 methanation was more sensitive to the reaction temperature and the space velocity than the CO methanation in the co-methanation process.
Keywords Mn promotion      nickel catalysts      CO2 methanation      co-methanation of CO and CO2     
Corresponding Author(s): Zhenhua Li   
Online First Date: 16 March 2016    Issue Date: 19 May 2016
 Cite this article:   
Kechao Zhao,Zhenhua Li,Li Bian. CO2 methanation and co-methanation of CO and CO2 over Mn-promoted Ni/Al2O3 catalysts[J]. Front. Chem. Sci. Eng., 2016, 10(2): 273-280.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1563-5
https://academic.hep.com.cn/fcse/EN/Y2016/V10/I2/273
Catalyst Surface area /(m2·g–1) Pore volumea) /(m3·g–1) Pore sizeb) /nm
Al2O3 242 0.45 5.7
Ni/Al2O3 174 0.33 5.6
0.86Mn-Ni/Al2O3 171 0.31 5.3
1.71Mn-Ni/Al2O3 169 0.31 5.4
2.54Mn-Ni/Al2O3 174 0.32 5.5
Tab.1  Physical properties of catalysts with different Mn content
Fig.1  (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves of the support and catalysts
Fig.2  XRD patterns of the fresh catalysts
Fig.3  H2-TPR profiles for the catalysts with different Mn loadings
Catalyst H2 uptake /(mL·g–1) Ni dispersion /% Ni specific metal surface area /(m2·g–1) Ni particle size /nm
Ni/Al2O3 2.61 10.46 69.80 9.66
0.86Mn-Ni/Al2O3 2.66 10.70 71.31 9.45
1.71Mn-Ni/Al2O3 4.26 17.10 114.01 5.91
2.54Mn-Ni/Al2O3 2.96 11.90 79.34 8.49
Tab.2  H2-TPD results for the catalysts
Fig.4  CO2-TPD profiles of the catalysts
Fig.5  TEM images of the catalysts before and after methanation reactions
Fig.6  CO2 conversion vs. reaction temperature for the catalysts
Fig.7  Methane selectivity vs. reaction temperature for the catalysts
Fig.8  COx conversion vs. reaction temperature in co-methanation test
Fig.9  Effect of WHSV on COx conversion at 450 °C and 0.1 MPa
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