Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model

doi:10.1016/j.cjche.2022.05.015

Abstract

Abstract: Dry reforming of methane (DRM) is an attractive technology for utilizing the greenhouse gases (CO₂ and CH₄) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al₂O₃ catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH₄/CO₂ molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible. The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.

Key words: Deactivation by coking, Dry reforming of methane, Pore network model, Diffusion limitation, Catalyst pellet

摘要： Dry reforming of methane (DRM) is an attractive technology for utilizing the greenhouse gases (CO₂ and CH₄) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al₂O₃ catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH₄/CO₂ molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible. The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.

关键词: Deactivation by coking, Dry reforming of methane, Pore network model, Diffusion limitation, Catalyst pellet

Yu Wang, Qunfeng Zhang, Xinlei Liu, Junqi Weng, Guanghua Ye, Xinggui Zhou. Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model[J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 293-303.

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