Kinetics study of Fischer-Tropsch reaction to lower olefins over MnOx-promoted Fe/SiO2 catalysts

doi:10.11949/j.issn.0438-1157.20150751

Abstract

Abstract:

The promotional effects of MnO_x on the synthesis of lower olefins via Fischer-Tropsch reaction over Fe/SiO₂ catalysts were investigated. It was found that CO conversion and STY(space time yield) of C₂-C₄ olefins was greatly enhanced with the addition of MnO_x. CO₂-TPD and CO-TPD (temperature program desorption) have evidenced that MnO_xcould enhance the surface basicity of Fe-based catalyst. The intrinsic kinetics for Fischer-Tropschto reaction to lower olefins (FTO) was measured under the realistic reaction conditions over Fe/SiO₂ catalysts with and without MnO_x by fitting power-law model. The apparent activation energies and reaction orders were calculated based on the formation of products and CO conversion. With combination of kinetics and temperature-programmed techniques, it was found that the MnO_x promoter can enhance the dissociation of CO and inhibite the readsorption of lower olefins, leading to the enhancement of STY and the selectivity to lower olefins. Finally, the FTO reaction mechanisms of Fe-based catalysts, especially, the promotional effects of MnO_x on Fe/SiO₂ for the production of lower olefins, were speculated.

Key words: lower olefins, intrinsic kinetics, Fe-based catalysts, MnO_x promoter, syngas, hydrogenation

摘要：

探讨了MnO_x助剂对Fe/SiO₂催化剂经由费-托反应(Fischer-Tropsch)制备低碳烯烃(FTO)的影响。通过浸渍法制备了Fe₂₀/SiO₂和Fe₂₀-Mn_1.0/SiO₂催化剂,结果表明MnO_x助剂显著提升了CO转化率和C₂～C₄烯烃的时空收率。程序升温吸附实验表明MnO_x助剂增加了Fe基催化剂表面碱性,促进了CO的解离吸附。运用幂指数模型,研究了Fe₂₀/SiO₂和Fe₂₀-Mn_1.0/SiO₂催化剂上FTO反应动力学,得到了各产物生成活化能与H₂/CO反应级数。最后,结合动力学研究与程序升温表征结果,对Fe基催化剂FTO反应机理,尤其是MnO_x助剂提高Fe₂₀/SiO₂催化剂上低碳烯烃选择性的作用进行了讨论。

关键词: 低碳烯烃, 动力学, 铁基催化剂, 锰助剂, 合成气, 加氢

CLC Number:

TQ028.8

DAI Weiwei, LIU Da, FU Donglong, ZHANG Zhengpai, ZHANG Jun, XU Jing, HAN Yifan. Kinetics study of Fischer-Tropsch reaction to lower olefins over MnO_x-promoted Fe/SiO₂ catalysts[J]. CIESC Journal, 2015, 66(9): 3444-3455.

戴薇薇, 刘达, 付东龙, 张征湃, 张俊, 徐晶, 韩一帆. MnO_x助剂对Fe/SiO₂催化剂费-托合成制低碳烯烃动力学的影响[J]. 化工学报, 2015, 66(9): 3444-3455.

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Kinetics study of Fischer-Tropsch reaction to lower olefins over MnO_x-promoted Fe/SiO₂ catalysts

MnO_x助剂对Fe/SiO₂催化剂费-托合成制低碳烯烃动力学的影响

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