Han Zhonghao, Qian Weixin, Ma Hongfang, Zhang Haitao, Sun Qiwen, Ying Weiyong
Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, State Key Laboratory of Chemical Engineering, East China University of Science and Technology Shanghai 200237 China
State Key Laboratory of Coal Liquefaction and Coal Chemical Technology Shanghai 201203 China.
RSC Adv. 2019 Oct 10;9(55):32240-32246. doi: 10.1039/c9ra05337a. eCollection 2019 Oct 7.
Sm-promoted FeMn catalysts were prepared by the co-precipitation method and characterized by N adsorption, XRD, CO-TPD, H-TPD, CO-TPD, H-TPR, XPS and MES. It was found that compared with the un-promoted catalyst, when Sm was added at a proper content, the catalyst showed a larger BET surface area and promoted the formation of iron particles with a smaller size. The presence of Sm could increase the surface charge density of iron, which enhanced the Fe-C bond and promoted the stability and amount of CO dissociated adsorption, as confirmed by XPS and CO-TPD. Furthermore, according to MES, Sm could promote the formation of FeC, which was the active phase of FTS. In addition, Sm could also enhance the basicity of the catalysts and suppress the H adsorption capacity, which inhibited the hydrogenation reaction and the conversion of olefins to paraffins, as verified by the results of CO-TPD and H-TPD. According to the FTS performance results, compared with the observations for the un-promoted catalysts, when the molar ratio of Sm to Fe was 1%, the CO conversion increased from 63.4% to 70.4%, the sum of light olefins in the product distribution increased from 26.6% to 32.6, and the ratio of olefins to paraffins increased to 4.18 from 4.09.
采用共沉淀法制备了Sm促进的FeMn催化剂,并通过N吸附、XRD、CO-TPD、H-TPD、CO-TPD、H-TPR、XPS和MES对其进行了表征。结果发现,与未促进的催化剂相比,当以适当含量添加Sm时,催化剂表现出更大的BET表面积,并促进了更小尺寸铁颗粒的形成。XPS和CO-TPD证实,Sm的存在可增加铁的表面电荷密度,增强Fe-C键,并促进CO解离吸附的稳定性和量。此外,根据MES,Sm可促进FTS活性相FeC的形成。此外,Sm还可增强催化剂的碱性并抑制H吸附能力,这抑制了加氢反应以及烯烃向石蜡的转化,CO-TPD和H-TPD的结果证实了这一点。根据FTS性能结果,与未促进催化剂的情况相比,当Sm与Fe的摩尔比为1%时,CO转化率从63.4%提高到70.4%,产物分布中轻质烯烃的总和从26.6%增加到32.6,烯烃与石蜡的比例从4.09提高到4.18。