失活加氢精制催化剂中硫铁相的高分辨透射电镜研究  

Study on the FexS Phase of Deactivated Hydrotreating Catalyst by High Resolution Transmission Electron Microscopy

作　　者：杨卫亚[1] 沈智奇[1] 杨占林[1] 王丽华[1] 凌凤香[1] 孙万付[1] 

机构地区：[1]中国石油化工股份有限公司抚顺石油化工研究院,辽宁抚顺113001

出　　处：《分析测试学报》2009年第7期842-845,共4页Journal of Instrumental Analysis

摘　　要：利用高分辨透射电镜(HRTEM)结合X射线能谱仪(EDS)和选区电子衍射(SAED)分析,对运转后的加氢精制催化剂中含有的微量未知相的化学组成、晶体结构进行了研究。通过X射线能谱仪确定该未知相主要成分为硫和铁。根据选区电子衍射结果,该硫铁相为单晶结构。采用样品倾转的方法,获得3幅不同取向的选区电子衍射图,根据衍射谱中衍射斑点对应的晶体学信息及3幅电子衍射图取向间的夹角关系,确定该硫铁化合物属于正交晶系的硫化亚铁,分子式为Fe0.91S。该催化剂应用于高温高压下的加氢环境中,其中原料油中的酸性物质,尤其是环烷酸对加氢设备材质的腐蚀是导致硫铁化合物相形成的主要原因,并由此探讨了硫铁化合物相的形成机制。High resolution transmission electron microscopy （HRTEM） coupled with X-ray energy disperse spectroscopy（EDS） and selected area electron diffraction （SAED） were used to study the chemical composition and the crystal structure of the unknown phase of the deactivated hydrotreating catalysts after running. The results of EDS showed that the unknown phase was mainly composed of S and Fe elements and those of SAED patterns showed that the FexS phase was of single crystal structure. With the aid of the double-tilt method, three SAED patterns of different orientations were obtained. According to the crystallographic information corresponding to the diffraction spot of the diffraction spectrum and the relationship between the orientation intersecting angles of three SAED patterns, the ferrous sulphide FexS phase was confirmed to be of orthorhombic syngony, and its molecular formula was Fe0.91S. It was found that the formation of FexS was resulted from the corrosion of the hydrotreating equipment material caused by the acidic component, such as naphthenic acid in the feed oil when the catalyst was used under high temperature and high pressure working conditions. Hence the selection of appropriate material for hydrotreating equipment should be taken into consideration.

关 键 词：加氢精制 催化剂 硫化亚铁 高分辨透射电镜 

分 类 号：O722.7[理学—晶体学]