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低温固相法制备非负载型介孔Ni-Mo-W 硫化物催化剂
安高军1,2,柴永明1,2,陈照军1,刘晨光1,2
(1.中国石油大学重貭油国家重点实验室,山东东营257061; 2.中国石油天然气集团公司催化重点实验室,山东东营257061)
摘要:
介绍了一种新型的柴油深度加氢改质催化剂的制备方法。以四硫代钼酸铵、四硫代钨酸铵和碱式碳酸镍为前 驱物,以化合物MS-1为模板剂,采用低温固相表面反应技术,制备出具有较高比表面、适宜孔容和介孔孔径分布的 非负载型Ni-Mo-W硫化物催化剂,并采用X射线衍射、低温N2吸附、扫描电镜、高分辨透射电镜等手段对所制备的 催化剂进行表征。将所制备的加氢催化剂以催化裂化柴油为原料,采用高压釜装置进行加氢活性评价。评价结果 表明,该方法制备的催化剂具有优异的加氢脱硫、加氢脱氮活性。
关键词:  四硫代钼酸铵  四硫代钨酸铵  模板剂  固相反应  介孔材料  催化剂
DOI:
分类号:
基金项目:国家“973”重点基础研究发展规划项目(2004CB217807)
Preparation of unsupported and mesoporous Ni-Mo-W sulfide catalysts by low temperature solid-state reaction
AN Gao-jun1,2,CHAI Yong-ming1,2,CHEN Zhao-jun1,LIU Chen-guang1,2
(1. State Key Laboratory of Heavy Oil Processing in China University of Petroleum, Dongying 257061,Shandong Province, China;2. Key Laboratory of Catalysis, CNPC, Dongying 257061,Shandong Province, China)
Abstract:
A novel preparation method of diesel oil deeply-hydrotreating catalysts was introduced. By using ammonium tetra-thiomolybdate, ammonium tetrathiotungstate and basic nickel carbonate as the catalyst precursors and compound MS-1 as the template unsupported Ni-Mo-W sulfide catalysts with higher specific surface area,proper pore volume and mesoporous structure were synthesized through the technology of low temperature solid-state surface reaction. The X-ray diffraction ( XRD), low temperature N2 adsorption ( BET method),scanning electron microscopy ( SEM) and high resolution transmission electron microscope ( HRTEM) were employed to characterize the as-synthesized sulfide catalysts. The as-synthesized catalysts were evaluated in the high-pressure vessel by utilizing FCC diesel oil as the material. The evaluation results show that the as-synthesized sulfide catalysts have excellent performance of hydrodesulfurization and hydrodenitrogenation.
Key words:  ammonium tetrathiomolybdate  ammonium tetrathiotungstate  template solid-state reaction  mesoporous material  catalysts
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