石油学报(石油加工) ›› 2021, Vol. 37 ›› Issue (1): 24-31.doi: 10.3969/j.issn.1001-8719.2021.01.003

• 研究报告 • 上一篇    下一篇

氮化物对多孔ZSM-5沸石和Al2O3负载NiMo催化剂加氢脱硫性能的影响

和法端,张磊   

  1. 常州大学 石油化工学院, 江苏 常州 213164
  • 收稿日期:2019-12-16 修回日期:2020-04-28 出版日期:2021-01-25 发布日期:2021-01-12
  • 通讯作者: 张磊,男,讲师,博士,从事多孔沸石催化材料的合成,表征以及催化性能的研究,E-mail:lqzhang@cczu.edu.cn E-mail:lqzhang@cczu.edu.cn
  • 作者简介:第一作者:和法瑞,男,硕士研究生,从事加氢脱硫催化剂的研究
  • 基金资助:
    江苏省高等学校自然科学研究面上项目(18KJB530002), 江苏省“六大人才高峰”高层次人才项目(2018-XCL-100)资助

Effects of Nitrogen Compounds on Hydrodesulfurization Performance of NiMo Catalysts Supported on Hierarchical Pore ZSM-5 Zeolite or Al2O3

HE Farui, ZHANG Lei   

  1. School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China
  • Received:2019-12-16 Revised:2020-04-28 Online:2021-01-25 Published:2021-01-12

摘要: 分别以多级孔ZSM-5沸石(ZSM-5-H)和γ-Al2O3为载体,制备了NiMoS/ZSM-5-H和NiMoS/γ-Al2O3催化剂,采用X射线衍射(XRD)、N2吸附-脱附、氨气程序升温脱附(NH3-TPD)等分析方法对催化剂的结构和性质进行了表征,考察了碱性氮化物喹啉和非碱性氮化物吲哚对4,6-二甲基二苯并噻吩(4,6-DMDBT)和二苯并噻吩(DBT)在2种催化剂上加氢脱硫性能的影响。结果表明:与ZSM-5相比,γ-Al2O3具有更大的介孔体积和更强的表面酸性。在不存在含氮化合物的情况下,NiMoS/ZSM-5-H催化剂对4,6-DMDBT加氢脱硫性能高于NiMoS/γ-Al2O3催化剂;含氮化合物的加入导致NiMoS/ZSM-5-H催化剂对4,6-DMDBT的加氢脱硫活性低于NiMoS/γ-Al2O3催化剂,主要原因是含氮化合物强烈地抑制了4,6-DMDBT的转化,但对DBT的加氢脱硫几乎无影响。

关键词: 加氢脱硫, 氮化物;4,6-二甲基二苯并噻吩;ZSM-5 沸石;NiMo催化剂

Abstract: Hierarchical pore ZSM-5 zeolite (ZSM-5-H) andγ-Al2O3 supported NiMo catalysts (NiMoS/ZSM-5-H and NiMoS/γ-Al2O3) were prepared and catalytically evaluated by the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in the absence and presence of nitrogen compounds (quinolone and indole). The supports and catalysts were characterized by X-ray diffraction (XRD), N2 adsorption-desorption and ammonia temperature-programmed desorption (NH3-TPD). The HDS results show that the HDS activity of NiMoS/ZSM-5-H catalyst is higher than that of NiMoS/γ-Al2O3 in the absence of nitrogen compound, althoughγ-Al2O3 has larger mesopore volume and stronger surface acidity than those of ZSM-5-H. In contrast, the HDS activity of NiMoS/ZSM-5-H catalyst is lower than that of NiMoS/γ-Al2O3 catalyst in the presence of nitrogen compound. In addition, the conversion of 4,6-DMDBT is reducing rapidly when adding nitrogen compounds, while the nitrogen compounds hardly have effect on the HDS of DBT.

Key words: hydrodesulfurization, nitrogen compounds, 4,6-dimethyldibenzothiophene, ZSM-5 zeolite, NiMo Catalysts