高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (5): 841.

• 研究简报 • 上一篇    下一篇

硫化态三组元NiMoP/γ-Al2O3催化剂的TPR表征及噻吩HDS活性的研究

齐兴义1, 徐春明2, 刘植昌2, 李文钊3, 辛勤3   

  1. 1. 北京航空航天大学材料科学与工程学院, 北京 100083;
    2. 石油大学化工学院, 北京 102200;
    3. 中国科学院大连化学物理研究所, 大连 116023
  • 收稿日期:2000-04-25 出版日期:2001-05-24 发布日期:2001-05-24
  • 通讯作者: 齐兴义(1956年出生),男,博士,副教授,从事加氢精制及选择氧化反应研究.E-mail:qixy@www.bjpeu.edu.cn E-mail:qixy@www.bjpeu.edu.cn
  • 基金资助:

    石油大学(北京)重质油加工国家重点实验室开放基金(批准号:199919)资助

Studies on Characterization of Sulfided Tertiary NiMoP/γ-Al2O3 Catalysts by TPR Technique and Their Thiophene HDS Activity

QI Xing-Yi1, XU Chun-Ming2, LIU Zhi-Chang2, LI Wen-Zhao3, XIN Qin3   

  1. Faculty of Material Science and Engineering, Beijing University of Aeronautics and Astronautics, Beijing 100083, China;
    2. Faculty of Chemical Engineering, University of Petroleum Beijing, Beijing 102200, China;
    3. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received:2000-04-25 Online:2001-05-24 Published:2001-05-24

关键词: 过渡金属硫化物, TPR, HDS

Abstract: Aseries of sulfided tertiary NiMoP/ γ-Al2O3 catalysts with different contents of MoO3 were prepared by using molybdophosphoric acid of Keggin structure(H3PMo12 O40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPRtechnique, with their HDSactivity being investigated with thiophene as a model substrate. For the sulfided Mo-0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 Kand attributed to the hydrogenation of the so-called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mox+ sites on the MoS2 phase(MoS2 slab). With the introduction of nickel into the active phase of the sulfided Mo-0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ-Al2O3 catalysts, the thiophene HDSrate and the quantity of hydrogen sulfide evolved during TPRprocess increase monotonously with the atomic ratio of molybdenum to nickel in the form of [n(Ni)+n(Mo)]/n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni-Mo-S slab due to the loss of Sduring TPRprocess and vacancies or sites related to the H2Sevolution peak IIshould be regarded as the mainly active reaction centers of thiophene HDS.

Key words: Transition metal sulfides, TPR, HDS

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