高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (6): 1207.doi: 10.7503/cjcu20190022

• 物理化学 • 上一篇    下一篇

钼改性页硅酸镍催化剂催化顺酐加氢性能

夏晓丽, 谭静静(), 卫彩云, 赵永祥()   

  1. 山西大学化学化工学院, 精细化学品教育部工程研究中心, 太原 030006
  • 收稿日期:2019-01-09 出版日期:2019-06-10 发布日期:2019-04-18
  • 作者简介:

    联系人简介: 谭静静, 女, 博士, 讲师, 主要从事生物质及其糖类衍生物、 煤基下游产品催化转化制备精细化学品及液体燃料的研究. E-mail: tanjingjing@sxu.edu.cn;赵永祥, 男, 博士, 教授, 主要从事煤下游高附加值重要化学品关键技术的研究. E-mail: yxzhao@sxu.edu.cn

  • 基金资助:
    山西省青年基金项目(批准号: 201701D221030)和国家国际科技合作专项(批准号: 2013DFA40460)资助.

Molybdenum Modified Nickel Phyllosilicates Catalyst for Maleic Anhydride Hydrogenation

XIA Xiaoli, TAN Jingjing(), WEI Caiyun, ZHAO Yongxiang()   

  1. Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
  • Received:2019-01-09 Online:2019-06-10 Published:2019-04-18
  • Supported by:
    † Supported by the Natural Science Foundation of Shanxi Province, China(No.201701D221030) and the National International Science and Technology Cooperation Foundation of China(No.2013DFA40460).

摘要:

通过蒸氨法合成了一系列钼改性的页硅酸镍催化剂, 考察了钼含量对催化剂结构及其催化顺酐液相加氢性能的影响. 采用氮气物理吸附-脱附、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 透射电子显微镜(TEM)、 氢气程序升温还原(H2-TPR)、 氨气程序升温脱附(NH3-TPD)、 吡啶吸附红外光谱(Py-IR)和原位X射线光子能谱(XPS)等手段对催化剂的结构和形貌等进行了表征. 结果表明, 助剂Mo的引入对催化剂结构形貌及其催化性能影响显著. Mo的引入提高了活性金属Ni的还原度, 增加了催化剂表面金属Ni0的数量, 金属Ni在还原过程产生氢溢流, 溢流氢将部分MoO3还原为具有酸性的MoOx物种, 由于金属Ni0与具有Lewis酸(L酸)特性的MoOx及Niσ+的协同效应, 显著提高了催化剂对顺酐C≡C和C≡O的加氢活性. 当Mo含量(质量分数)为3%时, 其催化活性最高, 在160 ℃和5 MPa H2气条件下, 反应3 h顺酐的转化率为100%, 产物γ-丁内酯的选择性为27%.

关键词: 钼改性, 页硅酸镍催化剂, Lewis酸, 顺酐, 加氢

Abstract:

A series of molybdenum-modified nickel phyllosilicates was synthesized by ammonia evaporation method. The effects of molybdenum content on the structure and catalytic performance of the catalyst for the liquid phase hydrogenation of maleic anhydride(MA) were investigated. The structure and morphology of the catalysts were characterized by N2 adsorption-desorption, XRD, FTIR, TEM, H2-TPR, NH3-TPD, Py-IR and in situ XPS. The results displayed that the introduction of molybdenum has a remarkable influence on the morphology of the catalysts and its catalytic properties. The reduction degree of the active metal Ni and the sites of Ni0 on the surface of the catalysts were increased with the addition of Mo. Meanwhile, the hydrogen spillover was generated during the Ni reduction process. Such overflowing active hydrogen have super reduction ability, which can promote partial of MoO3 to be reduced to MoOx species that possesses Lewis acid properties. Due to the synergistic effect between the surface Ni0 and the Lewis acid sites induced from partially reduced Ni(Niσ+) and MoOx, the catalytic performance of the catalyst was significantly improved for the hydrogenation of C≡C and C≡O groups in MA. The sample with the Mo doping content of 3% exhibits the highest activity. A 100% conversion of MA together with a γ-butyrolactone(GBL) selectivity of 27% was achieved within 3 h at 160 °C and the H2 pressure of 5 MPa.

Key words: Molybdenum modified, Nickel phyllosilicate, Lewis acid, Maleic anhydride, Hydrogenation

中图分类号: 

TrendMD: