催化学报 ›› 2012, Vol. 33 ›› Issue (3): 508-517.DOI: 10.1016/S1872-2067(11)60358-6

• 研究论文 • 上一篇    下一篇

磷化镍/介孔 TiO2 催化剂的制备及其催化加氢脱硫性能

杨祝红*, 李力成, 王艳芳, 刘金龙, 冯新, 陆小华   

  1. 南京工业大学材料化学工程国家重点实验室, 江苏南京 210009
  • 收稿日期:2011-09-05 修回日期:2011-12-30 出版日期:2012-03-15 发布日期:2015-07-27

Preparation of Nickel Phosphide/Mesoporous-TiO2 Catalyst and Its Hydrodesulfurization Performance

YANG Zhuhong*, LI Licheng, WANG Yanfang, LIU Jinlong, FENG Xin, LU Xiaohua   

  1. State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing 210009, Jiangsu, China
  • Received:2011-09-05 Revised:2011-12-30 Online:2012-03-15 Published:2015-07-27

摘要: 以介孔 TiO2 (m-TiO2) 为载体, 采用程序升温还原法制备了 Ni2P/m-TiO2 催化剂, 考察了不同起始 Ni/P 摩尔比及活性组分负载量对该催化剂结构及其催化加氢脱硫 (HDS) 性能的影响. 结果表明, 当 Ni/P 摩尔比为 1.25 时, 活性组分以 Ni2P 为主, 催化剂的最佳 Ni 负载量为 10%. 采用 X 射线衍射、低温 N2 吸附-脱附、场发射扫描电镜和程序升温还原等技术表征了 m-TiO2 及其它不同载体负载的 Ni2P 催化剂. 结果表明, 高结晶度 m-TiO2 载体使 Ni 和 P 物种的还原温度大幅度降低, 在 450~600 oC 还原制得的 Ni2P/m-TiO2 催化剂的结构参数基本一致, 比表面积均为 90 m2/g 左右, 具有很高的热稳定性和对二苯并噻吩的 HDS 催化性能. 在相同的反应条件下, m-TiO2 负载的 Ni2P 催化剂 HDS 性能最好, 各载体负载的 Ni2P 催化剂活性大小顺序为 Ni2P/m-TiO2 > Ni2P/SiO2 > Ni2P/P25.

关键词: 介孔, 二氧化钛, 磷化镍, 加氢脱硫, 二苯并噻吩

Abstract: Using mesoporous TiO2 (m-TiO2) as the support, novel nickel phosphide/m-TiO2 catalysts (Ni2P/m-TiO2) were prepared by a temperature-programmed reduction method. The influence of the Ni/P molar ratio and the amount of active component on the catalyst structure and the hydrodesulfurization (HDS) performance was investigated. The results indicated that the reduction of precursor with Ni/P = 1.25 yielded mainly Ni2P, and the optimum loading of Ni was 10%. The influence of m-TiO2 on the preparation and HDS performance of nickel phosphide catalysts was also evaluated by X-ray diffraction, N2 physisorption, field-emission scanning electron microscopy, and temperature-programmed reduction. The results showed that m-TiO2 with high crystallinity could dramatically decrease the reduction temperatures of Ni and P species. When the reduction temperatures were between 450 and 600 °C, the textures of the Ni2P/m-TiO2 catalysts were very similar and the specific surface areas were about 90 m2/g. The effects of the support on the dibenzothiophene HDS performance of the nickel phosphide catalysts were also investigated. The results showed that the order of dibenzothiophene conversion was Ni2P/m-TiO2 > Ni2P/SiO2 > Ni2P/P25.

Key words: mesoporous, titania, nickel phosphide, hydrodesulfuriztion, dibenzothiophene