物理化学学报 >> 2015, Vol. 31 >> Issue (8): 1559-1566.doi: 10.3866/PKU.WHXB201506083

催化和表面科学 上一篇    下一篇

氟添加方式对NiMo催化剂在浆态床上加氢脱硫性能的影响

石林,黄伟*(),宋书征,李志博,刘双强   

  • 收稿日期:2015-03-18 发布日期:2015-08-12
  • 通讯作者: 黄伟 E-mail:huangwei@tyut.edu.com
  • 基金资助:
    国家自然科学基金重点项目(21336006);国家自然科学基金面上项目(21176176);高等学校博士学科点专项(优先发展领域)(20111402130002)

Effect of the Fluorine Addition Method on the Hydrodesulfurization Performance of NiMo Catalysts over Slurry Bed

Lin. SHI,Wei. HUANG*(),Shu-Zheng. SONG,Zhi-Bo. LI,Shuang-Qiang. LIU   

  • Received:2015-03-18 Published:2015-08-12
  • Contact: Wei. HUANG E-mail:huangwei@tyut.edu.com
  • Supported by:
    the National Natural Science Foundation of China(21336006);General Program of National Natural ScienceFoundation of China(21176176);Research Fund for the Doctoral Program of Higher Education of China(20111402130002)

摘要:

以F为助剂,采用完全液相法制备了氟改性的NiMo/TiO2-Al2O3浆状催化剂,考察了氟的添加方式对催化剂在浆态床上4, 6-二甲基二苯并噻吩(4, 6-DMDBT)加氢脱硫性能的影响.采用X射线衍射(XRD)谱、氢气程序升温还原(H2-TPR)、N2吸脱附实验(BET)、X射线光电子能谱(XPS)、高分辨率透射电镜(HRTEM)对催化剂进行了表征.结果表明,在不添加浓硝酸的情况下,在活性组分加入之前引入氟能显著提高催化剂的比表面积和孔径,促进反应过程中金属镍在催化剂表面的分散,更大程度地减弱催化剂中活性金属与载体间的相互作用,有效提高Mo的硫化度及MoS2的堆积层数,从而生成了较多的II类Ni-Mo-S活性相,促进芳香环的加氢和C-S键的氢解,对4, 6-DMDBT有较高的加氢脱硫活性.

关键词: 完全液相法, 氟, 4, 6-二甲基二苯并噻吩, 浆态床

Abstract:

NiMo/TiO2-Al2O3 slurry catalysts with fluorine as an additive were prepared by complete liquidphase technology for hydrodesulfurization. The effect of different fluorine addition methods on the properties of the catalysts for 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) hydrodesulfurization were investigated. The catalysts were characterized by X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), N2 adsorption-desorption isotherms (BET), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM). The results reveal that in the absence of nitric acid, adding fluoride into the catalyst before the introduce of molybdenum and nickel ions can significantly increase the surface area and average pore size, improve the dispersion of metallic nickel on the surface of catalyst, and weaken the interaction between the metal and the support. This effectively increases the sulfidation degree of Mo, MoS2 slab stacking, and the content of the highly active Ni-Mo-S(II) phase, which can promote the hydrogenation of the aromatic ring and the hydrogenolysis of the C-S bond, and thus increase the hydrodesulfurization activity for 4, 6-DMDBT.

Key words: Complete liquid-phase technology, Fluoride, 4, 6-DMDBT, Slurry bed

MSC2000: 

  • O643