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)
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.Effect of the Fluorine Addition Method on the Hydrodesulfurization Performance of NiMo Catalysts over Slurry Bed[J].Acta Physico-Chimica Sinica,2015,31(8):1559-1566.
Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, P. R. China
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.
