Di Zhang,Lijun Xue,Yongqiang Xu,Lijuan Song,Xinmei Liu
Mesoporous γ-Al 2 O 3 supports with different pore structures were prepared by the cation-anion double hydrolysis method. Based on these samples, MoO 3 /γ-Al 2 O 3 catalysts were made via impregnation. The adsorptions of 4,6-dimethyldibenzothiophene (4,6-DMDBT) and collidine over the supports and catalysts were studied by FT-IR. The supports or catalysts with larger pores can adsorb more 4,6-DMDBT. The methyl groups on adsorbate molecules are very close to the sulfur atom , resulting in apparent steric hindrance . Increasing the pore size can promote the interaction between the adsorbates and supports or catalysts, enhancing the C C bond and weakening the C S bond of 4,6-DMDBT. 4,6-DMDBT molecules were coordinated with the unsaturated Mo atoms over the catalysts to form π-complexation adsorption. There was much difference between thiophene and 4,6-DMDBT adsorption. The adsorption of collidine over the catalysts also illustrated that there existed steric hindrance. Significantly, the catalyst with hierarchical mesopores was beneficial for the adsorbates with larger molecular dynamics diameter. Compared with the pore size, the specific surface area was not the key factor to affect the adsorptions of 4,6-DMDBT and collidine. The hydrodesulfurization reaction of 4,6-DMDBT illustrated that the catalysts with larger pore size or hierarchical pore structure presented higher desulfurization efficiency (above than 80%).
γ-Al 2 O 3 without amorphous domains was synthesized by cation-anion double hydrolysis method. The mesopore size in the range of 3.9–8.5 nm was easily controlled by regulating crystallization temperature, solution pH value and the concentration of NaAlO 2 . The introduction of MoO 3 to the γ-Al 2 O 3 via impregnation method can lead to a decrease of specific surface areas, pore sizes and pore volumes of the supports. The less steric hindrance of the larger mesopores (particularly 8.5 nm) exhibits the more Lewis acid sites over the γ-Al 2 O 3 . The MoO 3 /γ-Al 2 O 3 possesses more Bronsted acid sites compared to Lewis. The thiophene compounds can be adsorbed both on the supports and catalysts. The acid sites can facilitate the interaction between the thiophene compounds and catalysts (or supports). The more adsorbed thiophene and dibenzothiophene on the catalysts is attributed to the coordinately unsaturated metal sites and Bronsted acid sites on the surface of the catalysts. Of note is the supports and catalysts with larger pore size (especially 8.5 nm) could promote the adsorption of thiophene compounds. It demonstrates that there is pore confinement effect in the hydrodesulfurization catalysts.
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