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Ultradeep Hydrodesulfurization of Dibenzothiophene (DBT) Derivatives over Mo-Sulfide Catalysts Supported on TiO2-Coated Alumina Composite

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Abstract

The present paper reviews in detail the different studies now being conducted by our research team concerning the ultradeep hydrodesulfurization (HDS) of dibenzothiophene (DBT) derivatives over Mo/TiO2 and Mo/TiO2–Al2O3 catalysts. First, a detailed characterization of Mo/TiO2 (P-25 Degussa, 50 m2/g) catalysts prepared by equilibrium adsorption technique shows that Mo- species are highly and uniformly dispersed on the surface of titania up to 6.6 wt% MoO3 loading. Above this value, some aggregation of Mo occurs, leading to the formation of bulk MoO3. Below 6.6 wt% MoO3 loading, the Raman spectroscopy data of the calcined samples show that the supported Mo-species possess a highly distorted octahedral MoO6 structure. TiO2–Al2O3 composites were prepared by chemical vapor deposition (CVD) using TiCl4 as a precursor. Using several characterization techniques, we demonstrated that the support composite presents a high dispersion of TiO2 over γ-Al2O3 without forming precipitates up to ca. 11 wt% loading. Moreover, the textural properties of the composite support are comparable to those of alumina. Under the present sulfidation conditions (673 K, 5%H2S/95%H2), Mo-species supported on TiO2 are better sulfided than on alumina, as demonstrated using XPS. This can be attributed to the relatively lower interaction between Mo-species and titania. The state of sulfide species supported on the composite support can be considered as a transition state between TiO2 and Al2O3. However, at relatively higher TiO2 loadings (ca. 11 wt%), Mo/TiO2–Al2O3 catalysts exhibit sulfidability similar to that of Mo/TiO2. The HDS tests conducted in both the laboratory and in industry show that sulfide catalysts supported on TiO2–Al2O3 (ca. 11 wt% TiO2) are more active than those supported on TiO2 or Al2O3.

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  1. Department of Chemistry, Faculty of Science and Technology, 7-1 Kioi-cho, Chiyoda-ku, Tokyo, 102-8554, Japan

    Youssef Saih & Kohichi Segawa

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  1. Youssef Saih
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  2. Kohichi Segawa
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Correspondence to Kohichi Segawa.

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Saih, Y., Segawa, K. Ultradeep Hydrodesulfurization of Dibenzothiophene (DBT) Derivatives over Mo-Sulfide Catalysts Supported on TiO2-Coated Alumina Composite. Catalysis Surveys from Asia 7, 235–249 (2003). https://doi.org/10.1023/B:CATS.0000008163.06816.b7

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