Optimizing the Incorporation Modes of TiO2 in TiO2-Al2O3 Composites for Enhancing Hydrodesulfurization Performance of Corresponding NiMoP-Supported Catalysts

Abstract

TiO2-Al2O3 supports with different incorporation methods of titania were synthesized via three methods: impregnation (TA-I), co-precipitation (TA-CP), and co-precipitation–hydrothermal treatment (TA-HT). And the NiMoP catalysts prepared on the corresponding supports were evaluated for hydrodesulfurization (HDS) reactions. The results demonstrated that the Ti atoms in TA-I are attached to alumina through hydroxyl groups, while the Ti atoms in TA-CP and TA-HT can be dispersed in the alumina skeleton. Variations in the incorporation modes of TiO2 affect the support properties, consequently influencing the nature of the active metal on the supports. The Ti atoms dispersed in the Al2O3 skeleton allow an increase in the basic hydroxyl groups. Meanwhile, TiO2 in TA-CP and TA-HT can absorb hydrogen molecules and be partially reduced. Furthermore, metal species supported on the TA-CP and TA-HT are more easily reduced and better dispersed. For the NiMoP catalysts prepared with TA-CP and TA-HT, the Ti element promotes the sulfidation degree of Mo, besides shortening the average (Ni)MoS2 slab. The catalysts prepared with TA-CP exhibited superior activity for 4,6-DMDBT hydrodesulfurization. This can be ascribed not only to the relatively high sulfidation degree of Mo and proportion of the NiMoS active phase but also to the well-dispersed (Ni)MoS2 slabs. Moreover, the Ti4+ ions dispersed in the Al2O3 skeleton can be partially reduced to act as electron donors, enhancing the metallic character of the S layers in MoS2, which facilitates the improvement of the hydrogenation desulfurization activity.