Nanostructured SBA-15 Materials as Appropriate Supports for Active Hydrodesulfurization Catalysts Prepared from HSiW Heteropolyacid

Abstract

ABSTRACTA series of NiW catalysts supported on SBA-15-type materials modified with Al, Ti or Zr were prepared and tested in simultaneous hydrodesulfurization (HDS) of two model compounds: dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). Catalysts were prepared by incipient wetness impregnation of SBA-type materials (pure silica SBA-15, Al-SBA-15, Ti-SBA-15 or Zr-SBA-15) using Keggin-type heteropolyacid H4SiW12O40 as active phase precursor and nickel nitrate. Nominal composition of the catalysts was 19 wt.% of WO3 and 3 wt.% of NiO. The supports and catalysts were characterized by SEM-EDX, N2physisorption, small-angle and powder XRD, UV-Vis DRS, TPR and HRTEM. It was shown that a good dispersion of Al, Ti and Zr species on the SBA-15 surface was reached. The characteristic structure of the SBA-15 support was preserved in all supports and NiW catalysts. Addition of metal atoms (Al, Ti, Zr) on the SBA-15 surface prior to catalysts’ preparation improved dispersion of Ni and W oxide species in calcined catalysts. HRTEM characterization of sulfided catalysts showed that the dispersion of NiW active phase was also better on metal-containing SBA-15 supports than on the pure silica one. All NiW catalysts supported on metal-containing SBA-15 materials showed an outstanding catalytic performance in HDS of both model compounds used (DBT and 4,6-DMDBT). A good correlation was found between the dispersion of sulfided NiW active phase and catalytic activity results. The highest HDS activity was obtained with the NiW catalyst supported on Zr-containing SBA-15 molecular sieve, which makes it a promising catalytic system for ultra-deep hydrodesulfurization of diesel fuel.