Performance of V-Fe based catalysts on the oxidation of dibenzothiophenes

To obtain fossil fuels with ultra-low S levels at friendly conditions, different V oxides formulations on alumina modified with Fe were characterized and selected to oxidize dibenzothiophene (DBT), 4-methyl DBT and 4,6-dimethyl DBT prevailing in diesel fuel. V-Fe based catalysts (5 or 10 wt% of V) were obtained by impregnation of ammonium metavanadate solutions on Fe-modified alumina, obtained by impregnation of Mohr salt on pseudoboehmite (2 wt% of Fe). The catalysts were calcined in air atmosphere, and after were partially reduced with H₂ flux to obtain a mix of several oxidation states of V and Fe species, to evaluate the interaction of Fe in VO_x/Al₂O₃ catalysts and determine its effect on the oxidation processes. The structural and optical properties, as well as surface species, were determined by SEM-EDS, TPR, XRD, Raman, ATR-FTIR, photoluminescence, UV-Vis diffuse reflectance, and XPS spectroscopy. The catalytic performance was evaluated in oxidative desulfurization (ODS) and photocatalytic ODS (PODS) processes. The experimental results showed the addition of Fe promoted the catalytic activity of both ODS and PODS reactions. ODS activities of V-Fe catalysts increase up to 7.5 times with respect to V catalysts without Fe, and the most active catalyst (V5Fer) presents a characteristic oxidation time of 50 min for 4,6-DMDBT. The PODS activity of V10Fec was like ODS activity, showing it is possible to oxidize the dibenzothiophenes under friendly conditions to obtain lower S levels. The promoting effect of Fe was due to the interaction of Fe²⁺ and Fe³⁺ with the catalytic support, favoring the distribution of surface V³⁺ and V⁴⁺ species. Additionally, Fe improved the optical properties of the catalysts since the bandgap energy decrease and low recombination rate of the electron-hole pair were observed. Therefore, V-Fe based catalysts are photocatalytically actives to be used in PODS processes.