Simone Fernandes

An effective and sustainable oxidative desulfurization process for treating a multicomponent model fuel was successfully developed using as a heterogeneous catalyst a composite material containing as an active center the europium Lindqvist [Eu(W₅O₁₈)₂]⁹⁻ (abbreviated as EuW₁₀) encapsulated into the nanoporous ZIF-8 (zeolitic imidazolate framework) support. The EuW₁₀@ZIF-8 composite was obtained through an impregnation procedure, and its successful preparation was confirmed by various characterization techniques (FT-IR, XRD, SEM/EDS, ICP-OES). The catalytic activity of the composite and the isolated EuW₁₀ was evaluated in the desulfurization of a multicomponent model fuel containing dibenzothiophene derivatives (DBT, 4-MDBT and 4,6-DMDBT) with a total sulfur concentration of 1500 ppm. Oxidative desulfurization was performed using an ionic liquid as extraction solvent and aqueous hydrogen peroxide as oxidant. The catalytic results showed a remarkable desulfurization performance, with 99.5 and 94.7% sulfur removal in the first 180 min, for the homogeneous active center EuW₁₀ and the heterogeneous EuW₁₀@ZIF-8 catalysts, respectively. Furthermore, the stability of the nanocomposite catalyst was investigated by reusing and recycling processes. A superior retention of catalyst activity in consecutive desulfurization cycles was observed in the recycling studies when compared with the reusing experiments. Nevertheless, the nanostructure of ZIF-8 incorporating the active POM (polyoxometalate) was shown to be highly suitable for guaranteeing the absence of POM leaching, although structural modification was found for ZIF-8 after catalytic use that did not influenced catalytic performance.

A correlation between polyoxotungstate structures and their catalytic performance for oxidative desulfurization processes was investigated. Bridged lanthanopolyoxometalates that incorporate identical metallic centers with Keggin- Eu[PW₁₁O₃₉]¹¹⁻ and Lindqvist-type [Eu(W₅O₁₈)₂]⁹⁻ structures were used as catalysts for the oxidation of the most representative refractory sulfur compounds. Both compounds were able to desulfurize a multicomponent model diesel under sustainable conditions, i.e., using ionic liquid as an extraction solvent and hydrogen peroxide as an oxidant. However, the Lindqvist catalyst appeared to achieve complete desulfurization faster than the Keggin catalyst while using a lesser amount of catalyst and oxidant. Furthermore, the reusable capacity of the Lindqvist-type [Eu(W₅O₁₈)₂]⁹⁻ was confirmed for consecutive oxidative desulfurization processes. The contribution of the lanthanide metallic center for the catalytic performance of these compounds was investigated by studying the analogous [TB(W₅O₁₈)₂]⁹⁻ compound. Identical desulfurization efficiency was obtained, even reusing this catalyst in consecutive reaction cycles. These results indicate that the active catalytic center of these compounds is probably related to the octahedral tungsten centers. However, a higher number of tungsten centers in the polyoxometalate structure did not result in higher catalytic activity.

A nanocomposite material PMo₁₂@MOF-808 was prepared for the first time employing a straightforward in situ method, and it revealed remarkable catalytic activity for simultaneous oxidative desulfurization and denitrogenation of a model fuel.