Porous metal-organic framework (MOF) materials UiO-66(Zr) obtained by solvothermal and microwave advanced synthesis (MWAS) procedures were characterized, and their catalytic efficiency was investigated for oxidative desulfurization (ODS) processes using a multicomponent model diesel containing benzothiophene and dibenzothiophene derivatives. The preparation parameters as the cooling time after oven use in the solvothermal procedure, and also the reaction time in the MWAS method seemed to play an important role in the catalytic performance of the UiO-66(Zr) material, as well as in its recycle capacity. The material prepared by the solvothermal procedure with a fast cooling time showed the best catalytic performance (desulfurization efficiency of 99.5% after 3 h). However, the application of the UiO-66(Zr) material prepared by the MWAS method (desulfurization efficiency of 96% after 3 h) conciliated a higher number of advantages, such as shorter reaction time preparation (15 min) and high catalytic activity for a higher number of reaction cycles. The UiO-66(Zr) prepared by the MWAS method was used for the first time in an oxidative desulfurization process, and according to the catalytic results obtained (high recycle capacity and stability) and shorter reaction time preparation, seems to be a promising material for industrial application.

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.

An effective and sustainable process capable of simultaneously execute desulfurization and denitrogenation of fuels is in fact an actual necessity in the refinery industry. The key to achieve this goal is the parallel oxidation of sulfur and nitrogen compounds present in fuels, which is only achieved by an active and recovered catalyst. A novel heterogeneous catalyst was successfully prepared by the encapsulation of an imidazolium-based polyoxometalate (POM) into a ZIF-8 framework ([BMIM]PMo₁₂@ZIF-8). This composite material revealed exceptional catalytic efficiency to concurrently proceed with the oxidative desulfurization and denitrogenation of a multicomponent model fuel containing various sulfur and nitrogen compounds. A complete removal of all these compounds was achieved after only one hour and the catalyst system was able to be reused for ten consecutive cycles without loss of efficiency. In fact, an ionic liquid POM was incorporated in the ZIF-8 for the first time, and this composite compound was originally applied as a catalyst for simultaneous oxidative desulfurization and denitrogenation processes.

The valorization of the large amount of crude glycerol formed from the biodiesel industry is of primordial necessity. One possible direction with high interest to the biorefinery sector is the production of fuel additives such as solketal, through the acetalization of glycerol with acetone. This is a chemical process that conciliates high sustainability and economic interest, since solketal contributes to the fulfillment of a Circular Economy Model through its use in biodiesel blends. The key to guarantee high efficiency and high sustainability for solketal production is the use of recovery and recyclable heterogeneous catalysts. Reported works indicate that high yields are attributed to catalyst acidity, mainly the ones containing Brönsted acidic sites. On the other hand, the catalyst stability and its recycling capacity are completely dependent of the support material and the acidic sites incorporation methodology. This review intends to conciliate the information spread on this topic and indicate the most assertive strategies to achieve high solketal production in short reaction time during various reaction cycles.

An effective process to remove nitrogen-based compounds from fossil fuels without harming the process of sulfur removal is an actual gap in refineries. A success combination of desulfurization and denitrogenation processes capable of completely removing the most environmental contaminates in diesel under sustainable conditions was achieved in this work, applying polyoxometalates as catalysts, hydrogen peroxide as oxidant, and an immiscible ionic liquid as an extraction solvent. The developed process based in simultaneous oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) involved initial extraction of sulfur and nitrogen compounds followed by catalytic oxidation. Keggin-type polyoxomolybdates revealed much higher reusing capacity than the related polyoxotungstate. Effectively, the first catalysts practically allowed complete sulfur and nitrogen removal only in 1 h of reaction and for ten consecutive cycles, maintaining the original catalyst and ionic liquid samples.