Desulfurization of liquid fuels by extraction and sulfoxidation using H2O2 and [CpMo(CO)3R] as catalysts

Efficient and recyclable liquid–liquid extraction and catalytic oxidative desulfurization (ECODS) systems for the removal of refractory sulfur compounds from liquid fuels are reported that use the cyclopentadienyl molybdenum tricarbonyl complexes [CpMo(CO)3Me] (1), [CpMo(CO)3(CH2-pC6H4-CO2Me] (2) and [CpMo(CO)3CH2COOH] (3) as catalyst precursors. An ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate, was used as both extractant and reaction medium, entrapping the active homogeneous MoVI catalysts that are formed in situ under the operating catalytic conditions (aqueous H2O2 as oxidant, 50 °C). The high sulfoxidation activity of the catalyst formed from 1 was largely responsible for enabling >99% desulfurization within 1 h of a model oil containing 1-benzothiophene, dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene (2000 ppm S). The IL/catalyst phase could be repeatedly recycled with no loss of desulfurization efficiency. By sequentially performing extractive desulfurization and ECODS steps, 83–84% sulfur removal was achieved for untreated real diesel and jet fuel samples with initial sulfur contents of ca. 2300 and 1100 ppm, respectively.publishe

A sustainable peroxophosphomolybdate/H2O2 system for the oxidative removal of organosulfur compounds from simulated and real high-sulfur diesels

Highly efficient, deep desulfurization of a multi-component model diesel containing benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved by using the peroxophosphomolybdate [(n-C4H9)4N]3{PO4[MoO(O2)2]4} (Q3PMo4) directly as catalyst, and aqueous H2O2 as oxidant. Q3PMo4 behaves as a heterogeneous catalyst in the complete oxidation of the various sulfur compounds to the corresponding sulfones within 3 h at 70 °C, using a relatively low H2O2/S molar ratio of 3.7, and could be recycled for ten times with only a minimal decrease in activity. A study was performed to adapt the catalyst Q3PMo4 for the removal of sulfur from a real untreated diesel while maintaining a low, economically desirable, H2O2/S molar ratio of 3.7. The highest desulfurization performance was achieved in the presence of an extraction solvent during the catalytic oxidative stage, reinforced by two extraction steps before and after sulfur oxidation. Under these conditions, the sulfur content of the real diesel was reduced from 2300 to 500 ppm (78% desulfurization efficiency) after 3 h.publishe

Easy and Fast Production of Solketal from Glycerol Acetalization via Heteropolyacids

This work presents an effective and fast procedure to valorize the main waste produced from the biodiesel industry, i.e., the glycerol. The acetalization of glycerol with acetone represents an effective strategy to produce the valuable solketal, a fuel additive component. In this work, the catalytic efficiency of different commercial heteropolyacids (HPAas) was compared under a solvent-free system. The HPAs used were H3[PW12O40] (PW12), H3[PMo12O40] (PMo12) and H4[SiW12O40] (SiW12). The influence of reactional parameters such as reactants stoichiometry, catalyst concentration and reaction temperature were investigated in order to optimize experimental conditions to increase cost-efficiency and sustainability. HPAs demonstrated to be highly efficient for this type of reaction, presenting a high and fast glycerol conversion, with high selectivity to solketal under sustainable conditions (solvent-free system and room temperature medium). The activity of HPAs using 3% to glycerol weight and a glycerol/acetone ratio of 1:15 followed the order: PW12 (99.2%) > PMo12 (91.4%) > SiW12 (90.7%) as a result of the strong acidic sites after 5 min. In fact, only 5 min of reaction were needed to achieve 97% of solketal product in the presence of the PW12 as a catalyst. This last system presents an effective, selective and sustainable catalytic system to valorize glycerol

Polyoxomolybdate based ionic-liquids as active catalysts for oxidative desulfurization of simulated diesel

This work was partly funded through the Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (POCI-01-0145-FEDER-007265, UID/QUI/50006/2019) and CENIMAT, I3N (POCI-01-0145-FEDER-007688, UID/CTM/50025/2013), also financed by national funds through the FCT/MCTES, and when appropriate co-financed by the Fundo Europeu de Desenvolvimento Regional (FEDER) under the PT2020 Partnership Agreement. This work is funded by national funds (OE), through FCT – Fundação para a Ciência e a Tecnologia. European Social Fund through the program POPH of QREN. The authors also acknowledge the Portuguese Nuclear Magnetic Resonance Network (PTNMR).This work compares the stability and the catalytic efficiency of different ionic liquid phosphomolybdates ([BPy]3[PMo12O40] and [BMIM]3[PMo12O40]) with a cationic (propylpyridinium) functionalized mesoporous silica nanoparticle composite (PMo12O40@PPy-MSN). These were used as solid catalysts for the oxidative desulfurization of a multicomponent model diesel using hydrogen peroxide as oxidant and a polar immiscible extraction solvent. Ionic liquid ([BMIM][PF6] was successfully used as solvent to extract sulfur compounds from model diesel. The ionic liquid phosphomolybdates showed partial solubility in the ionic liquid phase, occurring some decomposition of their Keggin structure in the soluble reaction media, probably caused by their interaction with oxidant. On the other hand, the phosphomolybdate composite PMo12O40@PPy-MSN presented high structural stability and only negligible leaching occurrence after various consecutive reaction cycles. The model diesel was near complete desulfurized after 3 h and consecutive desulfurization cycles were performed without loss of activity. Therefore, the immobilization of Keggin phosphomolybdate structure [PMo12O40]3− using cationic propylpyridinium silica nanoparticle is an assertive strategy to produce stable and active heterogeneous catalysts.authorsversionpublishe

Polyoxomolybdate based ionic-liquids as active catalysts for oxidative desulfurization of simulated diesel

This work was partly funded through the Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (POCI-01-0145-FEDER-007265, UID/QUI/50006/2019) and CENIMAT, I3N (POCI-01-0145-FEDER-007688, UID/CTM/50025/2013), also financed by national funds through the FCT/MCTES, and when appropriate co-financed by the Fundo Europeu de Desenvolvimento Regional (FEDER) under the PT2020 Partnership Agreement. This work is funded by national funds (OE), through FCT – Fundação para a Ciência e a Tecnologia. European Social Fund through the program POPH of QREN. The authors also acknowledge the Portuguese Nuclear Magnetic Resonance Network (PTNMR).This work compares the stability and the catalytic efficiency of different ionic liquid phosphomolybdates ([BPy]3[PMo12O40] and [BMIM]3[PMo12O40]) with a cationic (propylpyridinium) functionalized mesoporous silica nanoparticle composite (PMo12O40@PPy-MSN). These were used as solid catalysts for the oxidative desulfurization of a multicomponent model diesel using hydrogen peroxide as oxidant and a polar immiscible extraction solvent. Ionic liquid ([BMIM][PF6] was successfully used as solvent to extract sulfur compounds from model diesel. The ionic liquid phosphomolybdates showed partial solubility in the ionic liquid phase, occurring some decomposition of their Keggin structure in the soluble reaction media, probably caused by their interaction with oxidant. On the other hand, the phosphomolybdate composite PMo12O40@PPy-MSN presented high structural stability and only negligible leaching occurrence after various consecutive reaction cycles. The model diesel was near complete desulfurized after 3 h and consecutive desulfurization cycles were performed without loss of activity. Therefore, the immobilization of Keggin phosphomolybdate structure [PMo12O40]3− using cationic propylpyridinium silica nanoparticle is an assertive strategy to produce stable and active heterogeneous catalysts.authorsversionpublishe

Lindqvist versus Keggin-Type Polyoxometalates as Catalysts for Effective Desulfurization of Fuels

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

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

Different methodologies were used to increase the oxidative desulfurization efficiency of the Keggin phosphotungstate [PW12O40]3− (PW12). One possibility was to replace the acid proton by three different ionic liquid cations, forming the novel hybrid polyoxometalates: [BMIM]3PW12 (BMIM as 1-butyl-3-methylimidazolium), [BPy]3PW12 (BPy as 1-butylpyridinium) and [HDPy]3PW12 (HDPy as hexadecylpyridinium. These hybrid Keggin compounds showed high oxidative desulfurization efficiency in the presence of [BMIM]PF6 solvent, achieving complete desulfurization of multicomponent model diesel (2000 ppm of S) after only 1 h, using a low excess of oxidant (H2O2/S = 8) at 70 °C. However, their stability and activity showed some weakness in continuous reused oxidative desulfurization cycles. An improvement of stability in continuous reused cycles was reached by the immobilization of the Keggin polyanion in a strategic positively-charged functionalized-SBA-15 support. The PW12@TM–SBA-15 composite (TM is the trimethylammonium functional group) presented similar oxidative desulfurization efficiency to the homogeneous IL–PW12 compounds, having the advantage of a high recycling capability in continuous cycles, increasing its activity from the first to the consecutive cycles. Therefore, the oxidative desulfurization system catalyzed by the Keggin-type composite has high performance under sustainable operational conditions, avoids waste production during recycling and allows catalyst recovery

Advanced Technologies Conciliating Desulfurization and Denitrogenation to Prepare Clean Fuels

The removal of sulfur- and nitrogen-containing compounds present in fuels is and will be crucial to accomplish actual strict regulations to avoid environmental and humanity health adversities. The conventional hydrodesulfurization and hydrodenitrogenation processes conducted by refineries are limited due to severe operating conditions, and even more importantly, they are inefficient for simultaneously removing nitrogen- and sulfur-containing compounds in fuels. On the other hand, non-hydrogen technologies are beneficial in terms of mild operating conditions, and during the last two decades, some successful works have shown that these can be highly effective at efficiently removing both sulfur- and nitrogen-containing compounds from liquid fuels. For more than four decades, extensive research (thousands of publications since the 1980s) has been dedicated to developing remote desulfurization technologies without taking into consideration the presence of a complex fuel matrix, or even taking into account the presence of other harmful pollutant elements, such as nitrogen. Even more recently, several effective non-hydrogen denitrogenation processes have been reported without considering the presence of sulfur compounds. This review paper is a reflection on the limited work that has been successfully performed to simultaneously remove sulfur- and nitrogen-containing compounds from fuels. An evaluation of different methodologies (adsorption, extraction, oxidative (photo)catalysis, ultrasound-assisted oxidation) is presented here. Furthermore, this review intends to define new future strategies that will allow the design of more suitable and economical technologies, effectively conciliating desulfurization and denitrogenation processes to produce more sustainable fuels

Effective Combination of the Metal Centers in MOF-Based Materials toward Sustainable Oxidation Catalysts

A successful encapsulation of Keggin-type polyoxomolybdate (H3[PMo12O40], PMo12) into metal-organic framework (MOF) materials with an identical framework but distinct metal centers (ZIF-8 with Zn2+ and ZIF-67 with Co2+) was accomplished by a straightforward room-temperature procedure. The presence of Zn2+ in the composite material PMo12@ZIF-8 instead of Co2+ in PMo12@ZIF-67 caused a remarkable increase in the catalytic activity that achieved a total oxidative desulfurization of a multicomponent model diesel under moderate and friendly conditions (oxidant: H2O2 and solvent: ionic liquid, IL). Interestingly, the parent ZIF-8-based composite with the Keggin-type polyoxotungstate (H3[PW12O40], PW12), PW12@ZIF-8, did not show the relevant catalytic activity. The ZIF-type supports present an appropriate framework to accommodate active polyoxometalates (POMs) into their cavities without leaching, but the nature of the metallic center from the POM and the metal present in the ZIF framework were vital for the catalytic performance of the composite materials