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WOx-ZrO2 (ZWx) based catalysts were prepared by equilibrium adsorption in basic condition (pH 10) with W content of 10.5, 19.7 and 27.0 wt.%, using hydrous zirconia [ZrO2(383)] as support. In order to determine the soluble fraction of W species which did not interact with the surface, samples were leached with NH3, dried and re-calcined [ZWx(NH3)y]. The W content was determined by spectrophotometric method, before and after the leaching. All catalysts were characterized by textural analysis (BET), X-ray diffraction (XRD) and Raman spectroscopy; the acidic strength was determined by potentiometric titration with n-butylamine. The catalytic behavior was analyzed for the selective oxidation of diphenyl sulfide (DPS) to diphenyl sulfoxide (DPSO) or diphenyl sulfone (DPSO2) using H2O2 as oxidizing agent. High conversion of DPS (∼100 %) and selectivity to DPSO2 (>90 %) at 60 min of reaction time were obtained for the ZWx series of catalysts. The ZWx(NH3)y series (W content: 3.65, 6.50 and 7.50 wt.%, respectively) also showed high selectivity to diphenyl sulfone but the maximum conversion (∼100 %) was achieved with reaction times longer (30 min) than those of the ZWx (10 min) samples. Polytungstate species strongly interacting with the support, identified by Raman spectroscopy in both series of samples, are considered the active phases.

A new type of catalyst was synthesized by immobilizing heteropolyacid on ionic liquid-modified mesostructured cellular silica foam (denoted as MCF) and applied to the oxidative desulfurization of fuel. The surface morphology and structure of the catalyst were characterized by XRD, TEM, N2 adsorption–desorption, FT-IR, EDS and XPS analysis. The catalyst exhibited good stability and desulfurization for various sulfur-containing compounds in oxidative desulfurization. Heteropolyacid ionic liquid-based MCF solved the shortage of the amount of ionic liquid and difficult separation in the process of oxidative desulfurization. Meanwhile, MCF had a special three-dimensional structure that was not only highly conducive to mass transfer but also greatly increased catalytic active sites and significantly improved catalytic efficiency. Accordingly, the prepared catalyst of 1-butyl-3-methyl imidazolium phosphomolybdic acid-based MCF (denoted as [BMIM]3PMo12O40-based MCF) exhibited high desulfurization activity in an oxidative desulfurization system. The removal of dibenzothiophene could achieve levels of 100% in 90 min. Additionally, four sulfur-containing compounds could be removed completely under mild conditions. Due to the stability of the structure, sulfur removal efficiency still reached 99.8% after the catalyst was recycled six times.

Funding Information: This research work received financial support from Portuguese national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the strategic project UIDB/50006/2020 (for LAQV-REQUIMTE), LA/P/0037/2020, UIDP/50025/2020, UIDB/50025/2020 (for I3N), and ROTEIRO/0031/2013 – PINFRA/22161/2016 (for PTNMR). The work also received funding from the European Union (FEDER funds through COMPETE POCI-01-0145-FEDER- 031983). Funding Information: L.C.-S., M.C.C. and S.S.B. thank FCT/MCTES for funding through the Individual Call to Scientific Employment Stimulus (Ref. CEECIND/00793/2018, Ref. 2021.03255.CEECIND and Ref. CEECIND/03877/2018, respectively). AMV thanks FCT/MCTES and ESF (European Social Fund) through POCH (Programa Operacional Capital Humano) for his PhD grant (Ref. SFRH/BD/150659/2020). Publisher Copyright: © 2023 by the authors. 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. publishersversion published

The widespread use of diesel fuel for transportation, industry, and electricity generation causes several environmental issues via an increase in the amount of sulfur compound emissions. Commercial diesel fuel must be free of sulfur-containing compounds since they can cause several environmental problems. Considering the currently available processes to eliminate sulfur compounds, oxidative desulfurization (ODS) is one of the effective means for this purpose. This work presented a simple, low cost, and efficient ODS system of high-sulfur diesel fuels using peroxide oxidation with the aid of citric, pimelic, and α-ketoglutaric acids. The aim of the study was to investigate the potential of these acids as hydrogen peroxide (H2O2) activators for ODS and to optimize the reaction conditions for maximum sulfur removal. The results showed that citric, pimelic, and α-ketoglutaric acids were effective catalysts for the desulfurization of high-sulfur diesel with an initial sulfur content of 2568 mg L−1, achieving a sulfur removal efficiency of up to 95%. The optimized reaction conditions were found to be 0.6 g of carboxylic acid dosage and 10 mL of H2O2 at 95 °C. The desulfurization efficiency of the real diesel sample (2568 mg L−1) was shown to be 27, 34, and 84.57%, using citric acid, α-ketoglutaric acid, and pimelic acid after 1h, respectively. The effectiveness of the oxidation process was characterized by gas chromatographic pulsed flame photometric detector (GC-PFPD) and Fourier-transform infrared spectroscopy (FTIR) techniques. The experimental results demonstrated that the developed system exhibited high efficiency for desulfurization of real high-sulfur diesel fuels that could be a good alternative for commercial application with a promising desulfurization efficiency.

In this study, the catalyst activity of Fe2O3 supported on Graphene for Iraqi gas oil oxidation desulfurization (ODS) by hydrogen peroxide (H2O2) was investigated. The prepared catalyst was synthesized by wet impregnation for ferric nitrate as a Fe2O3 precursor while Graphene represented as catalyst support. The synthesized catalyst was characterized by XRD, FTIR, and EDS analysis. The experiments were designed according to three-level for three variables by Box-Behnken experimental design; Stirring time, catalyst dosage and temperature while the sulfur removal efficiency acts as experiment response. Catalyst activity was studied by ODS reaction for Iraqi gas oil (sulfur content 9400 ppm) at temperature range (40-60 ºC), stirring time (160-240 minutes) and catalyst dosage (0.5-2.5 g), the results show maximum sulfur removal efficiency 90% at stirring time, catalyst dosage and temperature 240 min, 1.5 g, and 60 ºC, respectively. ANOVA analysis shows the important effect of each independent variable on sulfur removal efficiency (response) as following influential order; stirring time, reaction temperature and catalyst dosage. Kinetics calculation showed that the ODS reaction obeys pseudo first-order reaction with reaction rate constant equal 1.0837, 1.5893, and 2.5053 at temperature 40, 50, and 60 ºC, respectively, while activation energy equal 36.26 kJ/mol. Copyright © 2020 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

An ultrasound-assisted heterogeneous catalytic oxidation process was applied to eliminate sulfur from commercial diesel fuel oil. The studied variables were catalyst concentration, type of catalyst (homogeneous or heterogeneous), oxidizing agent concentration, and the application of ultrasound energy. Supported catalysts were prepared by impregnation of coal fly ash with an iron(II) sulfate aqueous solution using ultrasound energy. After drying, the catalyst was calcined at 500 °C for 4 h. The oxidizing agent was hydrogen peroxide. Ultrasound energy was applied with a frequency of 47 kHz and an intensity of 147 W. Ethanol was employed for extracting the oxidized compounds from the hydrocarbon mixture. Coal fly ash and ethanol were used with the purpose of applying low-cost raw materials in chemical processes. It was found that under the studied conditions, increasing oxidizing agent concentration and the application of ultrasound energy can enhance the sulfur removal from commercial diesel fuel oil. Catalyst concentration did not play a significant role in the process. Similar results were obtained using homogeneous or heterogeneous catalyst, which is important since the heterogeneous catalyst could be recovered, reactivated, and used in many cycles.

Angewandte Chemie / International edition International edition 58(27), 9160 - 9165 (2019). doi:10.1002/anie.201904347, While titanium‐based metal–organic frameworks (MOFs) have been widely studied for their (photo)catalytic potential, only a few TiIV MOFs have been reported owing to the high reactivity of the employed titanium precursors. The synthesis of COK‐47 is now presented, the first Ti carboxylate MOF based on sheets of TiIVO6 octahedra, which can be synthesized with a range of different linkers. COK‐47 can be synthesized as an inherently defective nanoparticulate material, rendering it a highly efficient catalyst for the oxidation of thiophenes. Its structure was determined by continuous rotation electron diffraction and studied in depth by X‐ray total scattering, EXAFS, and solid‐state NMR. Furthermore, its photoactivity was investigated by electron paramagnetic resonance and demonstrated by catalytic photodegradation of rhodamine 6G., Published by Wiley-VCH, Weinheim

This work was partly funded through the projects REQUIMTE-LAQV, POCI-01-0145-FEDER-007265 [FCT (Fundacao para a Ciencia e a Tecnologia) Ref. UID/QUI/50006/2013] and CICECO -Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. The FCT and the European Union are acknowledged for post-doctoral grants to C.M.G. (SFRH/BPD/109253/2015) and L.C.S. (SFRH/BPD/111899/2015) co-funded by MCTES and the European Social Fund through the program POPH of QREN. Mesoporous silica nanoparticles (MSNs) strategically functionalized were used to immobilize a homogeneous polyoxomolybdate catalyst [PMo 12 O 40 ] 3- (PMo 12 ), active but unstable. The PMo 12 @TBA-MSN composite (where TBA refers to surface-tethered tributylammonium groups) conferred high stability to the polyoxomolybdate catalytic center and displayed an increase in efficiency for the oxidative desulfurization (ECODS) of a diesel simulant under sustainable conditions (using H 2 O 2 as oxidant and an ionic liquid, [BMIM]PF 6 , as solvent). Continuous reuse of the catalyst and ionic liquid solvent in consecutive ECODS cycles was successfully performed, avoiding the production of residual wastes. The performance of the PMo 12 @TBA-MSN catalyst improved upon its reuse, leading to complete desulfurization of a multicomponent model diesel containing benzothiophene derivatives after just 1 h of the catalytic stage of the process. The robust nature of the supported catalyst was indicated by characterization of the recovered solid which showed retention of the structural and chemical integrities. authorsversion published

The effect of electric potential on the sulfide capacity of the CaO-SiO2-Al2O3 system was evaluated by applying voltages in the range of −1.5 to 1.5 V at 1823 K in a C/CO gas equilibrium. When the cathodic potential (−1.5 to 0 V) was applied, it was confirmed that the sulfur partition ratio increased based on the electrochemical reaction of sulfur (S + 2e− = S2−). However, the reversibility of the electrochemical resulfurization reaction (S2− = S + 2e−) in slag was not established in the reverse (anodic) potential region (0–1.5 V), yet the sulfur partition ratio increased. In particular, sulfur evaporation was observed in the anodic potential region. Therefore, in the present study, potential anodic electro-desulfurization mechanisms based on sulfur evaporation are proposed. To verify these mechanisms, sulfur evaporation is discussed in detail as a function of the thermodynamic stability of sulfur in the slag.

Supported ionic liquid (IL) catalysts [C n mim]3PMo12O40/Am TiO2 (amorphous TiO2) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization (ECODS) system. Characterizations such as FTIR, DRS, wide-angle XRD, N2 adsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [C16mim]3PMo12O40/Am TiO2 only dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.

Owing to the increasingly serious environmental issues caused by the sulfur burnt in fuel, desulfurization has become an important topic. In this work, an amphiphilic oxygen-defective tungsten oxide was synthesized by a colloidal chemistry method. The amphiphilic property and oxygen defects were well characterized, and the structure of the oxygen-defective tungsten oxide catalyst was investigated. In addition, the catalyst was employed in oxidative desulfurization system of fuel, and deep desulfurization was achieved. It was found that the very high oxidative desulfurization performance of oxygen-defective tungsten oxide catalyst resulted from both the amphiphilic property and oxygen defects. This work can provide a strategy for preparation of highly active metal oxide catalysts with oxygen defects in oxidative desulfurization reaction of fuel.

Вивчено вплив складу оксиданту на процес оксидаційного знесірчення кам’яного вугілля низького ступеня метаморфізму, що здійснювався з метою одержання сировини для виробництва пиловугільного палива. На основі сукупності всіх результатів експериментальних досліджень по вивченні вищезгаданого процесу розроблено експериментально- статистичну модель, яка дала можливість встановити оптимальні умови досліджуваного процесу. The effect of oxidant composition on the oxidative desulfurization of low grade coal has been studied to obtain raw materials for the production of pulverized coal. The experimental-statistical model has been developed that allowed to establish optimum conditions of the investigated process.

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.

The effect of reaction temperature, mixing speed and oxidant to catalyst volume ratio, including their interactions on the oxidative desulfurization of dibenzothiophene by using response surface methodology was studied. Hydrogen peroxide was used as oxidant and acetic acid as catalyst. The obtained model accurately predicts conversion of dibenzothiophene and the best conversion of 98.7% was observed at temperature 70°C, mixing speed of 1250 rpm and oxidant to catalyst volume ratio of 1:1. At high temperatures, a major limitation of the desulfurization process is the mass transfer and the high mixing speed is needed to achieve an efficient process.

In this paper, the current advantages and disadvantages of using metal-containing nanocatalysts (NCs) for deep chemical oxidative desulfurization (ODS) of liquid fuels are reviewed. A similar analysis is performed for the oxidative biodesulfurization of oil along the 4S-pathway, catalyzed by various aerobic bacterial cells of microorganisms. The preferences of using NCs for the oxidation of organic sulfur-containing compounds in various oil fractions seem obvious. The text discusses the development of new chemical and biocatalytic approaches to ODS, including the use of both heterogeneous NCs and anaerobic microbial biocatalysts that catalyze the reduction of chemically oxidized sulfur-containing compounds in the framework of methanogenesis. The addition of anaerobic biocatalytic stages to the ODS of liquid fuel based on NCs leads to the emergence of hybrid technologies that improve both the environmental characteristics and the economic efficiency of the overall process. The bioconversion of sulfur-containing extracts from fuels with accompanying hydrocarbon residues into biogas containing valuable components for the implementation of C-1 green chemistry processes, such as CH4, CO2, or H2, looks attractive for the implementation of such a hybrid process.

The desulfurization of four petroleum distillates i.e. kerosene, light gas oil (LGO), heavy gas oil (HGO) and light cycle oil (LCO), with sulfur content 0.206–1.272% w/w, was carried out using the hydrogen peroxide-acetic acid oxidative system, in combination with extractive desulfurization performed by imidazolium based ionic liquids. The 1-butyl-3-methylimidazolium bromide [BMIM][Br], and 1-butyl-3-methylimidazolium hydrogen sulfate [BMIM][HSO4] were synthesized, characterized with FT-IR and 1H NMR, and used as solvents in a six extraction cycle procedure. The influence of temperature in the extraction process was investigated. In each extraction cycle, the sulfur content and the physical properties of the raffinates were estimated. The used ionic liquids were recovered and regenerated, in a quite efficient regeneration process. The synthesized and recycled ionic liquids show a mild desulfurization capability, depending on the feed under extraction. In every case, [BMIM][Br] prevails over [BMIM][HSO4] in desulfurization efficiency.

The C@POM (carbon@polyoxometalate) containing H3PMo12O40 (PMo12), H5PMo10V2O40 (PMo10V2), H6PMo9V3O40 (PMo9V3), H7PMo8V4O40 (PMo8V4), H3PW12O40 (PW), and H4SiW12O40 (SiW) were prepared from natural potato as green, and cheap catalyst support source. The C@PMo10V2 was found to be a unique, effective, and eco-friendly catalyst for selective oxidation of sulfides, using 30% aq. H2O2. C@PMo10V2 composite was characterized by X-ray diffraction spectroscopy (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), Fourier transform infrared (FT-IR) spectrophotometry, zeta sizer, and zeta potential. The XRD results show that during immobilization PMo10V2 on the carbon catalyst support (CCS), the crystallite structure of PMo10V2 and CCS was not changed. The SEM results show that PMo10V2 crystals deposited on the surface CCS rods as composite nanorod structure. A variety of sulfides, sulfur-containing model and real oil were oxidized with the C@PMo10V2/H2O2 at room temperature. Recovered catalyst show excellent activity for at least four repeating cycles.

The preparation of novel wrapped carbon nanotubes poly(4-vinylpyridine)/methyl trioxorhenium based heterogeneous catalysts has been reported by two different procedures: a) the wrapping by grinding of multiwall carbon nanotubes with pre-formed adducts, respectively, [poly(4-vinylpyridine)·methyltrioxorhenium] or [poly(4-vinylpyridine)-N-oxide·methyltrioxorhenium] and, b) the loading of methyltrioxorhenium on previously wrapped multiwall carbon nanotubes with poly(4-vinylpyridine) and poly(4-vinylpyridine)-N-oxide resins. The novel catalysts were characterized by SEM, TEM, ICP-MS and XPS analyses. Both types of catalysts were efficient systems in the oxidation of recalcitrant aromatic sulfur derivatives with H2O2, as representative models of oxidative desulfurization processes, affording the corresponding sulfones with yields ranging from moderate to quantitative. The oxidation of a complex model fuel oil and of synthetic diesel fuel, under optimal experimental conditions, is also reported. The performance of novel catalysts was dependent on the specific procedure applied for the immobilization of the active species, and was more efficient for both model oil and synthetic diesel fuel samples (with quantitative conversions and selectivities to the corresponding sulfones), than for isolated substrates.

Acidic carboxyl functionalized poly(ionic liquid) (CFPIL) has been synthesized and characterized by various techniques like FT-NMR, Fourier transform infrared spectroscopy (FTIR). In this work, deep oxidative desulfurization of model oil (thiophene dissolved in iso-octane) by CFPIL catalyst was carried out in presence of 30 wt% H 2 O 2 solution as an oxidant. The effects of the hydrogen peroxide, amount of CFPIL, temperature-time and recyclability are scrutinized systematically. It was found that the effective molar proportion of H 2 O 2 to sulfur was 4:1 at 70 °C in 180 min with 0.6 g catalyst, removing 100% thiophene from model oil. This method has shown high efficiency for the removal of thiophene, which is difficult to remove from the oil than benzothiophene and dibenzothiophene. Additionally, an oxidative desulfurization mechanism has been proposed according to the experimental results. This catalytic system by CFPIL offers advantages such as higher efficiency, low amount of ionic liquid, simple work up for separating oil from the catalyst and ease of recycling. This protocol inclines to show that diesel fuels in industry can be purified to sulfur-free or ultra-low sulfur fuels by further deep oxidative desulfurization with CFPILs after hydrodesulfurization.

[EN] The monolacunary Keggin-type [PWO] (PW) heteropolyanion was immobilized on porous framework of mesoporous silicas, namely SBA-15 and an ethylene-bridged periodic mesoporous organosilica (PMOE). The supports were functionalized with a cationic group (N-trimethoxysilypropyl-N, N, N-trimethylammonium, TMA) for the successful anchoring of the anionic polyoxometalate. The PW@TMA-SBA-15 and PW@TMA-PMOE composites were evaluated as heterogeneous catalysts in the oxidative desulfurization of a model diesel. The PW@TMA-SBA-15 catalyst showed a remarkable desulfurization performance by reaching ultra-low sulfur levels (, This work was partly funded through the projects REQUIMTE-LAQV [FCT (Fundação para a Ciência e a Tecnologia) Ref. LAQV, REQUIMTE (POCI-01-0145-FEDER-007265, UID/QUI/50006/2019)], and CENIMAT/I3N (POCI-01-0145-FEDER-007688, UID/CTM/50025/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by the Fundo Europeu de Desenvolvimento Regional (FEDER) under the PT2020 Partnership Agreement. This work was funded by national funds (OE), through FCT—Fundação para a Ciência e a Tecnologia, I.P., in the scope of the framework contract foreseen in the numbers 4, 5, and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. The FCT and the European Union are acknowledged for the post-graduation grant SFRH/BD/95571/2013 (to SR) co-funded by Ministério da Ciência, Tecnologia e Ensino Superior (MCTES), and the European Social Fund through the program POPH of QREN. The authors also acknowledge the Portuguese Nuclear Magnetic Resonance Network (PTNMR—ROTEIRO/0031/2013, PINFRA/22161/2016) and the research group of Prof. Isabel Gonçalves from CICECO Laboratory, University of Aveiro, Portugal.

Anderson-type polyoxometalate (POM) catalysts were synthesized and applied for deep oxidative desulfurization of model fuel containing dibenzothiophene. O2 contained in air was used as oxidant under mild conditions. The influence of the nature of central heteroatom and that of the quaternary ammonium cation used on the conversion of DBT was investigated. For the first time to the best of our knowledge, the role of the solvent in aerobic oxidative desulfurization was investigated and the possible mechanism of DBT oxidation was suggested. It was shown that the key stage in the oxidation of the sulfur-containing compound is the generation of alkyl peroxides from the solvent.

12-Tungstophosphoric acid (PW) supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization (ODS) of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide (H2O2) as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-to-sulfur compounds (S-compounds) molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene (DBT) and mixed thiophenic model oil under atmospheric pressure at 75 °C in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.

The zinc-substituted polyoxotungstate [PW11Zn(H2O)O-39](5-) (PW11Zn) has been encapsulated within the aluminium(III) 2-aminoterephthalate NH2-MIL-101(Al) metal-organic framework (MOF) either directly through a one-pot microwave-assisted synthesis or by an impregnation method. The resultant composite materials were characterized by elemental analysis, powder X-ray diffraction, FTIR spectroscopy, and P-31 magic-angle spinning (MAS) NMR spectroscopy. The desulfurization of a model diesel containing three refractory organosulfur compounds (1-benzothiophene, dibenzothiophene, and 4,6-dimethyldibenzothiophene) was studied with the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate as an extractant, the PW11Zn@MOF composites as sulfoxidation catalysts, and aqueous H2O2 as an oxidant. The composite obtained by direct synthesis was the most efficient catalyst and led to almost complete desulfurization of the model diesel under mild conditions. Moreover, the solid catalyst could be recovered readily and recycled without significant loss of desulfurization performance. The application of this system to the treatment of a real diesel sample provided a very good sulfur removal of 83% when combined with liquid-liquid extraction.

Novel material catalysts based in the active zinc-substituted polyoxotungstate ([PW11Zn(H2O)39]5-, abbreviated as PW11Zn) were efficiently used in the oxidative desulfurization of real and model diesels. These active catalytic center was strategically immobilized in a less hydrophilic periodic mesoporous organosilicas (PMOs), containing ethane-bridge (PMOE) and benzene-bridge (PMOB) walls, functionalized with (3-aminopropyl)triethoxysilane (aptes). The efficiency of the novel catalytic composites (PW11Zn@aptesPMOE and PW11Zn@aptesPMOB) was studied under oxidative desulfurization system (CODS) without the presence of an extraction solvent and also using a biphasic (diesel/extraction solvent) oxidative desulfurization system (ECODS). Both composites presented higher desulfurization efficiency under the solvent-free system, reaching ultra-low levels of sulfur compounds after only 1 h and using low ratio of H2O2/S = 4. The catalysts could be recycled without loss of activity for ten consecutive cycles. However, after the first desulfurization cycle complete desulfurization was achieved within only 30 min using PW11Zn@aptesPMOE composite. Also, the structure of PW11Zn@aptesPMOE demonstrated to be more stable than PW11Zn@aptesPMOB, probably due to the occurrence of some PW11Zn leaching from the PMOB surface, probably caused by the lower interaction of PW11Zn with the benzene-bridge PMOB wall. The most robust catalyst PW11Zn@aptesPMOE was used to desulfurize a real diesel achieving 75.9% of desulfurization after 2 h. The catalyst was further recycled with success to treat real diesel.

Metal-carbon materials M/CNTs (M = Ce, Сu, Mo) were synthesized by incipient wetness impregnation and their physicochemical characteristics were studied using various methods (inductively coupled plasma optical emission spectrometry, thermal analysis coupled with mass spectrometry, low-temperature nitrogen adsorption, X-ray diffraction and structural analysis, scanning electron microscopy, and Raman spectroscopy). It was found that M/CNTs (M = Ce, Сu, Mo) are the mesoporous materials consisting of carbon nanotubes with deposited СeO2, Сu2O/Cu or МоО3/MoO2 particles, respectively. The dispersion of supported species and their deposition uniformity improve in the series Сu < Се < Мо. The type of metal was shown to affect thermal stability as well as the textural and structural properties of the samples. The thermal stability of materials increases in the series Ce < Cu ≈ Mo, which is caused by different redox properties of the metals and also by the composition of products of the metal precursor decomposition. It is promising to use the developed materials as the catalysts for deep purification of diesel fraction components from sulfur compounds.

The effect of electric potential on the sulfide capacity of the CaO-SiO2-Al2O3 system was evaluated by applying voltages in the range of −1.5 to 1.5 V at 1823 K in a C/CO gas equilibrium. When the cathodic potential (−1.5 to 0 V) was applied, it was confirmed that the sulfur partition ratio increased based on the electrochemical reaction of sulfur (S + 2e− = S2−). However, the reversibility of the electrochemical resulfurization reaction (S2− = S + 2e−) in slag was not established in the reverse (anodic) potential region (0–1.5 V), yet the sulfur partition ratio increased. In particular, sulfur evaporation was observed in the anodic potential region. Therefore, in the present study, potential anodic electro-desulfurization mechanisms based on sulfur evaporation are proposed. To verify these mechanisms, sulfur evaporation is discussed in detail as a function of the thermodynamic stability of sulfur in the slag.

Heavy fuel oils contain a high amount of sulfur. In this work, an extent amount of sulfur content waste tire pyrolysis oil (WTPO) was used as a fuel feedstock. A promising alternative oxidative desulfurization (ODS) method was applied in sulfur removal from WTPO using a S-ZrO2/SBA-15 solid acid catalyst, hydrogen peroxide (H2O2) as an oxidant and acetonitrile as an extracting solvent at varied conditions. The prepared catalyst was characterized by X-ray diffraction (XRD), Bruanuer-Emmet-Teller (BET) method and Fourier transform infrared spectroscopy (FTIR) analysis. The influence of reaction parameters such as reaction time (30-60 min), catalyst loading (0.5&ndash, 1.5 wt.%), oxidant to oil mole ratio (5&ndash, 15) at fixed reaction temperature 70 &deg, C on desulfurization of WTPO were investigated. Taguchi method was selected to design the experiment for optimizing the reaction parameters by maximizing the sulfur removal efficiency. The maximum desulfurization efficiency 59.49% was obtained under optimum conditions reaction time (60 min), catalyst loading (1.0 wt.%) and oxidant to sulfur mole ratio (10:1). A catalytic S-ZrO2/SBA-15 -H2O2 oxidation system for oxidative desulfurization of waste tire pyrolysis oil using at mild reaction conditions was developed.

In this work, an efficient oxidative desulfurization (ODS) process of real gas oil and model oils was introduced using (TBA)4PW11Fe@TiO2@PVA phase-transfer catalyst. The catalyst was successfully prepared by the composition of the quaternary ammonium salt of mono iron-substituted phosphotungstate (abbreviated as (TBA)4PW11Fe), titanium dioxide (TiO2), and polyvinyl alcohol (PVA). The nanocomposite obtained was characterized through FT-IR, UV–vis, XRD, and SEM techniques. The spectroscopic characterization revealed that the (TBA)4PW11Fe was immobilized on the surface of TiO2@PVA. The results of catalytic tests showed the outstanding ODS performance of (TBA)4PW11Fe@TiO2@PVA in the removal of thiophenic compounds. Under optimized reaction conditions, the ODS efficiencies of benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) reach 96, 99, 97, and 98%, respectively. The desulfurization system can be recycled five times with merely a slight decrease in activity.

A composite material comprising the chromium terephthalate metal-organic framework MIL-101 and the tetrabutylammonium (TBA) salt of a zinc-substituted polyoxotungstate anion, TBA(4.2)H(0.8)[PW11Zn(H2O)O-39] ( denoted PW11Zn), has been prepared by an impregnation method and characterized by powder X-ray diffraction, scanning electron microscopy, N-2 adsorption/desorption, thermogravimetric analysis, FT-IR, FT-Raman and P-31 magic-angle spinning (MAS) NMR spectroscopies. The characterization data reveal that the polyoxometalate was homogeneously encapsulated within the cages of the support without affecting its crystalline structure and morphology. Both the homogeneous catalyst PW11Zn and the composite material PW11Zn@MIL-101 exhibit high activity in the extractive and catalytic oxidative desulfurization of a model oil containing dibenzothiophene, 1-benzothiophene and 4,6-dimethyldibenzothiophene. Complete desulfurization of the model oil could be achieved within 2 h by using the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate as extraction solvent, aqueous 30% H2O2 as oxidant and a reaction temperature of 50 degrees C. When acetonitrile was used as extraction solvent instead of the IL, the heterogeneous catalyst PW11Zn@MIL-101 could be easily recovered and reused several times without leaching or loss of activity. (C) 2014 Elsevier B.V. All rights

In this research, the effects of process variables on the efficiency and mechanism of dibenzothiophene oxidation in formicacid/H2O2 system for deep desulfurization of a light hydrocarbon model were systematically studied by statistical modelling and optimization using response surface methodology and implementing the central composite design. A quadratic regression model was developed to predict the yield of sulfur oxidation as the model response. The model indicated that temperature was the most significant effective factor and suggested an important interaction between temperature and H2O2/sulfur ratio; at temperatures above 56°C, more excess oxidant was necessary because of instability of active peroxo intermediates and loss of H2O2 due to thermal decomposition. In contrast, the water hindrance effect of H2O2 aqueous solution in desulfurization progress was more significant at temperatures bellow 56°C. In the optimization process, minimizing H2O2/sulfur ratio and catalyst consumption for maximum yield of desulfurization was economically considerable. The optimal condition was obtained at temperature of 57 °C, H2O2/sulfur ratio of 2.5 mol/mol and catalyst dosage of 0.82 mL in 50 mL solution of DBT in n-hexane leading to a maximum oxidation yield of 95% after 1 hour reaction. Good agreement between predicted and experimental results (less than 4% error) was found.

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.

Hierarchical titanium silicalite-1 (HTS-1) zeolites are an important class of catalytic materials due to their enhanced mass transfer and improved catalytic performance. In this study, HTS-1 zeolites have been successfully prepared by the hydrothermal crystallization of carbon-silica-titania (CST) composites. Compared with the direct carbonization method, the mild carbonization of SiO2-TiO2/Tween 40 xerogel in the presence of sulfuric acid can effectively improve both the content and mesoporous structure of carbon material in the CST composites, which enables carbon materials to better play the role of a mesoporous template during the crystallization process. The resultant zeolite has both ordered micropores and interconnected mesopores and macropores, which are similar to the skeleton of the carbon template trapped in the TS−1 crystals. Moreover, the HTS−1 zeolite displays outstanding catalytic performance in oxidative desulfurization of bulky sulfur compounds.

Owing to the environmental regulations with respect to sulfur content and continuing challenges of finding a suitable catalyst of such impurity, a driving force for the development of more efficient technologies a deep research on new oxidative catalysts is considered an important issue in fuel quality improvement. Thus, the present study shows a novel percent of nano-catalyst with 18% zinc oxide (ZnO) of active component over nano-alumina that has not been reported in the public domain for sulfur removal from kerosene fuel by air (oxidative desulfurization (ODS) method). Where, such percent of the active component on the nano-alumina helps to add one or two atoms of oxygen to sulfur content in the kerosene. The nano-catalyst (ZnO/nano-alumina-particles composite) is prepared by precipitation of zinc oxide and loaded over nano-alumina in one-step. The activity of the prepared catalyst was tested utilizing ODS process of kerosene fuel by air in a batch reactor. A set of experiments were conducted with a wide range of operating conditions, where the reaction temperature was ranged from 150 to 190ºC, the reaction time from 30 to 50 min and the catalyst weight from 0.4 to 1 g. The experimental results showed that the chemical nature of zinc oxides showed higher conversion (70.52%) at reaction temperature of 190 ºC, reaction time of 50 min, and 1 g catalyst weight used in the batch reactor. A kinetic model related to the sulfur removal from kerosene via ODS process in the batch reactor was also investigated in this study for the purpose of estimating the best kinetic parameters of the relevant reactions. The results showed that the prepared catalyst (ZnO over nano-alumina) can be applied confidently to reactor design, operation and control in addition to improve the fuel quality. Following the kinetic model of ODS process, a very well agreement between the experimental and predicted results is obtained. Copyright © 2019 BCREC Group. All rights reservedReceived: 16th April 2018; Revised: 26th September 2018; Accepted: 30th September 2018; Available online: 25th January 2019; Published regularly: April 2019How to Cite: Nawaf, A.T., Jarullah, A.T., Abdulateef, L.T. (2019). Design of a Synthetic Zinc Oxide Catalyst over Nano-Alumina for Sulfur Removal by Air in a Batch Reactor. Bulletin of Chemical Reaction Engineering & Catalysis, 14 (1): 79-92 (doi:10.9767/bcrec.14.1.2507.79-92)Permalink/DOI: https://doi.org/10.9767/bcrec.14.1.2507.79-92

To lower the sulphur content below 500 ppm and to increase the quality of bitumen derived heavy oil, a combination of hydrotreating followed by oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) is proposed in this work. NiMo/&gamma, Al2O3 catalyst was synthesized and used to hydrotreat heavy gas oil (HGO) and light gas oil (LGO) at typical operating conditions of 370&ndash, 390 &deg, C, 9 MPa, 1&ndash, 1.5 h&minus, 1 space velocity and 600:1 H2 to oil ratio. &gamma, Alumina and alumina-titania supported Mo, P, Mn and W catalysts were synthesized and characterized using X-ray diffractions, N2 adsorption-desorption using Brunauer&ndash, Emmett&ndash, Teller (BET) method, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). All catalysts were tested for the oxidation of sulphur and nitrogen aromatic compounds present in LGO and HGO using tert-butyl hydroperoxide (TBHP) as oxidant. The oxidized sulphur and nitrogen compounds were extracted using adsorption on activated carbon and liquid-liquid extraction using methanol. The determination of oxidation states of each metal using XPS confirmed the structure of metal oxides in the catalyst. Thus, the catalytic activity determined in terms of sulphur and nitrogen removal is related to their physico-chemical properties. In agreement with literature, a simplistic mechanism for the oxidative desulfurization is also presented. Mo was found to be more active in comparison to W. Presence of Ti in the support has shown 8&ndash, 12% increase in ODS and ODN. The MnPMo/&gamma, Al2O3-TiO2 catalyst showed the best activity for sulphur and nitrogen removal. The role of Mn and P as promoters to molybdenum was also discussed. Further three-stage ODS and ODN was performed to achieve less than 500 ppm in HGO and LGO. The combination of hydrotreatment, ODS and ODN has resulted in removal of 98.8 wt.% sulphur and 94.7 wt.% nitrogen from HGO and removal of 98.5 wt.% sulphur and 97.8 wt.% nitrogen from LGO.

Three heteropolyanion substituted hydrotalcite-like compounds (HPA-HTLcs) including Mg9Al3(OH)24[PW12O40](MgAl-PW12), Mg9Al3(OH)24[PMo12O40] (MgAl-PMo12) and Mg12Al4(OH)32[SiW12O40] (MgAl-SiW12), were synthesized, characterized and used as catalysts for the oxidative desulfurization of simulated oil (dibenzothiophene, DBT, in n-octane). MgAl-PMo12 was identified as an effective catalyst for the oxidative removal of DBT under very mild conditions of atmospheric pressure and 60 °C in a biphasic system using hydrogen peroxide as oxidant and acetonitrile as extractant. The conversion of DBT was nearly 100%. As a result, because of the influence of the electron density and the space steric hindrance, the oxidation reactivity of the different sulfur compounds in simulated oil followed the order DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT) > thiophene (TH). When the reaction is finished, the catalysts can be recovered from the acetonitrile phase by filtration. The recovered MgAl-PMo12 retains nearly the same catalytic activity as the fresh material. Moreover, MgAl-PMo12 was found to exhibit an ideal catalytic activity in the oxidative desulfurization of real diesel resulting in a total remaining sulfur content of 9.12 ppm(w).

Titanium centers grafted on hydrophobic silica bearing long chain silanes (octadecyl or octyl) are able to oxidize dibenzothiophene (DBT), as well as simpler sulfides and 2,6-dimethyldibenzothiophene, to the corresponding sulfone in hydrocarbon solution with aqueous hydrogen peroxide in only a slight excess over the stoichiometric amount, without using any surfactant or cosolvent. The productivity per gram of catalyst or per Ti site can be optimized by tuning the silanization of the silica (or using a commercially available silanized silica) and the Ti loading of the catalyst. The catalyst preparation and the oxidation reaction are compatible with the use of an industrial grade aromatic solvent., The financial support of the Ministerio de Economía y Competitividad (INNPACTO program, IPT-310000-2010-021, and project CTQ2011-28124), Peroxychem Spain S.L. (former FMC-Foret S.A.), and the Diputación General de Aragón (E11 Group co-financed by the European Regional Development Funds) is gratefully acknowledged.

In this work the oxidation of benzo-, dibenzo-, 4-methyldibenzo-, and 4,6-dimethyildibenzothiophene in the presence of hydrogen peroxide and formic acid was studied over the temperature range of 20–65 °C. The experimental data were interpreted by means of a interfacial mass transfer and reaction model developed in the first part of this study. The parameters identification tool available in gPROMS environment allowed a regression of the Arrhenius constants of the rate determining step characterizing the considered oxidation reactions. The activation energies of the thiophenes oxidation reactions result in 34.6 kJ/mol and 29 ± 1 kJ/mol for BT and DBTs, respectively.

This work proposes an efficient desulfurization system to produce low sulfur diesel under sustainable and moderate experimental conditions. Treatment of a real diesel with a sulfur content of 2300 ppm led to 80% desulfurization after 2 h. The processes used conciliate liquid-liquid extraction and sulfur oxidative catalysis. The catalytic performance of the commercial Keggin-polyoxomolybdate H3[PMo12O40] (PMo12) was strategically increased by simple cation exchange, using a long carbon chain (ODAPMo12, ODA = CH3(CH2)17(CH3)3N), and by its incorporation into the Metal-Organic Framework (MOF) NH2-MIL-101(Cr), forming a new active heterogeneous PMo12@MOF composite catalyst. Activity of both catalysts was similar, however, the solid catalyst could be easily recovered and reused, and its stability was confirmed after multiple continuous cycles.

This study successfully improved the performance of oxidative desulfurization method to reduce sulfur content from residue oil (condensate) with modifications of oxidation and extraction steps which was repeated for several stages. Residue oil used in this study contain 386.2 ppm of initial sulfur content. In oxidation process, H2O2 as oxidizer and acid as catalyst were used within temperature range of 30–60 °C and time interval from 30 to 120 min. In extraction process, various alcohol solvents (methanol, ethanol, and propanol) were used with the temperature of 30 °C in 30 min for every residue oil ratio to solvent (v/v). The best reducing sulfur result achieved was 35.9 ppm or 90.7% desulfurization. This result was achieved after 4 recursively extractions using ethanol as solvent. This study successfully reduced sulfur content in residue oil to meet the international standard (< 50 ppm).

Unless important developments record new and renewable energy sources, the role of fossil fuels as an energy resource goes on. It is possible to detect sulfur, heavy metals, and tracer elements such as arsenic and selenium by decreasing calorific value of coals. Sulfur oxides, which are the main pollutants in atmosphere, are irritative to humans and plants, and erosion occurs on buildings. Although there are high lignite reservoirs, high sulfur content limits the efficient use of them. In this research, it is aimed to convert combustible sulfur in coal to non-combustible sulfur form in the ash by oxidizing it with permanganate solution. During this research, the effect of two different parameters of potassium permanganate concentration, processing time, and mean particle size were investigated at constant room temperature and shaking rate. The conversion of combustible sulfur to non-combustible sulfur form was achieved optimally with 0.14 M potassium permanganate solution, 0.1 mm mean particle size at 16 h of treatment time, and the combustible sulfur amount was decreased by 46.37% compared to undoped conditions.

Sulfur oxidation appears a very promising route for obtaining ultralow-sulfur fuels requested worldwide by the new regulation mandates. In this work, the oxidizing system constituted by hydrogen pe...

The use of peroxycarboxylic-acid-functionalized hexagonal mesoporous silica (HMS) as an oxidizing solid agent was investigated. The experimentation was performed on organic sulfur compounds that have been selected as representative of those contained in crude distillates. The results clearly show the potentiality of this oxidizing agent for the development of oxidative desulfurization (ODS) processes for the purpose of producing ultralow-sulfur fuels and sulfoxides and sulfones as secondary products.

Mestrado em Química Os polioxometalatos já foram empregues em diversas áreas, nomeadamente na biologia, química analítica, medicina, nanotecnologia, catálise, entre muitas outras. A catálise foi a utilização que mais se destacou em termos de publicações científicas, devido ao facto dos polioxometalatos serem compostos de baixo custo, benignos para o ambiente, possuindo vários locais ativos, permitindo aos substratos converterem-se num produto específico. Hoje em dia, a descoberta de novos polioxometalatos, mais complexos, nomeadamente os azuis de molibdénio, fez despertar interesse na utilização destes últimos na área da catálise. Neste trabalho estudou-se um dos azuis de molibdénio, nomeadamente o Na15[Mo126VIMo28VO462H14(H2O)70]0,5[Mo124VIMo28VO457H14(H2O)68]0,5 ca. 350H2O, como catalisador homogéneo na oxidação de três alcenos (cicloocteno, ciclo-hexeno e oct-1-eno), de três álcoois (ciclopentanol, ciclo-hexanol e álcool benzílico), de dois sulfuretos (tioanisol e sulfureto de difenilo) e de dois benzotiofenos (benzotiofeno (BT) e dibenzotiofeno (DBT)). Procedeu-se a uma otimização das condições de acordo com volume de solvente, temperatura, quantidade de agente oxidante, solvente e razão catalisador/substrato antes dos ensaios catalíticos. Obtiveram-se valores elevados de conversão para os alcenos, para os sulfuretos e para os benzotiofenos. Realizaram-se vários ensaios de dessulfuração oxidativa de um model fuel sintético (em hexano), contendo 500 ppm de enxofre total (BT, DBT, BT/DBT (1:1)), em que o solvente de extração foi o acetonitrilo, obtendo-se valores de extração inicial de 45% e 38%, para o BT e para o DBT, respetivamente. Por outro lado, alcançou-se 100% de dessulfuração do DBT, após 120 min de reação. Verificaram-se valores semelhantes de dessulfuração e de catálise homogénea para ambos os BT’s, apesar de terem sido utilizados solventes diferentes. Também se realizou um ensaio de catálise heterógena na oxidação de cicloocteno, tendo-se imobilizado o catalisador em lamelas de quartzo pelo método layer-by-layer (LBL). O resultado obtido foi de 5 % de conversão, valor equiparado com o respetivo branco. Previamente à catálise, realizou-se um mapeamento de Raman, varrendo-se uma área selecionada a número de onda fixo de 970 cm-1, verificando-se que o catalisador não estava distribuído uniformemente pela lamela. Fizeram-se também estudos de UV/Vis antes e depois da catálise. Além disso, o catalisador em estudo foi comparado com o TBA2[Mo6O19] (catalisador de comparação), na oxidação do cicloocteno, obtendo-se 82±2% de conversão, com o catalisador em estudo e 13% de conversão, com o catalisador de comparação, demonstrando que o catalisador estudado catalisa mais facilmente o substrato mencionado. O catalisador em estudo, assim como TBA2[Mo6O19], foram caraterizados por FT-Raman, FTIR, UV/Vis e TGA (apenas para o catalisador de comparação) e comparados com a literatura. Em alguns ensaios de catálise homogénea, verificou-se a formação de um sólido, sendo este analisado por FT-Raman e FTIR. The polyoxometalates have been employed in various fields, including biology, analytical chemistry, medicine, nanotechnology, catalysis, among many others. Catalysis was one of the outstanding applications in terms of scientific publications because of the polyoxometalates being low cost compounds, benign to the environment, showing various active sites that allow substrates to be converted into a specific product. Nowadays, the discovery of new and more complex polyoxometalates, in particular molybdenum blues, brought the interest in using them in the area of catalysis. In this work one of the molybdenum blues in particular Na15[Mo126VIMo28VO462H14(H2O)70]0,5[Mo124VIMo28VO457H14(H2O)68]0,5 ca. 350H2O was used as a homogeneous catalyst in the oxidation of three alkenes (cyclooctene, cyclohexene and oct-1-ene), three alcohols (cyclopentanol, cyclohexanol and benzyl alcohol), two sulfides (thioanisole, diphenyl sulphide) and two benzothiophenes (benzothiophene (BT) and dibenzothiophene (DBT)). There has been an optimization there of in accordance with the volume of solvent, temperature, amount of oxidizing agent, solvent and catalyst/ substrate ratio before catalytic testing. High conversion values for alkenes, sulfides and benzothiophenes were obtained. There were several oxidative desulfurization tests of a synthetic model fuel (hexane), containing 500 ppm total sulfur (BT, DBT, BT/DBT (1:1)), wherein the extraction solvent is acetonitrile, yielding initial extraction if values of 45% and 38%, for BT and DBT, respectively. Moreover, it reached 100% of the DBT desulphurisation after 120 min of reaction. There were similar values of desulfurization and homogeneous catalysis for both BTs, despite different solvents were used. It was also heterogenous catalysis tests for the oxidation of cyclooctene with the catalyst immobilized on quartz plates, by the layer-by-layer method (LBL). The result was 5% conversion, matching the respective blank. We made a Raman imaging prior to catalysis in a selected area, which is swept across the area with a fixed wave number of 970 cm-1, verifying that the catalyst was not distributed uniformly in the lamella Studies were also made of UV/Vis before and after catalysis. In addition, the catalyst of study was compared with TBA2[Mo6O19] (comparison catalyst) for cyclooctene oxidation get yields of 82±2%, with the catalyst on study and 13% with the comparison catalyst, demonstrating that the studied catalyst catalyses more easily the substrate. The catalyst under study, as well as the comparison catalyst, were characterized by FT-Raman, FTIR, UV/Vis and TGA (only for comparison catalyst) and compared with the literature. In some of the homogeneous catalysis tests, there was the formation of a solid which was analyzed by FT-Raman and FTIR.