Room Temperature Ultrafast Oxidative Desulfurization with Sodium Hypochlorite in the Presence of Silica-Supported Catalysts.

A series of silica-supported catalysts containing molybdenum, tungsten, and vanadium oxides as the active phase was investigated in the process of oxidative desulfurization with sodium hypochlorite. It was shown for the first time that catalysts containing vanadium oxide as the active phase are more stable under oxidation conditions with sodium hypochlorite and retain their effectiveness at increased dosages of the oxidant and at high initial sulfur contents. The catalysts were characterized in detail by a complex of methods: Fourier transform infrared, X-ray spectral fluorescence, transmission electron microscopy, scanning electron microscopy, and low-temperature nitrogen adsorption/desorption. Key factors affecting the oxidation of dibenzothiophene (DBT) were investigated: oxidant and catalyst amount, oxidation time, initial sulfur content, and acetonitrile amount. Under optimized conditions, the DBT conversion rate was 100% in 5 min at room temperature (25 °C), NaClO/S molar ratio 6:1, catalyst amount 2 wt %. In the real sample of the straight-run diesel fraction, the sulfur content was reduced from 10,100 to 3030 ppm. The V(10%)/SiO2 catalyst retains its activity for 5 oxidation-regeneration cycles.

Sulfur containing mixed wastes in anaerobic processing by new immobilized synthetic consortia.

Methanogenic biotransformation of unusual substrates (sulfur (S)-containing wastes: non-purified vacuum gas oil, straight-run gasoline fraction (Naphtha), gas condensate, and straight-run diesel fraction) coming from oil industry after their oxidative desulfurization was investigated. Nitrogen-containing wastes (hydrolysates of chicken manure and Chlorella vulgaris biomass) were added as co-substrates to mixture with oil industry wastes. The 100 % conversion of S-organic compounds to inorganic sulfide accumulated in the reaction liquid medium was achieved with simultaneous production of biogas containing high methane percent (greater than 70 %). Polishing of effluents from methane tank was carried out by denitrifying oxidation of ammonium (DEAMOX). The high process efficiency was due to use of original immobilized artificial consortia at the stage of methanogenesis and DEAMOX. This study reveals the real potential in the processing of very complex mixtures of large-scale wastes, usually inhibiting methanogenesis, by developing biocatalysts based on synthetic biology approaches.

New Type of Catalyst for Efficient Aerobic Oxidative Desulfurization Based On Tungsten Carbide Synthesized by the Microwave Method.

Herein, we present a new type of high-performance catalyst for aerobic oxidation of organosulfur compounds based on tungsten carbide. The synthesis of tungsten carbide was performed via microwave irradiation of the precursors, which makes it possible to obtain a catalyst in just 15 min. The synthesized catalyst was investigated by a variety of physicochemical methods: X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, electron microscopy, and N2 adsorption/desorption. It was shown that active centers containing tungsten in the transition oxidation state (+4) play a key role in the activation of oxygen. The main factors influencing the conversion of dibenzothiophene (DBT) were investigated. It should be noted that 100% conversion of DBT can be achieved under relatively mild conditions: 120 °C, 3 h, 6 bar, and 0.5% wt catalyst. The catalyst retained its activity for at least six oxidation/regeneration cycles. The simplicity and speed of synthesis of the proposed catalyst in combination with its high activity and stability open broad prospects for its further use both for oxidative desulfurization and for other reactions of aerobic oxidation of organic substrates.

Combined Heterogeneous Catalyst Based on Titanium Oxide for Highly Efficient Oxidative Desulfurization of Model Fuels.

In this work, new heterogeneous Mo-containing catalysts based on sulfonic titanium dioxide were developed for the oxidation of sulfur-containing model feed. The synergistic effect of molybdenum and sulfonic group modifiers allows for enhancing catalytic activity in dibenzothiophene oxidative transformation, and a strong interaction between support and active component for thus obtained catalysts provides increased stability for leaching. For the selected optimal conditions, the Mo/TiO2-SO3H catalyst exhibited 100% DBT conversion for 10 min (1 wt % catalyst, molar ratio of H2O2:DBT, 2:1; 80 °C). Complete oxidation of DBT in the presence of the synthesized catalyst is achieved when using a stoichiometric amount of oxidizing agent, which indicates its high selectivity. The enhanced stability for metal leaching was proved in recycling tests, where the catalyst was operated for seven oxidation cycles without regeneration with retainable activity in DBT-containing model feed oxidation with hydrogen peroxide under mild reaction conditions. In 30 min of the reaction (H2O2:S = 2:1 (mol), 0.5% catalyst, 5 mL of acetonitrile, 80 °C), it was possible to reduce the content of sulfur compounds in the diesel fraction by 88% (from 5600 to 600 ppm).

Model Fuel Oxidation in the Presence of Molybdenum-Containing Catalysts Based on SBA-15 with Hydrophobic Properties.

We have studied for the first time the role of hydrophobicity of the mesoporous silicate SBA-15 on the activity and the service life of a catalyst in the peroxide oxidation of sulfur-containing compounds. Immobilization of the molybdate anion on the SBA-15 support via ionic bonding with triethylammonium groups allows us not only to decrease the reaction temperature to a relatively low value of 60 °C without a drop in the dibenzothiophene conversion degree but also to increase the service life of the catalyst to many times that of the known analogs. The support and catalyst structures were investigated by low-temperature nitrogen adsorption/desorption, Fourier-transform infrared spectroscopy, X-ray fluorescence analysis, and transmission electron microscopy. Immobilization of the molybdate anion on the SBA-15 support, modified with ammonium species, prevents the leaching of active sites. However, only alkyl-substituted ammonium species minimize DBT sulfone adsorption, which significantly increases the catalyst's service life. The synthesized catalyst Mo/Et3N-SBA-15 with hydrophobic properties is not sensitive to the initial sulfur content and hydrogen peroxide amount and retains its activity for at least six cycles of oxidation without regeneration. These catalysts can be efficiently used for clean fuel production.

Formation and use of anaerobic consortia for the biotransformation of sulfur-containing extracts from pre-oxidized crude oil and oil fractions.

A new solution for fossil raw materials desulfurization based on a hybrid chemical-biocatalytic scheme with biogas and sulfide production is proposed.·H2O2, formic acid and Na2MoO4 were used for petroleum or oil fractions pre-oxidation. Ethanol or dimethylformamide was used as extractant to remove sulfur-contained compounds from pre-oxidized straight-run diesel oil fraction, non-hydro treated vacuum gas oil, gas condensate or crude oil. Compositions of cells (anaerobic sludge, Desulfovibrio vulgaris, Clostridium acetobutilycum, Rhodococcus ruber, Rhodococcus erythropolis) were specially developed, immobilized in poly(vinyl alcohol) cryogel and used for methanogenic treatment of sulfur-containing extracts, diluted with phosphate buffer (pH 7.2) and hydrolysates of renewable raw materials. The sulfur coming into the reactor with the extracts was 100% converted to inorganic sulfide or cell biomass. The ratio of methane in the biogas was 68-76%. Bioluminescent express-methods were used to control the possible toxicity of media and metabolic activity of cells used as biocatalysts.

Deep Oxidative Desulfurization of Fuels in the Presence of Brönsted Acidic Polyoxometalate-Based Ionic Liquids.

Polyoxometalate-based ionic liquid hybrid materials with a pyridinium cation, containing Brönsted acid sites, were synthesized and used as catalysts for the oxidation of model and real diesel fuels. Keggin-type polyoxometalates with the formulae [PMo12O40]3-, [PVMo11O40]4-, [PV2Mo10O40]4-, [PW12O40]3- were used as anions. It was shown that increasing the acid site strength leads to an increase of dibenzothiophene conversion to the corresponding sulfone. The best results were obtained in the presence of a catalyst, containing a nicotinic acid derivative as cation and phosphomolybdate as anion. The main factors affecting the process consisting of catalyst dosage, temperature, reaction time, oxidant dosage were investigated in detail. Under optimal conditions full oxidation of dibenzothiophene and more than a 90% desulfurization degree of real diesel fuel (initial sulfur content of 2050 ppm) were obtained (the oxidation conditions: NK-1 catalyst, molar ratio H2O2:S 10:1, molar ratio S:Mo 8:1, 1 mL MeCN, 70 °C, 1 h). The synthesized catalysts could be used five times with a slight decrease in activity.

Alkali Earth Catalysts Based on Mesoporous MCM-41 and Al-SBA-15 for Sulfone Removal from Middle Distillates.

Mg, Ca, and Ba catalysts supported on structured mesoporous silica oxides types MCM-41 and Al-SBA-15 were synthesized and investigated in sulfone cracking for sulfur removal from oxidized diesel fuel. Functional materials and catalysts were characterized by low-temperature nitrogen adsorption/desorption, transmission electron microscopy, and inductively coupled plasma atomic emission spectroscopy techniques. Catalytic tests were carried out in fixed-bed and batch reactors with a model compound dibenzothiophene sulfone and oxidized diesel fraction as a feed. MgO/MCM-41 and MgO/Al-MCM-41 possess high activity in sulfone cracking. The sulfur content in the diesel fraction decreases from initial 450 up to 100 ppmw. Catalysts can be regenerated for reuse in several cycles and may be potentially scaled up for industrial applications.

Prospective Approach to the Anaerobic Bioconversion of Benzo- and Dibenzothiophene Sulfones to Sulfide.

Sulfur recovery from organic molecules such as toxic sulfones is an actual problem, and its solution through the use of environmentally friendly and nature-like processes looks attractive for research and application. For the first time, the possible bioconversion of organic sulfones (benzo-and dibenzothiophene sulfones) to inorganic sulfide under anaerobic conditions with simultaneous biogas production from glucose within a methanogenesis process is demonstrated. Biogas with a methane content of 50.7%-82.1% was obtained without H2S impurities. Methanogenesis with 99.7%-100% efficiency and 97.8%-100% conversion of benzo- and dibenzothiophene sulfones (up to 0.45 mM) to inorganic sulfide were obtained in eight days by using a combination of various anaerobic biocatalysts immobilized in a poly(vinyl alcohol) cryogel. Pure cell cultures of sulfate-reducing bacteria and/or H2-producing bacteria were tested as additives to the methanogenic activated sludge. The immobilized activated sludge "enhanced" by bacterial additives appeared to retain its properties and be usable multiple times for the conversion of sulfones under batch conditions.