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

Nanocatalysts for Oxidative Desulfurization of Liquid Fuel: Modern Solutions and the Perspectives of Application in Hybrid Chemical-Biocatalytic Processes

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

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