http://www1.udel.edu/chem/polenova/PDF/Polyoxometalates/POMs_Catalysis_NMR_ChemRev1998.pdf

Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions

The oxidation of model sulfur compounds (thiophene derivatives, benzothiophene derivatives, and dibenzothiophene derivatives), straight run-light gas oil (SR-LGO, S:  1.35 wt %), and vacuum gas oil (VGO, S:  2.17 wt %) were conducted with a mixture of hydrogen peroxide and formic acid. The thiophene derivatives with 5.696 to 5.716 electron densities on the sulfur atoms could not be oxidized at 50 °C. Benzo[b]thiophene with 5.739 electron density and other benzothiophene and dibenzothiophenes with higher electron densities could be oxidized. The sulfur compounds in SR-LGO and VGO appeared to be oxidized to a detectable levels (c.a., 0.01 wt % S) by GC-FPD analysis. The IR spectra of oxidized SR-LGO and VGO showed that sulfones were formed by oxidation. The removal of sulfur compounds by extraction became more effective for the oxidized samples than for the original samples. Lighter sulfur compounds were preferentially extracted. The extraction efficiencies of solvents, i.e., N,N‘-dimethylformamide (DMF), a...

Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction

Sulfur compounds represent one of the most common impurities present in the crude oil. Sulfur in liquid fuel oil leads directly to the emission of SO2 and sulfate particulate matter (SPM) that endangers public health and community property; and reduces the life of the engine due to corrosion. Furthermore, the sulfur compounds in the exhaust gases of diesel engines can significantly impair the emission control technology designed to meet NOx and SPM emission standards. The research efforts for developing conventional hydrodesulfurization and alternative desulfurization methods such as selective adsorption, biodesulfurization, oxidation/extraction (oxidative desulfurization), etc. for removing these refractory sulfur compounds from petroleum products are on the rise. Research laboratories and refineries are spending huge amounts of money in finding a viable and feasible solution to reduce sulfur to a concentration of less than 10 mg l−1. This paper reviews the current status in detail of various desulphurization techniques being studied worldwide. It presents an overview of novel emerging technologies for ultra-deep desulfurization so as to produce ultra-low-sulfur fuels.

An evaluation of desulfurization technologies for sulfur removal from liquid fuels

Dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene are typical thiophenic sulfur compounds that exist in diesel fuels Using toluene solutions of the model compounds, experiments were carried out to compare the reactivity of the different dibenzothiophenes in oxidation reactions, a key step for oxidative desulfurizations A series of polyoxometalate/H2O2 systems were evaluated for dibenzothiophene oxidation The H2O2 solutions of phosphotungstic acid and its salt were very active catalyst systems for the model compound oxidation, while their molybdenum counterpart systems were much less active The H2O2 solutions of silicotungstic and silicomolybdic compounds were the least active catalyst systems for the reaction Oxidation reactivities decreased in the order of dibenzothiophene>4-methyldibenzothiophene>4,6-dimethyldibenzothiophene, the same reactivity trend that exists in HDS However, the oxidation of the dibenzothiophenes was achieved under mild reaction conditions and it was easy to increase reaction temperature or reaction time to achieve high oxidation conversions, even for the least reactive 4,6-dimethyldibenzothiophene Apparent activation energies of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene oxidation were 538, 560, and 587 kJ/mol, respectively These activation energies indicated a decrease in reactivity of dibenzothiophenes as methyl substitutes increased at the 4 and 6 positions on dibenzothiophene rings Interestingly, in a formic acid/H2O2 system, the oxidation reactivity of the dibenzothiophenes showed the reverse trend, suggesting that steric hindrance might play a role when bulky polyoxoperoxo species, which likely form in a hydrogen peroxide solution, act as catalysts

Oxidation reactivities of dibenzothiophenes in polyoxometalate/H2O2 and formic acid/H2O2 systems

Environmental concerns have introduced a need to remove sulfur-containing compounds from light oil. As oxidative desulfurization is conducted under very mild reaction conditions, much attention has recently been devoted to this process. In this contribution, the developments in selective removal of organosulfur compounds present in liquid fuels via oxidative desulfurization, including both chemical oxidation and biodesulfurization, are reviewed. At the end of each section, a brief account of the research directions needed in this field is also included.

/pdf/oxidative-processes-of-desulfurization-of-liquid-fuels-202j38crqo.pdf

Oxidative processes of desulfurization of liquid fuels

Oxidation of dibenzothiophene with hydrogen peroxide using phosphotungstic acid as catalyst and tetraoctylammonium bromide as phase transfer agent in a mixture of water and toluene has been studied. Catalysed decomposition of hydrogen peroxide competes with dibenzothiophene oxidation but by choice of suitable conditions yields of dibenzothiophene sulphone approaching 100% may be obtained. Treatment of gas oils with this technology shows that all the sulphur compounds present are oxidised by this catalyst system and highly substituted dibenzothiophenes are the most readily oxidised of species containing a thiophene nucleus. Oxidised sulphur compounds can be separated from the oil by adsorption on silica gel. The use of oxidation and adsorption in a process for desulphurisation of gas oils is discussed.

Christopher Sharp

Papers

Oxidative desulphurisation of oils via hydrogen peroxide and heteropolyanion catalysis