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Hydrosulfurization of Methanol on Y2O3-TiO2-ZrO2 Catalysts

Szalaty-Bujakowska A., Kujawa J., Ziółek M., Fiedorow R.

Polish Journal of Chemistry

2003

Vol. 77 / nr 5

789-796

Y2O3-TiO2-ZrO2 catalysts, where the contribution of oxide components ranges from 0 to 100 mol %, have been studied for their catalytic performance in methanol hydrosulfurization. Their activity and selectivity have shown a strong dependence on acid-base properties which, in turn, changed with catalyst composition. High yttria content favors selectivity to methanethiol, while catalysts highly active for the formation of dimethylsulfide were those containing 8 mol % Y2O3. The latter composition, which boosted selectivity to (CH3)2S, has created favorable conditions for the generation of acid centers in chemically mixed oxides as concluded on the ground of ESR studies and acidity measurements.

Oxidation of organic sulfides by peroxyl radicals; search for an adduct intermediate

Bonifacic M., Stefanic I.

Nukleonika

2000

Vol. 45, nr 1

39-44

The reaction mechanism of dimethyl sulfide oxidation by peroxyl radicals (CCl3OOź and CHCl2OOź) in aqueous/alcohol solutions has been studied by means of pulse radiolysis with optical detection in order to gain evidence for the formation of an adduct intermediate, ROO-źS(CH3)2. In the range of 300-650 nm, the only absorbing product was the one-electron oxidized species [(CH3)2S\S(CH3)2]+, and no indication of an additional absorption attributable to an adduct precursor was found. Under the condition of only 50% conversion of CHCl2OOź into the sulfide radical cation, however, addition of a small amount of I- resulted in formation of (CH3)2S\I as the only product and at a yield equal to that of CHCl2OOź radicals. This result is explained by the reaction of iodide ions with a precursor of [(CH3)2S\S(CH3)2]+ species, namely, the adduct CHCl2OO-źS(CH3)2 and is, thus, taken as conclusive, although indirect, evidence of the existence of this adduct intermediate.