화학공학소재연구정보센터
Chinese Journal of Chemical Engineering, Vol.17, No.2, 189-194, 2009
Oxidation of Benzothiophenes Using Tert-amyl Hydroperoxide
Homogeneous oxidation using an oil-soluble oxidant, tert-amyl hydroperoxide (TAHP), for ultra-deep desulfurization was performed under mild conditions in the presence of molybdenum oxide catalysts. Dibenzothiophene (DBT), benzothiophene (BT) and 4, 6-dimethyl-dibenzothiophene (DMDBT), which are the refractory sulfur compounds for hydrodesulfurization (HDS), were employed as model substrates for a simulated diesel fuel. Activity of molybdenum oxide supported on a macroporous weak acidic resin was investigated. The mass conversion of DBT reached near 100% at 90 degrees C and a TAHP/DBT molar ratio of 3 with 1% of molybdenum oxide supported on Amberlite IRC-748 resin for 1 h. It was further that the activities of the model substrates decreased in the order of DMDBT>DBT>BT. In the flow oxidation using TAHP as the oxidant, mass conversion of DBT increased remarkably from 61.3% to 98.5% when dropping the weight hourly space velocity (WHSV) from 40 h(1) to 10 h(1) . A series of experiments dealt with selectivity of this oxidation using TAHP revealed that the model unsaturated compounds, i.e. 4, 6, 8-trimethyl-2-nonylene, and 2-methylnapthalene did not affect the oxidation of DBT. Carbazole had nearly no effect on the conversion of DBT using TAHP, but had some influence on the one using tert-butyl hydroperoxide (TBHP). The mass conversion of DBT decreased remarkably from 75.2% to 3.6% when the content of carbazole increased from 0 to 500 mu g.g(-1). In the flow oxidation using TAHP as the oxidant, the concentration of DBT in model fuels was reduced from 500 mu g.g(-1) to 7.2 mu g.g(-1) at WHSV of 10 h (1), and then reduced to 3.8 mu g.g (1) by adsorption of Al2O3.