Oxidation of Benzothiophenes Using Tert-amyl Hydroperoxide

摘要/Abstract

摘要： 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.Dibenzothio-phene(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℃ 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 found 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-methylnaphthalene did not affect the oxidation of DBT.Car-bazole 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 μg·g^-1.In the flow oxidation using TAHP as the oxidant,the concentration of DBT in model fuels was reduced from 500 μg·g^-1 to 7.2 μg·g^-1 at WHSV of 10 h^-1,and then reduced to 3.8 μg·g^-1 by adsorption of Al₂O₃.

关键词: desulfurization, benzothiophene, tert-amyl hydroperoxide

Abstract: 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.Dibenzothio-phene(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℃ 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 found 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-methylnaphthalene did not affect the oxidation of DBT.Car-bazole 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 μg·g^-1.In the flow oxidation using TAHP as the oxidant,the concentration of DBT in model fuels was reduced from 500 μg·g^-1 to 7.2 μg·g^-1 at WHSV of 10 h^-1,and then reduced to 3.8 μg·g^-1 by adsorption of Al₂O₃.

Key words: desulfurization, benzothiophene, tert-amyl hydroperoxide

周新锐, 盖洪涛, 王静, 张珊珊, 杨锦宗, 张淑芬. Oxidation of Benzothiophenes Using Tert-amyl Hydroperoxide[J]. , 2009, 17(2): 189-194.

ZHOU Xinrui, GAI Hongtao, WANG Jing, ZHANG Shanshan, YANG Jinzong, ZHANG Shufen. Oxidation of Benzothiophenes Using Tert-amyl Hydroperoxide[J]. , 2009, 17(2): 189-194.

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