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),...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°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 found that the activities of the model substrates decreased in the or-der 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.展开更多
The adsorption properties of a novel macroporous weak acid resin (D152) for Pb2+ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb2+ is at pH 6.00 in HAc-NaAc medium. The s...The adsorption properties of a novel macroporous weak acid resin (D152) for Pb2+ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb2+ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb2+ adsorbed on D152 resin can be eluted with 0.05 mol/L HCl quantitatively. The adsorption rate constants determined under various temperatures are k288 K=2.22×10-5 s-1, k298 K=2.51×10-5 s-1, and k308 K= 2.95×10-5 s-1, respectively. The apparent activation energy, Ea is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are -HΘ=13.3 kJ/mol, -SΘ=119 J/(mol·K), and -GΘ298 K =-22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb2+ follows Langmuir model.展开更多
基金Supported by Program for Changjiang Scholars and Innovative Research Team in University
文摘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°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 found that the activities of the model substrates decreased in the or-der 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.
基金Project(2008F70059) supported by the Scientific and Technological Research Planning of Zhejiang Province, China
文摘The adsorption properties of a novel macroporous weak acid resin (D152) for Pb2+ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb2+ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb2+ adsorbed on D152 resin can be eluted with 0.05 mol/L HCl quantitatively. The adsorption rate constants determined under various temperatures are k288 K=2.22×10-5 s-1, k298 K=2.51×10-5 s-1, and k308 K= 2.95×10-5 s-1, respectively. The apparent activation energy, Ea is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are -HΘ=13.3 kJ/mol, -SΘ=119 J/(mol·K), and -GΘ298 K =-22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb2+ follows Langmuir model.
