In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction tempe...In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.展开更多
Hydroxyl radicals HO are generated under Fenton-like (Fe2++H2O2→HO?+OH?+Fe3+) catalytic conditions upon microwave irradiation. Liquid-phase direct catalytic oxidation of benzene to phenol was obtained using FeSO4 sup...Hydroxyl radicals HO are generated under Fenton-like (Fe2++H2O2→HO?+OH?+Fe3+) catalytic conditions upon microwave irradiation. Liquid-phase direct catalytic oxidation of benzene to phenol was obtained using FeSO4 supported on silica gel as a solid catalyst and hydrogen peroxide as the oxidant. The effects of various parameters, such as the different solvents, the amount of solvent used, the amount of catalyst used, the reaction time, the reaction temperature and the amount of hydrogen peroxide used on the yield of phenol were studied to identify optimum reaction conditions. Conventionally heated reaction gives a phenol yield of 0.6%. A higher phenol yield of 13.9% with a selectivity of 100% is obtained when the reaction mixture was irradiated with micro-wave energy. It is concluded that microwave irradiation offers more effective control of energy input for hydroxyl radical generation that is appropriate for various synthetic reactions.展开更多
Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction a...Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated.Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.展开更多
Oxidative coupling of α-bromoarylacetonitriles and oxidative decyanation of diarylacetonitriles are efficiently realized by solid-liquid phase transfer catalysis using anhydrous K 3 PO 4 as base and TBAB as catalyst ...Oxidative coupling of α-bromoarylacetonitriles and oxidative decyanation of diarylacetonitriles are efficiently realized by solid-liquid phase transfer catalysis using anhydrous K 3 PO 4 as base and TBAB as catalyst in acetone at room temperature. In this mild and convenient method, α,β-dicyanostilbenes and diarylketones were prepared in good to excellent yields.展开更多
文摘In this paper, a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed. The effects of the reaction temperature, catalyst concentration and ratio of catalyst on the lime evolution of the experimental concentration for the constituents including raw material, intermediates and product are investigated. The model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well nuxed. The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.
基金supported by the National Natural Science Foundation of China (No.50921002)
文摘Hydroxyl radicals HO are generated under Fenton-like (Fe2++H2O2→HO?+OH?+Fe3+) catalytic conditions upon microwave irradiation. Liquid-phase direct catalytic oxidation of benzene to phenol was obtained using FeSO4 supported on silica gel as a solid catalyst and hydrogen peroxide as the oxidant. The effects of various parameters, such as the different solvents, the amount of solvent used, the amount of catalyst used, the reaction time, the reaction temperature and the amount of hydrogen peroxide used on the yield of phenol were studied to identify optimum reaction conditions. Conventionally heated reaction gives a phenol yield of 0.6%. A higher phenol yield of 13.9% with a selectivity of 100% is obtained when the reaction mixture was irradiated with micro-wave energy. It is concluded that microwave irradiation offers more effective control of energy input for hydroxyl radical generation that is appropriate for various synthetic reactions.
基金Supported by the Fundamental Research Funds for the Central Universities,Ministry of Education,China
文摘Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated.Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.
基金Natural Science Foundation of China (Grant No.NSFC 20672009)
文摘Oxidative coupling of α-bromoarylacetonitriles and oxidative decyanation of diarylacetonitriles are efficiently realized by solid-liquid phase transfer catalysis using anhydrous K 3 PO 4 as base and TBAB as catalyst in acetone at room temperature. In this mild and convenient method, α,β-dicyanostilbenes and diarylketones were prepared in good to excellent yields.
