The highly dispersed Pt-ReOx （x _〈 1 ） sites ca. 0.5 nm in size were formed via a successive and strong inter- action of the Re precursor with titania and then of the Pt complex with deposited low-valent rhenium ox...The highly dispersed Pt-ReOx （x _〈 1 ） sites ca. 0.5 nm in size were formed via a successive and strong inter- action of the Re precursor with titania and then of the Pt complex with deposited low-valent rhenium oxide clusters. The size, charge and chemical composition were characterized by means of HRTEM/STEM with EDX mapping, XPS, and FTIRS. These sites with Re/Pt = 2 were shown to be highly active and selective in the hydrogenation of carboxylic acid to alcohol under very mild conditions （T = 130 ℃, P = 50 bar）. The reaction rate constant for the hydrogenation of hexanoic acid increased linearly with the Pt content. As for the homogeneous pincer-type Ru-organic complexes, the active Pt-ReOx sites can dissociate heterolytically the molecular hydrogen with the formation of hydroxyl groups and Pt hydride for hydrogenation of the carboxylic group. Indeed, TOF of 20 h 1 and selectivity of 98%-99% are approaching the values typical of homogeneous catalysts. The first order kinetics described well the experimental data obtained in a wide range of reaction conditions.展开更多
Medium-chain fatty acids (MCFA) are straight-chain fatty acids with aliphatic tails of 6 - 12 carbons, which can form medium-chain triglycerides. They are found mostly in animal fats and in the tropical vegetable oils...Medium-chain fatty acids (MCFA) are straight-chain fatty acids with aliphatic tails of 6 - 12 carbons, which can form medium-chain triglycerides. They are found mostly in animal fats and in the tropical vegetable oils. Because of their wide applications in industry, there is a growing demand of esters of medium-chain fatty acids production. The aim of our work was investigations of the kinetics of the synthesis of esters of MCFA in the presence of dowex catalyst in wide range of process parameters. Hexanoic, octanoic and decanoic acids were esterified with n-octyl alcohol in the presence of sulfuric acid and commercial dowex W50X8 as catalysts in an experimental semi-periodic glass tank reactor with instantaneous and complete water removal. Because of complete removal of water from the reacting mixture, thus eliminating the reverse hydrolysis reaction, the esterification can be assumed as irreversible reaction. The temperature range was 393 - 423 K, the range of initial mole ratio of alcohol to acid was 3 - 10. The kinetic parameters are given. The reaction kinetics appeared to be of the first order with respect to the acid. The effect of temperature on the reaction rate follows the Arrhenius equation well.展开更多
文摘The highly dispersed Pt-ReOx （x _〈 1 ） sites ca. 0.5 nm in size were formed via a successive and strong inter- action of the Re precursor with titania and then of the Pt complex with deposited low-valent rhenium oxide clusters. The size, charge and chemical composition were characterized by means of HRTEM/STEM with EDX mapping, XPS, and FTIRS. These sites with Re/Pt = 2 were shown to be highly active and selective in the hydrogenation of carboxylic acid to alcohol under very mild conditions （T = 130 ℃, P = 50 bar）. The reaction rate constant for the hydrogenation of hexanoic acid increased linearly with the Pt content. As for the homogeneous pincer-type Ru-organic complexes, the active Pt-ReOx sites can dissociate heterolytically the molecular hydrogen with the formation of hydroxyl groups and Pt hydride for hydrogenation of the carboxylic group. Indeed, TOF of 20 h 1 and selectivity of 98%-99% are approaching the values typical of homogeneous catalysts. The first order kinetics described well the experimental data obtained in a wide range of reaction conditions.
文摘Medium-chain fatty acids (MCFA) are straight-chain fatty acids with aliphatic tails of 6 - 12 carbons, which can form medium-chain triglycerides. They are found mostly in animal fats and in the tropical vegetable oils. Because of their wide applications in industry, there is a growing demand of esters of medium-chain fatty acids production. The aim of our work was investigations of the kinetics of the synthesis of esters of MCFA in the presence of dowex catalyst in wide range of process parameters. Hexanoic, octanoic and decanoic acids were esterified with n-octyl alcohol in the presence of sulfuric acid and commercial dowex W50X8 as catalysts in an experimental semi-periodic glass tank reactor with instantaneous and complete water removal. Because of complete removal of water from the reacting mixture, thus eliminating the reverse hydrolysis reaction, the esterification can be assumed as irreversible reaction. The temperature range was 393 - 423 K, the range of initial mole ratio of alcohol to acid was 3 - 10. The kinetic parameters are given. The reaction kinetics appeared to be of the first order with respect to the acid. The effect of temperature on the reaction rate follows the Arrhenius equation well.
