The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers (DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the react...The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers (DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.展开更多
基金supported by the National Natural Science Foundation of China(NSFC,No.21203220 and 21133011)China Postdoctoral Science Foundation(No.2014M551674)+1 种基金Jiangsu Planned Projects for Postdoctoral Research Funds(No.1302070C)the National Basic Research Program of China(973 Program,No.2011CB201404)
文摘The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers (DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.