钛硅分子筛TS-1催化氯丙烯环氧化反应动力学研究

 摘要：研究了钛硅分子筛催化氯丙烯环氧化反应的条件及动力学行为．\r\n结果表明，以钛硅分子筛为催化剂，氯丙烯可被高选择性地氧化为环氧\r\n氯丙烷．环氧化反应速度与分子筛中骨架钛的含量及分子筛的用量呈正\r\n比关系，是一级反应．对于氧化剂H2O2，只有当c（H2O2）＜0．4mol／\r\nL时，环氧化反应为一级反应；而c（H2O2）＞1．0mol／L时，为零级反\r\n应．对于氯丙烯，随着其浓度的变化，环氧化反应的级数在1和0之间．\r\n然而，只有当氯丙烯浓度很高时，环氧化反应的级数才有明显的降低．\r\n根据实验结果和Eley－Rideal单分子吸附方程，提出了氯丙烯环氧化反\r\n应的动力学模型．\r\n关键词：钛硅分子筛，氯丙烯，过氧化氢，环氧化，环氧氯丙烷，反应\r\n动力学

Reaction Kinetics of Epoxidation of Allyl Chloride with Hydrogen Peroxide Catalyzed by Titanium Silicalite-1

The different parameters affecting epoxidation of allyl chloride with hydrogen peroxide catalyzed by titanium silicalite 1 (TS 1), as well as the reaction kinetics were described. The epoxidation of allyl chloride with hydrogen peroxide is first order reaction with respect to the catalyst amount and the titanium content in the zeolite, and is between zero and unity order with respect to the substrate concentration and the oxidant concentration. For hydrogen peroxide, the epoxidation is first order reaction when its concentration is very low (lower than 0 4 mol/L) and zero order reaction when its concentration is higher than 1 0 mol/L. For allyl chloride, only in its very high concentration, the obvious decrease of the reaction order from 1 to 0 was observed. Finally, the possible kinetic model was supposed according to the results of experiment and Eley Rideal isotherms, being in agreement with the experimental data.