【摘要】 过氧乙酸是一种用途广泛的有机过氧化物.利用固体酸催化剂催化氧化乙酸从而间接氧化环己酮合成ε-己内酯是一种绿色生产过程,其中催化氧化乙酸生成过氧乙酸是关键步骤.借助化学滴定分析法,使用Mg/Sn/W复合氧化物为催化剂,以H2O2为氧化剂,以乙酸丁酯为共沸剂研究氧化乙酸生成过氧乙酸过程的本征动力学及过程中H2O2分解动力学.当催化剂粒径为160～200目时,内扩散影响可基本消除,当搅拌速度大于800r·min-1时,外扩散可以忽略.使用幂函数型模型对动力学过程进行描述,研究结果表明,过氧乙酸生成反应本征动力学速率方程对H2O2、乙酸均为一级,反应活化能为6.76141×104 J·mol-1,指前因子为6.78090×106;适用于该反应过程体系的H2O2分解反应动力学的反应级数为1.59345,反应活化能为7.59041×104 J·mol-1,指前因子为1.08795×108.更多还原

【Abstract】 Peracetic acid is a widely used organic peroxide.Catalytic oxidation of acetic acid by solid acid catalyst to indirectly oxidize cyclohexanone for synthesizingε-caprolactone is a green production process,in which catalytic oxidation of acetic acid to peroxyacetic acid is a key step.The intrinsic kinetics of synthesis of peracetic acid and H₂O₂ decomposition kinetics were investigated by chemical titration analysis,using Mg/Sn/W composite oxide as catalyst,H₂O₂ as oxidant and butyl acetate as entrainer.Internal diffusion effect was basically eliminated when the catalyst particle size is 160 to200 mesh and external diffusion effect was neglected when stirring speed is greater than800 r· min-1.The power function model was used to describe the kinetic process.Research results showed that the intrinsic kinetic rate equation of peracetic acid formation reaction is of first order for H₂O₂ and acetic acid,with the activation energy of6.761141×104 J·mol-1,and the pre-exponential factor of 6.78090×106.The reaction order of H₂O₂ decomposition reaction kinetic suitable for this reaction process system is1.59335,with the activation energy of 7.59041×104 J·mol-1,and the pre-exponential factor of 1.08785×10⁸.更多还原