HTS-1催化H2O2氧化1-烯烃断键

The Oxidative Cleavage of 1-Alkenes Catalyzed by HTS-1 with H2O2

工业上,采用过氧化氢(HPPO)法生产环氧丙烷过程中,往往会出现甲醛与甲醇缩合生成的微量二甲氧基甲烷(DMM),这是生产高品质环氧丙烷必须抑制的一个组分,因此,探索烯烃C=C键氧化裂解反应中的催化行为是生产技术发展的迫切需要。本文以1-己烯为探针,研究了新型钛硅分子筛(HTS-1)催化H2O2氧化烯烃的反应,探索了溶剂、添加剂等因素对烯烃转化率和氧化产物分布的影响。结果表明,除了环氧化产物外,在该体系中还通过双键氧化裂解产生醛。乙酸乙酯为溶剂有利于醛的生成,而添加剂Na 2HPO4·12H 2O(A)和NaH2PO4(B)对醛的生成有明显的抑制作用。

Trace dimethoxymethane(DMM)was formed by aldol condensation of formaldehyde with methanol in industrial propene oxide production via a hydrogen peroxide(HPPO process).Probing the behaviour of catalytic action in oxidative cleavage reaction of C=C bond of alkene is urgently needed for the development of production technology.Using 1-hexene as a probe,the oxidation of alkenes with H2O2 was investigated via titanium silicalite-1(HTS-1)catalysis.Influences of solvent,additives and H2O2/alkene molar ratio on alkene conversion and oxidation product distribution were studied.Interestingly,besides the epoxidation products,aldehydes were also produced by double-bond oxidative cleavage in this system.The results showed that ethyl acetate as solvent was favor for the generation of aldehyde,but the additives[Na2HPO4·12H2O(A)and NaH2PO4(B)]could signifificantly inhibit it.