Catalytic performance of TS-1 in oxidative cleavage of 1-alkenes with H2O2
Catalytic performance of TS-1 in oxidative cleavage of 1-alkenes with H2O2
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TS-1 在 H2O2 氧化裂解 1-烯烃中的催化性能
DOI：
10.1016/j.catcom.2019.04.021
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发表时间：
2019
影响因子：
3.7
通讯作者：
Liqiu Mao
中科院分区：
文献类型：
--
作者：
Xuanyan Liu;Jun Liu;Yue Xia;Dulin Yin;Robert Kirk Steven;Liqiu Mao
在过氧化氢法生产环氧丙烷的工业生产中，甲醛与甲醇发生羟醛缩合反应，生成微量的二甲氧基甲烷。探索烯烃C双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。以1-己烯为探针，研究了钛硅分子筛TS-1催化H2 O2氧化烯烃的反应。考察了溶剂、温度、添加剂和H2 O2/烯烃摩尔比对烯烃转化率和氧化产物分布的影响。有趣的是，在该体系中，除了环氧化产物外，还通过双键的氧化断裂产生了醛。结果表明，乙酸乙酯作为溶剂有利于醛的生成，而添加剂[Na 2 HPO 4·12 H2O（A）和NaH 2 PO 4（B）]则对醛的生成有明显的抑制作用，表明TS-1/H2 O2体系中1-己烯的催化氧化裂解可能是在酸性环境下的加成-裂解氧化过程。
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 Cdouble bondC bond of alkene is urgently needed for the development of production technology. Using 1-hexene as a probe, the oxidation of alkenes with H2O2was investigated via titanium silicalite-1 (TS-1) catalysis. Influences of solvent, temperature, 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 significantly inhibit it. These phenomena indicated that the catalytic oxidative cleavage of 1-hexene in TS-1/H2O2system was probably based on an addition and cleavage oxidation process in an acidic environment.