丙酮氨氧化制备丙酮肟过程中副反应研究  

Study on the Side Reaction in Acetone Oxime Synthesis from Ammoxidation of Actone

作　　者：林勇 张胜建[2] 罗署 赵迎宪[2] 段云凤 王毅[2] 

机构地区：[1]宁波欧迅化学新材料技术有限公司,浙江宁波315203 [2]浙江大学宁波理工学院,浙江宁波315100

出　　处：《浙江化工》2014年第9期31-36,共6页Zhejiang Chemical Industry

基　　金：浙江省自然科学基金(LY13B030003)

摘　　要：通过GC-MS、LC-MS等方法表征TS-1催化丙酮氨氧化制备丙酮肟过程中的副产物结构,分析副反应类型。结果表明:在此反应体系中,副反应主要产生途径有:(1)碱催化酮缩合,导致副产物骨架的生成;(2)亲核氨解,生成各种有机胺,导致体系碱性增强,起到自催化的作用;(3)消除脱水生成烯烃,然后烯烃被H2O2环氧化;(4)酮类副产物肟化;(5)酮肟氧化偶联反应生成2,3-二硝基-2,3-二甲基丁烷(DMNB);(6)其它氧化过程生成不饱和度高的副产物等。Acetone oxime was prepared by catalytic ammoxidation of acetone over TS-1 zeolite. The structure of by-products from this synthetic process were characterization by GC-MS, LC-MS, etc. The types of side reactions were discussed in detail. The results showed that this reaction system mainly included the following side-reactions： （1） ketone condensation catalyzed by base to form skeletal structure of products; （2）nu- cleophilic ammonolysis of hydroxyl to form various organic amines, increase the alkalinity of the system raised, and enhance the side reaction by self-catalysis; （3）dehydration to form olefins, and then epoxidation by H2O2; （4） ketone oximation to form oximes; （5）oxidation-coupling of acetone oxime to form 2,3-dimethly- 2,3-dinitro-butane（DMNB）; （6） other oxidation processes to form various highly unsaturated by-products; etc.

关 键 词：钛硅分子筛 丙酮肟 副反应 H2O2 自催化 

分 类 号：O621.25[理学—有机化学]