模板剂改性的镁锡氧化物催化双氧水氧化环己酮合成ε-己内酯研究  

Synthesis of ε-caprolactone by oxidation of cyclohexanone over template-modified Mg-Sn oxide catalyst using hydrogen peroxide as oxidant

作　　者：王媛媛 胡珊珊 张明 刘赛赛 王星文 朱明乔[1] WANG Yuanyuan;HU Shanshan;ZHANG Ming;LIU Saisai;WANG Xingwen;ZHU Mingqiao(College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027;Taizhou Yuanzhong Pharmaceutical Co.,Ltd.,Taizhou 318000)

机构地区：[1]浙江大学化学工程与生物工程学院,浙江杭州310027 [2]台州市源众药业有限公司,浙江台州318000

出　　处：《合成纤维工业》2019年第5期19-25,共7页China Synthetic Fiber Industry

基　　金：浙江省自然科学基金(Y4080247);浙江省重大科技计划项目(2010C01035);广西石化资源加工及过程强化技术重点实验室开放课题基金(K002);工业控制技术国家重点实验室开放课题基金(ICT1224);浙江台州市源众药业有限公司资助

摘　　要：采用共沉淀法及水热沉淀法合成了一系列模板剂修饰的镁锡氧化物催化剂,借助X射线衍射、扫描电镜、氮气吸附脱附等手段对催化剂的结构进行了表征。将该催化剂用于催化双氧水氧化环己酮合成ε-己内酯的反应,考察不同模板剂及合成方式对催化剂性能的影响。结果表明:模板剂的加入令催化剂的颗粒分散度得到提高且结构稳定性增强,其中共沉淀法制备的以十六烷基三甲基氯化铵为模板剂的镁锡氧化物催化剂对反应具有较好的催化效果。通过单因素实验,得到较合适的反应条件:环己酮用量以12 mmol计,催化剂:环己酮:双氧水的摩尔比为0.4:1:8,乙腈10 mL,75℃下反应6 h,此时环己酮的转化率达到89.63%,ε-己内酯选择性为91.26%。A series of template-modified Mg-Sn oxide catalysts were synthesized by coprecipitation and hydrothermal precipitation. The structure of the catalysts was characterized by X-ray diffraction,scanning electron microscopy and N2 adsorption-desorption. These catalysts were used to catalyze the oxidation of cyclohexanone to ε-caprolactone with hydrogen peroxide as an oxidant.The effects of different templates and synthesis methods on the catalytic performance were investigated. The results showed that the addition of template improved the particle dispersion and structural stability of the catalyst;the Mg-Sn oxide prepared by coprecipitation with cetyltrimethylammonium chloride as template exhibited good catalytic performance on the oxidation;and the conversion rate of cyclohexanone and the selectivity of ε-caprolactone reached 89.63% and 91.26%,respectively,when the suitable reaction conditions were obtained through single factor experiments as followed: the amount of cyclohexanone measured by 12 mmol,the molar ratio of catalyst,cyclohexanone and hydrogen peroxide 0.4∶1∶8,acetonitrile 10 m L,and reaction time 6 h at 75 ℃.

关 键 词：模板剂 镁锡氧化物 环己酮 双氧水 Ε-己内酯 

分 类 号：TQ234.2[化学工程—有机化工]