SCM-14分子筛高效催化环己酮氧化制备ε-己内酯  

Oxidation of Cylcohexanone toε-Caprolactone over SCM-14 Zeolite

作　　者：李相呈 刘闯[1] 王振东[1] 杨为民[1] LI Xiangcheng;LIU Chuang;WANG Zhendong;YANG Weimin(State Key Laboratory of Green Chemical Engineering and Industrial Catalysis,Shanghai Research Institute of Petrochemical Technology,SINOPEC,Shanghai 201208,China)

机构地区：[1]中国石油化工股份有限公司上海石油化工研究院绿色化工与工业催化国家重点实验室,上海201208

出　　处：《化学反应工程与工艺》2019年第5期385-392,共8页Chemical Reaction Engineering and Technology

基　　金：国家重点研发计划(2017YFB0702800);国家自然科学基金(21972168)。

摘　　要：采用4-吡咯烷基吡啶作为有机结构导向剂,在水热条件下合成了结构稳定的新结构硅锗酸盐SCM-14分子筛,并对该材料的结构和酸性质进行了表征。研究发现,SCM-14分子筛不仅具有较高的比表面积(166 m^2/g),同时具有Brønsted酸和Lewis酸两种酸物种。通过SCM-14分子筛中的Lewis酸来催化环己酮Baeyer-Villiger氧化高效制备ε-己内酯,进一步考察了反应溶剂、H2O2浓度、催化剂用量、氧酮比、反应温度和时间等因素对环己酮转化率和ε-己内酯选择性的影响。在较佳的反应条件下,环己酮转化率为46.5%,ε-己内酯选择性为63.8%,其收率达29.7%,同时SCM-14分子筛具有良好的循环稳定性。A new stable germanosilicate zeolite SCM-14 was hydrothermally synthesized using commercially available 4-pyrrolidinopyridine as organic structure-directing agents.The structure and properties of the catalysts were systematically characterized.These studies indicated that SCM-14 zeolite not only had a large surface area(166 m^2/g),but also had Lewis and Brønsted acid sites.The Baeyer-Villiger oxidation of cyclohexanone toε-caprolactone was catalyzed by Lewis acid sites of SCM-14 zeolite.The influence of several variables including solvent,H2O2 concentration,catalyst dosage,H2O2/cyclohexanone ratio,reaction temperature and time on the extent of cyclohexanone conversion andε-caprolactone selectivity were studied.Under optimal conditions,theε-caprolactone selectivity reached 63.8%with 46.5%cyclohexanone conversion.Besides,SCM-14 zeolite had a good stability.

关 键 词：SCM-14分子筛 硅锗酸盐 Baeyer-Villiger 氧化 环己酮 Ε-己内酯 

分 类 号：O643.38[理学—物理化学]