H_(2)O_(2)/乙腈体系下MgO催化环己酮Baeyer-Villiger绿色氧化合成ε-己内酯的研究  

Study on synthesis of ε-caprolactone with MgO catalysis by Baeyer-Villiger green oxidation of cyclohexanone in H_(2)O_(2)/acetonitrile system

作　　者：朱倩倩 靳海波[1] 郭晓燕[1] 何广湘[1] 马磊 张荣月[1] 谷庆阳[1] 杨索和[1] ZHU Qianqian;JIN Haibo;GUO Xiaoyan;HE Guangxiang;MA Lei;ZHANG Rongyue;GU Qingyang;YANG Suohe(School of Chemical Engineering,Beijing Institute of Petrochemical and Technology/Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology,Beijing 102617,China)

机构地区：[1]北京石油化工学院化学工程学院/燃料清洁化及高效催化减排技术北京重点实验室,北京102617

出　　处：《化工学报》2021年第5期2638-2646,共9页CIESC Journal

基　　金：国家自然科学基金项目(91634101);北京市属高校高水平教师队伍建设支持计划高水平创新团队建设计划项目(IDHT20180508)。

摘　　要：在H_(2)O_(2)/乙腈体系下以沉淀法制备的MgO为催化剂催化Baeyer-Villiger(B-V)氧化环己酮合成ε-己内酯,考察了制备条件和反应条件对环己酮转化率和己内酯收率的影响。根据实验结果,Mg(NO_(3))_(2)·6H_(2)O为前体,在煅烧温度为600℃、煅烧时间为2 h时制备MgO氧化性能最佳,由X射线衍射(XRD)、扫描电镜(SEM)进行了分析,可知随温度升高MgO粒径逐渐增大,500~800℃范围内,MgO晶粒尺寸由9.53 nm增大到29.49 nm。在n(催化剂)∶n(环己酮)=0.45∶1、n(乙腈)∶n(环己酮)=12∶1、n(双氧水)∶n(环己酮)=10∶1、70℃、6 h时获得环己酮转化率95.2%及ε-己内酯收率83.1%。对双氧水B-V氧化环己酮机理进行了深入的研究,采用在线原位红外光谱对反应进行实时监测与分析,验证了其过氧缩酰胺反应路径。In the H_(2)O_(2)/acetonitrile system,MgO prepared by precipitation method was used as a catalyst to catalyze the Baeyer-Villiger(B-V)oxidation of cyclohexanone to synthesize ε-caprolactone.The effect of the preparation conditions and reaction conditions on the conversion to cyclohexanone and the yield toε-caprolactone were discussed.According to the experimental results,Mg(NO_(3))_(2)·6H_(2)O was used as the precursor,and the best oxidation performance was obtained when the calcination temperature was 600℃ and the calcination time was 2 h.X-ray diffraction(XRD)and scanning electron microscopy(SEM)were used.The analysis results show that the MgO particle increases from 9.53 nm to 29.49 nm when the temperature is in the range of 500℃ to 800℃.In n(catalyst)∶n(cyclohexanone)=0.45∶1,n(acetonitrile)∶n(cyclohexanone)=12∶1,n(hydrogen peroxide)∶n(cyclohexanone)=10∶1,70℃,6 h,the conversion rate of cyclohexanone was 95.2% and the yield of ε-caprolactone was 83.1%.The mechanism of hydrogen peroxide B-V oxidation of cyclohexanone was studied indepth,and the reaction was analyzed in real time by online in-situ infrared spectroscopy.The peroxyacetal reaction path was verified.

关 键 词：环己酮 Ε-己内酯 有机化合物 氧化 反应机理 

分 类 号：TQ255[化学工程—有机化工]