非催化分子氧氧化环己酮制ε-己内酯工艺研究  

Process of non-catalytic molecular oxygen oxidation of cyclohexanone toε-caprolactone

作　　者：罗晓琳 郑燕春 莫学坤 王康 朱明乔[1,2] 江向阳 童张法 LUO Xiaolin;ZHENG Yanchun;MO Xuekun;WANG Kang;ZHU Mingqiao;JIANG Xiangyang;TONG Zhangfa(College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027;Institute of Zhejiang University-Quzhou,Quzhou 324000;Polytechnic Institute,Zhejiang University,Hangzhou 310015;Quzhou Juhua Polyamide Fibre Co.,Ltd.,Quzhou 324000;Zhejiang CHXIN Oil Technology Co.,Ltd.,Huzhou 313000;Zhejiang Central Glass Chemspec Co.,Ltd.,Quzhou 324000;Key Laboratory of Guangxi Petrochemical Resources Processing and Process Enhancement Technology,Guangxi University,Nanning 530004)

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]浙江大学衢州研究院,浙江衢州324000 [3]浙江大学工程师学院,浙江杭州310015 [4]衢州巨化锦纶有限责任公司,浙江衢州324000 [5]浙江正信石油科技有限公司,浙江湖州313000 [6]浙江中硝康鹏化学有限公司,浙江衢州324000 [7]广西大学广西石化资源加工及过程强化技术重点实验室,广西南宁530004

出　　处：《合成纤维工业》2024年第1期1-6,共6页China Synthetic Fiber Industry

基　　金：浙江大学衢州研究院科技计划项目(IZQ2022KJ3011);衢州市科技计划项目(2022K05);衢州市科技计划项目(2021F012);浙江省生产制造方式转型示范项目(2207-330851-04-02-952183);广西大学广西石化资源加工及过程强化重点实验室开放项目(2020K0004)。

摘　　要：采用巴豆醛氧化与环己酮氧化耦合即共氧化法制备ε-己内酯,以巴豆醛代替苯甲醛,在非催化条件下进行氧化反应,主要考察了溶剂种类和用量、反应温度、反应时间、氧气流量及原料投料比对氧化反应的影响。结果表明:使用极性较大的乙酸乙酯作为反应溶剂,反应效果较好;较佳的反应条件为乙酸乙酯15 mL、环己酮投入量12 mmol、巴豆醛投入量24 mmol、反应温度40℃、反应时间12 h、氧气流量10 mL/min,在上述条件下进行氧气/巴豆醛氧化环己酮反应制备ε-己内酯,环己酮转化率为41.77%,ε-己内酯选择性为94.06%,巴豆醛转化率为83.07%,巴豆酸选择性为95.49%;采用共氧化法工艺制备ε-己内酯是可行的,同时能得到附加值较高的副产物巴豆酸。ε-caprolactone was prepared by coupling of crotonaldehyde oxidation instead of benzaldehyde oxidation and cyclohexanone oxidation,i.e.,co-oxidation method,under non-catalytic conditions.The effects of solvent type and dosage,reaction temperature,reaction time,oxygen flow rate and feed ratio on the oxidation reaction were mainly investigated.The results showed that the satisfying reaction efficiency could be achieved when ethyl acetate with high polarity was used as the reaction solvent;the conversion rate of cyclohexanone was 41.77%,the selectivity ofε-caprolactone was 94.06%,the conversion rate of crotonaldehyde was 83.07%,and the selectivity of crotonic acid was 95.49%when the oxygen/crotonaldehyde oxidation of cyclohexanone toε-caprolactone was carried out under the optimal reaction conditions as follows:15 mL ethyl acetate,12 mmol cyclohexanone,24 mmol crotonaldehyde,reaction temperature of 40℃,reaction time of 12 h and oxygen flow rate of 10 mL/min;and it was feasible to prepareε-caprolactone by co-oxidation process while yielding the by-product crotonic acid with high added value.

关 键 词：环己酮 巴豆醛 Ε-己内酯 非催化氧化 转化率 选择性 

分 类 号：TQ234.21[化学工程—有机化工]