文献类型：期刊文献

英文题名：Kinetically guided high-yield and rapid production of ε-caprolactone in a microreactor system

作者：Yang, Yue[1];Du, Wei[1];Qian, Gang[1];Duan, Xuezhi[1];Gu, Xiongyi[1];Zhou, Xinggui[1];Yang, Zhirong[1];Zhang, Jing[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：69

期号：3

外文期刊名：AICHE JOURNAL

收录：;EI(收录号：20223912783108);WOS:【SCI-EXPANDED(收录号:WOS:000850285800001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (21991103, 21991104, 22008074, 22008072); Natural Science Foundation of Shanghai (20ZR1415700), China Postdoctoral Science Foundation (2020M671025, 2019TQ0093). The authors thank Prof. Zhen Liu from East China University of Science and Technology for the helpful discussion of DFT calculations.

语种：英文

外文关键词：Baeyer-Villiger oxidation; hydrolysis; microreactor; reaction kinetics; epsilon-caprolactone

摘要：Industrial production of epsilon-caprolactone, the monomer of biodegradable polycaprolactone, consists of acetic acid peroxidation and the Baeyer-Villiger oxidation of cyclo-hexanone in semi-batch reactors. The strong exothermic feature of the latter and ease of epsilon-caprolactone hydrolysis significantly affects the production efficiency. Here, collective effects of kinetic studies and density functional theory (DFT) calculations reveal activation energy of the Baeyer-Villiger oxidation is higher than that of epsilon-caprolactone hydrolysis and the hydrolysis barrier is controlled by hydrogen bond energy of the reaction medium. Then, we developed a microreactor system to intensify heat transfer thereby allowing safe and efficient production of epsilon-caprolactone. A yield of 99.6% was achieved within minutes via consecutive two-step reactions of peroxidation and the Baeyer-Villiger oxidation, as compared with state-of-the-art yield of 96% in hours of industrial operation. The high selectivity is attributed to high reaction temperature allowed by the microreactor and DFT-guided choice of solvent to mitigate the hydrolysis.