文献类型：期刊文献

英文题名：Reaction-kinetics-driven process optimization for production of high-purity 2-chloro-1,3-butadiene via dehydrochlorination of 3,4-dichlorobut-1-ene

作者：Yuan, Bin[1];Shen, Lin[2];Yuan, Pei-Qing[1];Ling, Hao[1];Zhu, Xue-Dong[1];Li, Rui-Jiang[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Changzhi Huojia Ind Co Ltd, Changzhi 046032, Shanxi, Peoples R China

年份：2026

卷号：227

起止页码：446

外文期刊名：CHEMICAL ENGINEERING RESEARCH & DESIGN

收录：;EI(收录号：20260720056040);WOS:【SCI-EXPANDED(收录号:WOS:001689572200001)】；

基金：The authors acknowledge the supports from Changzhi Huojia Industry Co., Ltd. of China and NSFC (Grant No. 22178113)

语种：英文

外文关键词：4-dichlorobut-1-ene; 2-chloro-1; 3-butadiene; Bimolecular elimination; Density functional theory; Reaction kinetics

摘要：High-purity 2-chloro-1,3-butadiene (2CP) is critical for the polymerization performance and process stability of chloroprene rubber. To enhance 2CP selectivity, we investigated the dehydrochlorination of 3,4-dichlorobut-1ene (34DCB) by density functional theory and experiment. The E2 elimination affords three products, 2CP, (E)-1chloro-1,3-butadiene ((E)-1CP) and (Z)-1-chloro-1,3-butadiene ((Z)-1CP). Thermodynamic analysis shows that their stabilities are very similar, indicating a limited thermodynamic contribution to selectivity. In contrast, transition-state and kinetic analyses reveal a much lower activation energy for the 2CP pathway (13.06 kJ/mol) than for the 1CP pathways (about 42 kJ/mol), so 2CP forms much faster than 1CP. Experiments under processrelevant conditions confirm that at temperatures below 313.15 K the 2CP selectivity remains above 98.5 %, with 1CP below 1.5 wt%, and is insensitive to reaction time and conversion; low-temperature conversion can be increased by extending residence time. These results establish kinetic control of 34DCB dehydrochlorination and guide highly selective 2CP production.