四氢呋喃
1,4-丁二醇
脱水
硫酸盐
化学
催化作用
离子液体
离子键合
有机化学
化学工程
离子
溶剂
生物化学
工程类
作者
Ziyi Wang,Cong Luo,Binshen Wang,Tong Lai,Hong Yang,Guohua Gao
出处
期刊:Fuel
[Elsevier]
日期:2024-05-01
卷期号:363: 130806-130806
标识
DOI:10.1016/j.fuel.2023.130806
摘要
Tetrahydrofuran is a widely used bulk chemical in both laboratory and industry. In this study, a homogeneous catalytic system composed of sulfate ionic liquids and FeCl3 was applied for the synthesis of tetrahydrofuran by the dehydration of 1,4-butanediol with a high yield of 89.2%. Kinetic studies showed that the reaction rate constant (k) of the dehydration of 1,4-butanediol catalyzed by the combination of 1-ethyl-3-methylimidazolium ethyl sulfate ionic liquid ([EMIm][EtSO4]) and FeCl3 was significantly higher than that of [EMIm][EtSO4] or FeCl3 as catalyst alone. Besides, the activation energy (Ea) of this reaction over [EMIm][EtSO4] and FeCl3 was lower than either of them as catalyst. Higher reaction rate constant and lower Ea indicated that [EMIm][EtSO4] and FeCl3 had a synergistic catalytic effect. Mechanism studies showed that 1-ethyl-3-methylimidazolium hydroxybutyl sulfate ionic liquid [EMIm][HO-BuSO4], generated by the transesterification of [EMIm][EtSO4] with 1,4-butanediol over FeCl3, acted as an active species to synergistically catalyze the dehydration reaction of 1,4-butanediol with FeCl3. Density functional theory (DFT) calculations demonstrated the synergistic catalytic mechanism of [EMIm][HO-BuSO4] and FeCl3, and revealed that the intramolecular nucleophilic attack was the rate-determining step of the dehydration reaction. Continuous reactive distillation of 1,4-butanediol showed [EMIm][EtSO4] and FeCl3 could be used continuously for 54 h with the TON of 182 without any loss in activity. The catalysts also exhibited good substrate generality in the dehydration of various diols to cyclic ethers.
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