1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征

doi:10.12034/j.issn.1009-606X.217202

过程工程学报 ›› 2017, Vol. 17 ›› Issue (6): 1265-1273.DOI: 10.12034/j.issn.1009-606X.217202

1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征

李敏^1,2，李英波^1*，罗海燕^1,2，咸漠³，梁向峰³，刘会洲^1,3*

1. 中国科学院过程工程研究所绿色过程工程重点实验室，北京 100190；2. 中国科学院大学化学化工学院，北京 100049； 3. 中国科学院青岛生物能源与过程研究所，山东青岛 266101

收稿日期:2017-03-31 修回日期:2017-04-18 出版日期:2017-12-20 发布日期:2017-12-05
通讯作者: 刘会洲 hzliu@home.ipe.ac.cn

Acetalization of 1,2,4-Butanetriol with Aldehydes in Dilute Aqueous Solutions: Thermodynamic and Kinetic Characteristic

Min LI^1,2, Yingbo LI^1*, Haiyan LUO^1,2, Mo XIAN³, Xiangfeng LIANG³, Huizhou LIU^1,3*

1. Key Laboratory of Green Process and Engineering, Institute of Process Engineering, CAS, Beijing 100190, China; 2. School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China; 3. Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong 266101, China

Received:2017-03-31 Revised:2017-04-18 Online:2017-12-20 Published:2017-12-05
Contact: LIU Hui-zhou hzliu@home.ipe.ac.cn

摘要/Abstract

摘要： 以正丁醛、正戊醛和正己醛为反应底物，研究了催化剂用量、醛醇比、反应温度等对1,2,4-丁三醇缩醛反应的影响，通过热力学平衡研究，获得了热力学平衡常数、反应焓变、反应熵变、反应吉布斯自由能变化等热力学参数，建立了该反应的动力学模型，利用线性自由能关系定量分析了醛的烷基链长度对缩醛反应的影响. 结果表明，在298?323 K温度范围内，该反应为放热反应，明显受热力学限制. 所建模型能很好地描述缩醛反应过程，反应的表观活化能为51.1?52.3 kJ/mol. 缩醛反应的平衡常数和反应速率均与极性效应常数(?*)有良好的线性关系.

关键词: 缩醛反应, 热力, 动力学, 1,2,4-丁三醇, 醛

Abstract: The acetalization reaction between 1,2,4-butanetriol and aldehydes (butyaldehyde, valeraldehyde and hexaldehyde) to produce butanetriol acetals (AC) was investigated with different catalyst amounts, molar ratios and temperatures. Through the study of the reaction thermodynamic equilibrium, the value of the equilibrium constant as a function of temperature and the corresponding thermodynamic parameters ?rH0298K, ?rS0298K, and ?rG0298K were obtained. The results showed that the reaction in the temperature range of 298?323 K was exothermic and significantly thermodynamic limitations. A simple kinetic model well describing the reaction process was presented. The activation energy of the overall acetalization reaction was 51.1?52.3 kJ/mol. Furthermore, the effect of alkyl of various aldehydes on acetalization was quantitatively analyzed using LFER and it demonstrated that excellent correlation between reaction equilibrium and rate constants and polar effect parameter (?*) was found.

Key words: acetalization, thermodynamic, kinetic, 1,2,4-butanetriol, aldehydes

李敏李英波罗海燕咸漠梁向峰刘会洲. 1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征[J]. 过程工程学报, 2017, 17(6): 1265-1273.

Min LI Yingbo LI Haiyan LUO Mo XIAN Xiangfeng LIANG Huizhou LIU. Acetalization of 1,2,4-Butanetriol with Aldehydes in Dilute Aqueous Solutions: Thermodynamic and Kinetic Characteristic[J]. Chin. J. Process Eng., 2017, 17(6): 1265-1273.

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1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征

Acetalization of 1,2,4-Butanetriol with Aldehydes in Dilute Aqueous Solutions: Thermodynamic and Kinetic Characteristic

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