环烷酸酯化反应的热力学研究

石油炼制与化工 ›› 2020, Vol. 51 ›› Issue (4): 69-73.

环烷酸酯化反应的热力学研究

何柏¹,郭银应¹,连欣¹,任玉婷¹,邓昕婷²

1. 重庆科技学院化工学院
2. 中国石油西南油气田公司重庆天然气净化总厂

收稿日期:2019-10-22 修回日期:2019-11-19 出版日期:2020-04-12 发布日期:2020-04-28
通讯作者: 何柏 E-mail:hbai2004@126.com
基金资助:

STUDY ON THERMODYNAMICS OF ESTERIFICATION OF NAPHTHENIC ACID COMPOUNDS

Received:2019-10-22 Revised:2019-11-19 Online:2020-04-12 Published:2020-04-28
Supported by:

摘要/Abstract

摘要： 针对文献报道的环烷酸与醇发生酯化反应的热力学分析中环烷酸模型化合物选取单一的不足，并为了避免基团贡献法的计算结果与实际情况往往有较大差距的缺点，选取含五元环或（和）六元环的单环、双环以及三环的共6种代表性环烷酸模型化合物，采用Gaussian 09程序包里的B3LYP算法，在423.15~563.15 K温度范围内对6种环烷酸分别与常用的甲醇、乙醇和乙二醇发生酯化反应的热力学参数进行了计算，得到了酯化反应体系各物质的焓变、熵变和吉布斯自由能变并进行分析。结果表明：在423.15~563.15 K温度范围内，环己烷酸比其他环烷酸分子更容易与醇类发生酯化反应；较高的反应温度有利于酯化反应的进行。对热力学结果进行了分子前线轨道分析，也进一步验证了前述规律和结论。

关键词: 环烷酸, 酯化反应, 热力学分析, 算法

Abstract: In order to avoid the drawbacks of thermodynamics analysis for esterification of naphthenic compounds reported in the literatures, where use only one type of naphthenic compound, and the great deviation between the actual situation and the calculated results by the group contribution method, six model naphthenic acid compounds were selected including five-membered and/or six-membered ones with single, double and triple rings, respectively. The B3LYP algorithm of the Gaussian 09 program was used to calculate the thermodynamics parameters (ΔH,ΔS,ΔG) of the esterification of the model compounds with methanol, ethanol and ethylene glycol at temperature of 423.15-563.15K, and the parameter results were analyzed. It was showed that cyclohexanoic acid is easier than other naphthenic acid to react with the alcohols; the higher reaction temperature is favorable for the esterification. The thermodynamic results were analyzed and verified by molecular frontier orbital analysis.

Key words: naphthenic acid, esterification, thermodynamic analysis, algorithm

中图分类号:

何柏郭银应连欣任玉婷邓昕婷. 环烷酸酯化反应的热力学研究[J]. 石油炼制与化工, 2020, 51(4): 69-73.

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