枞酸与甲醇酯化反应的基团贡献法热力学分析

doi:10.3969/j.issn.0438-1157.2013.06.002

化工学报 ›› 2013, Vol. 64 ›› Issue (6): 1900-1906.DOI: 10.3969/j.issn.0438-1157.2013.06.002

枞酸与甲醇酯化反应的基团贡献法热力学分析

王琳琳, 陈建云, 梁杰珍, 陈小鹏, 陈远萍, 唐开韦

广西大学化学化工学院,广西石化资源加工及过程强化技术重点实验室,广西南宁530004

收稿日期:2012-10-09 修回日期:2013-01-23 出版日期:2013-06-05 发布日期:2013-06-05
通讯作者: 陈小鹏
作者简介:王琳琳(1971—),女,教授。
基金资助:
国家自然科学基金项目(31060102);广西自然科学基金项目(2010GXNSFA013042);广西石化资源加工及过程强化技术重点实验室主任基金项目(Z001)。

Thermodynamic analysis for esterification of abietic acid with methanol by group-contribution method

WANG Linlin, CHEN Jianyun, LIANG Jiezhen, CHEN Xiaopeng, CHEN Yuanping, TANG Kaiwei

College of Chemistry and Chemical Engineering, Guangxi University, Guangxi Key Laboratory of Petrochemical Resource Processing Intensification Technology, Nanning 530004, Guangxi, China

Received:2012-10-09 Revised:2013-01-23 Online:2013-06-05 Published:2013-06-05
Supported by:
supported by the National Natural Science Foundation of China(31060102), the Natural Science Foundation of Guangxi Province(2010GXNSFA013042)and the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(Z001).

摘要/Abstract

摘要： 以枞酸为模型化合物、枞酸与甲醇的酯化为探针反应,采用基团贡献法对枞酸与甲醇酯化反应进行了热力学分析,计算了473～653 K、0.1～20 MPa反应体系的反应焓变、反应熵变、反应Gibbs自由能变以及反应平衡常数,探讨了温度与压力对酯化反应的影响。计算结果表明,反应的焓变为-46.31～-10.10 kJ·mol^-1,枞酸与甲醇的甲酯化反应为放热反应;反应Gibbs自由能变为-53.26～-25.49 kJ·mol^-1,反应为自发过程;标准压力下反应平衡常数为136.32～748.89,5～20 MPa下反应平衡常数为(1.1×10⁴)～(3.2×10⁴)。实验结果表明,在无催化剂条件下,超/亚临界甲醇与枞酸酯化反应的转化率分别为85.94%～94.89%、73.80%～81.20%,实验结果与基团贡献法热力学计算值相一致。

关键词: 枞酸, 甲醇, 枞酸甲酯, 基团贡献法, 热力学

Abstract: The esterification of abietic acid with methanol was selected as a probe reaction.The thermodynamics of reaction was analyzed by group-contribution method.The reaction enthalpy, entropy, Gibbs free energy and equilibrium constant were calculated in the temperature range of 473—653 K and the pressure range of 0.1—20 MPa.The effects of temperature and pressure on the reaction were also discussed.The calculation indicates that the reaction enthalpy is -46.31—-10.10 kJ·mol^-1 and free energy is -53.26—-25.49 kJ·mol^-1, showing an exothermic and spontaneous reaction.The equilibrium constant is 136.32—748.89 at standard pressure and (1.1×10⁴)—(3.2×10⁴) in the range of 5—20 MPa.The experimental results show the conversion of abietic acid of 85.94%—94.89% and 73.80%—81.20% without catalyst in super/subcritical methanol, which is in agreement with thermodynamic calculation by the group-contribution method.

Key words: abietic acid, methanol, methyl abietate, group contribution, thermodynamic

中图分类号:

王琳琳, 陈建云, 梁杰珍, 陈小鹏, 陈远萍, 唐开韦. 枞酸与甲醇酯化反应的基团贡献法热力学分析[J]. 化工学报, 2013, 64(6): 1900-1906.

WANG Linlin, CHEN Jianyun, LIANG Jiezhen, CHEN Xiaopeng, CHEN Yuanping, TANG Kaiwei. Thermodynamic analysis for esterification of abietic acid with methanol by group-contribution method[J]. CIESC Journal, 2013, 64(6): 1900-1906.

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枞酸与甲醇酯化反应的基团贡献法热力学分析

Thermodynamic analysis for esterification of abietic acid with methanol by group-contribution method

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