尿素法合成甲苯二氨基甲酸苯酯反应体系的热力学分析

doi:10.11949/j.issn.0438-1157.20150879

化工学报 ›› 2015, Vol. 66 ›› Issue (9): 3367-3376.DOI: 10.11949/j.issn.0438-1157.20150879

尿素法合成甲苯二氨基甲酸苯酯反应体系的热力学分析

崔雪霞, 王桂荣, 赵茜, 李欣, 赵新强, 王延吉

河北工业大学化工学院, 天津 300130

收稿日期:2015-06-09 修回日期:2015-06-10 出版日期:2015-09-05 发布日期:2015-09-05
通讯作者: 王桂荣
基金资助:
河北省自然科学基金项目(B2011202054);河北省高等学校科学技术研究项目(Z2013062);高等学校博士学科点专项科研基金项目(20121317110009)。

Thermodynamic analysis on synthesis of diphenyl toluene dicarbamate via urea route

CUI Xuexia, WANG Guirong, ZHAO Qian, LI Xin, ZHAO Xinqiang, WANG Yanji

School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China

Received:2015-06-09 Revised:2015-06-10 Online:2015-09-05 Published:2015-09-05
Supported by:
supported by the Natural Science Foundation of Hebei Province (B2011202054), the Science and Technology Research Projects of Higher Education of Hebei Province (Z2013062) and the Specialized Research Fund for the Doctoral Program of Higher Education of China (20121317110009).

摘要/Abstract

摘要：

尿素、甲苯二胺与苯酚反应合成甲苯二氨基甲酸苯酯为一复合反应体系。对该类反应体系进行分析并提出了本反应的4种可能反应路径,采用基团贡献法对4种反应路径中各组分的热力学数据以及各反应的焓变、Gibbs自由能变和平衡常数进行了计算,依据热力学计算结果并结合文献实验数据分析反应路径的可行性及难易程度。结果表明,由尿素、甲苯二胺与苯酚合成甲苯二氨基甲酸苯酯的较好反应路径为:尿素首先与苯酚反应合成氨基甲酸苯酯,然后氨基甲酸苯酯与甲苯二胺反应得到终产物甲苯二氨基甲酸苯酯。计算及分析结果可为该反应的实验研究及过程开发提供理论指导。

关键词: 甲苯二胺, 甲苯二氨基甲酸苯酯, 基团贡献法, 热力学分析

Abstract:

The synthesis of diphenyl toluene dicarbamate from urea, toluene diamine and phenol is a complex reaction system. On the basis of the analysis for similar reaction system, four possible reaction pathways for synthesizing diphenyl toluene dicarbamate via urea route were proposed. The fundamental thermodynamic data of components in this reaction system were calculated by several methods of group contribution. The reaction enthalpy, Gibbs free energy change and equilibrium constant of all the reactions of the four possible reaction pathways were obtained. According to the results of thermodynamic calculation and experimental data in literature, the feasibility and difficulty of each reaction pathway were discussed. The results show that a better reaction pathway is urea reaction with phenol to give phenyl carbamate and then phenyl carbamate interacting with toluene diamine to form diphenyl toluene dicarbamate. The results from thermodynamic calculation and analysis can provide a theoretical basis for the experimental study and process development of the reaction.

Key words: toluene diamine, diphenyl toluene dicarbamate, methods of group contribution, thermodynamic analysis

中图分类号:

TQ013.1
O642

崔雪霞, 王桂荣, 赵茜, 李欣, 赵新强, 王延吉. 尿素法合成甲苯二氨基甲酸苯酯反应体系的热力学分析[J]. 化工学报, 2015, 66(9): 3367-3376.

CUI Xuexia, WANG Guirong, ZHAO Qian, LI Xin, ZHAO Xinqiang, WANG Yanji. Thermodynamic analysis on synthesis of diphenyl toluene dicarbamate via urea route[J]. CIESC Journal, 2015, 66(9): 3367-3376.

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尿素法合成甲苯二氨基甲酸苯酯反应体系的热力学分析

Thermodynamic analysis on synthesis of diphenyl toluene dicarbamate via urea route

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