Thermodynamic analysis on synthesis of 4,4-methylenedianiline by reaction of aniline and formaldehyde

王晨晔1; 2; 李会泉1; 曹妍1; 柳海涛1; 侯新娟1; 张懿1

doi:10.3969/j.issn.0438-1157.2012.08.003

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Thermodynamic analysis on synthesis of 4,4-methylenedianiline by reaction of aniline and formaldehyde

更新时间：2025-12-10

- Thermodynamic analysis on synthesis of 4,4-methylenedianiline by reaction of aniline and formaldehyde
- CIESC Journal Issue 8, Pages: 2348-2355(2012)
- 作者机构：
  
  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
- 作者简介：
- 基金信息：
- DOI：10.3969/j.issn.0438-1157.2012.08.003
  CLC： 642
- Online First：05 August 2012，
  
  Published：05 August 2012
- 稿件说明：
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王晨晔1, 2, 李会泉1, et al. Thermodynamic analysis on synthesis of 4,4-methylenedianiline by reaction of aniline and formaldehyde[J]. CIESC Journal, 2012, (8): 2348-2355.
DOI：

王晨晔1, 2, 李会泉1, et al. Thermodynamic analysis on synthesis of 4,4-methylenedianiline by reaction of aniline and formaldehyde[J]. CIESC Journal, 2012, (8): 2348-2355. DOI： 10.3969/j.issn.0438-1157.2012.08.003.

摘要

苯胺与甲醛合成4

4-二氨基二苯甲烷（MDA）是一个复杂的反应体系。采用多种基团贡献法，计算了该反应体系涉及多种物质的基础热力学数据，以及主要反应的反应焓变、反应Gibbs自由能变以及各反应的平衡常数。结合热力学模拟计算，分析了体系温度、苯胺与甲醛的原料配比对该反应体系平衡转化过程的影响，并与实验数据进行对比验证。研究结果表明：由苯胺与甲醛合成MDA的反应为放热反应，升高体系温度有利于抑制副产物的生成，同时可获得较高的MDA收率。选取原料配比为3作为较优操作条件，可减少副产物的产生量，并降低后续产物分离能耗。

Abstract

Synthesis of 4

4-methylenedianiline(MDA)from aniline and formaldehyde is a complex reaction system.The fundamental thermodynamic data of substances in the reaction system were calculated with various group contribution methods.The reaction enthalpy，Gibbs free energy change and equilibrium constant of the main reactions were calculated.The influence of reaction temperature and raw material ratio of aniline to formaldehyde on the reaction equilibrium was investigated by thermodynamic simulation and validated by comparison with experimental data.It is shown that higher reaction temperature restrains the formation of byproducts，so higher yield of MDA can be obtained.The optimized molar ratio of aniline to formaldehyde is 3∶1.Under this reaction condition，by-products are less and subsequence separation of aniline is easier.The comparison with experimental data shows that the calculation results are reasonable.

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