摘要
以二元醇为循环剂液相法合成三聚氰酸是一个由醇解、消去和环加成反应构成的连串反应体系。采用基团贡献法计算了该反应体系中各组分热力学数据以及各步反应的焓变、Gibbs自由能变和平衡常数,依据热力学计算结果并结合已有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:醇解和消去反应为吸热反应,升温有利于反应,但反应平衡常数小;环加成反应为放热反应且进行较为完全,适当强化条件下三步连串反应可顺利进行。计算及分析结果可为该体系的工业放大工艺过程开发提供理论指导。
The liquid-phase synthesis of cyanuric acid using glycol as a circulating agent is a series reaction system consisting of alcoholysis,elimination and cycloaddition reactions.The thermophysical properties of components,enthalpy changes,Gibbs free energy changes and equilibrium constant of this reaction system were carried out by group contribution method.Then feasibility and difficulty of the reactions were analyzed on the basis of thermodynamic calculation combined with available experimental data.The results show that alcoholysis and elimination are both endothermic process and the equilibrium constants of the two reactions are small,which can be promoted forward by improving temperature.Cycloaddition reaction is exothermic and can be fully proceeded.The consecutive reaction can proceed under the appropriate conditions.The outcome from thermodynamic calculation and analysis can provide theoretical guidance for the development of the industrial scale-up process of the reaction.
作者
晁惠雨
白振敏
侯汉青
田立志
李洪
房晓权
石晓华
CHAO Huiyu;BAI Zhenmin;HOU Hanqing;TIAN Lizhi;LI Hong;FANG Xiaoquan;SHI Xiaohua(School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,Henan,China;China BlueChemical Ltd.,Beijing 572600,China;CNOOC Huahe Coal Chemical Company Limited,Hegang 154100,Heilongjiang,China)
出处
《化工学报》
EI
CSCD
北大核心
2024年第6期2157-2165,共9页
CIESC Journal
关键词
三聚氰酸
尿素
醇
双氨基甲酸酯
热解
热力学
基团贡献法
cyanuric acid
urea
alcohol
dicarbamate
pyrolysis
thermodynamics
group contribution method
