乙二醇和1,2-丁二醇混合物与丙醛的缩合反应动力学  

Acetalization reaction kinetics of ethylene glycol and 1,2-butanediol mixture with propyl aldehyde

作　　者：张航 张楠 李梦甜 王瑞[1] ZHANG Hang;ZHANG Nan;LI Mengtian;WANG Rui(School of Chemistry&Chemical Engineering,Tianjin University of Technology,Tianjin 300384,China)

机构地区：[1]天津理工大学化学化工学院,天津300384

出　　处：《化学工程》2024年第6期58-63,共6页Chemical Engineering(China)

基　　金：天津市自然科学基金资助项目(22JCQNJC00720);天津理工大学创新训练计划项目(202210060079)。

摘　　要：采用阳离子交换树脂催化剂KRD001,在釜式反应器中对EG(乙二醇)和1,2-BDO(1,2-丁二醇)混合物与丙醛的缩合反应动力学进行研究,考察传质阻力、催化剂用量、进料摩尔比和反应温度等对反应速率的影响,分析反应机理,建立反应动力学模型,并回归得到相应的动力学参数。结果表明:醛醇进料摩尔比对EG、1,2-BDO的平衡转化率和反应选择性差异影响较大。反应体系中同时发生EG与丙醛的缩合反应、1,2-BDO与丙醛的缩合反应及半缩醛(AC_(1))与1,2-BDO生成半缩醛(AC_(2))和EG的缩醛交换反应。缩醛反应过程放热,丙醛与EG的反应焓为-18.73 kJ/mol,丙醛与1,2-BDO的反应焓为-37.31 kJ/mol。二阶拟均相模型对实验数据具有良好的拟合效果,EG与丙醛正、逆反应的活化能分别是43.7和62.4 kJ/mol;1,2-BDO与丙醛正、逆反应的活化能分别是50.0和87.3 kJ/mol。The acetalization reaction kinetics of EG(ethylene glycol)and 1,2-BDO(1,2-butanediol)mixture with propyl aldehyde was studied in a kettle reactor using cation exchange resin catalyst KRD001,the effects of mass transfer resistance,catalyst loading,feed molar ratio and reaction temperature on the reaction rate were investigated,the reaction mechanism was analyzed,the reaction kinetic model was established,and the corresponding kinetic parameters were regressed.The results show that the propyl aldehyde to diols feed molar ratio has significant effect on the equilibrium conversions and reactien selectivity difference of EG and 1,2-BDO.The acetalization reactions of EG with propyl aldehyde,1,2-BDO with propyl aldehyde,and the trans acetalization reaction of AC_(1)and 1,2-BDO to AC_(2)and EG occur simultaneously in the system.The acetalization reactions are exothermic,the enthalpy of the reaction between propyl aldehyde and EG is-18.73 kJ/mol,and the enthalpy of the reaction between propyl aldehyde and 1,2-BDO is-37.31 kJ/mol.The second-order quasi-homogeneous model describs the experimental data well,and the activation energies of the positive and reverse reactions of EG and propyl aldehyde are 43.7 kJ/mol and 62.4 kJ/mol,respectively.The activation energies of the forward and reverse reactions of 1,2-BDO and propyl aldehyde are 50.0 kJ/mol and 87.3 kJ/mol,respectively.

关 键 词：乙二醇 1 2-丁二醇 反应动力学 缩醛反应 反应选择性差异 

分 类 号：TQ013.22[化学工程]