丙酸异龙脑酯的合成、反应热力学和反应动力学研究

Study on thermodynamics and kinetics of synthesis of isobornyl propionate

选用大孔阳离子交换树脂作催化剂,250 mL的三口烧瓶作为搅拌釜反应器,研究了莰烯与丙酸在不同反应条件下(搅拌速率、树脂类型、树脂含量、配比、温度、催化剂重复使用次数)对合成丙酸异龙脑酯的影响,并得到了优化的工艺条件.采用UNIFAC基团贡献法估算活度系数,获得了不同温度下反应的平衡常数以及该反应的焓变、熵变、吉布斯自由能等热力学数据.采用拟均相模型计算出此反应的反应速率常数及反应活化能等动力学数据.此外,在固定床反应器上进行了对比实验,结果表明该反应在两种反应器中的效果基本相似.

The macroporous cation exchange resin was used as a catalyst to study the reaction between camphene and propionic acid in a 250 mL three-necked flask under different reaction conditions. The effects of various parameters,such as stirring rate,resin type,resin content,ratio,temperature,catalyst repetition,effect on synthesis of isobornyl propionate and optimum process conditions were obtained. In order to correct the non-ideality of the solution,the UNIFAC group contribution method was used to estimate the activity coefficient. The equilibrium constants of the reaction at different temperatures were calculated,and the thermodynamic data such as the enthalpy change,entropy change and Gibbs free energy of the reaction were calculated. The pseudo-homogeneous model was used to calculate the kinetic constants for the reaction rate constant and reaction activation energy. In addition,comparative experiments were carried out on a fixed bed reactor,and the results showed that the effects of the reaction in the two reactors were substantially similar.