环丁烯砜合成反应的基团贡献法热力学分析

采用基团贡献法对环丁烯砜合成反应进行了热力学分析,计算了300~600 K、0.1~10 MPa反应体系的反应焓变、反应熵变、反应Gibbs自由能变和反应平衡常数,并分析了温度、压力和组成对平衡转化率的影响。结果表明,标准压力下,环丁烯砜合成反应是可逆放热反应,温度小于460 K范围内可以自发进行,降低温度和升高压力有利于反应向正向进行。温度、压力和组成对平衡转化率均有影响,温度影响最为显著。降低温度、升高压力或增大过量比有利于提高平衡转化率,最大平衡转化率接近于1。基团贡献法所得的平衡转化率预测值与实验值吻合较好,相对偏差在10%以内。

Thermodynamic analysis on synthesis of sulfolene by group-contribution method

The thermodynamic analysis of sulfolene synthesis reaction was carried out by group-contribution method. The reaction enthalpy, entropy, Gibbs free energy and equilibrium constant were calculated in the temperature range of 300-600 K and the pressure range of 0.1-10 MPa. The effects of temperature, pressure and reactant ratio on equilibrium conversion were also discussed. The calculation results indicate that sulfolene synthesis is a reversible exothermic reaction, and it is spontaneous when the temperature is less than 460 K at standard pressure. The reaction occurs more easily at lower temperatures and higher pressures. Temperature, pressure and the reactants ratio all show significant effect on equilibrium conversion, and the temperature is the most significant factor. Lower temperature, higher pressure and higher reactant ratio favor the promotion of equilibrium conversion, and the maximum equilibrium conversion is close to 1. The experimental results show good agreement with the thermodynamic calculation, and the relative deviation is less than 10%.