水合物反应液中水活度系数模型研究进展

水合物反应液中水活度系数的计算对水合物相平衡特性的研究及水合物技术的应用具有重要意义。 通过调研大量的国内外资料,概括了Margules、Wilson、NRTL、UNIQUAC及UNIFAC活度系数方程及其关联式等模型及其应用,结果表明,Margules模型常用于二元体系活度系数的计算,但对高温高压体系条件下的溶液适用性较差;Wilson模型参数回归误差稍大且不适于溶质与离子不能完全互溶体系;UNIQUAC模型在含水或咪唑类离子反应液体系中误差较大;多元离子体系相平衡的研究中常选择NRTL模型;UNIFAC模型拟合效果较好,可实现较高浓度体系活度系数的精确计算,应用较广泛。 水活度关联方程参数拟合效果好,且准确度高,但在高温高压水合物反应液体系中的计算仍是一个技术难点,是今后的研究方向。

Research Development of Activity Coefficient Models in Hydrate Reaction Media

Activity coefficient calculation is of great significance to the phase equilibrium of hydrate and the development of hydrate technology. Margules, Wilson, NRTL, UNIQUAC and UNIFAC models were studied by large amounts of survey with detailed analysis. The results show that Margules activity coefficient model is widely used in binary systems. Wilson activity coefficient model is not suitable for the system that solute and ion can not mix completely. The error of UNIQUAC in the calculation of aqueous or imidazole ion is bigger. We often choose NRTL for multiple ion systems. UNIFAC is widely used and can achieve precise calculation in high concentration solutions. Activity correlation equation parameters can be fit very well with high accuracy, but it is still difficult for systems of high temperature and pressure and needs to be developed in the future.