On the basis of reported experimental vapor-liquid equilibrium （VLE） data of NH3-1-ethyl-3-methylimidazolium acetate （NH3-[Emim]Ac）, NH3-1-butyl-3-methylimidazolium tetrafluoroborate （NH3-[Bmim][BF4]）, NH3-1,3-d...On the basis of reported experimental vapor-liquid equilibrium （VLE） data of NH3-1-ethyl-3-methylimidazolium acetate （NH3-[Emim]Ac）, NH3-1-butyl-3-methylimidazolium tetrafluoroborate （NH3-[Bmim][BF4]）, NH3-1,3-dimethylimidazolium dimethyl phosphate （NH3-[Mmim]DMP） and NH3-1-ethyl-3-methylimidazolium ethylsulfate （NH3-[Emim]EtOSO3） binary systems, the interaction parameters of 14 new groups have been regressed by means of the UNIFAC model. To validate the reliability of the method, these parameters have been used to calculate the VLE data with the average relative deviation of pressures of less than 9.35%. The infinite dilution activity coefficient （ γ1∞ ） and the absorption potential （ φ1 ） are important evaluation criterions of the affinity between working pair species of the absorption cycle. The UNIFAC model is implemented to predict the values of and φ1 of t6 sets of NH3-ionic liquid （1L） systems. The work found that the φ1 gradually increases following the impact order： φ1（[Cnmim][BF4]）〈φ1（[Cnmim]EtOSO3）〈φ1（[Cnmim]DMP）〈φ1（[Cnmim]Ac） （n= 1, 2, 3, … ） at a given cation of IL species and constant temperature, and φ1（[Mmim]X）〈φ1（[Emim]X）〈φ1（[Pmim]X）〈 φ1（[Bmim]X）（X= Ac, [BF4], DMP or EtOSO3） at a given anion of IL species and constant temperature. Furthermore, the φ1 gradually increases with increasing temperature. Then, it could be concluded that the working pair NH3-[BmimlAc has the best potential research value relatively.展开更多
An extended liquid-liquid equilibrium(LLE) UNIFAC model is proposed to describe phase equilibria of mixtures containing caprolactam.In this model,caprolactam is introduced as a new group.New group interaction paramete...An extended liquid-liquid equilibrium(LLE) UNIFAC model is proposed to describe phase equilibria of mixtures containing caprolactam.In this model,caprolactam is introduced as a new group.New group interaction parameters are calibrated from 156 sets of liquid-liquid equilibrium data.The present model gives satisfactory correlation and prediction in liquid-liquid equilibrium,including quaternary systems containing the mixed solvent of an alcohol and an alkane.The model can be applied to predict caprolactam solubility in water and benzene accurately.Freezing point and vapor-liquid equilibrium of binary systems containing caprolactam are also predicted with the extended LLE UNIFAC model.Satisfactory prediction results are obtained.展开更多
离子液体(ILs)具有高稳定性、溶解性能好、可设计性、易回收等优点,尤其因高CO_(2)溶解度在碳捕集方面显示了巨大潜力。但由于ILs种类繁多且价格昂贵,依靠实验研究耗时费力,因此构建ILs体系的热力学预测模型至关重要。UNIFAC模型在ILs...离子液体(ILs)具有高稳定性、溶解性能好、可设计性、易回收等优点,尤其因高CO_(2)溶解度在碳捕集方面显示了巨大潜力。但由于ILs种类繁多且价格昂贵,依靠实验研究耗时费力,因此构建ILs体系的热力学预测模型至关重要。UNIFAC模型在ILs气体分离工艺设计与优化领域具有重要的理论价值和工程应用意义,基于此,本研究构建了应用于ILs-CO_(2)体系活度系数预测的UNIFAC模型。本文系统收集了CO_(2)在ILs中的溶解度实验数据,并结合相平衡计算出活度系数,建立了ILs-CO_(2)体系活度系数数据库。采用COSMO方法和van der Waals规则分别获得了UNIFAC模型中基团的重要参数(R_(k)和Q_(k))。基于实验值,拟合了UNIFAC相互作用参数。通过平均相对误差(AARD),比较了两种方法建立的UNIFAC模型的预测效果。结果表明:通过COSMO方法(AARD=7.68%)建立的UNIFAC模型对ILs-CO_(2)体系的活度系数预测误差比van der Waals方法(AARD=12.57%)降低了4.89个百分点。并在此基础上建立了ILs-CO_(2)体系UNIFAC模型,获得了近100对基团的相互作用参数数据库。由于UNIFAC模型的基团贡献特点,本工作建立的UNIFAC模型可预测数据库中包含的基团组成的新型ILs与CO_(2)体系的活度系数,从而为后续ILs法气体吸收的分子设计奠定了扎实基础。展开更多
基金Supported by the National Natural Science Foundation of China(50890184,51276010)the National Basic Research Program of China(2010CB227304)
文摘On the basis of reported experimental vapor-liquid equilibrium （VLE） data of NH3-1-ethyl-3-methylimidazolium acetate （NH3-[Emim]Ac）, NH3-1-butyl-3-methylimidazolium tetrafluoroborate （NH3-[Bmim][BF4]）, NH3-1,3-dimethylimidazolium dimethyl phosphate （NH3-[Mmim]DMP） and NH3-1-ethyl-3-methylimidazolium ethylsulfate （NH3-[Emim]EtOSO3） binary systems, the interaction parameters of 14 new groups have been regressed by means of the UNIFAC model. To validate the reliability of the method, these parameters have been used to calculate the VLE data with the average relative deviation of pressures of less than 9.35%. The infinite dilution activity coefficient （ γ1∞ ） and the absorption potential （ φ1 ） are important evaluation criterions of the affinity between working pair species of the absorption cycle. The UNIFAC model is implemented to predict the values of and φ1 of t6 sets of NH3-ionic liquid （1L） systems. The work found that the φ1 gradually increases following the impact order： φ1（[Cnmim][BF4]）〈φ1（[Cnmim]EtOSO3）〈φ1（[Cnmim]DMP）〈φ1（[Cnmim]Ac） （n= 1, 2, 3, … ） at a given cation of IL species and constant temperature, and φ1（[Mmim]X）〈φ1（[Emim]X）〈φ1（[Pmim]X）〈 φ1（[Bmim]X）（X= Ac, [BF4], DMP or EtOSO3） at a given anion of IL species and constant temperature. Furthermore, the φ1 gradually increases with increasing temperature. Then, it could be concluded that the working pair NH3-[BmimlAc has the best potential research value relatively.
基金Supported by the National Natural Science Foundation of China（20490200 20525622） the National Basic Research Program of China（2007CB714302）
文摘An extended liquid-liquid equilibrium(LLE) UNIFAC model is proposed to describe phase equilibria of mixtures containing caprolactam.In this model,caprolactam is introduced as a new group.New group interaction parameters are calibrated from 156 sets of liquid-liquid equilibrium data.The present model gives satisfactory correlation and prediction in liquid-liquid equilibrium,including quaternary systems containing the mixed solvent of an alcohol and an alkane.The model can be applied to predict caprolactam solubility in water and benzene accurately.Freezing point and vapor-liquid equilibrium of binary systems containing caprolactam are also predicted with the extended LLE UNIFAC model.Satisfactory prediction results are obtained.
文摘离子液体(ILs)具有高稳定性、溶解性能好、可设计性、易回收等优点,尤其因高CO_(2)溶解度在碳捕集方面显示了巨大潜力。但由于ILs种类繁多且价格昂贵,依靠实验研究耗时费力,因此构建ILs体系的热力学预测模型至关重要。UNIFAC模型在ILs气体分离工艺设计与优化领域具有重要的理论价值和工程应用意义,基于此,本研究构建了应用于ILs-CO_(2)体系活度系数预测的UNIFAC模型。本文系统收集了CO_(2)在ILs中的溶解度实验数据,并结合相平衡计算出活度系数,建立了ILs-CO_(2)体系活度系数数据库。采用COSMO方法和van der Waals规则分别获得了UNIFAC模型中基团的重要参数(R_(k)和Q_(k))。基于实验值,拟合了UNIFAC相互作用参数。通过平均相对误差(AARD),比较了两种方法建立的UNIFAC模型的预测效果。结果表明:通过COSMO方法(AARD=7.68%)建立的UNIFAC模型对ILs-CO_(2)体系的活度系数预测误差比van der Waals方法(AARD=12.57%)降低了4.89个百分点。并在此基础上建立了ILs-CO_(2)体系UNIFAC模型,获得了近100对基团的相互作用参数数据库。由于UNIFAC模型的基团贡献特点,本工作建立的UNIFAC模型可预测数据库中包含的基团组成的新型ILs与CO_(2)体系的活度系数,从而为后续ILs法气体吸收的分子设计奠定了扎实基础。
