电解质NRTL模型是重要的热力学局部组成模型。本文阐述了电解质NRTL模型的研究进展过程,包括模型的提出、修正、改进和扩展,同时指出了不同模型的适用范围。介绍了模型在各种复杂电解质溶液体系关联计算中的应用,可以为一些工业生产过程的模拟、设计和优化提供理论指导。电解质NRTL模型的主要优势是适用的温度和浓度范围宽,不需二元以上高阶参数;但模型自身也存在缺陷,如参数的回归工作量大、在溶液体系临界点处的预测精度较差等,故模型仍需进一步完善。

The electrolyte NRTL model is a kind of important thermodynamic local composition model. This paper describes the research progress of the electrolyte NRTL model,including proposition, improvement,modification and extension of the model and the scope of application of different models. Some applications for correlation calculation of various kinds of complex electrolyte solutions are introduced,providing theoretical directions for process simulation,design and optimization. The main advantage of the electrolyte NRTL model is that it is applicable to a wide range of temperature and concentration with no need for high-order parameters. The disadvantages of the model are heavy regression work for parameters,and poor prediction accuracy at the critical point of electrolyte solution.

测定了水-仲丁醇-乙酸仲丁酯三元体系在303.15,323.15,343.15,353.15 K下的液液相平衡数据,并用NRTL模型和 UNIQUAC模型对相平衡数据进行关联,应用单纯形法求得相应的模型参数.计算值与实验值比较结果表明:NRTL模型与UNIQUAC模型的计算值与实验数据吻合良好.

Liquid-liquid equilibrium (LLE) data of the water +sec-butyl alcohol + sec-butyl acetate ternary system were measured at 303.15 K, 323.15 K, 343.15 K and 353.15 K under atmospheric pressure. The active coefficients in the LLE equations were calculated by the NRTL and UNIQUAC models, and the calculated LLE data of water+sec-butyl alcohol+sec-butyl acetate ternary system were compared with the experimental data. Based on the NRTL and UNIQUAC models, the calculated equilibrium compositions of the studied ternary system are in good agreement with the experimental data.

采用汽液双循环平衡釜，在常压（101.3 kPa）下测定了丙酮-丙酮连氮二元组分物系以及部分丙酮-水-丙酮连氮三元组分物系的汽液平衡数据。实验数据经Herington面积积分法检验符合热力学一致性。通过化工过程模拟软件，分别采用 Wilson、NRTL、UNIQUAC 活度系数模型对丙酮-丙酮连氮二元组分物系实验数据进行关联得到模型参数。并对汽液平衡的计算值与实验值进行比较，3种模型都吻合良好，其中由NRTL方程关联得到的计算结果最为适合，平均温度偏差和汽相组成偏差分别为0.0639 K和0.0048。从三元汽液相平衡数据中拟合出了丙酮-丙酮连氮、丙酮-水、水-丙酮连氮之间的 NRTL 方程相互作用参数。为验证数据及其二元相互作用参数的可靠性，利用关联出的丙酮-丙酮连氮模型参数计算出汽相组成与丙酮-丙酮连氮的二元数据比较，二者符合较好。实验和关联的结果为精馏分离丙酮-水-丙酮连氮汽液平衡体系提供了一定的基础数据。

Vapor-liquid equilibrium (VLE) data for acetone-azine binary system and parts of acetone water azine ternary system were determined in an Othmer equilibrium at atmospheric pressure (101.3 kPa). The experimental data was verified by Herington method and were consistent with thermodynamics. The data of acetone-azine binary system were correlated with the NRTL,Wilson and UNIQUAC models by using chemical engineering analogue software. Respectively,all the models were correlated well with the VLE data. NRTL model produced best data,with the average deviations of temperature of 0.0639 K and vapor-phase mole fraction of methanol of 0.0048. The NRTL model was used to correlate the VLE data of the ternary system,and the interaction parameters of acetone-azine,water-azine,and acetone-water were obtained. In order to verify the reliability of the VLE data of the ternary system and these interacting binary parameters,the vapor compositions were calculated and compared with the corresponding experi

采用平衡釜法测定了三元体系（环己烷＋正庚烷＋N，N-二甲基甲酰胺）在常压不同温度（30，40，50℃）下的液液相平衡数据。实验数据用Bachaman及Othmer-Tobias进行可靠性关联，关联结果表明数据的可靠性较好，根据实验结果绘制了三元相图。对不同温度下的液液平衡实验数据，分别用NRTL和UNIQUAC活度系数方程进行了关联，求得方程的二元交互作用系数，关联结果表明NRTL和UNIQUAC方程对该体系适用较好。由实验数据计算得到衡量N，N-二甲基甲酰胺抽提性能的参数（分配系数、分离因子、选择性系数）。

Liquid-liquid equilibrium (LLE) data were measured for ternary system (n-heptane-cyclohexane-N,N-dimethylformamide) at atmospheric pressure and different temperatures (30, 40, 50 ℃).The experimental data were correlated using the Bachman and the Othmer-Tobias correlation , and the results showed a good correlation . Complete phase diagrams were obtained by tie-line data and determining solubility .The universal quasichemical activity coefficient ( UNIQUAC) and the non-random two-liquid equation ( NRTL) were used to predict the phase equilibrium in the system by the interaction parameters from the experimental data .It shows that UNIQUAC and NRTL used for LLE can provide a good correlation .The separation factors , distribution coefficients and selectivity were obtained according to the experimental data .

采用自制的Rose釜在绝压2 kPa下测定γ-丁内酯-二乙二醇二元系的汽液平衡数据,并对所测得的数据进行热力学一致性检验,结果表明实验数据符合热力学一致性。以汽相组成的误差平方和作为目标函数,分别用Wilson和NRTL方程关联实验数据,得到分子交互作用能量参数,并对汽液平衡计算值与实验值进行比较,发现二者最大偏差为0.0143,平均偏差0.0063。采用溶液浓度三次方程分别对Wilson和NRTL方程进行修正,修正后二者最大偏差0.0094,平均偏差0.0036,明显优于修正前的结果,可满足工程上分离设计的需要。

The vapor-liquid equilibrium (VLE) data of the γ-butyrolactone-diethylene glycol system were measured at 2kPa using a home-made Rose vapor-liquid equilibrium device, and the thermodynamic consistency of the experimental data were examined. The results show that the experimental data are thermodynamically consistent. The VLE data obtained were correlated with Wilson and NRTL equation respectively, and model parameters were determined. Comparison of the experimental data with fitting equation results shows that the maximum deviation and the average absolute deviation are 0.0143 and 0.0063, respectively. A cubic polynomial modification of the Wilson and NRTL equation considering the molar composition of the liquid phase was proposed. The results show that the maximum deviation and the average absolute deviation of the modified equations are 0.0094 and 0.0036, which indicates that the modified models are better for engineering separation design.