LIQUID-LIQUID EQUILIBRIA OF ORGANIC COMPOUNDS: MEASUREMENT,CORRELATION AND PREDICTION†

The knowledge of phase equilibria is an important step in the development of extraction processes. This knowledge is usually gained from experiments. However, this procedure is expensive when a suitable solvent has to be found for a specific separation. Therefore methods for predicting phase equilibria are needed. While formerly these methods were largely based on empirical assumptions, the use of the concept of local compositions by Wilson⁶ offers a semi-empirical approach.

There is one disadvantage of this approach: the parameters of models like UNIQUAC or NRTL have to be fitted to different types of data, to liquid-liquid equilibria (LLE) for the immiscible pairs of components and to vapour-liquid equilibria (VLE) or other data for the miscible pairs in a system with mutual solubility.

To demonstrate the problem we performed measurements in the binary systems: n-octane/aniline and methylcylohexane/aniline. of both liquid-liquid equilibrium and vapour-liquid equilibrium: for the second type of measurements ebulliomeiry was used. The prediction of LLE has been improved with two new concepts. One is based on the well-known UNIFAC method. The use of the Lyngby-Dorlmund data bank made it possible to determine a new parameter table merely based on LLE data.

The second method is based on common UNIQUAC parameters which have been determined with the data base.     

1-甲氧基-2-丙醇水癸烷的液液平衡

通过测定可作界面活性剂的 1 甲氧基 2 丙醇、癸烷和水的液液相平衡数据 ,考察 1 甲氧基 2 丙醇、癸烷以及水的混合液三元体系的相行为 ,并将实验结果和extendedUNIQUAC溶液模型的计算结果进行比较。结果表明 :在 2 98.15K时测得 1 甲氧基 2 丙醇、癸烷和水的相平衡数据和用extendedUNIQUAC模型推算结果相当吻合 ,extendedUNIQUAC模型成功地描述了 1 甲氧基 2 丙醇、癸烷和水混合溶液的液液相平衡。     

水-丙烯酸-醋酸-甲苯四元体系液液平衡数据的测定与关联

采用液液平衡釜,在常压下,测定了293.15,303.15,313.15 K时水-丙烯酸-醋酸-甲苯四元体系的液液平衡数据,为萃取-非均相共沸精馏法精制丙烯酸选择适宜的溶剂提供依据.使用Othmer-Tobias方程对实验数据进行线性拟合.分别采用非随机双液(NRTL)和通用似化学(UNlQUAC)活度系数模型对实验体...     

甲基异丙基甲酮-苯酚-对苯二酚-水的液液相平衡数据测定、模型关联及萃取过程模拟

液液相平衡测定为溶剂萃取及回收的准确模拟、设计和过程开发提供基础数据。以甲基异丙基甲酮为萃取剂,在处理高浓煤化工含酚废水的三元液液相平衡萃取基础上,选定其中典型单元酚苯酚和多元酚对苯二酚为代表物,测定甲基异丙基甲酮-苯酚-对苯二酚-水在常压40℃下的液液相平衡数据。采用NRTL和UNIQUAC活度系数模型对实验数据进行热力学关联,回归得到该四元体系的二元交互作用参数。结果表明该模型可以很好地关联实验数据,两种模型的相对均方根偏差分别小于0.190%和0.266%。进一步将得到的二元交互参数导入流程模拟系统,对萃取单元模块进行计算。当萃取温度40℃、萃取级数5级、相比1：7.72时,甲基异丙基甲酮能将总酚12700 mg×L^-1,多元酚4250 mg×L^-1的含酚废水的酚浓度分别降低至300 mg×L^-1和299 mg×L^-1以下。     

Measurements and correlation of liquid–liquid equilibrium data for the ternary(methyl tert-butyl ketone + o,m, p-benzenediol + water)system at(333.2, 343.2 and 353.2) K

In this work, liquid–liquid equilibria(LLE) data for the ternary system methyl tert-butyl ketone(MTBK) + o, m,p-benzenediol + water were investigated at 333.2 K, 343.2 K and 353.2 K under 101.3 kPa. The performance of MTBK to extract o, m, p-benzenediol from wastewaters was estimated by partition coefficients and separation factors. The Hand and Bachman equations were both applied to check the reliability of the experimental LLE data. Furthermore, the Non-Random Two-Liquid(NRTL) and Universal Quasi Chemical(UNIQUAC) models were applied to correlate the measured LLE data. The results showed a good agreement with the determined ternary LLE data with the root-mean-square error(RMSE) values below 0.71%. MTBK was proved to be a promising extracting agent in extracting benzenediols from effluents.     

Ternary phase equilibria of tetrahydrofuran-polystyrene-polytetrahydrofuran

Phase diagrams including tie lines for three ternary solvent-polymer-polymer systems consisting of tetrahydrofuran-polystyrene-polytetrahydrofuran at 30°C have been obtained using size exclusion chromatography. The effect of molecular weight on polymer-polymer compatibility has been investigated. A liquid-liquid equilibria (LLE) database has been used to compare UNIQUAC and a modified Flory-Huggins model with respect to their ability to correlate LLE data. Both models contain six adjustable parameters. As previously observed in the literature, the estimation of the UNIQUAC parameters is troublesome due to the model's complexity and the intercorrelation of the parameters. On the basis of better performance and ease of use, the Flory-Huggins model is recommended. The Flory-Huggins model is capable of accurately describing LLE of systems which exhibit quite complex tie line behavior. © 1993 John Wiley & Sons, Inc.     

CONTROL OF A PULSED LIQUID-LIQUID EXTRACTION COLUMN BASED ON A MULTILEVEL SYSTEM OF AUTOMATA

This paper presents the real-time application of the learning control theory to the control of a chemical pilot plant: a pulsed liquid-liquid extraction column.

The behaviour of an agitated liquid-liquid extraction column can be related to random mechanisms such as the phenomena of droplets breakage and coalescence. Previous studies on hydrodynamic and mass transfer aspects showed that a pulsed liquid-liquid extraction column had an optimal behaviour for operating conditions close to flooding. These results led to choose the following strategy to control the column in its optimal behaviour zone:

- the measure of the conductivity of the liquid medium below the distributor which gives a good information about flooding, is the controlled variable

-the pulse frequency is the control action.

The learning control algorithm is based on a multilevel system of automata which operates in a random environment. By means of an evaluation unit of the performances of the column which generates either penalty (inaction) or reward on the basis of heuristic rules, the automaton chooses a value of the pulse frequency. This approach is essentially connected to artificial intelligence in so far as human knowledge on the plant is included in these rules.

This algorithm has been implemented on a microcomputer for control purposes. The experimental results presented show the good performances of the approach.     

Mischungsfunktionen im binären System N-Methylcaprolactam – n-Tetradecan

Mixing Functions of the Binary System N-Methylcaprolactam – n-Tetradecane The liquid-liquid equilibria(LLE) and the vapour-liquid equilibria(VLE) at 60°C were measured in the binary system N-methylcaprolactam (1) – n-tetradecane (2). The enthalpy of mixing H^E of the same system was extrapolated from H^E – measurements of N-methylcaprolactam with other alkanes. The limiting activity coefficients f_∞1 and f_∞2 were obtained by extrapolation from values of resp. in other alkanes. For a comparison the vapour pressures of the mixture were calculated by model equations with constants from the two limiting activity coefficients and with temperature dependent constants extracted from the LLE and H^E measurements.     

不同温度DMF—正庚烷—甲苯体系液—液平衡的关联

本文对六个温度下DMF-正庚烷-甲苯体系的液-液平衡进行了等温和非等温情况下的关联。本文用NRTL、UNIQUAC等六种活度系数模型进行了关联,并提出一个修正的Wilson活度系数模型,修正了温度对活度系数的贡献。本文提出的活度系数模型能够较好地同时关联不同温度下的液-液平衡。计算误差明显小于进行温度修正后的NRTL等模型,参数也较后者为少。     

On the concentration dependence of the UNIQUAC/UNIFAC models

The UNIQUAC/UNIFAC models can not in general represent vapor-liquid and liquid-liquid equilibria simultaneously with satisfactory results. Recent modifications of the models take into account association and solvation effects by means of chemical theory. However, this approach leads to complicated expressions for the activity coefficients and the improvements are only moderate. A modification of the UNIQUAC/UNIFAC models is presented which takes into account solvation and association by allowing the interaction energies to vary with composition. This approach leads to explicit expressions for the activity coefficients. It is shown that the modified models in simultaneous correlations lead to quantitative representation of vapor-liquid equilibrium data and semi-quantitative representation of binary and ternary liquid-liquid equilibrium data.     

TERNARY EXTRACTION MODELING USING THE REDLICH-KISTER EXPANSION

Mathematical models for liquid-liquid extraction processes are not widely available. The correlation of liquid-liquid equilibrium for such a model is often difficult. One correlation, based upon the Redlich-Kister expansion for the molar excess Gibb's free energy, has been shown to accurately represent ternary liquid-liquid equilibrium systems used in liquid-liquid extraction operations.

The use of this correlation in an extraction model was investigated and found to be suitable for a ternary liquid-liquid extraction model with only minor limitations. A successful ternary liquid-liquid extraction model was developed using this equilibrium correlation.     

Isothermal vapour-liquid equilibria for the isopropyl benzene-ammonia system

Vapour-liquid equilibrium data were obtained for the isopropyl benzene-ammonia system at 273.15, 288.15, 293.15 and 298.15 K. This system has an upper critical solution temperature at 293.15 K. Since the liquid mixture changes from two liquid phases to one liquid phase with rising temperature, vapour-liquid-liquid equilibria also are evaluated. Experimental vapour-liquid equilibrium data were compared with calculated values from the UNIQUAC equation, and show good agreement.     

醋酸甲酯-甲醇-水三元物系液液平衡数据的测定与关联

测定了常压下20、30、40、50℃时醋酸甲酯 水二元体系及醋酸甲酯 甲醇 水三元体系的液液平衡(LLE)数据,并与文献中已有的醋酸甲酯 水的液液平衡数据进行比较,证明了测定方法的可靠性。采用二元与三元液液平衡数据相结合的关联方法,并用NRTL和UNIQUAC模型对所测数据进行了热力学关联,得出了相应的模型参数。用该模型对三元体系进行计算,结果令人满意。用VisualBasic6.0语言开发了液液相平衡关联软件,可方便地用于二元和三元液液相平衡的计算。     

含甲基叔丁基醚的四元体系液液相平衡

为了考察甲基叔丁基醚对汽油主要成分烃类化合物与水相互溶解性的影响,在298.15 K和常压下,测定了2个四元体系水-甲基叔丁基醚-异辛烷-异丙醇和水-甲基叔丁基醚-异辛烷-甲苯的液液相平衡数据,并用含有二元、三元和四元相互作用参数的Extended UNIQUAC模型和Modified UNIQUAC模型对液液相平衡数据进行了关联计算。结果表明:在298.15 K时测得的四元体系液液相平衡数据和模型的计算结果很吻合,Extended UNIQUAC和Modified UNIQUAC模型成功地描述了四元混合液的液液相平衡,这些基础数据对化工生产过程的设计和分离操作条件的选择都是非常有意义的。     

Determination and correlation of LLE and SLE data for the system aniline+cyclohexane

A newly developed laser light scattering technique was used for the determination of mutual solubilities in the aniline+cydohexane system at moderate pressures. The liquid-liquid equilibria (LLE) were measured from the region of solid-liquid equilibria (SLE) to the upper critical solution temperature. Freezing points in this system were determined by a cooling curve method. The solubility data were correlated with the NRTL equation.     

正丁醇-水-醋酸丁酯三元物系液-液平衡数据的测定、关联和预测

测定了由正丁醇、水和醋酸丁酯形成的三元物系及部分互溶二元物系在20℃、30℃和40℃的LLE(液液平衡)数据,并与文献中已有的正丁醇-水的LLE实测数据核对,说明了测定方法的可靠性.用NRTL和UNIQUAC方程分别进行了三元和二元LLE数据的关联和预测.根据溶液热力学特性对二元LLE模型参数进行了鉴别.在三元LLE数据的关联中,对两种目标函数(摩尔分数和分配系数)进行了比较,并对前一种目标函数中的权重取值问题进行了考察.通过对部分互溶二元物系参数的评选,提高了利用二元参数对三元物系进行预测的准确度.     

甲基丙烯酸甲酯-甲醇体系的双溶剂萃取

针对甲基丙烯酸甲酯（MMA）-甲醇共沸体系,常规精馏难以分离。提出采用己烷-水双溶剂体系萃取分离MMA的新工艺。测定了不同温度下MMA（1）+甲醇（2）+正己烷（3）+水（4）、MMA（1）+甲醇（2）+环己烷（3）+水（4）两个体系的相平衡数据,考察了不同温度下溶剂正己烷/环己烷、水的用量对萃取分配系数和选择性系数的影响。在实验数据的基础上,进一步采用UNIQUAC模型对该体系的相平衡进行了拟合,获得了模型参数。     

Isobaric vapour-liquid equilibria of the ternary system hexane-benzene-sulpholane

Isobaric vapour-liquid equilibria for the ternary system hexane-benezene-sulpholane have been determined at 760 mmHg pressure. The data have been compared with those calculated using the NRTL equation. The NRTL constants obtained from the literature were evaluated from ternary liquid-liquid equilibrium data for this system. The agreement between experimental and calculated values is reasonable.     

Tie-line data for aqueous mixtures of butyric acid with isobutyl acetate at various temperatures

Experimental liquid-liquid equilibrium (LLE) data for the system of (water+butyric acid+iso-butyl acetate) were obtained at T=(298.2, 303.2, 308.2, and 313.2) K and atmospheric pressure. This ternary system exhibits type-1 behavior of LLE. The experimental tie-line data were correlated using the UNIQUAC and NRTL models. The reliability of the experimental tie-line data was determined by applying the Othmer-Tobias and Hand correlations. Distribution coefficients and separation factors were calculated over the immiscibility regions.     

The vapour-liquid equilibrium of ternary systems with limited miscibility at atmospheric pressure

The complete study of the vapour-liquid equilibrium of ternary systems with limited miscibility requires vapour-liquid equilibrium determinations and liquid-liquid equilibrium determinations at boiling point. The vapour-liquid equilibrium was determined by means of an equilibrium still based on the principle of Giilespie but modified in such a way that an accurate boiling point measurement, even for systems with heterogeneous liquid was possible and that the vapour phase was analysed without previous condensation. Two ternary systems have been studied: the system methanol-ethylacetate-water and the system ethanol-ethylacetate-water. The ternary data have been predicted by means of the equation of Renon and Prausnitz. The parameters are determined by correlating the binary data. The ternary vapour-liquid equilibrium are predicted within 1-2. 10 ^?2 mol fraction for the vapour composition and 1°C for the boiling point. The position of the predicted tielines of the liquid-liquid equilibrium at boiling point was almost coinciding with the position of the experimental tielines. There was a slight deviation of the predicted and experimental binodal.