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.     

Liquid-liquid and vapour-liquid behaviour of oleyl alcohol applied to extractive fermentation processing

Investigations into the product recovery step of the extractive ethanol fermentation through partition experiments for ethanol-water-Adol^r? 85 NF ternary systems were undertaken. Experimental liquid-liquid equilibrium data for this ternary system were compared with numerical predictions based on the UNIFAC method. The influence of salts on distribution coefficients for ethanol extraction was also examined. An improvement in extraction characteristics was observed for ternary systems with salts. Flash vaporisation was used to subsequently examine the effect of liquid-liquid ternary compositions on vapour-liquid partitioning. The UNIFAC model was found to be very useful for semi-quantitative analysis of such liquid extraction systems.     

丁酮肟-水-异辛醇物系液液相平衡的研究

在甲基三丁酮肟基硅烷的生产过程中会产生部分含丁酮肟的废水,用萃取方法可回收丁酮肟。为获得萃取工艺所需的基础数据,在常压、60℃温度下,以工业实际废水为物料,进行液液相平衡实验,用拟三元方法处理丁酮肟-水-异辛醇三元体系的液液相平衡数据,获得了三元体系平衡相图。实验数据用非随机两相液体(NRTL)模型进行了关联,得出了该三元体系的NRTL模型参数。将实验数据与关联结果进行比较,结果表明,NRTL模型能对该三元体系进行较准确的关联。     

1-甲基萘-正癸烷-1-十四烯-环丁砜体系液液相平衡数据测定及关联

采用溶剂萃取分离催化裂化柴油中的芳烃是催化裂化柴油改质一条有效的途径。测定了常压下323.15、333.15和343.15 K时1-甲基萘-正癸烷-1-十四烯-环丁砜体系的液液相平衡数据,得到该体系的三元相图,1-甲基萘对非芳烃的选择性系数保持在2~55之间,说明环丁砜溶剂萃取分离1-甲基萘是可行的。采用Hand方程和Othmer-Tobias方程对相平衡数据进行关联,相关性系数均大于0.99,表明相平衡数据具有较好的一致性。利用NRTL方程进行关联,获得二元交互作用参数,NRTL模型计算值与实验值的均方根偏差很小,说明NRTL模型适合该体系的液液相平衡。     

丁酮-水-丙三醇三元体系液液平衡数据的测定与关联

为了给以丙三醇为溶剂萃取分离丁酮-水体系的过程设计和流程模拟计算提供基础数据,在常压,20,40,60℃下,测定了丁酮-水-丙三醇三元体系的液液平衡数据,得到了三元体系的共轭相组成并由此绘得相平衡曲线。实验数据用UNIQUAC和NRTL模型进行了关联,利用关联出的模型参数计算了相应的液相组成,并与实验值比较,其平均偏差小于0.003 8,计算值与实验数据吻合良好。求得了溶剂对溶质的选择性系数,验证了丙三醇是液液萃取分离丁酮-水的良好溶剂。     

正己烷–异丙醇共沸体系液液相平衡数据测定及关联

为了给溶剂萃取分离正己烷–异丙醇混合物的过程设计和流程模拟计算提供基础数据,以二甲亚砜、1,4-丁二醇、1,2-丙二醇、乙腈、糠醛和N,N-二甲基甲酰胺为萃取剂,测定了30℃下萃取分离正己烷–异丙醇混合物的液液相平衡数据,并利用分离因子评价不同萃取剂的萃取分离性能。根据Hand方程对实验数据进行一致性和可靠性检验,拟合方程的相关系数都在0.98以上。随后,采用Aspen Plus软件选取NRTL活度系数模型对相平衡数据进行关联,得到相应的二元交互作用参数,并以此计算相应的相平衡组成。结果显示,计算值和实验值的均方根偏差小于1.0%,表明NRTL模型能够准确描述三元体系的液液相平衡。     

甲基异丁基酮-水-苯酚三元物系液液相平衡数据的测定与关联

为了给以甲基异丁基酮为溶剂的含酚废水萃取过程设计和流程模拟计算提供基础数据,实验测定了常压,25、40和50℃下甲基异丁基酮-水-苯酚三元物系在稀酚水范围内的液液相平衡数据。采用NRTL活度系数模型对实验数据进行了关联,回归得到了该三元物系的二元交互参数。运用回归得到的模型参数,对该三元物系的相平衡数据进行预测计算,结果表明该模型可以很好地关联实验数据,模型计算值与实验值的相对均方根误差和绝对平均误差均在2％以内。     

丁酮-水共沸物系的萃取分离

采用液液萃取进行丁酮-水共沸物系的分离。测定了三元体系丁酮-水-（1-乙基-3-甲基咪唑醋酸盐）的液液平衡,采用NRTL活度系数方程对液液平衡数据进行回归得到组分间的二元交互作用参数。利用流程模拟软件ChemCAD进行了以离子液体为萃取剂的液液萃取过程的模拟,研究了理论板数、溶剂比（萃取剂摩尔流量和原料摩尔流量的比值）对萃取过程的影响,通过灵敏度分析,获得了优化的操作参数。在最适宜操作条件下,丁酮的摩尔分数可达0.999 4,离子液体经过回收能够直接循环使用。     

水-丙烯酸-甲基异丁基甲酮体系液液平衡数据的测定与关联

为萃取-共沸精馏法分离丙烯酸水溶液选择适宜的溶剂,采用液液平衡釜,在常压下测定了293.15,303.15,313.15 K下水-丙烯酸-甲基异丁基甲酮三元体系的液液平衡数据.使用Hand方程对实验数据进行拟合,相关性系数的平方均大于0.99.利用Aspen Plus过程模拟软件的数据回归系统,分别采用非随机双液(NR...     

二乙氧基甲烷-乙醇-水-甘油体系部分组分液液平衡

用液液平衡釜测定了二乙氧基甲烷-水、二乙氧基甲烷-甘油2组二元和二乙氧基甲烷-水-甘油、二乙氧基甲烷-乙醇-甘油、二乙氧基甲烷-水-乙醇3组三元体系常温、常压下的液液平衡数据。用NRTL和UNIQUAC方程对所测二元体系的平衡数据进行了处理。采用单参数法关联了乙醇-甘油体系的模型参数。结合三元体系的液液平衡数据,用NRTL和UNIQUAC方程关联出了三元体系中的第3对模型参数。确定了二乙氧基甲烷-乙醇-水-甘油体系合适的模型及参数,为含二乙氧基甲烷体系的实际分离过程提供了依据。     

Hydrocarbon-propionitrile systems

Perfluorocyclic oxide is proposed as an antisolvent for studying the behaviour of binary systems by liquid-liquid equilibrium. The experimental results, obtained for the ternary systems perfluorocyclic oxide — hydrocarbon — propionitrile, are correlated with the NRTL equation. The values of NRTL parameters allow the prediction of the behaviour of ternary systems hydrocarbon A — hydrocarbon B — propionitrile. The use of liquid-liquid extraction with mixed solvent (perfluorocyclic oxide and propionitrile) is suggested for the separation of hydrocarbon mixtures.     

甲苯-正庚烷-环丁砜、环丁砜-正庚烷-水——三元体系液液平衡数据的测定与热力学关联

本文测定了甲苯-正庚烷-环丁砜三元体系在30℃和50℃下的液液分层曲线和结线数据,采用了以液液分层曲线和体系物性相结合的分析方法,获得了可靠的数据.本文还测定了环丁砜—正庚烷-水三元体系在50℃下的液液分层曲线,作出了结线.对前一休系的数据进行了热力学关联,求出30℃及50℃时UNIQUAC方程参数.对两个体系均用UNIFAC方法进行预测.计算所得结果相当满意.     

Solvent extraction of aromatics from middle distillates: Equilibria prediction method by group contribution

This work describes a method of calculating liquid-liquid aromatics extraction of a middle distillate. The group contribution models of the ASOG and UNIFAC type are investigated. Four vapour liquid equilibrium (VLE), two solid-liquid equilibrium (SLE), three binary and six ternary liquid-liquid equilibrium (LLE) have been measured. The parameters of the models are based mainly on the data of the systems having 10–20 carbon number. VLE, SLE, and infinite dilution activity coefficient data (17–245°C) have been used for calculating interaction parameters between hydrocarbon groups and LLE data (20–80°C) for interaction parameters of dimethylformamide-hydrocarbon groups. Middle distillate representation is based on mass spectrometric and gas chromatographic analysis and on limited data of middle distillate-DMF liquid-liquid equilibrium. It is shown that the performance of ASOG and UNIFAC models are sufficiently valid in representation of data base and in extraction calculations. Considering the predictive character and the rapidi of its application this method can be useful in the preliminary study of extraction processes.     

含辛烯醛体系的液液、汽液相平衡研究

测定了水-辛烯醛、水-正丁醇二元系在常压下的液液平衡数据及26.66kPa下的正丁醇-辛烯醛二元系和水-正丁醇-辛烯醛三元系的汽液平衡数据.由测定的3对二元数据求取了NRTL常数及有规参数,并与三元数据进行拟合,计算值与实验值符台良好,液液平衡与汽液平衡得到了统一的关联.     

N,N-二甲基甲酰胺-三氯甲烷-水物系液液相平衡研究

为了获得制革DMF废水萃取回收工艺所需的基础数据,在常压20℃温度下,测定了三氯甲烷-N,N-二甲基甲酰胺-水拟三元体系的液液平衡数据,得到了三元体系平衡相图。实验数据点用NRTL模型进行了关联,得出了三氯甲烷-N,N-二甲基甲酰胺-水拟三元体系的模型参数。将实验数据与关联结果比较,表明NRTL模型能对该物系进行较准确关联。     

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。     

LIQUID PARTITIONING OF AMPHIPHILIC SOLUTIONS RELATED TO THE SOLVENT EXTRACTION OF BITUMEN FROM TAR SANDS

The Wood-Beaver process is a solvent extraction process which uses a fatty acid blend (light hydrocarbons, aromatics, and fatty acids) as the solvent and utilizes amphiphilic phase behavior and phase shift to recover the fatty acids from the solvated bitumen. The process consists of mixing the solvated bitumen with an alcohol-water wash which precipitates the bitumen as the bottom phase of the primary settler. The top phase of the settler contains the fatty acid/alcohol/water/light hydrocarbons components. The fatty acid and light hydrocarbons are then recovered in a secondary settler by shifting the phase equilibrium by either over-dosing with water or by driving off alcohol by the application of heat.

This paper presents experimental equilibrium phase behavior data and the correlations resulting from an analysis for the quaternary system of oleic acid, bitumen, isopropyl alcohol, and water. The data are presented in the form of psuedo ternary diagrams. The NRTL modelling equation was applied to the oleic acid/brine/isopropyl alcohol system in order to determine a set of interactive and non-randomness parameters that adequately describe the liquid-liquid phase behavior of this ternary system. The phase envelope and accompanying tie lines reproduced from the model showed acceptable agreement with the experimental data.     

基于COSMO-SAC模型的离子液体萃取剂的选择

COSMO-SAC模型是计算无限稀释活度因子的一种有效方法,只需知道分子结构,即可进行有机物或离子液体的无限稀释活度因子计算。COSMO-SAC模型中最耗时的计算步骤是产生σ-图谱(σ-profile)的量子化学计算。利用Materials Studio软件中的DMol3模块,建立了包含32种离子液体阴离子和191种离子液体阳离子的σ-图谱数据库。利用σ-图谱数据库和COSMO-SAC模型,针对离子液体液液萃取过程,提出了离子液体萃取剂的计算机辅助分子设计方法。以乙醇-乙酸乙酯体系为研究对象,选择了适宜的离子液体萃取剂,采用乙醇-乙酸乙酯-离子液体三元体系的液液平衡文献数据进行了验证。     

Liquid+liquid equilibria of ternary water+carboxylic acid+solvent systems at 288.15 K

The experimental liquid-liquid equilibrium (LLE) data for six ternary systems containing (chloroform+propionic acid+water), (chloroform+acetic acid+water), (diethyl ether+propionic acid+water), (diethyl ether+acetic acid+water), (trichloroethylene+propionic acid+water) and (trichloroethylene+acetic acid+water) were measured at 288.15 K and at atmospheric pressure. An accurate and simple titration method was used for determining of the concentration of carboxylic acid in the both liquid phases at equilibrium. The reliability of the experimental tie-line data was confirmed by using the Othmer-Tobias correlation. The distribution coefficients and selectivity factors were presented to evaluate the efficiency of the solvents for extraction of carboxylic acid from water. The results show that chloroform and diethyl ether are satisfactory solvents for extraction of carboxylic acids from water. Trichloroethylene separates propionic acid from water; however, it cannot be used as a solvent for separation of acetic acid.     

基于COSMO-RS模型的分离油酚混合物的离子液体萃取剂筛选

低温煤焦油中酚类化合物的分离对其充分利用具有重要意义。基于COSMO-RS模型,以间甲酚和异丙苯作为模型化合物,研究了离子液体在分离油酚体系中的应用;利用Turbomole软件建立了包含27种离子液体阴离子和48种离子液体阳离子的s-图谱数据库,结合COSMOtherm软件对组成的1296种离子液体进行筛选,探讨了阴阳离子对间甲酚分离效果的影响,并对筛选得到适宜的离子液体进行液液相平衡实验验证。结果表明,离子液体阴离子对间甲酚分离效果影响较大,以Cl^-和CH₃COO^-为阴离子的离子液体与间甲酚之间具有较强的氢键相互作用,因此具有较好的分离效果;阳离子对间甲酚分离效果影响较小,碳链或支链的增加能适当提高离子液体对间甲酚的分离效果。实验得到的bmimOAc、bmimCl、emimOAc、TPAC四种离子液体-间甲酚-异丙苯的液液相平衡数据表明,四种离子液体对间甲酚均具有较大的分配系数和选择性,且萃取分离效果的顺序为：emimOAc > bmimOAc > TPAC > bmimCl,与COSMO-RS模拟筛选得到的结果一致,表明筛选具有较高的准确性。