叔丁醇-异丙醇-水汽液平衡数据的测定及关联

采用单级循环汽液平衡釜测定常压下叔丁醇、异丙醇和水体系中的二元和三元的汽液平衡数据,并对其进行微分检验法热力学一致性校验;分别以WILSON,NRTL,UNIQUAC方程为相平衡模型,采用最小方差法对二元体系数据进行关联,确定模型参数;采用3对二元体系模型参数对三元体系的汽液平衡数据进行关联,比较汽液平衡数据的测定值与计算值,确定适宜的相平衡模型。文中为萃取精馏分离叔丁醇、异丙醇和水的混合液提供基础数据。     

醋酸甲酯-甲醇-水-醋酸四元体系液液相平衡数据的测定与关联

为获得提高醋酸甲酯催化精馏的水解转化率所需的基础数据,实验在常压下测定了20,30,40,50℃时醋酸甲酯-水-醋酸三元体系和醋酸甲酯-甲醇-水-醋酸四元体系的液液相平衡数据,用NRTL和UNIQUAC模型对所测的数据进行热力学关联,应用单纯形法得出相应的模型参数。四元体系的计算值与实验值比较结果表明:NRTL与UNIQUAC模型的计算值与实验数据吻合良好,模型计算的总平均绝对误差分别为0.001142和0.001329,总平均相对误差分别为3.025%和3.839%。     

常压下丙酮-异丙醇-水体系汽液平衡测定与关联

采用单级循环汽液平衡装置测定了常压下丙酮-异丙醇-水体系中丙酮-异丙醇、丙酮-水、异丙醇-水二元及丙酮-异丙醇-水三元体系的汽液平衡数据,采用Herington方法对二元汽液平衡数据进行热力学一致性检验。分别以Wilson,NRTL及UNIQUAC为相平衡模型,采用最小方差法对二元汽液平衡数据进行关联,由关联的3对二元体系模型参数计算三元体系的汽液平衡数据,并与实验值进行比较。结果表明:计算值与实验值的相对偏差均≤5%,说明实验值与计算值一致,其中UNIQUAC模型误差较小。该结果为丙酮-异丙醇-水混合物的分离提供了一定基础数据。     

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。     

四氢呋喃-水-正己烷体系等压汽液平衡研究

用改进Rose釜测定了100 kPa下四氢呋喃-水、四氢呋喃-正己烷、四氢呋喃-水-正己烷体系(互溶区域)的等压汽液平衡数据。汽相非理想性通过逸度系数的计算进行校正,液相非理想性归结到活度系数中予以校正。用非线性最小二乘法关联了二元体系的汽液平衡数据,得到NRTL/UNIQUAC模型参数。利用得到的二元模型参数,结合部分三元汽液平衡数据,关联得到水-正己烷体系的模型参数。由关联得到的3对二元模型参数预测另一部分的三元汽液平衡数据,实验值与预测值基本吻合。     

甲酸-水-甲酸丁酯体系的等压汽液相平衡研究

用改进的Rose釜测定了101.33 kPa下甲酸-水、甲酸-甲酸丁酯、甲酸-水-甲酸丁酯(互溶区内)的等压汽液相平衡数据。考虑了甲酸在汽相中的缔合效应和非理想性,用Hayden-O’connell关联式修正了汽相的非理想性,用NRTL模型对甲酸-水和甲酸-甲酸丁酯体系的汽液平衡数据进行了关联,得到了相应的模型参数。利用得到的二元体系模型参数,结合部分三元体系汽液平衡数据,关联得到水-甲酸丁酯体系的模型参数。由关联得到的3对二元NRTL模型参数预测三元体系汽液平衡数据,温度平均偏差为1.20℃,甲酸的汽相平均偏差为0.0152,甲酸丁酯的汽相平均偏差为0.0184,实验值与预测值基本吻合。     

水-乙醇-甲基异丁基甲酮体系液液相平衡数据的测定与关联

在常压下测定了水-乙醇-甲基异丁基甲酮体系在308.15,318.15,328.15 K的液液相平衡数据。用Hand方程和Othmer-Tobias方程对实验数据进行拟合,结果表明:Hand方程拟合效果优于Othmer-Tobias方程。采用NRTL模型和UNIQUAC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;并对此物系的相平衡数据进行了预测,由模型计算值和实验值的均方根偏差知,NRTL模型能更好地与实验数据吻合。     

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。     

甲酸-水-甲酸戊酯体系的等压汽液平衡研究

用改进的Rose釜测定了101.325 kPa下甲酸-水、甲酸-甲酸戊酯、甲酸-水-甲酸戊酯体系的等压汽液平衡数据.考虑到甲酸在汽相中的缔合效应,用Hayden-O'connell关联式修正了汽相的非理想性,用非线性最小二乘法关联了甲酸-水和甲酸-甲酸戊酯体系的汽液平衡数据,获得了NRTL和UNIQUAC方程的模型参数.利用得到的二元体系NRTL模型参数,结合部分三元体系汽液平衡数据,关联得到水-甲酸戊酯体系的NRTL模型参数.由关联得到的三对二元NRTL模型参数预测部分三元体系汽液平衡数据,计算值与实验值基本吻合.     

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.     

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.     

Application of UNIFAC models for prediction of vapor-liquid and liquid-liquid equilibria relevant to separation and purification processes of crude biodiesel fuel

Vapor-liquid equilibrium (VLE) of the methanol-biodiesel (BDF)/glycerin binary system and liquid-liquid equilibrium (LLE) of the water-BDF binary system and the methanol-BDF-glycerin and methanol-water-BDF ternary systems were predicted using several UNIFAC models: the latest original UNIFAC model, Kikic’s model, Fornari’s model, Dortmund-UNIFAC model, and LLE-UNIFAC model. The former VLE and latter LLE are used to design methanol recovery processes and separation and purification processes of crude BDF, respectively. Unfortunately, LLE data on the water-BDF binary system was not available. Instead, solubility of water in fatty acid methyl ester (one of the BDF constituents) was measured. By examining the deviation between predicted and experimental results, we determined which of the UNIFAC models was more useful for the design of those processes as follows: either the original UNIFAC model or Dortmund-UNIFAC model should be used for the methanol recovery process. The LLE-UNIFAC model and Dortmund-UNIFAC model were more useful for the recovery and water-washing processes of crude BDF and purification process of water-washed BDF, respectively.     

Thermodynamics and separation process for quaternary acrylic systems

Vapor‐liquid equilibrium (VLE) and liquid‐liquid equilibrium (LLE) data of binary and ternary acrylic systems were systematically measured. Subsequently, VLLE phase diagrams of binary systems, tridimensional VLE phase diagrams of methyl acrylate (MA)‐methanol (Me)‐H₂O ternary system, and quaternary LLE phase diagrams of MA‐Me‐H₂O‐methyl acetate (MeOAc) system were constructed. These diagrams clearly demonstrated the effects of temperature on phase equilibrium. The experimental data was fitted by the NRTL and UNIQUAC models, and the best‐fitted parameters were used to predict interaction properties of ternary and quaternary mixture. Therefore, the phase equilibrium data were provided as reference for the design of acrylic systems rectification or extraction process. Residue curve was mapped out for MA‐Me‐H₂O system through Aspen plus software. Finally, using thermodynamics and residue curve as theoretical basis, two novel separation processes were proposed and applied to the quaternary acrylic systems. © 2015 American Institute of Chemical Engineers AIChE J, 62: 228–240, 2016     

甲苯-正己烯-二甲基亚砜液-液平衡数据的测定与关联

裂解汽油是含有烯烃的重要芳烃资源,二甲基亚砜(DMSO)能够从高烯烃含量组分中选择性萃取芳烃,测定相应体系液-液平衡是裂解汽油中的芳烃萃取过程研究开发的理论基础。测定了常压下293.15、298.15、303.15 K时甲苯-正己烯-DMSO体系液-液平衡数据,获得了三元体系的相图和褶点,并采用Hand方程和NRTL方程进行关联。体系中甲苯对正己烯选择性系数为2～6,表明DMSO萃取分离甲苯和正己烯理论上可行。通过体系液-液平衡关联获得了NRTL方程模型参数,利用NRTL模型对该体系进行计算,计算值与实验值的平均偏差较小,说明NRTL模型适用于该体系的液-液平衡。     

Measurement and correlation of liquid-liquid equilibrium for the ternary system (water + 1,2-dichloroethane + sulfolane) at 288.15, 298.15, and 308.15 K

Sulfolane is an important aprotic polar solvent. Liquid-liquid equilibrium(LLE) data for the ternary systems of water + 1,2-dichloroethane + sulfolane were measured at temperatures of 288.15, 298.15 and 308.15 K under the atmospheric pressure. The distribution coefficient and selectivity were determined from the measured LLE data, which showed that 1,2-dichloroethane is a suitable extractant for the recovery of sulfolane from its aqueous solution. The nonrandom two-liquid(NRTL) model and the uni...     

Measurement and correlation of phase equilibrium data of the mixtures consisting of water,resorcinol, mesityl oxide at different temperatures

Liquid-liquid equilibrium (LLE) data were measured for the ternary system of water+resorcinol+mesityl oxide under atmospheric pressure at temperatures of (298.2, 323.2, 333.2, 343.2 and 353.2) K. The reliability of the experimental data was verified by the Hand and Bachman equations. The distribution coefficient and selectivity were calculated from the experimental LLE data, which showed high efficiency of mesityl oxide extracting resorcinol from the aqueous solution. The NRTL and UNIQUAC models were employed to fit the measured experimental LLE data and yield corresponding binary interaction parameters.     

DETERMINATION,CORRELATION AND PREDICTION OF LIQUID-LIQUID EQUILIBRIUM DATA OF n-BUTYL ALCOHOL-WATER-BUTYL ACETATE TERNARY SYSTEM

Liquid-liquid equilibrium(LLE)data have been determined for the n-butyl alcohol-water-butyl acetateternary system and the related binary systems at 293.15,303.15 and 313.15 K.The experimentally determinedLLE data for the n-butyl alcohol-water binary system have been found to be in satisfactory agreementwith the available literature data.The correlation and prediction of the LLE data have been done byusing NRTL and UNIQUAC models.The model parameters of binary systems have been identified witha thermodynamic criterion.In the correlation of ternary LLE data,two objective functions(mole fractionand distribution constant)have been used for purpose of comparison.The effect of weighting in the firstobjective function has been examined.In predicting the ternary LLE with different sets of parameter valuesobtained for each of the constitutent binary systems,improved prediction results have been obtained bycomparing the results of different combinations of the sets of parameter values and choosing those givingthe best result.     

丙烯酸正丁酯-正丁醇-水体系汽-液、液-液相平衡研究

测定了丙烯酸正丁酯-水、正丁醇-水二元系在常压下的液-液平衡数据及200×1.333×10~2Pa下的丙烯酸正丁酯-正丁醇二元系和丙烯酸正丁酯-正丁醇-水三元系的汽-液平衡数据。由测定的三对二元数据求取了NRTL常数,并与三元实验数据进行拟合,计算值与实验值符合良好,从而使液-液平衡与汽-液平衡得到了统一的关联。     

甲基戊烯酮-水-邻苯二酚三元物系液液相平衡数据的测定与关联

为了给甲基戊烯酮萃取脱酚过程的设计和开发提供数据支撑,采用液液平衡釜分别测出常压下30、40和50℃甲基戊烯酮-水-邻苯二酚体系的液液相平衡组成,并通过Hand方程、Bachman方程对结果进行可靠性检验,其相关性系数的平方均大于0.99。同时利用Aspen Plus软件选取NRTL模型对实验数据进行关联,得到该三元物系相应的热力学模型参数,并以此计算相应的相平衡组成,与实验数据对比两者间的相对均方根误差和绝对平均误差均为1%。因此,NRTL模型及其参数可准确描述该物系的相平衡行为。