乙醇-水-复合溶剂体系汽液平衡

用改进的Othmer汽液平衡釜测定了101 3kPa下乙醇-水-复合溶剂6个体系在不同溶剂比下的汽液平衡数据,6种复合溶剂为:乙二醇+氯化锂,乙二醇+氯化钙,乙二醇+醋酸钾,乙二醇+氯化锂+氢氧化钾,乙二醇+氯化钙+氢氧化钾,乙二醇+醋酸钾+氢氧化钾。并用Wilson模型和NRTL模型对实验数据进行了关联,结果良好,大部分体系汽相组成平均偏差小于0 02,泡点温度平均偏差小于1K。     

乙二醇-1,4-丁二醇二元物系6.67kPa下汽液平衡研究

煤制乙二醇过程中产生的副产物1,4-丁二醇对获得高纯度的乙二醇有着重要影响。采用真空精馏方法分离提纯,进行设计计算时,需要乙二醇-1,4-丁二醇汽液平衡数据。为此在6.67 k Pa压力下测定了乙二醇-1,4-丁二醇的汽液相平衡数据,并进行了热力学一致性检验,结果表明实验数据符合热力学一致性。分别用Wilson和NRTL模型对实验数据进行关联,发现两个模型误差都不大,均可满足工程设计的需要。     

20 kPa下己酸+乙酸/乙酸丁酯/环己酮/ε-己内酯体系汽液平衡的测定与关联

在20 kPa下,用Rose汽液平衡釜测定己酸+乙酸、己酸+乙酸丁酯、己酸+环己酮、己酸+ε-己内酯,4个体系的二元汽液平衡数据,采用Herington面积积分法对汽液平衡数据进行热力学一致性检验,结果显示所有的实验数据均符合热力学一致性。采用NRTL和Wilson活度系数模型对4个二元实验数据进行关联,得到4个二元交互参数。将模型模拟的计算值与实验值进行比较,结果表明Wilson活度系数模型更适用于该4个组分体系的汽液平衡计算。     

丙酮-乙酸异丙烯酯二元体系常压汽液平衡

用改进的埃利斯(Ellis)平衡蒸馏器测定了丙酮-乙酸异丙烯酯二元系统在常压下的汽液平衡数据,用液相活度模型Wilson、NRTL方程对测定数据进行关联,采用非线性最小二乘法回归出二元系统在常压下的Wilson、NRTL方程参数,Wilson模型与试验值符合良好.汽液相平衡数据经Herrington面积法检验满足热力学一致性.     

碳酸二甲酯-甲醇-乙二醇等压汽液平衡的测定与关联

为验证乙二醇作为萃取精馏分离碳酸二甲酯+甲醇共沸体系萃取剂的可行性,在100 k Pa下,采用改进的Othmer釜测定了(碳酸二甲酯-甲醇-乙二醇)3组分物系的等压汽液平衡数据。实验结果表明,乙二醇萃取剂的加入,碳酸二甲酯对甲醇的相对挥发度增加,体系的汽液平衡温度升高。碳酸二甲酯+甲醇二组分物系的汽液平衡线发生偏离;乙二醇摩尔分数越大,偏离程度越大。用NRTL模型对汽液平衡的实验数据进行了关联,碳酸二甲酯-甲醇-乙二醇三组分物系温度实验值与计算值的标准偏差为0.82 K。     

Measurement and correlation of VLE data for α-pinene + limonene and p-cymene + limonene systems under atmospheric pressure

利用改进的Ellis平衡釜测定了α-蒎烯+柠檬烯和对伞花烃+柠檬烯两个二元体系在100.7 kPa条件下的汽液平衡数据, 所测数据符合热力学一致性。以压力为目标函数使用最小二乘法拟合了Liebermann-Fried、Wilson、NRTL、UNIQUAC模型能量参数, 并将4个溶液模型的汽液平衡计算结果与UNIFAC模型的计算结果做比较。结果显示Liebermann-Fried模型对等压汽液平衡数据的拟合效果较精确。     

α-蒎烯+柠檬烯和对伞花烃+柠檬烯体系常压汽液平衡的测定与关联

利用改进的Ellis平衡釜测定了α-蒎烯+柠檬烯和对伞花烃+柠檬烯两个二元体系在100.7 kPa条件下的汽液平衡数据, 所测数据符合热力学一致性。以压力为目标函数使用最小二乘法拟合了Liebermann-Fried、Wilson、NRTL、UNIQUAC模型能量参数, 并将4个溶液模型的汽液平衡计算结果与UNIFAC模型的计算结果做比较。结果显示Liebermann-Fried模型对等压汽液平衡数据的拟合效果较精确。     

乙苯+甲苯和乙苯+正丙醇二元体系汽液平衡

采用改进的Rose-William汽液平衡釜测定了二元体系乙苯+甲苯和乙苯+正丙醇在101.3k Pa下的汽液平衡数据。使用Herington方法对实验数据进行检验,两组数据均通过热力学一致性检验。利用NRTL,Wilson和UNIQUAC活度系数模型进行关联,并获取二元交互作用参数。结果表明UNIQUAC模型为最佳拟合模型。本文为精馏设计提供了基础数据。     

2kPa下γ-丁内酯-二乙二醇二元系汽液平衡研究

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。     

乙酸异戊酯+异戊醇和乙酸异戊酯+正己醇体系汽液平衡

在50.00和101.33 kPa下,采用改进的Rose汽液平衡釜测量乙酸异戊酯+异戊醇和乙酸异戊酯+正己醇体系的汽液平衡数据。乙酸异戊酯+异戊醇在50.00 kPa下形成最低共沸物。使用Herington法对汽液平衡数据进行热力学一次性检验,结果表明测得的汽液平衡数据符合热力学一致性。对实验数据使用NRTL、Wilson和UNIQUAC活度系数模型进行关联,回归获得相应的二元交互参数,模型计算的温度和组成与实验值相比均方差小于0.20 K和0.0050,表明3种模型的拟合结果与实验数据吻合较好。通过Wilson模型预测乙酸异戊酯+异戊醇体系在98.4 kPa时共沸点消失。为化工数据库增添了内容,为乙酸异戊酯体系的工程设计和进一步深入研究奠定了基础。     

基于UNIFAC模型的基团-OCOO-与-CH3,ACH,CH3OH和CH3COO-的交互作用参数估算与验证

Isobaric vapor-liquid equilibria (VLE) are experimentally measured for the binary systems of dimethyl carbonate (DMC) ethylene carbonate and methanol ethylene carbonate at 101.325kPa. The thermodynamic consistency of these experimental data is tested with an available statistic method. Interaction parameters of the carbonate group —OCOO— with the group —CH3, ACH, CH3OH and CHACO0— in UNIFAC model are determined using the experimental and literature VLE data. The results show that the calculated VLE data using the new UNIFAG parameters agree excellently with the experimental data in this work and in literature. These results are useful in the research on DMG and diphenyl carbonate synthesis by transesterification in design of reactor and distillation tower.     

聚合物溶液汽液相平衡测定及关联

建立了一套用差压法测定聚合物溶液汽液相平衡数据的实验装置．用乙醇纯溶剂及聚苯乙烯／甲苯溶液作为标准体系,对实验装置进行了校核．在温度范围为303.15K～333.15K及常压下,用本实验装置测定了4种聚合物（聚苯乙烯,聚氯乙烯,聚乙二醇,聚甲基丙烯酸甲酯）+6种溶剂（间-二甲苯,水,氯仿,乙酸乙酯,2-丁酮,环己酮）的14个二元体系汽液平衡数据,用简化空穴理论状态方程对实验数据进行了关联．     

Phase behavior measurement for the ethylene glycol dimethacrylate in supercritical carbon dioxide at temperatures between (313.2 and 393.2) K and pressures from (5.8 to 22) MPa

High pressure experimental data are presented on the phase equilibrium of ethylene glycol dimethacrylate in supercritical carbon dioxide. Pressure-composition (P-x) isotherms were measured in static method at five temperatures of (313.2, 333.2, 353.2, 373.2 and 393.2) K and at pressures up to 22.0MPa. This (carbon dioxide+ethylene glycol dimethacrylate) system has continuous critical mixture curves that exhibit maximums in pressure at temperatures between the critical temperatures of carbon dioxide and ethylene glycol dimethacrylate. At a fixed pressure, the solubility of ethylene glycol dimethacrylate for the (carbon dioxide+ethylene glycol dimethacrylate) system increases with increasing temperature. The (carbon dioxide+ethylene glycol dimethacrylate) system exhibits type-I phase behavior. The experimental result for the (carbon dioxide+ethylene glycol dimethacrylate) system is correlated with Peng-Robinson equation of state using mixing rule including two adjustable parameters. The critical property of ethylene glycol dimethacrylate is predicted with Joback and Lee-Kesler method.     

Isobaric vapor–liquid equilibrium for ternary system of ethanol,ethyl propionate and para-xylene at 101.3 kPa

Isobaric vapor–liquid equilibrium(VLE) data for the binary system ethyl propionate(2) + para-xylene(3) and ternary system ethanol(1) + ethyl propionate(2) + para-xylene(2) at atmospheric pressure(101.3 k Pa)were obtained by a VLE modified othmer still. All the experimental data passed a point to point consistency test of Van Ness method, which verified the data reliability. The Wilson and UNIQUAC activity coefficient models were employed to correlate the binary VLE data to obtain binary interaction parameters. Based on binary interaction parameters, ternary VLE data of ethanol(1) + ethyl propionate(2) + para-xylene(3) were predicted by Wilson and UNIQUAC models, which proved that predicted values are consistent with the experimental data.Furthermore, azeotropic phenomenon between ethanol and ethyl propionate disappears when the mole ratio of para-xylene and binary system of ethanol and ethyl propionate is 1:1. Therefore, this paper convinced that para-xylene is a proper extractive additive that could be used in extractive distillation to separate the binary azeotropic system of ethanol and ethyl propionate.     

正戊醇、正己醇与二甘醇二元体系汽液相平衡测定

以双循环平衡釜测定了120×1.333×10~2Pa下正戊醇-二甘醇和正己醇-二甘醇二元体系的汽液相平衡组成,数据用微分法检验其热力学一致性,并以常用活度系数方程作了关联。     

Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: Applicability of an extended flory–huggins equation

For some binary systems, an extended Flory–Huggins equation is applicable to both vaporliquid equilibria (VLE) and liquid–liquid equilibria (LLE) using the same adjustable parameters. New LLE and VLE data are reported for polystyrene (PS) (MW = 100,000)/cyclohexane and for poly(ethylene glycol) (PEG) (MW = 8,000)/water. Experimental results for the PS/cyclohexane system agree well with the semiempirical model, whereas those for PEG/water do not, probably because, for PEG/water, the temperature range of the VLE data is about 55°C lower than that of the LLE data. Excellent fits were obtained for our previously published experimental results for PS/cyclohexane (upper critical solution temperature, UCST), PS/ethyl acetate (lower critical solution temperature, LCST), PS/tert-butyl acetate and PS/methyl acetate (both UCST and LCST), and PEG/water (closed-loop). The semiempirical model also fits well with new data obtained for the polymer blend PS/poly(vinyl methyl ether). © 1993 John Wiley & Sons, Inc.     

挥发性强电解质混合溶剂体系的汽液平衡研究

本文报导了101.3 kPa下HCL+H_2O+CH_3aOH体系汽液平衡的实测结果。在对H_2O+CH_3OH混合溶剂中HCI的电离情况进行研讨,并求得HCl在该混合溶剂中亨利常数的基础上,从二元体系的性质出发,用笔者扩展的Pitzer(1980年)模型预测了HCl+H_2O+CH_3OH体系的汽液平衡,得到与实测数据极为一致的结果。     

Liquid–liquid equilibria of ternary mixtures of methanol + MEG + n-C5, ethanol + MEG + n-C5, and n-butanol + MEG + n-C5

New liquid–liquid equilibrium data of ternary systems of mono ethylene glycol + n-pentane + methanol, mono-ethylene glycol (MEG) + n-pentane + ethanol, and mono ethylene glycol + n-pentane + n-butanol from 283.15 to 293 K are presented in this work. Binodal curves were obtained by the cloud point titration method. Tie-line compositions were obtained through density and sound velocity measurements of phases in equilibrium. Results show that the solubility increases with temperature in all systems and decreases as the alcohol chain increases. The relative solubility data indicate that the alcohols are more soluble in MEG than in n-C5. The obtained experimental data were successfully correlated using the CPA and the PC-SAFT equation with appropriate binary interaction parameters.     

α-蒎烯+β-蒎烯+对伞花烃常压汽液平衡测定与关联

采用改进的Ellis平衡釜测定了在常压(100.7 kPa)下三个二元物系α-蒎烯＋β-蒎烯(428.82 K ~ 438.13 K)，α-蒎烯＋对伞花烃(429.05 K ~ 447.15 K)，β-蒎烯＋对伞花烃(439.20 K ~ 448.66 K)和一个三元物系α-蒎烯＋β-蒎烯＋对伞花烃(432.17 K ~ 448.11 K)的汽液相平衡数据,并利用Herington规则，以积分检验法对实验数据进行了热力学一致性检验。选用Wilson、NRTL、UNIQUAC和UNIFAC活度系数方程进行关联和估算，用最小二乘法求出二元物系的最佳配偶液相活度系数模型的能量参数，并比较了汽相组成的计算值与实验值，其平均相对偏差均小于0.40 %。将得到的最佳Wilson二元模型参数直接用于该体系三元体系汽液相平衡数据的预测，计算的平衡温度与实验测得的平衡温度平均偏差为0.16 K。     

Experimental Measurements and Correlations Isobaric Vapor-Liquid Equilibria for Water + Acetic Acid + Sec-butyl Acetate at 101.3 kPa

Isobaric vapor-liquid equilibrium(VLE) data for acetic acid+sec-butyl acetate and water+acetic acid+sec-butyl acetate systems were determined at 101.3 kPa using a modified Rose type. The nonideality of the vapor phase caused by the association of the acetic acid was corrected by the chemical theory and Hayden-O’Connell method. Thermodynamic consistency was tested for the binary VLE data. The experimental data were correlated successfully with the Non-Random Two Liquids (NRTL) model. The Root Mean Square Deviation (RMSD) of the ternary system was 0.0038. The saturation vapor pressure of sec-butyl acetate at 329 to 385 K was measured by means of two connected equilibrium cells. The vapor pressures of water and sec-butyl acetate were correlated with the Antoine equation. The binary interaction parameters and the ternary VLE data were obtained from this work.