汽液平衡计算与立方型状态方程

本文综述应用于汽液平衡计算的立方型状态方程的发展和研究动向。     

从液体混合物的粘度数据推算汽液平衡数据

<正>液体混合物的汽液平衡数据和粘度数据都是基本的物性数据,人们很早就开始了对它们的研究,并取得了不小的进展.对于汽液平衡的研究,人们提出了许多溶液理论和活度系数方程,例如Flory-Huggins方程,Van Laar方程,Margules方程,Wilson方程和其修正方程,NRTL方程以及UNIQUAC方程等;对于液体混合物的粘度,人们也提出了许多流体粘度理论,其中最著名的是Eyring反应速率理论.作者曾应用这一理论建立了一个新的液体混合物粘度方程,用于关联二元体系的粘度数据和推算多元体系的粘度数据,结果令人满意.     

乙腈+水+离子液体等压汽液平衡测定与计算

采用改进的Ellis平衡蒸馏仪测定了乙腈+水+1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM][DEP])、乙腈+水+{1-乙基-3-甲基咪唑醋酸盐([EMIM][OAC])+[EMIM][DEP]}常压(101.3 kPa)等压汽液平衡(VLE)数据。实验结果表明，备选离子液体可促进水+乙腈混合物的分离并消除其共沸点。借助NRTL模型成功关联了含离子液体的三元和四元VLE实验数据，获得了乙腈-[EMIM][DEP]、水-[EMIM][DEP]和[EMIM][OAC]-[EMIM][DEP]二元交互作用参数。应用COSMO-SAC预测了实验VLE，结果令人满意。量化计算表明可与水形成强相互作用的离子液体更易促进乙腈与水的分离。     

含离子液体液液平衡的UNIQUAC模拟

为了解决UNIQUAC模型在关联含离子液体液液平衡数据时,因离子液体的分子结构参数r和q不完全而使其应用受限的问题,文中采用量子化学法计算了近几年报道的液液平衡文献中涉及的8种离子液体的分子结构参数r和q。利用密度泛函理论优化离子液体的分子结构,得到离子液体的最优结构和最优能,然后采用极化连续介质模型计算最优分子结构的体积和表面积,进而得到离子液体分子结构的r和q值。使用含上述数值的UNIQUAC模型关联了20种含离子液体的三元体系在不同温度下的液液平衡数据,并计算出模型的预测值与实验值的均方根偏差,187个连结点数据的均方根偏差值平均为0.011 7。结果表明:计算的离子液体的r和q值用于UNIQUAC方程中能较好地关联三元体系液液平衡数据。     

用NRTL方程计算含离子液体体系的汽液平衡

离子液体作为环境友好溶剂在反应和分离过程中具有良好的应用前景,含离子液体体系汽液平衡的计算及模型化研究具有重要的理论和实际意义.采用非电解质溶液NRTL方程表示溶液的非理想性,关联了［bmim］［PF₆］H₂O及［C₈mim］［PF₆］H₂O二元体系的等温汽液平衡,关联误差在2%之内;预测了这些体系在其他温度下的汽液平衡,预测的总平均误差均在5%之内.通过关联不同温度下有机物在离子液体C₈H₁₄S₂O₄F₆N₃和C₉H₁₆S₂O₄F₆N₃中的无限稀释活度因子的实验数据,得到了有关NRTL方程的二元作用参数,在此基础上预测了离子液体对二元共沸体系汽液平衡的影响.结果表明,含离子液体体系的汽液平衡可以采用传统的非电解质溶液模型如NRTL方程来描述,离子液体的“盐效应”可以显著改善组分的相对挥发度甚至消除共沸现象.     

含硫酸氢盐离子液体的水+乙酸体系汽液平衡数据测定

为探究离子液体(ILs)作为催化剂对酯化反应精馏体系汽液平衡产生的影响,采用Dvorak-Boublik平衡釜测定了5种压力下水(1)+乙酸(2)二元体系的汽液平衡数据,并测定了不同压力和不同离子液体摩尔分数下的水(1)+乙酸(2)+1-磺酸丁基-2-甲基吡啶硫酸氢盐([HSO3-BMPy][HSO4])(3)三元体系的汽液平衡数据。通过COSMOlogic软件对[HSO3-BMPy][HSO4]几何结构进行优化,模拟获取屏蔽电荷密度图(σ-Profile)。结果表明,加入[HSO3-BMPy][HSO4]提高了二元体系的平衡温度,且对水的影响更大,减压使其平衡温度降低。[HSO3-BMPy][HSO4]易与水结合,使水与乙酸更难分离。测得的汽液平衡数据可为含[HSO3-BMPy][HSO4]体系的酯化反应精馏模拟计算提供热力学基础数据。     

含离子液体水-醋酸物系等压汽液平衡

在100 kPa下,用改进的Ellis双循环汽液平衡釜测定了含离子液体三乙基铵醋酸盐([N2,2,2,H][AC])质量分数分别为5%,10%,20%时水-醋酸体系的等压汽液平衡数据,并研究了离子液体对水-醋酸体系汽液平衡的影响。实验结果表明:当水-醋酸体系中[N2,2,2,H][AC]的质量分数为5%时水-醋酸二组分物系的汽液平衡线就开始偏离,但是偏离程度比较小;当[N2,2,2,H][AC]的质量分数增加为10%和20%时,偏离程度增大,[N2,2,2,H][AC]对水-醋酸体系表现出明显的盐效应,使水对醋酸的相对挥发度发生改变;随着离子液体[N2,2,2,H][AC]质量分数增大,水-醋酸体系的盐效应越明显,水对醋酸的相对挥发度也随着增加。[N2,2,2,H][AC]可以做为水-醋酸物系萃取精馏分离的有机盐,所测得的汽液平衡数据可为水-醋酸物系萃取精馏的工艺改进、模拟计算提供热力学基础数据。     

状态方程模拟醇胺系统的密度和汽液相平衡

通过考虑醇胺分子间的缔合作用,结合先前开发的非缔合变阱宽链流体状态方程(SWCF-VREOS)建立了一个缔合方阱链流体状态方程,并利用方程模拟了醇胺系统的密度和汽液相平衡。通过关联不同温度下醇胺的饱和蒸气压和液体体积得到了18种醇胺流体的分子参数,新方程计算的饱和蒸气压和液体密度总的平均误差分别为0.94%和0.88%。结合简单的混合规则,将此方程扩展到混合系统。研究发现,建立的方程可预测二元和三元醇胺混合物的密度。当引入一个与温度无关的可调参数时,方程能满意关联二元系统的汽液相平衡数据,并可进一步预测多元混合系统的汽液相平衡,预示着新方程可模拟醇胺系统的相行为。     

用状态方程同时描述烃醇体系的汽液平衡和混合热

研究了用ＰＲＳＶ状态方程及Ｗｏｎｇ－Ｓａｎｄｌｅｒ混合规则同时描述１０个烃醇体系的汽液平衡和混合热的可行性．将３个不同的Ｇ￣Ｅ模型（Ｗｉｌｓｏｎ、ＮＲＴＬ及由沈树宝等提出的模型）结合到ＰＲＳＶ状态方程中以资比较．由甲醇－正己烷的计算结果显示：不同的Ｇ￣Ｅ模型会得到不同的结果，在用活度系数法关联汽液平衡中合适的模型未必适用于与状态方程的结合．沈树宝等提出的Ｇ￣Ｅ模型结合到ＰＲＳＶ状态方程中的计算结果最优，将此结合模型推广到其它９个烃醇体系的汽液平衡及混合热同时关联计算，也获得了令人满意的结果．     

含离子液体乙腈-正丙醇体系的等压汽液平衡

常压(101.3 kPa)下, 测定了如下体系的汽液平衡数据:乙腈-正丙醇-氯化1-苄基-3-甲基咪唑([BzMIM][Cl])、乙腈-正丙醇-溴化1-苄基-3-甲基咪唑([BzMIM][Br])、乙腈-正丙醇-溴化1-己基-3-甲基咪唑([HMIM][Br]), 考察了3种离子液体对乙腈-正丙醇体系相平衡行为的影响。实验结果表明, 3种离子液体都能够提高乙腈对正丙醇的相对挥发度, 3种离子液体提高相对挥发度的顺序为 [BzMIM][Cl] > [BzMIM][Br] > [HMIM][Br]。用NRTL模型对测得的汽液平衡数据进行了关联, 关联结果与实验结果具有良好的一致性。     

用变阱宽方阱链流体状态方程模拟离子液体相行为

An equation of state (EOS) for square-well chain fluids with variable range (SWCF-VR) developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature (pVT) and phase equilibrium of pure ionic liquids (ILs) and their mixtures. The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges. The molecular parameters of ILs composed of homologous organic cation and an identical anion such as [Cxmim][NTf2] are good linear with respect to their molecular weight, indicating that the molecular pa-rameters of homologous substances, subsequently pVT and vapor-liquid equilibria vapor-liquid equilibria (VLE) can be predicted using the generalized parameter when no experimental data were available. The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one tem-perature-independent binary interaction parameter.     

A GE/Equation of State Mixing Rule for Vapor-Liquid Equilibria

A new excess Gibbs free energy/equation of state type mixing 0rule was derived byremoving the infinite pressure boundary condition imposed by Wong and Sandler.The mixing rulewas extensively tested in terms of a comprehensive data base,consisting of 52 simple nonpolar-nonpolar,carbon dioxide containing,hydrocarbon-hydrocarbon,CFC,polar-polar,nonpolar-polarbinary and multicomponent systems.Focused on the complete predictive capability,a comparisonbetween the Wong-Sandler and the mixing rule proposed was conducted.The results indicate that thenew mixing rule is in general superior to the Wong-Sandler's,and the binary interaction parameteras required by the latter is removed,which reduces computing effort and is reliable in predictions ofvapor-liquid equilibria from low pressures to high pressures.     

A GE/Equation of State Mixing Rule for Vapor-Liquid Equilibria

A new excess Gibbs free energy/equation of state type mixing 0rule was derived by removing the infinite pressure boundary condition imposed by Wong and Sandler. The mixing rule was extensively tested in terms of a comprehensive data base, consisting of 52 simple nonpolar-nonpolar, carbon dioxide containing, hydrocarbon-hydrocarbon, CFC, polar-polar, nonpolar- polar binary and multicomponent systems. Focused on the complete predictive capability, a comparison between the Wong-Sandler and the mixing rule proposed was conducted. The results indicate that the new mixing rule is in general superior to the Wong -Sandler’s, and the binary interaction parameter as required by the latter is removed, which reduces computing effort and is reliable in predictions of vapor-liquid equilibria from low pressures to high pressures.     

用修正的UNIFAC模型参数及HVOS规则预测汽液平衡

利用Orbey和Sandler提出的HVOS混合规则,PR状态方程与Larsen的活度系数模型相结合建立了无限压力下汽液平衡模型,模型给定状态方程中不随温度变化的参数C*=-0.623 23。用大量的汽液平衡数据在广泛的温度范围内修正了12组MLUNIFAC基团相互作用参数,并用修正的和原始的参数分别对含醇、酸、酮、水、腈和胺等极性二元体系进行了预测。结果表明,体系预测精度显著提高,大部分体系汽相组成的绝对偏差低于4.00×10-2,压力的相对偏差低于6.00%。     

水-乙醇-1-丁基-3-甲基咪唑乙酸盐三元体系汽液平衡测定及模型

Vapor-liquid equilibrium (VLE) data were measured for ternary system water + ethanol + 1-butyl-3- methylimidazolium acetate ([bmim][OAc]), in a relatively wide range of ionic liquid (IL) mass fractions up to 0.8. Six sets of complete T-x-y data were obtained, in which the mole fraction of ethanol on IL-free basis was fixed separately at 0.1, 0.2, 0.4, 0.6, 0.8, and approximate 0.98. The non-random-two-liquid (NRTL) and electrolyte non-random-two-liquid (eNRTL) equations were used for correlation, showing similar deviations. The ternary VLE was also modeled with the correlation from two data sets, with the mole fractions of ethanol on IL-free basis being 0.1 and approximate 0.98. The VLE data were also reproduced satisfactorily. With the eNRTL model, the root-mean-square deviation for temperature is 0.79 K and that for vapor-phase mole fraction is 0.0094. The calculations are in good agreement with experimental data. The effect of the IL on the VLE behavior of the volatile components is also illustrated.     

费托合成反应体系的气液平衡研究进展

对费托合成反应体系的气液平衡研究进展进行了归纳和分析,对该体系的物质进行了分类,讨论了不同计算方法的适用性和计算准确性. 可将体系划分为烃类产物和小分子气体两部分,烃类产物又可分为C18以下的轻质烃类和C18以上的重质烃类. 在兼顾计算准确性和简单性的前提下,C18及以下的轻质烃类的气液平衡可采用Raoult定律计算,重质烃类由于存在扩散限制作用,其气液平衡可通过状态方程计算,PR方程计算结果准确性较高. 小分子气体的溶解平衡计算较多应用Henry定律法和状态方程法,Henry定律法计算过程较简单且准确性较高.     

离子液体的合成及在分离中的应用

采用两步法合成了三种离子液体[CH2CH2OHMIM][BF4]、[CH2COOHMIM][BF4]、[CH2COOCH3MIM][BF4],并用新的双循环沸点仪测定了乙醇-水-ILs的汽液平衡。实验表明：三种离子液体均能消除乙醇-水的共沸点。     

应用PSRK状态方程预测高压汽液平衡

为预测高压汽液平衡,将过量吉布斯自由能混合规则和UNIFAC活度系数模型与SRK状态方程相结合,建立基团贡献状态方程PSRK。利用该状态方程对5个体系在不同压力和温度下的汽液平衡数据进行了关联实验测定的汽相压力和汽相组成与计算结果相比所得的相对平均偏差分别为2．16％和1．01％。结果表明,PSRK状态方程可以成功地预测高压下汽液平衡,其精度高于MHV1和MHV2模型。     

Measurement of Isoplethic Vapor-Liquid Equilibrium Data by Using Inclined Ebulliometer

Isoplethic VLE data for the systems benzene-hexane at 9 different compositions in the temperature range from 298K to 331K, chloroform-benzene at 11 different compositions in the temperatuge range from 308K to 350K and chloroform-hexane at 9 different compomtions in the temperatuge range faxnn 311K to 337K were determined by using an inclined ebulHometer with a pump-like stirrer. Isothermal and isobaric VLE were cak-ulated from the isoplethic results with a extended UNIQUAC equation and these date agree well with the literature data.