丙烯腈、己二腈和丙腈与水的二元体系液-液相平衡数据的测定和关联(英文)

采用平衡法测定了丙烯腈+水、己二腈+水、丙腈+水三个二元体系在不同温度(303.15、313.15、323.15、333.15K)下的液-液相平衡数据;并采用NRTL(α=0.2,α=0.3)模型和UNIQUAC模型对液-液平衡数据进行了关联.结果显示,NRTL和UNIQUAC模型对三个二元体系在不同温度下的互溶度关联的目标函数值均小于1×10-17,实验值与计算值吻合较好,绝对偏差小于0.009,关联精度较高.该研究结果可为丙烯腈、丙腈和水三元平衡溶解度数据的模拟和预测提供可靠的基础数据,并对电解二聚法生产己二腈中电解液的分离提纯工艺具有一定的指导意义.     

甲酸-乙酸-水-醋酸钠体系汽液平衡的盐效应

采用Otsuki-Williams式汽液平衡釜测定了甲酸-乙酸-水-醋酸钠体系在9.866×10⁴Pa下汽液平衡数据。醋酸钠的加入量为2mol/(kg溶剂)。结果表明:醋酸钠对体系起物理化学作用,也起化学作用。它涉及到了两种盐对各组分的盐溶、盐析和盐效应的不规则现象。根据实验数据,绘制了汽液平衡相图、各组分挥发度等于1的曲线和甲酸-乙酸在体系中相对挥发度等于1的曲线,用以判别、分析盐效应的作用。     

甲酸-乙酸-水-氯化钙体系汽液平衡盐效应的研究

本文采用Otsuki-Williams式汽液平衡釜测定了甲酸-乙酸-水体系及甲酸-乙酸-水-氯化钙体系在98658.28Pa下汽液平衡数据。氯化钙的加入量为0.5mol/(kg溶剂)。结合盐效应的作用情况,对相图进行了分析。研究结果表明:氯化钙的加入对体系起了物理化学作用,它与盐溶、盐析现象有关。     

苯—正庚烷—乙醇三元体系加压汽液平衡的研究

用双循环武加压汽液平衡装置测定了苯-正庚烷-乙醇三元体系在101.3、302.5、506.8、709.3、810.6 kPa下的汽液平衡数据。根据有关二元体系在对应压力下的汽液平衡数据所求得的能量配偶参数,对该体系的汽液平衡进行了预测,计算值与实验值符合良好。     

硫酸锂-乙醇-水体系的溶解度和汽-液平衡的研究

系统地研究了Li₂SO₄-C₂H₅OH-H₂O体系的相关系和汽-液平衡,分别测定了-20℃,0℃,25℃,30℃和50℃时的平衡溶解度。提出了一个经验公式,关联不同温度下的溶解度,相对误差<2%。用盐和溶剂间的相互作用解释了盐对乙醇-水体系粘度和密度的影响。同时对该体系在25℃和580mmHg等压下的汽一液平衡结果,采用判别乙醇和水的汽相携尔分数之和是否大于1的方法,计算平衡温度和汽相组成。该方法新颖合理。25℃时等温蒸气压的计算值与实验值一致,恒压下活度系数值与的实验值吻合。     

二氧化碳和碳酸二甲酯二元体系的气液相平衡数据

实验测定了二氧化碳和碳酸二甲酯(DMC)二元体系的高压气液相平衡数据. 实验温度为333.0 到393.0 K, 实验压力为3.98 到13.75 MPa. 应用Peng-Robison (PR)立方形状态方程和van der Waals-1 混合规则对实验数据进行了关联计算, 同时得到了二元相互作用参数. 计算结果与实验数据具有很好的一致性.     

糠醛水溶液的液-液萃取分离

糠醛是重要的化工溶剂和中间体,传统生产过程流程复杂[1],能耗高。近年已提出用不同溶剂萃取分离糠醛和水[2]。本文在前文基础上[3]选择醋酸丁酯为萃取剂测定糖醛-水-醋酸丁酯体系的LLE数据,由二组二元体系和三元体系液液平衡数据确定UNIQUAC模型中三对模型参数,并采用UNIQUAC模型模拟计算糖醛水溶液萃取分离结果,以便为错流和逆流萃取试验提供依据。1　实验部分糠醛水溶液和醋酸丁酯加入液液平衡釜[4],磁力搅拌器搅拌30分钟,待温度稳定后,静置40分钟,取上相和下相分析。平衡釜采用CS501型超级恒温水浴控温,平衡结果由SP-6800…     

若干酮－醇体系的汽液平衡

本文用流动汽液平衡釜测定了①戊酮－３－正丙醇③丁酮－戊醇－１两个体系三个温度下的等温汽液平衡数据，三个温度下的数据均通过热力学一致性检验，并用Ｗｉｌｓｏｎ方程和ＵＮＩ－ＱＵＡＣ方程对数据进行了关联，平均汽相偏差小于０．０１，精度令人满意。     

甲酸—乙酸—水—氯化镁体系汽液平衡中的盐效应

采用Otsuiki-Williams式汽液平衡仪在9.866×10~4Pa下测定了甲酸-水、乙酸-水、甲酸-乙酸、甲酸-乙酸-水体系无盐和加氯化镁后各体系的汽液平衡数据,绘制了两组分和三组分体系相图。相图表明氯化镁有明显的盐效应。     

若干酮—醇体系的汽液平衡

本文用流动汽液平衡釜测定了戊酮－３－正丙醇丁酮－戊醇－１－两个体系三个温度下的等温液平衡数据，三个温度下的数据均通过热力学一致性检验，并用Ｗｉｌｓｏｎ方程和ＵＮＩ－ＱＵＡＣ方程对数据进行了关联，平均汽相偏差小于０．０１，精度令人满意。     

Vapor-liquid and liquid-liquid equilibria of water, 2-methoxyethanol and cyclohexanone: Experiment and correlation

Vapor-liquid equilibria and liquid-liquid equilibria of a ternary mixture consisting of water, 2-methoxyethanol and cyclohexanone and in addition of all binary subsystems were studied experimentally at several temperatures. A ternary corrective term in the expression for the Gibbs free energy based on the NRTL model improves simultaneous representation of binary and ternary phase equilibria.     

Thermodynamic modeling of the phase behavior of binary systems of ionic liquids and carbon dioxide with the group contribution equation of state

The group contribution equation of state (GC-EOS) was applied to predict the phase behavior of binary systems of ionic liquids of the homologous families 1-alkyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate with CO2. Pure group parameters for the new ionic liquid functional groups [-mim][PF6] and [-mim][BF4] and interaction parameters between these groups and the paraffin (CH3, CH2) and CO2 groups were estimated. The GC-EOS extended with the new parameters was applied to predict high-pressure phase equilibria in binary mixtures of the ionic liquids [emim][PF6], [bmim][PF6], [hmim][PF6], [bmim][BF4], [hmim][BF4], and [omim][BF4] with CO2. The agreement between experimental and predicted bubble point data for the ionic liquids was excellent for pressures up to 20 MPa, and even for pressures up to about 100 MPa, the agreement was good. The results show the capability of the GC-EOS to describe phase equilibria of systems consisting of ionic liquids.     

高压下CO2-乙醇二元系统的气液平衡

在带有可视石英窗的可变体积高压釜内,在60－180 ℃温度范围、 4.0－14.5 MPa压力范围下测定了CO2和乙醇二元系统的相平衡数据.根据实验结果预测了pc,Tc,xc.用Peng Robinson方程和Wong Sandler混合规则进行了拟合,所得结果与实验数据基本相符.     

高压下CO_2-乙醇二元系统的气液平衡

在带有可视石英窗的可变体积高压釜内 ,在 60－ 180℃温度范围、 4.0－ 14.5 MPa压力范围下测定了 CO2和乙醇二元系统的相平衡数据 .根据实验结果预测了 pc,Tc,xc.用 Peng-Robinson方程和 Wong-Sandler混合规则进行了拟合 ,所得结果与实验数据基本相符 .     

Modeling the phase equilibria of hydrogen sulfide and carbon dioxide in mixture with hydrocarbons and water using the PCP-SAFT equation of state

The perturbed-chain polar statistical associating fluid theory (PCP-SAFT) equation of state is applied to correlate phase equilibria for mixtures of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) with alkanes, with aromatics, and with water over wide temperature and pressure ranges. The binary mixtures of H₂S–methane and CO₂–methane are studied in detail including vapor–liquid, liquid–liquid and fluid–solid phase equilibria. Very satisfying results were obtained for the binary mixtures as well as for the ternary mixture of H₂S–CO₂–methane using the (constant) interaction parameters of the binary pairs.     

Calculating binary and ternary multiphase equilibria: extensions of the integral area method

The area method was proposed in 1992 to calculate binary and ternary 2-phase equilibria. In its integral form, the method provides both the necessary and sufficient conditions required for the determination of the global minimum reduced Gibbs energy of mixing (Φ). The method has since been applied to the calculation of both pure component and ternary multiphase equilibria in a differential form. However, the extension of the original (2 point) integral area method to the direct calculation of both binary and ternary multiphase equilibria has not been completed. Direct 3 point and modified 2 point search methods have therefore been developed here and used to estimate the phase compositions of a representative binary vapour-liquid-liquid system. The 2 point area method principle has been extended and applied to the calculation of ternary multiphase equilibria using a net volume approach. However, this volume method was found to fail due to an underlying inconsistency in the bounding of the integrated Φ surface by the trial 3-phase region. A new method is proposed that overcomes this problem by minimising the area of intersection between a tangent plane and the Φ surface. This new method has successfully calculated the 3-phase compositions of two simple test systems from a variety of initial mixture starting points.     

Application of a generalized van der Waals equation of state to several nonpolar mixtures

A generalized van der Waals equation of state, applied recently (Nguyen Van Nhu and Kohler, 1995) to the calculation of excess properties and phase equilibria for the mixture methane + ethane, is now extended to several nonpolar binary mixtures.Improved mixing rules for the van der Waals attractive term and for the correction term are proposed. With these mixing rules, the equation gives good agreement for vapour-liquid and liquid-liquid equilibria over a large temperature range for 29 binary mixtures. The agreement of mixture volumes and cross second virial coefficients is also satisfactory.     

Vapor-liquid equilibrium properties for confined binary mixtures involving CO2, CH4, and N2 from Gibbs ensemble Monte Carlo simulations

The effects of solid-fluid interactions on the vapor-liquid phase diagram,coexistence density,relative volatility and vaporization enthalpy have been investigated for confined binary systems of CO 2-CH 4,CO 2-N 2 and CH 4-N 2.The Gibbs ensemble Monte Carlo(GEMC) simulation results indicate that the confinement and the solid-fluid interaction have significant influences on the vapor-liquid equilibrium properties.The confinement and the strength of the solid-fluid interaction make the p-x i phase diagram move to higher pressure regions.They also make the two-phase region become narrower for each binary mixture.The strength of the solid-fluid interactions can cause increases in the coexistence liquid and vapor densities,and cause the decrease of the relative volatility and the vaporization enthalpy for the systems studied.As the pore width is decreased,the two-phase region of the binary mixture becomes narrower.     

Towards predictive association theories

Association equations of state like SAFT, CPA and NRHB have been previously applied to many complex mixtures. In this work we focus on two of these models, the CPA and the NRHB equations of state and the emphasis is on the analysis of their predictive capabilities for a wide range of applications. We use the term predictive in two situations: (i) with no use of binary interaction parameters, and (ii) multicomponent calculations using binary interaction parameters based solely on binary data. It is shown that the CPA equation of state can satisfactorily predict CO₂-water-glycols-alkanes VLE and water-MEG-aliphatic hydrocarbons LLE using interaction parameters obtained from the binary data alone. Moreover, it is demonstrated that the NRHB equation of state is a versatile tool which can be employed equally well to mixtures with pharmaceuticals and solvents, including mixed solvents, as well as phase equilibria in mixtures containing glycols. The importance of considering the solvation of CO₂-water (in CPA) when the model is applied to multicomponent mixtures as well as of the multiple associations in heavy glycol-water mixtures (in NRHB) is investigated.     

CO2 capture from binary mixture via forming hydrate with the help of tetra-n-butyl ammonium bromide

Hydrate formation rate and separation effect on the capture of CO2 from binary mixture v/a forming hydrate with 5 wt% tetra-n-butyl ammonium bromide (TBAB) solution were studied.The results showed that the induction time was 5 min,and the hydrate formation process pressure of 7.30 MPa.The CO2 recovery was about 45% in the feed pressure range from 4.30 to 7.30 MPa.Under the feed pressure of 4.30 MPa,the maximum separation factor and CO2 concentration in hydrate phase were 7.3 and 38.2 tool%,respectively.The results demonstrated that TBAB accelerated hydrate formation and enriched CO2 in hydrate phase under the gentle condition.