离子液体萃取有机物的研究进展

离子液体具有结构可调控、不挥发以及对目标物具有一定选择性等特点;因而近来在萃取领域的应用日益受到关注;被认为是一种可替代传统溶剂的新型绿色溶剂。本文从液-液萃取、固相萃取、液相微萃取、固相微萃取、超声萃取、微波萃取6个方面综述了离子液体在萃取有机物中的应用。     

CO2/离子液体混合物相平衡的研究进展

离子液体对二氧化碳有良好的溶解性能,可以实现二氧化碳的固定与转化。超临界二氧化碳可以从离子液体/有机物体系中选择性萃取有机物,避免相间的交叉污染,实现离子液体的回收。从CO2在离子液体中的溶解度实验测定方法、CO2/离子液体二元体系高压相平衡测定、SC-CO2/离子液体/有机物的三元体系相平衡研究以及模型预测四个方面介绍了CO2/离子液体体系相平衡研究的最近进展,分析了这一研究领域的发展方向。     

离子液体在萃取有机物方面的应用

近些年来,世界各国学者对离子液体的研究越来越多,随着对离子液体研究的深入,离子液体的应用逐渐渗透到各个领域中。主要介绍近年来离子液体在萃取有机物方面的应用进展。     

含离子液体体系液液相平衡的计算

含有离子液体体系的液液平衡数据是离子液体实际应用最重要的基础数据之一。文中在扩展的NRTL方程中进一步引入了分子体积修正项,计算结果表明,该修正能更好地提高模型预测含离子液体体系的精度。因此,文中利用该模型关联了文献报道的多种常见离子液体和醇类二元体系,所有体系计算值与实验值的质量分数最大绝对误差小于3.5%,平均绝对误差小于1.5%;同时,文中利用拟合得到的二元模型参数,成功预测了23℃和50℃时水-正丁醇-[bmim]PF6三元体系的液液平衡相图。     

离子液体-水体系的相平衡

通过对1-丁基-3-甲基咪唑四氟硼酸盐([bmim][PF4])离子液体 水体系相平衡及NaCl、NaBF4和氯化1-丁基-3-甲基咪唑([bmim]Cl)对离子液体 水体系相平衡的影响进行了研究,结果表明: 离子液体[bmim][BF4] H2O二元体系具有典型的最高上临界溶解温度(UCST)行为,其最高上临界温度为5.3℃左右,临界组成为50%(水的质量分数); NaCl和NaBF4降低 [bmim][BF4] H2O体系的混溶性,而[bmim]Cl增加该体系的混溶性.由此得到一种简单定性地判断离子液体[bmim][BF4]中可能存在的杂质种类和水平的方法,并利用此结果可设计纯化该离子液体的绿色工艺.     

含离子液体苯-正丙醇体系等压气液相平衡

选择癸基咪唑醋酸盐([DMIM] [OAc])离子液体作为萃取精馏分离苯-正丙醇共沸体系的萃取剂.在101.3 kPa下测定了苯-正丙醇-癸基咪唑醋酸盐三元体系的等压气液相平衡数据,使用非随机双液体模型(NRTL模型)对所得数据进行了关联,得到了模型参数.实验结果表明:[DMIM][OAc]的加入对体系中的苯产生了显著...     

反相高效液相色谱法直接测定离子液体中咪唑杂质含量

研究了高效液相色谱法测定离子液体中的杂质(4-甲基咪唑)含量的测定方法。在不同色谱条件下,分离效果不同。在AllsphereODSC18色谱柱上,以水-甲醇为流动相,两者流速比为水∶甲醇=1∶9,流速为1.0mL/min,在215nm处进行紫外检测,离子液体能与4-甲基咪唑很好的分离。另外,在HypersilBDSC18色谱柱上用类似的条件分离效果也较好。采用该法的线性范围,检出限分析考察,结果表明,其灵敏度高、定量准确、重现性好,适合于离子液体中4-甲基咪唑这种杂质含量的测定。     

含离子液体苯-甲醇物系等压气液相平衡

在常压下测定了苯+甲醇+三辛基甲基醋酸铵([N1,8,8,8][OAc])三元物系的等压气液相平衡数据.实验结果表明:[N1,8,8,8][OAc]的加入可以显著提高苯对甲醇的相对挥发度,当[N1,8,8,8][OAc]的摩尔分数为0.08时共沸现象完全消失.分别采用Wilson和NRTL热力学模型对该气液相平衡数据进...     

非极性有机物蒸发热与正常沸点的关联

通过对正烷烃蒸发热、正常沸点与碳数关系的研究,理论推导出蒸发热与正常沸点之间的关系,并拟合得一简单适用的公式:Hυ=23.234×BP1.21256+1502.13。应用于上百种常见非极性有机物,误差较小。     

Preparation and Application of Ionic Liquid-Modified Stationary Phases in High Performance Liquid Chromatography

Ionic liquid-modified stationary phases are an important class of stationary phase. They have been shown to have a capability of separating various classes of compounds in HPLC. In this review, we focus on the preparation and application of ionic liquid-modified stationary phases in HPLC. First, two common theories of retention mechanism in the ionic liquid-modified stationary phases in HPLC were discussed. Then, the preparations of two important types of stationary phase, ionic liquid-modified and poly(ionic liquids)-grafted silicas, were illustrated. Finally, applications of the ionic liquid-modified stationary phases in HPLC were reviewed, giving regard to the varieties of compounds separated or analyzed.     

Liquid‐liquid phase split in ionic liquid + toluene mixtures induced by CO2

High pressure carbon dioxide was dissolved in ionic liquid + toluene mixtures to obtain the conditions of pressure and composition where a liquid‐liquid phase split occurs at constant temperature. Ionic liquids (ILs) with four different cations paired with the bis(trifluoromethylsulfonyl)imide ([Tf₂N]^?) anion were selected: 1‐hexyl‐3‐methylimidazolium ([hmim]⁺), 1‐hexyl‐3‐methylpyridinium ([hmpy]⁺), triethyloctylphosphonium ([P₂₂₂₈]⁺), and tetradecyltrihexylphosphonium ([P₆₆₆₁₄]⁺). The solubility of CO₂ was measured in the liquid mixtures at temperatures between 298 and 333 K and at pressures up to 8 MPa, or until the second liquid phase appeared, for initial liquid phase compositions of 0.30, 0.50, and 0.70 mole fraction of IL. Ternary isotherms were compared with the binary solubility of CO₂ in each IL and pure toluene. The lowest pressure for separating toluene in a second liquid phase was achieved by decreasing the temperature of the system, increasing the amount of toluene in the initial liquid mixture and using [hmim][Tf₂N]. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2968–2976, 2015     

Framework for correlating the effect of temperature on nonelectrolyte and ionic liquid activity coefficients

A power‐law expression is proposed for correlating the temperature dependence of infinite‐dilution activity coefficients ( ) for nonelectrolyte solute–solvent binary pairs and for pairs including an ionic liquid: , where θ_ij = 0 for Lewis–Randall ideal solutions, θ_ij = 1 for classic enthalpy‐based Scatchard–Hildebrand regular solution and van Laar models, and ?5 < θ_ij < 5 for most real binaries. The exponent θ_ij is a function of partial molar excess enthalpy ( ) and entropy ( ) such that . Real binaries are classified into seven types corresponding to distinct domains of and θ_ij. The new method provides a framework for correlating phase‐equilibrium driven temperature effects for a wide variety of chemical and environmental applications. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3675–3690, 2014     

Ionic liquids: Solubility parameters and selectivities for organic solutes

Ionic liquids (ILs) are innovative solvents for chemical processing. In this work, a database on activity coefficients of organic solutes at infinite dilution in ILs was collected from literature sources. The activity coefficients have been correlated by activity coefficient model for the regular solution and have been used to estimate the solubility parameter of ILs. The solubility parameters of ILs have been further correlated based on a concept of the group contribution method. Through the analysis of the database and the prediction results of selectivities, it was shown here that as compared with conventional organic solvents, higher selectivity can be achieved by using ILs as working solvents for separation of alkane/aromatic, aromatic/aromatic hydrocarbon mixtures via extraction or supported liquid membrane. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3034–3041, 2013     

Pervaporation of High Boiling Point Organic Compounds with Composite PDMS Membrane

High Boiling Point Organic Compounds (HBOCs ^{1 1}HBOCs: High Boiling Point Organic Compounds ) are defined as those organic compounds with boiling point over water (100°C). It is a challenging problem to separate HBOCs from their mixtures with water. Three HBOCs, propargyl alcohol, butanol, and pyridine, were selected as the experimental samples for observing their separation behaviors from water mixtures by PDMS membrane pervaporation. These HBOCs could preferentially permeate the PDMS membrane and were selectively extracted from the mixtures through the membrane. The experimental tests showed that the permeation flux of propargyl alcohol, butanol, and pyridine was 243.24, 976.5, and 904.70 gm^?2h^?1, with the corresponding selectivity of 3.78, 29.65, and 26.09, respectively. The effects of the feed flow rate, feed concentration, and temperature on the separation behaviors were examined. By comparison with distillation that separates different components in a mixture on the basis of boiling point, the membrane pervaporation seems to behave a “reverse direction” selective separation for the HBOCs. For those aqueous mixtures with tiny content of HBOCs, the “reverse selective separation” by membrane pervaporation should be considered as a promising and effective technology.     

季铵盐型离子液体合成与应用的研究进展

总结了离子液体的通用合成方法,归纳了季铵盐型离子液体在Friedel-Crafts烷基化反应、Heck反应、酯化反应和电化学及萃取等领域的应用。     

A molecular design method based on the COSMO‐SAC model for solvent selection in ionic liquid extractive distillation

In this study, a molecular design method was used to select solvents for extractive distillation. A COSMO‐SAC model was used to screen for prospective solvents from a wide variety of ionic liquids for extractive distillation. Based on the COSMO‐SAC model, the σ‐profile database of ILs was established. Selectivity and solubility were used as the indexes for solvent screening. According to the molecular design method, three suitable extractive distillation solvents were determined for acetonitrile‐water and ethanol‐cyclohexane systems. Vapor ‐ liquid equilibrium experiment were used to test chosen ILs. This study showed that the experimental and design results were consistent with each other. Therefore, this method is effective and applicable to pick ILs solvents for extractive distillation, and the results could provide a theoretical foundation for industrial production. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2853–2869, 2016     

吡啶基离子液体+有机盐双水相体系相图的测定及盐析性能研究

测定了离子液体N-乙基吡啶四氟硼酸盐([EPy]BF₄)+有机盐[丁二酸钠(CH₂COONa)₂/柠檬酸铵C₆H₅O₇(NH₄)₃/柠檬酸钠C₆H₅O₇Na₃]+水双水相体系在303.15、308.15和313.15 K下的双节线及系线数据。基于相图中的杠杆定律通过质量法研究双水相体系的系线,并用Othmer-Tobias方程、Bancroft方程等经验方程以及NRTL活度系数模型对数据进行关联。采用有效排除体积和Setschenow-type的拟合参数深入研究三种有机盐的盐析能力。结果表明,双节线的三个经验式拟合效果良好,但较多参数的经验式会导致部分参数失去意义;双水相体系的系线满足经验方程,数据可靠性较好,且均方根偏差表明系线数据很好地符合NRTL模型;低温更有利于该双水相体系的形成;三种盐都能和[EPy]BF4离子液体形...     

Application of Ionic Liquids in High Performance Reversed-Phase Chromatography

Ionic liquids, considered “green” chemicals, are widely used in many areas of analytical chemistry due to their unique properties. Recently, ionic liquids have been used as a kind of novel additive in separation and combined with silica to synthesize new stationary phase as separation media. This review will focus on the properties and mechanisms of ionic liquids and their potential applications as mobile phase modifier and surface-bonded stationary phase in reversed-phase high performance liquid chromatography (RP-HPLC). Ionic liquids demonstrate advantages and potential in chromatographic field.