Determination of Extractant Solubility in Ionic Liquids by Thermogravimetric Analysis

The high thermal stability typical of many room temperature ionic liquids (RTILs) is exploited as the basis of a method employing thermogravimetric analysis (TGA) for the determination of the solubility of various metal ion extractants in these solvents. The approach is simple, applicable to extractants lacking functional groups that would permit their ready quantification by other methods, and requires only small (mg) quantities of sample. These features of the method, along with its limitations, are illustrated by the determination of the solubility of representative examples of several common extractant families, including bis(2-ethylhexyl)phosphoric acid (HDEHP) and di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6), in a series of 1,3-dialkylimidazolium (C_nmim⁺)-based ionic liquids.     

离子液体及其在有机合成中的应用

简要介绍了离子液体的组成和制备方法，归纳了离子液体的优越性质，综述了离子液体作为催化剂和绿色溶剂在催化加氢、Diels-Alder反应等有机合成反应中的应用，提出离子液体解决了催化剂的回收问题，避免了挥发性溶剂对环境的污染，实现了有机合成的绿色化。展望了离子液体在日化及其相关行业合成中的应用前景。     

Modelling of Hydrocarbon Solubility in Isomeric Ionic Liquids Using Mathematical Regressions

Linear Regression and Radial Basis Network models were explored for the prediction of heptane and toluene solubility in eleven ionic liquids at 313.15 K. The ILs were grouped in three groups of isomers. The models fitting performance was analyzed calculating statistical parameters (correlation coefficient and mean prediction error). For every model tested, the mean prediction error values in all three systems studied is less than 9.26 and 0.8% for linear regression and radial basis network models, respectively.     

The Solubility Parameters of Ionic Liquids

The Hildebrand’s solubility parameters have been calculated for 18 ionic liquids from the inverse gas chromatography measurements of the activity coefficients at infinite dilution. Retention data were used for the calculation. The solubility parameters are helpful for the prediction of the solubility in the binary solvent mixtures. From the solubility parameters, the standard enthalpies of vaporization of ionic liquids were estimated.     

Ionic liquids and proteases: a clean alliance for semisynthesis

Herein we present the first report on protease-catalysed ligation of cleavage-sensitive peptide and protein fragments in ionic-liquid-containing solvent systems. By applying the newly established [MMIM][Me2PO4]/buffer mixture as a reaction medium, significant advantages over purely aqueous or conventional organic solvent-containing media could be identified, including in particular the use of active wild-type proteases as biocatalysts, the suppression of any competitive proteolytic side reactions, the high turnover rates compared to classical organic solvents and the high stability of chemically labile reactants.     

离子液体及其应用的研究新进展(续完)

叙述了离子液体在化学反应、分离过程、功能材料、电化学、石油化工和色谱等各个方面中的应用研究进展.     

Solubility of CO2 in three cellulose-dissolving ionic liquids

The solubility of CO₂ in three cellulose-dissolving ionic liquids (1-ethyl-3-methylimidazolium diethylphosphate, [Emim][DEP], 1-allyl-3-methylimidazolium chloride, [Amim][Cl], and 1-butyl-3-methylimidazolium chloride, [Bmim][Cl]) at temperatures within 298 and 356 K and pressures up to 6.5 MPa was determined using a Van Ness-type apparatus (static isochoric). It was demonstrated that this device can work in isothermal and isoplethal modes, being the latter faster and more precise. Moreover, it was possible to determine CO₂ solubilities in metastable liquid [Bmim][Cl]. Experimental data were modeled using the Extended Henry's law correlation and the group contribution equation of state. New parameters for the binary interaction of CO₂ with ionic liquid groups were calculated.     

离子液体膜材料分离二氧化碳的研究进展

离子液体由于具有不易挥发、结构可调、对CO₂有良好的吸收性能等特点而成为当前CO₂分离领域的研究热点,但因高黏度和高成本问题而限制了其工业化应用。将离子液体与气体分离膜材料结合,得到的新型分离膜材料兼具离子液体和膜的优势,成为当前离子液体研究领域的趋势之一。针对这一热点问题,综述了离子液体支撑液膜、聚离子液体膜和离子液体共混/杂化膜在CO₂分离方面的研究现状和进展,讨论了离子液体结构和含量对膜分离性能、稳定性等的影响。相关研究表明,离子液体共混/杂化膜具有较高的分离性能和稳定性,是一种很有应用前景的CO₂分离材料。提出该领域的重点发展方向,即开发新的功能化离子液体共混/杂化膜材料是解决高渗透通量与高稳定性之间矛盾、强化CO₂分离性能的有效途径,深入研究离子液体共混/杂化膜的形成机制、气体在膜中的渗透行为以及CO₂分离机理。     

The solubility of gases in ionic liquids

In this Perspective, we provide a detailed discussion of the techniques and methods used for determining the solubility of gases in ionic liquids (ILs). This includes various experimental measurement techniques, equation of state (EOS) modeling, and predictive molecular‐based modeling. Many of the key papers from the past 15 years are discussed and put into the context of the latest advances in the field. Limitations of these methods plus future developments and new research opportunities are discussed. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

离子液体与芳香类高沸点有机物相平衡

采用超临界CO2萃取方法得到了高纯度的离子液体[bmim]PF6、[bmim]BF4 和[bupy]BF4。用反相键合相高效液相色谱法（HPLC）测定了三种离子液体中萘、菲、联苯、二苯并噻吩（DBT）和二苯基二硫醚在280～340K的溶解度,分别用两参数和三参数的NRTL方程关联了测得的溶解度数据。溶解度计算值与实验值的相对平均偏差在3.86～9.94％之间。显然,可以用NRTL方程描述这些固体物质与离子液体的固液相平衡。同样条件下,测定了乙苯—[bmim]PF6、十二烷基苯—[bmim]PF6 液液相平衡数据。前者的规律也可以用NRTL方程描述,两相溶解度计算值与实验值的平均偏差分别是10.20、3.37％。     

Ionic liquids as active pharmaceutical ingredients

Ionic liquids (ILs) are ionic compounds that possess a melting temperature below 100 °C. Their physical and chemical properties are attractive for various applications. Several organic materials that are now classified as ionic liquids were described as far back as the mid-19th century. The search for new and different ILs has led to the progressive development and application of three generations of ILs: 1) The focus of the first generation was mainly on their unique intrinsic physical and chemical properties, such as density, viscosity, conductivity, solubility, and high thermal and chemical stability. 2) The second generation of ILs offered the potential to tune some of these physical and chemical properties, allowing the formation of "task-specific ionic liquids" which can have application as lubricants, energetic materials (in the case of selective separation and extraction processes), and as more environmentally friendly (greener) reaction solvents, among others. 3) The third and most recent generation of ILs involve active pharmaceutical ingredients (API), which are being used to produce ILs with biological activity. Herein we summarize recent developments in the area of third-generation ionic liquids that are being used as APIs, with a particular focus on efforts to overcome current hurdles encountered by APIs. We also offer some innovative solutions in new medical treatment and delivery options.     

有机物在离子液体中无限稀释活度因子及液液界面张力的定量机构-性质关系

用PM3半经验量子化学方法计算了烷烃、烯烃和芳烃等的疏水性参数lgP、偶极矩、前线分子轨道能隙和水合能等结构描述符,与实验测定的烃类在1-丁基-3-甲基咪唑六氟磷酸盐（［C₄MIM］［PF₆］）、1-烯丙基-3-甲基咪唑四氟硼酸盐（［AMIM］［BF₄］）、1-异丁烯基-3-甲基咪唑四氟硼酸盐（［MPMIM］［BF₄］）和［MPMIM］［BF₄］-AgBF₄ 4种离子液体中的无限稀释活度因子进行定量结构-性质关系（QSPR）研究,建立的QSPR模型具有良好的关联和预测能力.同时测定了烃类等溶质与离子液体［C₄MIM］［PF₆］的液液界面张力,发现其与无限稀释活度因子有相似的变化趋势,据此采用同样的结构描述符,建立了溶质与［C₄MIM］［PF₆］界面张力的QSPR模型,模型的关联能力良好.     

离子液体捕集二氧化碳的研究进展(英文)

Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.     

离子液体及其在绿色有机合成中的应用

简要介绍了离子液体的组成和制备方法,归纳了离子液体的优越性质,概述了离子液体作为催化剂和绿色溶剂在催化加氢、Diels-Alder反应等有机合成反应中的应用,提出离子液体解决了催化剂的回收问题,避免了挥发性溶剂对环境的污染,实现了有机合成的绿色化。     

Ionic liquids for highly efficient methyl chloride capture and dehydration

A new methyl chloride (CH₃Cl) capture and dehydration process using two ionic liquids (ILs) was designed and systematically studied. ILs [EMIM][Ac] and [EMIM][BF₄] were screened out as CH₃Cl capture and drying absorbents through the COSMO-RS model. The result of solubility experiment suggests [EMIM][Ac] has an excellent solvent capacity for CH₃Cl at mild operation conditions. The bench-scale CH₃Cl absorption experiments further confirmed the outstanding CH₃Cl capture ability of [EMIM][Ac]. Besides, the water content of outlet gas can be decreased to 452 ppm (mass fraction) using [EMIM][BF₄] in the dehydration experiment. The industrial-scale CH₃Cl capture and dehydration process was simulated and optimized. Compared to the benchmarked triethylene glycol process, IL process has higher product purity (99.99 wt%), and lower energy consumption. The quantum chemical calculations clearly revealed the relationship between hydrogen bond and separation performance. This study provides a decision-making basis for designing green process associated with volatile organic compounds.     

苯并咪唑型离子液体的合成及物理性质研究

由1-乙基-2-甲基苯并咪唑和苄氯合成了中间体氯化苯并咪唑盐,经离子交换得到4种不同阴离子的目标化合物,1HNMR、13CNMR、MS和FT-IR表征了其结构,并探讨了这4种离子液体的水溶性、熔点、粘度和溶解性等性质.     

Screening ionic liquids as candidates for separation of acid gases: Solubility of hydrogen sulfide,methane, and ethane

The solubility of the major constituents of natural gas in ionic liquids (ILs) can be used to identify their potential for acid gas removal from a producing gas stream. We have developed models for the solubility of H₂S, CH₄, and C₂H₆ in ILs at typical conditions encountered in natural gas treatment. In this work, a conductor‐like screening model for realistic solvation was used to predict the activity coefficients for solutes in ILs and a cubic EOS was used for vapor‐phase corrections from ideality. Empirical correlations were developed to extrapolate solubilities where experimental data are not available at desired conditions; targeted in this study at 298.15 K and 2000 kPa. Over 400 possible ILs were ranked based on the higher selectivity of absorption of CO₂ and H₂S over CH₄ and C₂H₆. The best 15% (58) of promising ILs for sour gas treatment predominantly contain the anions BF₄, NO₃, and CH₃SO₄ and the cations N₄₁₁₁, pmg, and tmg. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2993–3005, 2013     

Solubility of light alkanes and alkenes in ionic liquids

The solubility of light hydrocarbons in a variety of ionic liquids was studied, and it was found that ionic liquids containing Cu(Ⅰ) had higher solubility for hydrocarbons and alkene/alkane solubility selectivity, and Et₃NHCl-2.1CuCl ionic liquid was preferred. The effects of temperature and pressure on the solubility of light hydrocarbons were investigated for the selected ionic liquid. It was found that low temperature and high pressure were favorable for the dissolution of light hydrocarbons, and the alkene/alkane solubility selectivity decreased with the increase of temperature and pressure. The alkene/alkane solubility selectivity was above 8.3 at the temperature of 30℃ and the pressure of 0.2 MPa. The initial dissolution rate of hydrocarbons in ionic liquid was large, but it decreased rapidly with prolonging time, and the dissolution rate of alkenes was higher than that of alkanes at the same conditions. The alkene/alkane separation selectivity increased with decreasing content of alkenes in the mixture of alkenes and alkanes. Light hydrocarbons dissolved in ionic liquids could be desorbed by means of increasing temperature, restoring the dissolution capability of ionic liquids to hydrocarbons. Alkanes were easier to be desorbed than alkenes, and small-molecule hydrocarbons were easier to be desorbed than large-molecule hydrocarbons. The desorption percentage exceeded 92% under optimal conditions. Ionic liquid had a good reusable performance in the absorption and separation of light alkanes and alkenes. The solubility only decreased by less than 5% when it was reused five times, and the alkane/alkane solubility selectivity was basically not affected by reusing times. Software Gaussian 09 was used to study the interaction between anions of ionic liquids and light alkanes and alkanes, and the solubility difference of light alkenes and alkanes in different ionic liquids was well explained.     

小分子烷烃与烯烃在离子液体中的溶解性能

研究了多种离子液体对小分子烃类的溶解性能,发现含有Cu(Ⅰ)的离子液体对烃类具有较高的溶解度和烯烃/烷烃溶解选择性,优选出了Et3NHCl-2.1CuCl离子液体。考察了温度和压力对小分子烃类溶解性能的影响规律,发现低温和高压有利烃类的溶解,烯烃/烷烃溶解选择性随温度和压力的升高而减小;在30℃和0.2 MPa的条件下,烯烃/烷烃溶解选择性均在8.3以上。烃类在离子液体中的初始溶解速率较大,但随时间的延长快速降低,相同条件下烯烃的溶解速率高于烷烃的溶解速率。烯烃/烷烃分离选择性随混合气中烯烃含量的减小而增大。升温可以解吸出离子液体中的烃类,烷烃比烯烃容易解吸,优化条件下的解吸率可达92%以上。离子液体对小分子烷烃和烯烃的吸收分离具有良好的重复使用性能。利用Gaussian 09软件对离子液体的阴离子与烯烃、烷烃的作用进行了计算分析,解释了烯烃和烷烃在不同离子液体中溶解性能差异的原因。     

咪唑类离子液体及其催化有机不对称反应

离子液体作为一种新型绿色溶剂,具有许多独特的物理化学性质,近年来逐渐被人们所认知,并发现可用在许多重要领域.本文简单介绍离子液体及其特点,重点介绍在咪唑类离子液体中典型的不对称加氢反应、不对称Michael加成反应、不对称Aldol反应、不对称烯丙基反应和不对称氟化反应.