Ionic Liquids as Extraction Solvents: Where do We Stand?

Abstract

The unique physicochemical properties of ionic liquids (ILs) and the relative ease with which these properties can be fine‐tuned by altering the cationic or anionic moieties comprising the IL have led to intense interest in their use as alternatives to conventional organic solvents in a wide range of synthetic, catalytic, and electrochemical applications. Recent work by a number of investigators has been directed at the application of ionic liquids in various separation processes, among them the liquid‐liquid extraction of metal ions. Although certain IL‐extractant combinations have been shown to yield metal ion extraction efficiencies far greater than those obtained with molecular organic solvents, other work suggests that the utility of ILs may be limited by solubilization losses and difficulty in recovering extracted metal ions. In this report, recent efforts to overcome these limitations are described, and progress both in achieving an improved understanding of the fundamental aspects of metal ion transfer into ILs and in devising viable IL‐based systems for metal ion separation is detailed. In addition, areas upon which future research efforts might profitably be focused are identified.     

A Striking Effect of Ionic‐Liquid Anions in the Extraction of Sr2+ and Cs+ by Dicyclohexano‐18‐Crown‐6

Abstract

The nature of the ionic‐liquid (IL) anion has been found to have a remarkable effect on the solvent extraction of Sr²⁺ and Cs⁺ by dicyclohexano‐18‐crown‐6 dissolved in ionic liquids. In particular, the extraction efficiency increases with the hydrophobicity of the IL anion as reflected by the solubility in water of ILs having a common cation. Since a cation‐exchange mechanism is operating in these systems, the influence of the IL anion is in large part attributable to an expected Le Chatelier effect in which a greater aqueous concentration of IL cation, obtained when using an IL anion of lower hydrophobicity, opposes cation exchange. This dependence is opposite to that found for IL cations, indicating a significant advantage of using ILs with hydrophobic anions for cation extraction. Furthermore, the extraction selectivity for Sr²⁺ over Na⁺, K⁺, and Cs⁺ can be significantly improved through the use of hydrophobic anions for the ILs containing 1‐ethyl‐3‐methylimidazolium or 1‐butyl‐3‐methylimidazolium cations.     

Temperature-Assisted Removal of Triphenylmethane Dyes from Water with Novel Hydrophobic Benzothiazolium Ionic Liquids

In this work, a simple and effective extraction method for triphenylmethane dyes from their aqueous solution was developed. Three novel task-specific ionic liquids based on N-alkylbenzothiazolium cations were prepared and their extraction performance in this new method was evaluated in self-prepared and real water samples. Through the control of temperature, the ionic liquids could be dispersed into the aqueous solution, first, to fully contact with the dyes and then easily recovered as tiny particles enriching these target compounds. Parameters of the extraction conditions including the amount of the ionic liquid, volume of the dispersing solvent, dissolving temperature, extraction time, pH value, and ionic strength have been investigated. The results showed that the major driven forces for the extraction were hydrogen bonding and hydrophobic interactions between the ionic liquids and the dyes. The proposed method combined the advantages of both homogeneous mixing and heterogeneous solid-liquid separation in extraction process, which was expected to lay the foundation for actual application in future.     

Prediction of CO2/O2 absorption selectivity using supported ionic liquid membranes (SILMs) for gas–liquid membrane contactor

Given their unique and tunable properties as solvents, ionic liquids (ILs) have become a favorable solvent option in separation processes, particularly for capturing carbon dioxide (CO₂). In this work, a simple method that can be used to screen the suitable IL candidates was implemented in our modified gas–liquid membrane contactor system. Solubilities, selectivities of CO₂, nitrogen (N₂), and oxygen (O₂) gases in imidazolium-based ILs and its activity coefficients in water and monoethanolamine (MEA) were predicted using conductor-like screening model for real solvent (COSMO-RS) method over a wide range of temperature (298.15–348.15?K). Results from the analysis revealed that [emim] [NTf₂] IL is a good candidate for further absorption process attributed to its good hydrophobicity and CO₂/O₂ selectivity characteristics. While their miscibility with pure MEA was somehow higher, utilizing the aqueous phase of MEA would be beneficial in this stage. Data on absorption performances and selectivity of CO₂/O₂ are scarce especially in gas–liquid membrane contactor system. Therefore, considering [emim] [NTf₂] IL as a supporting material in supported ionic liquid membranes (SILMs), using aqueous phase of MEA as an absorbent would result in a great membrane-solvent combination system in furthering our gas–liquid membrane contactor process. In conclusion, COSMO-RS is a potentially great predictive utility to screen ILs for specified separation applications. In addition, this work provides useful results for the [emim] [NTf₂]-SILMs to be extensively applied in the field of CO₂ capture and selective O₂ removal.     

Recent Advances in Centrifugal Contactor Design

Abstract

Advances are being made in the design of the Argonne centrifugal contactor for solvent extraction. These contactors are being built, tested, and used to implement the TRUEX process for the cleanup of nuclear waste liquids. These advances include 1) using off-the-shelf, face-mounted motors; 2) modifying the contactor so that relatively volatile solvents can be used; 3) adding a high-level liquid detector that can be used to alert the plant operator of process upsets; 4) providing secondary feed ports; 5) optimizing support frame design; 6) devising a linear design with external interstage lines so that stages can be allocated as needed for extraction, scrub, strip, and solvent cleanup operations; and 7) developing features that facilitate contactor operation in remote facilities.     

绿色离子液体的合成与应用

离子液体作为一种新型绿色溶剂,目前被广泛应用于有机合成、溶剂、萃取和分离、电化学等领域。本文主要介绍了离子液体的特点和几种合成方法。分析比较了不同合成方法的特点,介绍了离子液体作为溶剂的原理和应用。     

Experimental study of the hydraulic operation of an annular centrifugal contactor with various mixing vane geometries

The annular centrifugal contactor is a combination mixer/centrifuge that has been developed for solvent extraction processes for recycling used nuclear reactor fuel. The experimental observations presented were part of a simulation‐focused research effort aimed at providing a more complete understanding of the fluid flow within these contactors to enable further advancements in design and operation of future units and greater confidence for use of such contactors in a variety of other solvent extraction applications. Laser doppler velocimetry (LDV), particle image velocimetry (PIV), pressure measurements, and high‐speed video imaging for a range of flow rates and rotor speeds were performed to characterize the flow of water in the annular mixing region of the contactor using three different mixing vane geometries. It was found that the geometry of the mixing vanes has a significant impact on the annular liquid height and general flow in the contactor mixing zone. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

ANNULAR CENTRIFUGAL CONTACTORS FOR MULTIPLE STAGE EXTRACTION PROCESSES

The annular centrifugal contactor is a vertical, liquid - liquid, direct drive, centrifuge capable of both mixing and separating. Efficient mixing is achieved in the annulus between the spinning rotor and the stationary lower housing. Separation occurs in the rotor due to the enhanced density difference of two liquids at increased gravitational force. In this design, mixing and disengaging times of three and ten to thirty seconds, respectively, are typical. System equilibrium is reached in minutes, even for multiple stage processes, due to the low operating volume of these devices

Annular centrifugal contactors, capable of nearly one theoretical stage per unit, are readily employed in complex processes. They can be directly coupled to one another because the rotor pumps the liquids from the annular mixing zone to a height sufficient to feed the next unit. New designs have recently become available which offer such enhancements as interchangeable heavy phase weirs, a low mix option, and a clean in place rotor. This commercially available technology is now being utilized for polymer, organic peroxide, pharmaceutical, and metals recovery processes to improve throughput and efficiency, lower process inventory, and reduce waste. The ability to process during complete phase ratio changes, intermittent flows, and changes in flow rate without loss of performance make these contactors an attractive extraction tool.     

微反应器耦合离子液体强化萃取过程的研究进展

离子液体作为一种绿色溶剂在强化萃取过程中获得了广泛的应用，但是高昂的生产成本以及以高黏度为特征的流体力学性质阻碍了其工业化应用。微化工技术为基于离子液体的连续化萃取提供了一种高效的过程强化平台。近年来，微化工技术与离子液体技术的耦合强化在萃取分离领域越来越受到关注。本文主要综述了微流动萃取技术的基本现状、离子液体参与的萃取过程特征、微反应器内涉及离子液体的互不相溶液-液两相流型、传质及其强化机制，重点介绍了微反应器在基于离子液体萃取金属、有机物等过程中的应用、微流动萃取过程放大的研究进展，并对涉及离子液体的多级萃取、功能化离子液体的萃取应用及其相应的微流动萃取放大等研究方向进行了展望。     

Ionic Liquid (IL) Cation and Anion Structural Effects on Metal Ion Extraction into Quaternary Ammonium-based ILs

Numerous factors have previously been shown to influence the mode of extraction of alkali and alkaline earth cations from an acidic aqueous phase into 1, 3-dialkylimidazolium-based ionic liquids (ILs) by a crown ether, among them the hydrophobicity of both the IL anion and cation. To determine if this observation is “generic” and thus, could provide the basis for guidelines for the rational design of ILs to be used as solvents in metal ion extraction, other families of ILs must be studied. A series of quaternary ammonium-based ILs have therefore been examined as solvents for the extraction of various metal ions from acidic nitrate- and chloride-containing aqueous phases by dicyclohexano-18-crown-6 (DCH18C6). Although the overall metal ion extraction behavior in these systems is similar to that observed for 1, 3-dialkylimidazolium-based ILs, significant differences in metal ion separation factors (e.g., α_Sr/Na) are observed under certain conditions, differences that may be sufficient to influence the choice of IL in separations applications.     

基于离子液体的燃料油萃取脱硫过程

以咪唑类离子液体作为萃取脱硫剂,在正戊烷和甲苯的混合溶液中加入少量的噻吩构成油品模拟体系. 采用正交实验,系统考察了单级萃取中温度、时间、剂油比以及离子液体碳数对脱硫效率的影响,得到了较优的脱硫条件：温度约40℃,反应时间约50 min,剂油比为1:1,侧链碳数为10. 回归得到了模拟油品中脱除噻吩的萃取动力学方程. 该研究为基于离子液体的燃料油脱硫工艺提供了重要的基础.     

离子液体/低共熔溶剂在煤基液体分离中的应用

为了实现煤基液体各组分利用价值最大化,本文综述了离子液体和低共熔溶剂对组分组成复杂的煤基液体进行高效萃取分离的研究进展。首先介绍了离子液体和低共熔溶剂的性质及分类;其次根据分离目标的不同,将离子液体和低共熔溶剂对煤基液体典型组分的萃取分离分为四个方面进行阐述：煤基液体提酚、燃料油萃取脱硫、燃料油萃取脱氮、芳烃和脂肪烃的分离。分析表明,离子液体和低共熔溶剂对实际煤基液体的提酚效果较好,能分离出绝大多数的酚类化合物;燃料油萃取脱硫时,离子液体和低共熔溶剂对实际煤基液体的单次脱硫率均不高,需3～5次重复萃取后才能获得理想效果;燃料油中的碱性及非碱性含氮化合物很难被同一种离子液体或低共熔溶剂一次性分离出,导致实际油品的脱氮率较低;大多数离子液体和低共熔溶剂进行芳烃和脂肪烃的分离时不能获得理想的分配系数和选择性,尚无法用于实际芳烃和脂肪烃的分离。氢键、π-π、CH-π、范德华力等分子间相互作用的差异是实现离子液体或低共熔溶剂进行煤基液体典型组分分离的主要原因。依据分离对象,设计合适的离子液体和低共熔溶剂,提高实际煤基液体分离时的萃取率和选择性;分析并解决离子液体和低共熔溶剂用于实际煤基液体各组分分离时可能出现的问题,势必会推进煤基液体高值化分离的工业化进程。     

Toward greener separations of rare earths: Bifunctional ionic liquid extractants in biodiesel

Ionic liquids (ILs) containing quaternary phosphonium cations and phosphonic acid anions were explored as novel extractants for rare earths (RE) separation. They were considered to be bifunctional ionic liquid extractants (bif‐ILEs), since both cations and anions of ILs were involved in the extraction. Trihexyl(tetradecyl)phosphonium bis 2,4,4‐trimethylpentylphosphinate (Cyphos IL 104), as a bif‐ILE, together with propylene carbonate (PC), dimethyl carbonate (DMC), and soybean oil methyl ester (SBME, biodiesel) as diluents was employed in the extraction of RE(III) from aqueous solutions. Acidified Cyphos IL 104 (HNO₃‐Cyphos IL 104) exhibited high solubility in three diluents, and higher extraction efficiency than bis(2,4,4‐trimethylpentyl)phosphinic acid (Cyanex 272) because of the coextraction of RE(III) by quaternary phosphonium cation and phosphonic acid anion in organic phase. Additionally, this coextraction mechanism could eliminate the loss of IL. The physical properties and miscibility test results indicated that SBME was an excellent solvent for RE(III) extraction. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Liquid Phase Extraction and Separation of Noble Organometallic Catalysts by Functionalized Ionic Liquids

Abstract

The separation of two noble organometallic catalysts from a homogeneous organic phase was investigated using liquid phase extraction with functionalized ionic liquids. Thirteen functionalized ionic liquids containing amino, hydroxy, thioether, carboxylic, or olefin functional groups were prepared by a standard neutralization method. The extractions of Jacobsen's catalyst and Wilkinson's catalyst were conducted using the functionalized ionic liquids as the extraction phase without adding any other metal complexing extractant. The distribution factors between the ionic liquid (IL) phase and toluene (organic solution phase) demonstrated that the functional groups in ILs exhibited moderate to high affinity with the metal complexes. The influence of the ionic liquid structure on the distribution factors was also investigated.     

Extraction and recovery of cerium(IV) along with fluorine(I) from bastnasite leaching liquor by DEHEHP in [C8mim]PF6

BACKGROUND: Ionic liquids (ILs) as environmentally benign solvents have been widely studied in the application of solvent extraction. However, few applications have been successfully industrialized because of the difficult stripping of metal ions or the loss of components of the ILs. More work needs to be done to investigate the extraction behaviour of IL‐based extraction systems. In this work, the extraction behaviour of Ce(IV), Th(IV) and some trivalent rare earth (RE) nitrates by di(2‐ethylhexyl) 2‐ethylhexylphosphonate (DEHEHP) in the IL, 1‐methyl‐3‐octylimidazolium hexafluorophosphate ([C₈mim]PF₆), was investigated and compared with that in the n‐heptane system. In particular, the effect of F(I) on the extraction mechanism for Ce(IV) and its separation from Th(IV) was investigated. Otherwise, the recovery efficiency of Ce(IV) and F(I) from a practical bastnasite leach liquor was examined using IL based extraction. RESULTS: Similar selectivity (Ce(IV) > Th(IV) ? RE(III)) was observed in both the IL and n‐heptane systems. The existence of F(I) had a large negative impact on the extraction and separation of Ce(IV). An identical process for the extraction of Ce(NO₃)₄ containing F(I) by DEHEHP in both IL and n‐heptane was achieved under appropriate conditions. The Ce(IV) in the IL phase may be quantitatively back extracted and may be recovered as part of high purity CeF₃ and cerium sulfate. CONCLUSION: It is possible for IL to act as an environmentally benign solvent for the recovery of Ce(IV) and F(I) from bastnasite in rare earth hydrometallurgy. Copyright © 2009 Society of Chemical Industry     

Computer‐aided design of ionic liquids as solvents for extractive desulfurization

Although ionic liquids (ILs) have been widely explored as solvents for extractive desulfurization (EDS) of fuel oils, systematic studying of the optimal design of ILs for this process is still scarce. The UNIFAC‐IL model is extended first to describe the EDS system based on exhaustive experimental data. Then, based on the obtained UNIFAC‐IL model and group contribution models for predicting the melting point and viscosity of ILs, a mixed‐integer nonlinear programming (MINLP) problem is formulated for the purpose of computer‐aided ionic liquid design (CAILD). The MINLP problem is solved to optimize the liquid‐liquid extraction performance of ILs in a given multicomponent model EDS system, under consideration of constraints regarding the IL structure, thermodynamic and physical properties. The top five IL candidates preidentified from CAILD are further evaluated by means of process simulation using ASPEN Plus. Thereby, [C₅MPy][C(CN)₃] is identified as the most suitable solvent for EDS. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1013–1025, 2018     

Homogeneous Liquid–Liquid Extraction of Rare Earths with the Betaine—Betainium Bis(trifluoromethylsulfonyl)imide Ionic Liquid System

Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature.     

The use of an ionic liquid in a Karr reciprocating plate extraction column

Ionic liquids offer an alternative to volatile organic solvents for extraction of a range of materials. This work examines the mass transfer performance of a Karr reciprocating plate column with an ionic liquid as an alternative solvent for the extraction of phenol from water. The results indicate that ionic liquids can be used in existing solvent extraction equipment and that existing correlations and models can be used to predict mass transfer performance.     

Dearomatization of pyrolysis gasoline with an ionic liquid mixture: Experimental study and process simulation

The pyrolysis gasoline is the main source of benzene, toluene, and xylenes. The dearomatization of this stream is currently performed by liquid – liquid extraction using sulfolane. However, the sulfolane process has high operating costs that could be minimized by employing ionic liquids as solvents because of their non‐volatile character. In this work, we proposed a novel process to perform the dearomatization of pyrolysis gasoline using a binary mixture of 1‐ethyl‐3‐methylimidazolium tricyanomethanide ([emim][TCM]) and 1‐ethyl‐4‐methylpyridinium bis(trifluoromethylsulfonyl)imide ([4empy][Tf₂N]) ILs. The composition in the IL mixture was optimized considering their extractive and thermophysical properties. The Kremser method was applied using the experimental data to determine the number of equilibrium stages in the liquid – liquid extractor which provides the same extraction yields of aromatics using the IL mixture that those of the sulfolane process. The recovery section was designed and simulated from the experimental vapor – liquid equilibrium between the hydrocarbons and the IL mixture. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4054–4065, 2017     

Selective extraction of organic compounds from transesterification reaction mixtures by using ionic liquids

In this article, we describe assays carried out to determine the suitability of 13 ionic liquids based on 1‐n‐alkyl‐3‐methylimidazolium and n‐alkylpyridinium cations and a wide range of anions (hexafluorophophate, bis{(trifluoromethyl)sulfonyl}imide, tetrafluoroborate, methylsulfate, 2(2‐methoxyethoxy)ethylsulfate, ethylsulfate, n‐octylsulfate, dicyanamide, nitrate, tetrafluoroborate and chloride) to carry out the selective separation of the organic compounds involved in a transesterification reaction (butyl butyrate, vinyl butyrate, 1‐butanol, and butyric acid) from hexane solutions. The assayed ionic liquids were shown to be suitable solvents for the selective separation of the target compounds, the extraction process being controlled by the hydrophobicity of the compounds. The anion composition of the ionic liquid was seen to strongly influence the average extraction ratio, the highest value being reached with the chloride‐based ionic liquid. As regards the cation composition of the ionic liquids, it was seen that the average distribution ratio increased with decreasing length of alkyl chain. © 2010 American Institute of Chemical Engineers AIChE J, 2010