Journal of Membrane Science 376 (2011) 114

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Review

Recent advances in supported ionic liquid membrane technology

L.J. Lozano a, , C. Godnez a , A.P. de los Ros a , F.J. Hernndez-Fernndez a , S. Snchez-Segado a , F.J. Alguacil b
a b

Department of Chemical and Environmental Engineering, Technical University of Cartagena, Campus La Muralla, C/Doctor Fleming S/N, E-30202 Cartagena, Murcia, Spain National Center for Metallurgical Research, Spanish National Research Council (CENIM-CSIC), Avda. Gregorio del Amo, 8, Ciudad Universitaria, E-28040 Madrid, Spain

a r t i c l e

i n f o

a b s t r a c t
Novel processes based on supported liquid membranes have been proposed as effective methods for the selective separation of different chemical species in dilute streams, such as metal ions, organic compounds or biologically important compounds and gas mixtures. However, the industrial use of supported liquid membranes based on conventional liquids is limited by their relative instability and short lifetime. The use of ionic liquids as a liquid membrane phase could overcome these inconveniences due to their negligible vapour pressure and the possibility of minimizing their solubility in the surrounding phases by adequate selection of the cation and anion. The possibility of designing suitable ionic liquids for specic separation problems has also opened up new potential elds of industrial application of supported ionic liquid membranes. In this review an overview is given of recent advances in supported membranes based on ionic liquids, including issues such as methods of preparation, transport mechanisms, congurations, stability, elds of application and process intensication using supported ionic liquid membranes. 2011 Elsevier B.V. All rights reserved.

Article history: Received 4 October 2010 Received in revised form 14 March 2011 Accepted 19 March 2011 Available online 29 March 2011 Dedicated to Professor Diego Juan Garcia on the occasion of his Seventieth Birthday, 1st April 2010. Keywords: Supported ionic liquid membrane Ionic liquid Membrane transport Operational stability Mechanism Green solvent

Contents 1. 2. 3. 4. 5. 6. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods of preparation of supported ionic liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mechanism of transport through supported ionic liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Congurations of supported ionic liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Stability of supported ionic liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fields of application of supported liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Separation of organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Separation of mixed gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3. Pervaporation and vapour permeation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4. Separation of ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5. Analytical applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.6. Electrochemical applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Process intensication using SILM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ionic liquids: green aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2 3 5 6 7 7 8 9 9 10 10 10 11 11 12

7. 8. 9.

1. Introduction Membrane science has taken its place among the most important topics of research in the world today, with sales of membrane systems topping US$ 1 billion annually [1]. Among the processes being developed, supported liquid membranes (SLMs), porous supports whose pores are impregnated with a solvent, have been

Corresponding author. Tel.: +34 968 325 416. E-mail address: luisja.lozano@upct.es (L.J. Lozano). 0376-7388/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2011.03.036

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showing tremendous potential in different applications [24]. The SLM technique is a combination of three simultaneously occurring processes: molecule extraction from the feed phase to the SLM, diffusion through SLM and re-extraction to the received phase. Among their numerous advantages are specicity, the minimal amount of solvent needed and the fact that extraction and stripping steps are combined into a single step [5]. Unfortunately, few large scale SLM applications are found in the literature, mainly due to insufcient membrane stability [6,7]. To explain this low SLM stability various mechanisms have been proposed: loss of organic phase from the supporting membrane, either by evaporation or dissolution/dispersion into the adjacent phases, pressure difference, etc. [8]. Unlike the solvents previously used in SLMs, ILs possess unique properties that are interesting in the context of liquid membranes [911]. ILs are organic salts remaining as liquids under ambient temperatures. They normally consist of an organic cation (e.g. imidazolium, pyridinium, pyrrolidinium, phosphonium, ammonium), and a polyatomic inorganic anion (e.g. tetrauoroborate, hexauorophosphate, chloride) or, more and more current, an organic anion (e.g. triuoromethylsulfonate, bis[(triuoromethyl)sulfonyl]imide) [12]. The structures of common cations and anions of ILs are shown in Fig. 1. The main advantage of these media are their near-zero vapour pressure and their good chemical and thermal stabilities, having a large temperature range where they are stable with a negligible vapour pressure. Therefore, they have been considered as environmental benign solvents as compared to volatile organic solvents. Additionally, the properties of ionic liquids (hydrophobicity, viscosity, solubility, etc.) can be varied by altering the substitutive group on the cation or the combined anion [12,13] to make them more widely applicable in many physical and chemical elds. Indeed, ionic liquids have been used in replacement of volatile organic solvents in a wide variety of chemical processes at laboratory scale, such as separation and purication [1420], reaction media in biochemical [2123] and chemical catalysis [2427]. The use of these new solvents as a liquid membrane phase results in the stabilization of the SLMs due to their negligible vapour pressure, the possibility of minimizing their solubility in the surrounding phases by adequate selection of the cation and anion [28], and their high viscosity (up to 500 cP) which could slow down the displacement of the liquids from the micron pores under pressure. Other interesting properties of ILs in the context of liquid membranes are their high ion conductivity [29] and high solvent power [30]. All these mentioned properties have led ILs to being considered green designer solvents [31]. In the last decade some researchers have reported that SLMs based on ILs achieved selective transport organic compounds such as amines, alcohols, organic acids, ketones, ethers, and aromatic hydrocarbons [14,15,17,32,33], mixed gases [34,35] and metal ions [3638]. This review focuses on the development and application of supported ionic liquid membranes. An overview of the recent advances in supported ionic liquid membrane technology is given, including issues such as methods of preparation, transport mechanisms, congurations, stability, elds of application and process intensication using supported ionic liquid membranes.

2. Methods of preparation of supported ionic liquid membranes Due to the relatively high viscosity of the ionic liquids, the method of preparation of supported ionic liquid membranes can play an important role on the membrane performance. Three

methods are commonly used for the preparation of supported ionic liquid membranes: direct immersion, pressure or vacuum [18,39,40]. In the former case, immobilization takes places by contacting the supporting membrane with the ionic liquid, allowing it to soap up the liquid [18]. In the pressure method, the immobilization is achieved by placing the membrane in an ultraltration unit, adding an amount of ionic liquid and applying nitrogen pressure to force the ionic liquid to ow into the pores of the membrane, and therefore, displacing air from the pores of the membrane with the ionic liquid [39]. In the vacuum method, the supporting membrane is submerged in a volume of IL and vacuum is applied to release all air occluded in the pores of the membranes [40]. After all procedures, the excess ionic liquid should be removed from the membrane surface either by leaving to drip overnight or by blotting with paper tissue. Scanning electron microscopy (SEM) combined with energy dispersive X-ray (EDX) analysis was used to analyse the inuence of the immobilization method on the SILMs performance [39]. This technique allows the characterization of the membrane surface morphology and the examination the global chemical composition of the membranes and the distribution of the ILs within them. Fig. 2 shows examples of SEM micrographs of a plain Nylon membrane and supported liquid membranes based on [bmim+ ][PF6 ] prepared by using the pressure and the vacuum methods, respectively. The morphological study showed that, after impregnation by either method, the IL was homogeneously distributed in the pores of the membrane, except for the largest macropores that remained partially lled. These pictures also show the presence of a small amount of excess IL located on the external membrane surface. The SEMEDX and weight studies showed that the amount of IL immobilized was independent of the ionic liquid used when the immobilization was carried out under pressure. In contrast, following immobilization under vacuum, less ionic liquid was adsorbed into the membranes when more viscous ILs were used. This behaviour could be explained by the fact that the high viscosity of these ILs makes it difcult their penetration into the middle of the deeper pores of the membrane under vacuum. From these ndings it was concluded that immobilization under vacuum can be considered suitable for low viscosity ionic liquids, with the added advantage that it is also an easier preparation method. However, for high viscosity ionic liquids, immobilization of the ionic liquid should use pressure in order to ensure that all membrane pores are lled with liquid. The nature of the supporting membrane also plays an important role in the performance of supporting ionic liquid membranes. In this context, De los Rios et al. [9] studied the used of two polymeric membranes, Nylon and Mitex, as supporting membranes. Nylon membrane was a hydrophilic polyamide membrane with a pore size of 0.45 m and a thickness of 170 m. Mitex membrane was a hydrophobic polytetrauoroethylene membrane with a pore size of 10 m and a thickness of 130 m. It was observed that less ionic liquid was absorbed into the Mitex membranes, which was explained by the different textural properties and the high hydrophobic character of these membranes, which probably restrict interaction with the hydrophilic ionic liquids [41] used. Simple determination of the wettability has been also used as criteria in the selection of a proper supporting membrane [32]. The use of nanoltration membranes as supporting membranes has been also reported [42]. In this case, direct ltration of ionic liquids through the nanoltration membrane was not possible at a gas pressure up to 7 bar. The ionic liquids make up of cations which contain straight or branched hydrocarbon chains were easily absorbed into the polymeric membrane allowing the nanoporous structure soaked up and saturated with the ionic liquids.

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R3

N R1 R2

R1= CH2CH3 R 2= H R 2= H R1= NH2(CH2)3CH3 R 2= H R1= (CH2)3CH3 R 2= H R1= (CH2)5CH3 R 2= H R1= (CH2)7CH3 R1= (CH2)9CH3 R 2= H R 2= H R1= CH3CH2OCH2CH2 R1= CH3OCH2CH2 R2 = H R1= CH3CH2 (OCH2CH2)2 R2= H R1= CH3CH2(OCH2CH2)3 R2= H R 2= H R1= CH2CH2

R3=CH3 R3=CH3 R3=CH3 R3=CH3 R3=CH3 R3= (CH2)3 R3=CH3 R3=CH3 R3=CH3 R3=CH3 R3=CH2CH3

1-ethyl-3-methylmidazolium (emim+) N-aminopropyl-3-methylmidazolium (NH2pmim+) 1-butyl-3-methylmidazolium (bmim+) 1-Hexyl-3-methylmidazolium (hmim+) 1-octyl-3-methylmidazolium (omim+) 1-decyl-3-methylmidazolium (dmim+) 1-(2-ethoxyethyl)-3-methylmidazolium (EtOEtmim+) 1-(2-methoxyethyl)-3-methylmidazolium (MeOEtmim+) 1-[2-(2-ethoxyethoxy)-ethyl]-3-methylmidazolium (Et(OEt)2+) 1-[2-(2-[2-ethoxyethoxy]-ethoxy)-ethyl]-3-methylmidazolium (Et(OEt)3+) 1-ethenyl-3-ethyl-imidazolium (eneim+)

R1 R4 N R3 R1 N R1= (CH2)7CH3 N R2 R 2= H 1-octylpyridinium(OPy) R2 R1= CH2CH3 R1= (CH2)2CH3 R1= (CH2)7CH3 R2=CH2CH3 R2= (CH2)2CH3 R2= (CH2)7CH3 R3=CH3 R3=(CH2)2CH3 R3=(CH2)7CH3 R4= CH3OCH2CH2 Diethylmethyl(2-methoxyethyl)ammonium (Et2MeMoEtN+) R4= (CH2)2CH3 Tretrapropilammonium(Pr 4N+) R4= CH3 Triocthylmethylammonium(Oc 3MeN+)

ANIONS
CF3 O S N O S CF3 CF3CF2 O S O N O S O CF2CF3

Cl

Chloride (Cl-)

O O bis((trifluoromethyl)sulfonyl)imide (NTf2-) F P

bis((perfluoroethyl)sulfonyl)imide (BETI-)
N

NO3 Nitrate (NO3 ) O CF3 S O

-

F F

F F

F B F CN

F F Hexafluorophosphate (PF6-) O CH3(CH2)7 O S

CN

F Tetrafluoroborate (BF 4-)

Dicyanamide (dca-) O

CH3O(CH2)2O(CH 2)2 O S O O Diethylenglykolmonomethyl ethersulphate (MDEGSO4-) CN

O Trifluoromethanesulfonate(TfO -) O CH3 O S O

O Octylsulfate(OcSO4-)

O CH3CH2 O S O NC

B CN

CN

CH3-COOAcetate (CH3COO-)

O Methylsulfate(MeSO4-)

O Ethylsulfate(EtSO4-)

Tetracyanoborate (B(CN) 4-])

Fig. 1. Example of ions involved in ILs.

3. Mechanism of transport through supported ionic liquid membranes The solution-diffusion model has been used to explain the transport mechanism of organic molecules through supported ionic liquid membranes [15,19]. In this model, the driving force is due to the concentration gradient existing between the feed and receiving phases, so the ux of the organic species is assumed to be given by the Fick rsts law. Under the hypothesis of the absence of concentration polarization phenomena in the membrane interfaces, since both compartments are vigorously stirred, the transport process of the solute from the feed phase to the receiving phase involves ve consecutives steps (Fig. 3): 1. Forced convection from the bulk of the feed solution to the feedmembrane interface. 2. Partition of the substrates between the feed phase (Cf ) and the IL immobilized in the organic membrane (C ).

3. Diffusion across the liquid membrane to the membranereceiving interface under the action of the concentration gradient. 4. Partition of the substrates between the IL immobilized in the organic membrane (Cri ) and the receiving phase (Cr ). 5. Forced convection from the membrane-receiving interface to the bulk of the receiving phase. Assuming no accumulation of the solutes in the membrane and liquids lms, the overall equation of the permeation is: J = P(Cf Cr ) (1)

where J is the mass ux of solute and P is the permeability of the membrane. Based on the solution-diffusion model, the permeability of a specic compound can be expressed in terms of the partition coefcient of this compound between the liquid membrane phase (ionic

L.J. Lozano et al. / Journal of Membrane Science 376 (2011) 114

Fig. 3. Schematic drawing of the concentration prole in a supported liquid membrane (SLM) process.

between the ionic liquid phase immobilized in the membrane and the feed/receive phase (K) has been observed by several authors [14,17], nding that the increase in the K values for the compounds was reected in an increase in the P values. A mathematical correlation between these parameters has been established by de los Ros et al. [19], being the diffusion coefcient into the ionic liquid phase calculated by the empirical WilkeChang equation, with the bulk diffusion coefcient dened as D = 7.4 108
0.5 M 0.5 T

Vm 0.6

(3)

where M, and are the molecular weight (g mol1 ), the association parameter and the viscosity (cP) of the solvent (ionic liquid), respectively. Vm is the molar volume of the diffusant (solute) at its normal boiling point (cm3 mol1 ) and T is the temperature (K). The WilkeChang equation can be substituted in Eq. (2), yielding Eq. (4): P=C K Vm 0.6 (4)

where C is a constant term at a xed temperature for each supported liquid membrane (Eq. (5)): C = 7.4 108
0.5 M 0.5 T

(5)

Fig. 2. Scanning electron micrographs of the (a) Nylon membrane (3040) (scale bar = 5 m) and the Nylon membrane impregnated with [bmim+ ][PF6 ] by pressure (b) (1010) (scale bar = 10 m) and by vacuum (c) (1010) (scale bar = 10 m).

liquid) and the feed/receiving phase, the diffusion coefcient and the thickness of the membrane as indicates Eq. (2) [43]: P = KD l (2)

This relationship between the permeability values of several com pounds (P) and the partition coefcient of these compounds

As can be seen in Eq. (4), the permeability can be expressed in terms of the partition coefcient (K) and the molar volume of the diffusant (Vm ) for each supported liquid membrane. Fig. 4 shows the plot of the permeability values of different organic compounds from one organic phase (n-hexane) to another organic phase (n-hexane) versus K/Vm 0.6 for the SLM based on [bmim+ ][PF6 ]. As can be seen, a straight-line passing through the origin was obtained, showing that the relationship between P and K and Vm was adequately established. This relationship allows the easy prediction of the capability of a given SLM based on IL to separate two compounds by simply evaluating the partition coefcient of each compound between the ionic liquid and the feed/receiving phase and the molar volume of each compound at its boiling point. Exceptions to the solution-diffusion model as the transport mechanism of organic molecules through supported ionic liquid membranes have been reported. In this context, the transport of four solutes including proline benzyl ester, phenylalanine methyl ester, phenylglycine methyl ester and the zwitterionic form of phenylalanine through a SILM was evaluated by Fortunato et al. [40]. The partition coefcient (K) of each solute between the ionic liquid and the aqueous phase was also determinate by these authors, founding rather differences between them, being the K value for phenyl alanine near cero. However, the permeability values were very similar for the different solutes, which was quite surprising if we consider solution-diffusion model as the transport mechanism. These results were explained by the fact that the

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These basic equations are applicable in ideal situations where the solubility and diffusivity of the permeating gas molecules are constant and independent of molecular concentration and interactions between the molecules and the media in which they travel. Several predictive correlations for gas solubilities in ionic liquids [13,4752] and gas diffusivities in ionic liquids [5357] have been proposed in the last years. The most useful models to predict gas solubilities in RTILs are those based on the regular solution behaviour of RTILs [58], specically the Camper Molar Volume Model (limited to imidazolium-based ionic liquids) [59,60] and the Kilaru Viscosity Model [61]. Correlations to predict diffusivity of gases have been developed for imidazolium- [5355], ammonium[57] and phosphonium-based ionic liquids [56]. 4. Congurations of supported ionic liquid membranes Since the concept of SILMs is quite similar to that of conventional SLMs, it seems logical that the same membrane congurations used in the latter will be useful when ionic liquids are used as carriers in supported membrane operation. Flat-sheet supported liquid membranes (FSSLMs) are useful to obtain rst data about the permeation of a given solute. With this purpose, FSSLMs based on ionic liquids have been used for studying the separation of organic compounds [1417] and gases [34,35]. However, for practical purposes, membrane congurations with higher surface area to volume ratio, such as spiral wound and hollow ber modules are required. In hollow ber modules, the ionic liquid is conned, by capillarity, within the pores of the hollow bers, and the aqueous feed and strip solutions circulate by each side of the ber, thus, the solid membrane serves both as a support for the ionic liquid and as a uniform barrier between the aqueous solutions, which usually circulate within the inner (feed solution) and the outer (strip solution) of the ber. This results in two aqueous/ionic liquid interfaces with well dened transfer areas. This conguration has been successfully applied for the separation and recovery of lactic acid using quaternary ammonium salt (Aliquat 336) and phosphonium salt (CYPHOS IL101) as membrane solvent [62]. Other useful SILMs congurations are: - Gelation of SILMs, a gel is formed to avoid the owing of the ionic liquid away from the gelled membrane. It is worthy to note that enhanced CO2 gas transport have been achieved by using physically gelled ionic liquid membranes compared to similar IL-based solid polymers [63]. - Polymer inclusion membranes, in which the solid support is created with the carrier phase included within. Recently, polymer inclusion membranes based on ionic liquids have been used as proton exchange membranes in fuel cells at elevated temperatures [64]. Furthermore, these membranes have been successfully used for the removal of chromium(III) from acidic aqueous using 2-ethylhexylphosphonic acid (D2 EHPA) as an ion carrier and tricaprylylmethylammonium chloride (Aliquat 336) as a plasticizer [65]. - Other advanced SILMs technologies, though not essentially supported ionic liquid membranes in themselves, used a solid microporous barrier to separate the aqueous phases from the organic solution. Including in this concept is: non-dispersive solvent extraction (NDSX) and pseudo-emulsion hollow ber strip dispersion (PEHFSD). In NDSX operation mode two hollow bers modules, similar to those used in supported liquid membranes with hollow ber modules, are needed to complete the operation; in the rst module, the ionic liquid circulates by one side of the bers, whereas

Fig. 4. Plot of the permeability values of the different organic compounds from one organic phase (n-hexane) to another organic phase (n-hexane) versus K/Vm 0.6 for the SLM based on [bmim+ ][PF6 ].

transport mechanism is mainly regulated by the mobility of water inside the IL, rather than the ionic liquid selectivity towards the solute. In these systems, in an initial period, transport is mainly regulated by the ionic liquids selectivity towards each solute. However, in the course of the experiment, water microenvironments are formed and, therefore, transport through these microenvironments becomes the dominant mechanism. The formation of water microenvironments inside the organic phase, which constitute new, non-selective environments for solute transport, leading to a deterioration of the SLM performance and selectivity. It is worthy to note that molecular dynamics simulations can help to prevent the formation of these water microenvironments. In this context, a recent work [44] analysed by molecular dynamics simulations the structure and dynamic of water microenvironments in ionic liquid of different cation and anion composition, concluding that, at low water mole fractions, the water structure is dependent upon the strength of the wateranion attraction and that the IL cations have a noticeable impact on the water rotational motion. The transport mechanism of gases through supported ionic liquid membranes has also been studied over the last years by a number of groups [42,45,46]. The basic governing principle in solution-diffusion-based mass transport process applicable to gas separation in ionic liquids is embodied in the following Eq. (6): Ji = Pi l pi (6)

where Ji is the steady-state ux through the membrane of the gas i, Pi the permeability coefcient and pi the change in partial pressure across the membrane, respectively. In a dense liquid or solid lm, it is assumed that solutiondiffusion is the mode of gas transport and, therefore, the ideal permeability (Pi ) of a given gas can be expressed in terms of the solubility coefcient (Si ) (in moles per volume per partial pressure) and diffusion coefcient (Di ) (Eq. (7)): Pi = Si Di (7)

The ideal selectivity for a given gas pair (i/j ) is calculated as the ratio of the ideal permeabilities of the gases of interest and can be separated into both solubility and diffusion contributions (Eq. (8)): i/j = Pi SD = i i Pj SjDj (8)

L.J. Lozano et al. / Journal of Membrane Science 376 (2011) 114

Fig. 5. Schematic view of transport mechanism of Fe(III) from sulfuric acid media with the ionic liquid (PJMTH+ )2 (SO4 2 ) by PEHFSD with single hollow ber module.

the feed solution circulates by the other side of the ber bundle, the loaded ionic liquid phase then passed to the second module where the stripping operation is carrying out. Then, the ionic liquid is recirculated to the rst module. An interesting application of nondispersive solvent extraction using ionic liquids has been reported by Luis et al. [66] They carried out the sulfur dioxide removal from a gas stream with a typical composition of roasting processes using a ceramic hollow ber contactor with an ionic liquid, 1-ethyl-3methylimidazolium ethylsulfate, as absorption solvent. PEHFSD process comprises a unique membrane module for extraction and stripping, one stirred tank for feed phase homogenization and one stirred tank for preparation of a pseudo-emulsion. This pseudo-emulsion consists of an organic phase, which contains an ionic liquid, and a strip solution which is dispersed into the organic solution. Both phases are pumping to the module by two gear pumps capable of variable ows. When the process begins, the organic phase of the pseudo-emulsion wet the microporous wall of the ber because of its hydrophobic nature. When the operation ends, the characteristics of the pseudo-emulsion should be such that it should have clear and fast phase separation when mixing is stopped. The recovery of the extracted solute from pseudo-emulsion can be accomplished, pseudo-emulsion breaks down after the mixing of the organic and receiving phases stopped, and strip and organic phases separate (typically very few minutes) automatically. Recently, the pseudoemulsion based hollow ber strip dispersion technology has been successfully applied to the removal of chromium(III) [36] and iron(III) [37] from acidic media using ionic liquids as carriers dissolved in an organic solvent. Fig. 5 shows an schematic view of transport mechanism of Fe(III) from sulfuric acid media with the ionic liquid (JET+ )2 (SO4 )2 by PEHFSD with single hollow ber module. In the two above advanced membrane technologies, the interface between the aqueous/organic phases was maintaining at the pore by applying a higher pressure to the aqueous phase than to the organic or pseudo-emulsion phases. The differential pressure was always kept below the breakthrough pressure. Also, these technologies can work either in countercurrent or concurrent ows of the respective phases, and in the recirculation or one through modes of the feed solution. 5. Stability of supported ionic liquid membranes One of the most important properties for the industrial application of SILMs is their stability. This aspect is of special interest in liquid-liquid contacting since, in this case, there is partitioning

Fig. 6. EDX spectra of the Nylon membranes impregnated with [bmim+ ][PF6 ], [bmim+ ][BF4 ] and [bmim+ ][NTf2 ] (a) before and (b) after seven days operation in n-hexane/n-hexane.

of the ionic liquid and contacting phases which can minimized but normally not eliminated. Therefore, stability studies of SILMs prepared by several methods at different operating conditions (e.g. surrounding phases, pressure and temperature) have been reported [40,6772]. The immobilization method was also found to have inuence on the membrane stability. A comparative study of the preparation of SILMs by two different methods, under pressure and vacuum was reported by Hernandez Fernandez et al. [39]. They use the ionic liquids [bmim+ ][Cl ], [bmim+ ][BF4 ], [bmim+ ][PF6 ] and [bmim+ ][NTf2 ] as liquid phase supported on a Nylon membrane. Small losses of ionic liquid were observed when the ionic liquid was immobilized under pressure after 7 days of operation in a diffusion cell. However, the losses of IL were higher when immobilization was carried out under vacuum, specially with the most viscous ionic liquids ([bmim+ ][PF6 ] and [bmim+ ][Cl ]). This behaviour was explained by the higher viscosity of these ILs which makes it difcult to penetrate into the middle of the deeper pores of the membrane and the ionic liquid was mainly immobilized on the most external layer of the membrane and, consequently, the immobilized ionic liquid is more easily removed during operation. The inuence of the ionic liquid composition on the stability of the resulting SILM in organic environments has also been analysed. In this context, de los Rios et al. [9] analysed the stability of SILMs based on [bmim+ ][PF6 ], [bmim+ ][BF4 ] and [bmim+ ][NTf2 ] using Nylon membranes as support in n-hexane/n-hexane. Stability tests were performed by keeping the respective impregnated membranes immersed for a week in a diffusion cell including two independent compartments and using n-hexane/n-hexane as the respective feed and receiving phases. Fig. 6 shows the microstructure of the Nylon membrane impregnated with [bmim+ ][PF6 ] after cell operation, which could be compared with the appearance of the SILM before cell operation (Fig. 2b). It was concluded that most of the ionic liquid from the external surface of the membrane disappeared during cell operation. However, comparison of the SEMEDX spectra taken from membranes before (Fig. 7a) and after (Fig. 7b) immersion in the n-hexane/nhexane solution showed that they were very similar. The EDX spectra are taken from a sample of up to a few micrometers thick/depth and shows that the contribution of ionic liquid within the membrane pores is more important than the accumulated liquid found on the surface. Consequently, from the SEM study it was deduced that only the ionic liquid deposited on the external mem-

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Fig. 7. Scanning electron micrograph of the Nylon membrane impregnated with [bmim+ ][PF6 ] after seven days operation (3040) (scale bar = 5 m) in n-hexane/nhexane.

brane surface has been stripped off during operation. The amount of ionic liquid retained in the membrane pores, however, was apparently kept constant and, consequently, the membrane was stable against the possible solvent action of n-hexane. From the SEMEDX study, it was concluded that, in all three cases studied of ILs supported on Nylon membranes, no substantial losses of ionic liquid occurred after a week of operation in an nhexane/n-hexane diffusion cell. Only minimal losses of the ionic liquid accumulated on the external surface of SLMs were detected qualitatively by the SEM pictures. The stability of a SILM based on [bmim+ ][BF4 ] supported in a Nylon membrane has been also been analysed in other organic solvents, such as n-hexane/tert-butyl methyl ether and n-hexane/dimethyl sulfoxide [67]. The SEMEDX study of the membranes after continuous operation showed that the stability of the supported liquid membrane increase with the decrease of the polarity of the solvent used. The relationship established between polarity and stability allows the design of more stable SILMs for use in organic environments. The stability of SILMs based on 1-n-alkyl-3-methylimidazolium hexauorophosphate (n = 4, 8, 10) supported in PVDF membrane towards contacting aqueous phase has been also analysed [10,40,68], resulting to be stable at the assayed conditions. These authors highlighted the importance of the consideration of two main possible effects on the performance and stability of SILMs in water mediums: (a) the loss of ionic liquids organic phase from the supporting membrane to the adjacent aqueous solutions by

dissolution/emulsication and (b) the formation of water microenvironments inside the ionic liquids organic phase, which constitute new, non-selective environments for solute transport, leading to a deterioration of the SLM performance and selectivity. Stability studies of SILM have been also carried with gases as contacting phases [46,69,70]. The stability of SILMs based on the ionic liquid [Et(OEt)2 + ][PF6 ] supported in Durapore hydrophobic PVDF was studied at 25 C with a pressure difference of 1.2 bar [69]. Experiments concerning stability showed that after eight cycles the permeability of H2 slightly decreased while the CO2 /H2 ideal selectivity improved. Other interesting example was reported by Hanioka et al. [70], who examined the long term stability of a SLM based on a functionalized ionic liquid ([NH2 pmim+ ][NTf2 ]) in the separation of the CO2 /CH4 gas mixture at atmospherical pressure. These authors did not found observable change in permeability or selectivity after 260 days operation. Scovazzo et al. [46] analysed the stability of SILMs used in the separation of gas pairs CO2 /CH4 and CO2 /N2 using continuous ows of the mixed gases. They achieved long-term stability in continuous operation, from 24 to 106 days, by using imidazolium ionic liquids supported in hydrophilicPVDF or hydrophilicPES membranes, respectively, without performance degradation under CO2 -partial pressures of at least 207 kPa. Temperature stability has a great interest for some applications of SILMs in gas separation, such as capture of CO2 from coal gasication plants. Ilconich et al. [71] analysed the stability of a SILM based on [hmim+ ][NTf2 ] supported in a polysulfone organic membranes in the selective separation of CO2 from He at high temperature. This membrane was found to be stable up to 125 C, the failure of the membranes above that temperature being attributable to support failure rather than any effect on the ionic liquid. Recently, Myers et al. [72] reported operating [hmim+ ][NTf2 ] supported in Nylon membranes up to 300 C. It was also found that permeability in this [hmim+ ][NTf2 ]-membrane increased with temperature while the selectivity decreased. All the above mentioned SILMs were prepared using microltration membranes and operated with low varying pressure differential (<2 bar). To avoid the pitfall of liquid instability associated with micron porous membranes, nanoltration membranes were used which greatly reduce the instability problem, but potentially at the expense of increased gas transport resistance provided by the NF membranes [42]. Experimental stability tests demonstrated that the impregnated ionic liquids did not discharge from the NF membrane structure even under a high transmembrane pressure of 10 bar. The test results suggest that SILMs supported on nanoltration membranes offer a good stability able to sustain high gas phase pressure relevant to practical applications. 6. Fields of application of supported liquid membranes The use of supported ionic liquid membranes in different elds of application has received growing attention in the last decade, due to the advantages that SILMs offer, presenting the number of paper published in this eld per years an exponential growth. Some representative examples of these applications will now be described. 6.1. Separation of organic compounds One of the most studied applications of SILMs is the selective separation of organic compounds. The rst example was reported by Branco et al. [14], who studied the selective transport of 1,4-dioxane, 1-propanol, 1-butanol, cyclohexanol, cyclohexanone, morpholine and methylmorpholine as a model seven-component mixture of representative organic compounds. For that, four ionic

L.J. Lozano et al. / Journal of Membrane Science 376 (2011) 114

Acetaldehyde

CH3-CHO R2-OH R1-COO-R2+ CH2=CHOH

flavour ester

R1COO-CH=CH2

LIPASE

+
LIPASE

+
H2 O R1-COOH + CH2=CHOH CH3-CHO

Fig. 8. Stoichiometric scheme of kinetically controlled synthesis of avour esters by transesterication from vinyl esters and alcohols catalysed by CaLB.

liquid based on the 1-n-alkyl-3 methylimidazolium combined with the anions hexauorophosphate or tetrauoroborate, immobilized in different organic polymeric membranes were used. The use of the ionic liquid [bmim+ ][PF6 ] immobilized in a polyvinylidene uoride membrane; allowed an extremely highly selective transport of secondary amines over tertiary amines (up to a 55:1 ratio). Other interesting examples were reported on the use of SILM for the selective separation of the substrates and products of transesterication reactions. The biosynthesis of organic esters commonly used in the perfumery and avour industries can be carried out by transesterication from vinyl esters and alcohols catalysed by enzymes in non-conventional media (i.e. n-hexane [32] and ionic liquid [73]) at low water content. Therefore, as can be observed in Fig. 8, when the biochemical reaction reach the equilibrium, the reaction medium could consist of a mixture of alcohol, vinyl ester, organic acid and alkyl ester (avour ester). The possibility of using SILMs for the selective separation of these reaction mixtures has been extensively analysed [33,7477]. No appreciable permeability differences between the organic compounds were observed with the plain Nylon membranes, suggesting that such membranes cannot be used for selective separation of the target compounds. The situation changed dramatically when imidazolium-based ionic liquids containing [PF6 ], [BF4 ] or [dca ] anions were supported in the polymeric membranes. In these cases, substantial permeability differences between the target compounds were found on the basis of not only their functional groups but also of their alkyl chain lengths. These results were quite encouraging and suggested that these SLMs based on ILs could be use for the selective separation of the organic esters from the reaction mixture. After knowing the feasibility of using the IL as liquid phase for the selective separation of transesterication reaction mixtures, researchers have tried to establish rules for the optimal design of ILs for use in these separations [77]. For that, the permeability of four different compounds involved in a transesterication reaction (vinyl butyrate, 1-butanol, butyl butyrate and butyric acid) through thirteen supported liquid membranes based on 1-n-alkyl-3methylimidazolium and 1-n-alkyl-3-methylpyridinium cations and different anions (bis{(triuoromethyl)sulfonyl}imide, hexauorophosphate, methylsulfate, 2(2-methoxyethoxy)ethylsulfate, ethylsulfate, n-octylsulfate, dicyanamide, nitrate, tetrauoroborate and chloride) immobilized in Nylon membranes were determined. It was found that selectivity values were mostly dependent on the anion composition of the ionic liquid, being increasing for a given cation ([bmim]) in the sequence: [OcSO4 ] < [PF6 ] < [NO3 ] < [BF4 ] < [dca ] < [Cl ] < [EtSO4 ] < [MDEGSO4 ] < [MeSO4 ]. As regards cation composition, it was observed that more effective supported liquid membranes were obtained with the use of dialkylimidazolium-based ionic liquid respect to the dialkylpyridinium ones. Furthermore, the decrease

in the chain length of the alkyl substituent of the imidazolium rings from [omim+ ] to [bmim+ ] (i.e. [omim+ ][PF6 ]/[bmim+ ][PF6 ]) and from [bmim+ ] to [emim+ ] (i.e. [bmim+ ][EtSO4 ]/[emim+ ][EtSO4 ] pair) led to an increase in the selectivity. Therefore, it was concluded from these results that ionic liquids containing dialkylimidazolium cations with a short alkyl chain length and sulfate anions with a short alkyl substituent could allow the separation of the target compounds with high selectivity. In a previous work, Miyako et al. [78] reported the transport of organic acids through a supported liquid membrane based on organic solvent (i.e. isooctane, toluene, n-hexane). In this case, the transport of these acids was achieved by the use of lipases. This enzyme-facilitative transport consist in the fact that organic acids are estericated by lipase in the feed phase, and the resulting ester partitions into the organic phase of the SLM and diffuses across the SLM. At the receiving phase, a lipase catalyses the ester hydrolysis into an alcohol and the initial organic acid, which are aqueous soluble. After all, the organic acid was transported through the SLM. As it has been reported above [33,7477], the advantage of the use of supported ionic liquid membrane deals with the possibility of transport of organic acids through the supported liquid membranes without the need of enzymes. SILMs have also been used for the separation of aromatic hydrocarbons from aliphatic hydrocarbons. In this context, the selective separation of benzene, toluene and p-xylene from nheptane was analysed using SILMs based on [bmim+ ][PF6 ], [hmim+ ][PF6 ], [omim+ ][PF6 ] and [Et2 MeMoEtN+ ][Tf2 N ] supported in a polyvinylidene uoride membrane [15]. It was found that aromatic hydrocarbons were successfully transported through the membrane based on these ionic liquids, the maximum selectivity to n-heptane being reached using benzene in the aromatic permeation and [bmim+ ][PF6 ] in the liquid membrane phase. The concentration of organic compounds of pharmaceutical interest from diluted buffered solutions using SILMs has been also reported. One interesting example was the concentration of penicillin G using SILMs based on [bmim+ ][PF6 ], [hmim+ ][PF6 ], [omim+ ] [PF6 ] and [Oc3 MeN+ ][Cl ] supported in polyvinylidene uoride membranes [79]. Uphill transport was achieved by using [Oc3 MeN+ ][Cl ] as a membrane solution and chloride concentration difference as a driving force of permeation. Ionic liquids have been also used as extract agent diluted in an organic solvent in SILM [16]. Martk et al. [16] reported the effectively transport of lactic acid through a SILM based on the ionic liquid tetradecyl(trihexyl)phosphonium bis(2,4,4trimethylpentyl)phosphinate dissolved in n-dodecane. 6.2. Separation of mixed gases Other interesting eld of application of supported ionic liquid membranes is the separation of mixed gases. Since SILMs may have the potential for industrial applications, specically, low pressure systems such as the treatment of bio-methane from anaerobic digesters and CO2 capture from ue gases, much effort and many resources have been expended on developing new SILMs [42,46,70,71,8083]. Scovazzo et al. [46] explored the selective separation of the gas pairs CO2 /CH4 and CO2 /N2 using continuous ows of the mixed gases using [emim][BF4 ] [emim+ ][TfO ] and [emim+ ][dca ] supported in polyvinylidene uoride and [emim+ ][Tf2 N ], [hmim+ ][Tf2 N ] and [emim+ ][BETI ] supported in a polyethersulfone membrane. The highest CO2 /CH4 and CO2 /N2 selectivities were 27 and 21.2 using the ionic liquids [emim+ ][BF4 ] and [emim+ ][Tf2 N ], respectively. The separation of CO2 , from N2 and CH4 was also successfully carried out with polymer lms of ILs synthesized from monomers of ILs with polymerizable groups such as styrene and acrylate [81]. CO2 /CH4 separations were also

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reported using SILMs based on a task-specic ionic liquids such us [NH2 pmim+ ][Tf2 N ] and [NH2 pmim+ ][CF3 SO3 ], which have functional groups capable of chemically complexing with CO2 [70]. These SILMs, with the amine-terminated ionic liquids, facilitated CO2 transport through the membrane, showing higher selectivities than with [bmim+ ][NTf2 ] for CO2 separation from the CO2 /CH4 gas mixture. The separation and enrichment of bio-hydrogen from CO2 and N2 has also been assayed using SILMs [34,69]. This separation is a previous step required for utilization of gaseous mixture obtained in the fermentation process (H2 , CO2 and N2 ) in fuel cells since the concentration of hydrogen in this gaseous mixture is not high enough for its direct application. A wide range of ionic liquids such as [bmim+ ][BF4 ], [bmim+ ][PF6 ] [hmim+ ][PF6 ], [omim+ ][PF6 ], [EtOEtmim+ ][PF6 ], [MeOEtmim+ ][PF6 ], [Et(OEt)2 mim+ ][PF6 ] and [Et(OEt)2 mim+ ][PF6 ] supported in PVDF were used. It was observed that the SILMs prepared have a much higher permeability to CO2 than to N2 and H2 . The higher selectivity values towards CO2 were reached by using [bmim+ ][BF4 ] (CO2 /N2 = 35 and CO2 /H2 = 11). Hydrogen can also be produced from a wide variety of resources, including petroleum coke, coal, and even biomass. These resources can be gasied to produce syngas (a mixture of CO and H2 ) and the resulting gas stream can be further reacted with water to produce CO2 and more H2 . The nal gas stream is a mixture of CO2 and H2 , therefore, a separation and enrichment step is needed. SILMs have been also applied to this separation process [72]. For that, an amine functionalized ionic liquid ([NH2 pmim+ ][NTf2 ]) supported in a nylon support was used. High selectivity and permeability values were reached with this membrane, since the supporting ionic liquid facilitates the transport of CO2 . Gan et al. [42] analysed the permeation of H2 , O2 , N2 , and CO in four types of ionic liquids ([bmim+ ][NTf2 ], [dmim+ ][NTf2 ], [Oc3 Me+ ][NTf2 ], [oPy+ ][NTf2 ]) supported on nanoltration membranes. It was found that gas permeation exhibited an exponential increase with increasing gas phase pressure in the range from 3.0 to 7.0 bar. The best H2 /CO selectivity was reached with [Oc3 Me+ ][NTf2 ], being the separation factor around 4, but offered permeation rate far less than [oPy][NTf2 ] which had the best permeation performance but the worst selectivity. Other interesting gas separations using SILM have been reported such as CO2 /He [71] and H2 S/CH4 [82] separations, in which selectivities up to 8.7 and 260, respectively, were reached. The effect of different operating conditions in gas separations has also been analysed. In this context, Neves et al. [84] studied the potential of using supported ionic liquid membranes based on the 1-n-alkyl-3 methylimidazolium cation for CO2 /N2 and CO2 /CH4 gas separations, analyzing, among other factors, the effect of presence of water vapour in the gas stream on gas permeability and selectivity. These authors reported that the presence of water vapour in a gas stream increases the SILMs gas permeability but decreased their CO2 /N2 and CO2 /CH4 selectivity signicantly, when comparing with a dry gas stream. This decrease in selectivity was attributed to the formation of water clusters inside the membrane, being this effect more signicant for the less hydrophobic ILs. Cserjesi et al. [80] studied the permeability for H2 , N2 , CO2 and CH4 gases and the selectivity of SILM based on a wide variety of ionic liquids at different temperatures and trans membrane pressures. They found that their permeability increased with the increase in temperature and decreased with the increase in trans membrane pressure. Furthermore, the resulting SILMs exhibited a relatively high long term stability since their permeability did not show any signicant change during the experiments. Generally authors investigating the gas separation properties of SILMs all concluded that SILMs could be used in gas separation due to their adequate permeability and high selectivity values. In

this context, Scovazzo et al. [18,46] reported that in most cases, RTIL-membranes have better ideal-separation performance than the industry standard, polymer membranes. Since selectivity depends mainly on the nature of the IL used as liquid phase, simple experiments can be done to nd a suitable IL and then the morphology (liquid, gel, polymer) to use can be decided. In this context, a polymer version could prevent in more extend the displacement of the liquid from the support pores by a pressure difference. 6.3. Pervaporation and vapour permeation Supported ionic liquid membranes have also been successfully applied to the separation of various liquids or vapour mixtures by pervaporation and vapour permeation [8587]. The major problem associated with solute recovery by these techniques is the restrictive compromise between selectivity and ux: high solute selectivity involves the use of conditions that lead to relatively low mass uxes in the membrane. This problem would be overcome, if the feed solvent could not permeate through the membrane, for example using SLMs based on ILs. In this case, solute to solvent selectivity would be unlimited and the process could be operated under conditions that provide high uxes [85]. In this context, the use of SLMs based on the ionic liquid [Pr4 N+ ][B(CN)4 ] in a nanoltration ceramic module allowed the removal of 1,3-propanediol from aqueous solution by pervaporation, increasing the selectivity of the process by more than two orders of magnitude while the permeability was only in one order of magnitude slower [85]. The removal of acetone and butan-1-ol from aqueous solution was also carried out by pervaporation using ultraltration membranes impregnated by two ionic liquids ([eneim+ ][PF6 ] and [Pr4 N+ ][B(CN)4 ]) and polydimethylsiloxane [86], founding a higher average enrichment factor of butan-1-ol using SILMs based on ionic liquids than that obtained with polydimethylsiloxane membranes. These membranes were also applied to the pervaporation separation of water and butan-1-ol binary mixtures, the higher permeation ux and enrichment factors of butan-1-ol being reached with the supported ionic liquid membranes. An interesting example reported on the use supported ionic liquid membranes in vapour permeation processes was the separation of benzene and cyclohexane [87]. It was found that benzene selectively permeated the SILMs and the separation factor increased with the increase in ionic liquid hydrophilicity. The hydrophilic liquid membrane that used N,N-diethyl-N-methyl-N(2-methoxyethyl) ammonium tetrauoroborate gave the highest separation factor, 185 for 53 wt.% benzene and 950 for 11 wt.% benzene for the vapour permeation. This separation was also carried out using membranes of poly(vinyl alcohol) containing Ag(I) ions as the carrier, founding a separation factor of 84% when a starting solution containing 22 wt.% of benzene was used as the feed phase [88]. The comparison of these two separation systems point out the high efciency of SILMs as selective membranes. 6.4. Separation of ions An interesting eld of application of supported ionic liquid membranes is the removal of metal ions from aqueous solutions. In this context, Alguacil et al. [3638] evaluated the use of ionic liquids as carrier, diluted in an organic solvent, for the extraction of Cr(VI), Cr(III) and Fe(III) from aqueous solutions. They studied the transport of chromium(VI) from hydrochloric acid medium by pseudoemulsion membrane strip dispersion (PEMSD) using CYPHOS IL101 (phosphonium salt) as ionophore. Under the follow conditions, [Cr(VI)]0 = 0.01 g/L and [HCl]0 = 0.01 M in the feed phase and organic solution of 10% (v/v) CYPHOS IL101 in cumene, extractions exceeding 95% were obtained, and it was possible to strip

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using 1 M NaOH solution with recoveries in the 60% range [38]. Similar results were reported for the removal of Cr(VI) anions from chloride acidic aqueous solutions using polymer inclusion membranes (PIMs) based on organic solvents, which contains 41 wt.% of cellulose triacetate as the support, 23 wt.% of tri-n-octylamine as the ionic carrier, and 36 wt.% of o-nitrophenyl pentyl ether as the plasticizer [89]. Alguacil et al. also investigated the use of pseudo-emulsion based hollow ber strip dispersion (PEHFSD) for recovery of Cr(III) [36] from alkaline solutions and of iron(III) from acidic solutions [37]. They found that the permeation of chromium(III) was successfully carried out using the ionic liquid trioctyl methylammonium chloride (TOMACl) as carrier and the transport of iron(III) was facilitated by the ionic liquid (PJMTH+ )2 (SO4 )2 , generated by direct reaction of the commercially available primary amine Primene JMT and sulfuric acid. Polymer inclusion membranes has been also studied for the removal of chromium(III) from acidic aqueous using 2-ethylhexylphosphonic acid (D2 EHPA) as an ion carrier and tricaprylylmethylammonium chloride (Aliquat 336) as a plasticizer [66]. Transport of small ions such as sodium (Na+ ) and chloride (Cl ) through SILM based on 1-n-alkyl-3-methylimidazolium cation has been studied [11]. The mechanism of water transport through these SILMs was analysed founding that it was mainly regulated by the mobility of water microenvironments inside the IL, rather than by molecular diffusion through the bulk of the ionic liquid. Sodium and chloride, with low afnity towards the ILs used, were found to be mainly transported through the SILM, by transport through water microenvironments inside the IL.

6.6. Electrochemical applications The observation that the electrical resistance values for supported ionic liquid membranes are comparable to those of a typically charged membrane, such as Naon 117 has suggested the possibility of using supported ionic liquid membranes in the same type of electrochemical applications than Naon membranes and in the design of new tailor-made proton conducting membranes, namely for fuel cells applications [96]. Furthermore, the relatively low resistance values obtained for the supported ionic liquid membranes also open the possibility of using this type of membranes in devices with low resistance requirements [96]. Several authors have studied the incorporation of protic ionic liquids into different polymers, including Naon, [9799] resulting in membranes with an excellent stability and proton conductivity at high temperature (100200 C), where the use of the plain polymeric membranes is limited. It was observed that the conductivity of the modied membranes was mainly dependent on the relative amount of the ionic liquid inside the membrane [98]. Furthermore, it has been recently demonstrated that it is possible to obtain membranes with tailored properties depending on the type of IL cation and its degree of incorporation [100]. Polymer gel electrolytes consisted of ionic liquids based on sulfate anion, imidazolium cation, and alkali metal cation mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt have been also prepared. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 104 to 103 S cm1 at room temperature [101]. Others types gel-type electrolyte membranes have been prepared by immobilizing N-n-butyl-N ethylpyrrolidinium N,N-bis(triuoromethane)sulfonimide-lithium N,Nbis(triuoromethane)sulfonimide (Py24 TFSI-LiTFSI) ionic liquid, IL, solutions in a poly(vinylidene uoride)hexauoropropylene copolymer (PVdFHFP) matrix. The resulting membranes were freestanding, transparent, exible and have a room temperature conductivity ranging from 3.4 to 9.4 104 S cm1 . These IL-based gel type membranes can operate without degradation up to a temperature of 110 C where they reach conductivity values of the order of 102 S cm1 . The addition of a discrete amount of ethylene and propylene carbonate (ECPC), solvent mixture to the membranes resulted in an improvement of the ionic conductivity and in a stabilization of the interface with the lithium electrode [102]. A series of polymerizable ionic liquid have been also synthesized and polymerized to prepare new type polymer electrolytes. Both systems of polycation- and polyanion-type ionic liquids having exible spacer between vinyl group and ionic liquid structure showed the ionic conductivity of over 104 S cm1 at room temperature [103].

6.5. Analytical applications Supported ionic liquid membranes have also found application in analytical chemistry, specically in the trace determination of toxic. Because of the low concentration of some toxic and the complexity of the environmental samples, an enrichment step is usually needed prior to the instrumental analysis. Liquid-liquid extraction (LLE) and solid-phase extraction (SPE) are the most commonly used techniques for separation or preconcentration of toxic in environmental samples. However, these techniques often require large amounts of organic solvents, which are harmful (as VOCs) for the environment. Therefore, a variety of microextraction techniques that use no or small amounts of solvent were developed in recent years. Among them, liquid-phase microextraction (LPME) and solid-phase microextraction (SPME) are the two predominant extraction techniques for analysis of toxic [90]. Several examples of the application of ionic liquids as liquid membrane in hollow ber supported liquid-phase microextraction have been reported [91,92]. This technique, combined with HPLC, was used for the determination of chlorophenols and sulfonamides in environmental water samples. Regarding the application of ionic liquids in solid-phase microextraction (SPME), a Naon membrane-supported ionic liquid (IL)-solid phase microextraction coupled to gas chromatographymass spectrometry (GCMS) technique were developed for the simultaneous sampling and determination of ultra trace polycyclic aromatic hydrocarbons (PAHs) in aqueous samples [93]. Other example of SPME using ILs was reported by Zhao et al. [94], who developed polymeric imidazolium-based IL coatings for the extraction of esters. In the same context, Lpez-Darias et al. [95] carried out the determination of a group of eighteen pollutants in waters, including polycyclic aromatic hydrocarbons and substituted phenols, in direct immersion solid-phase microextraction (SPME) using the polymeric ionic liquid (PIL) poly(1-vinyl-3-hexadecylimidazolium) bis[(triuoromethyl)sulfonyl]imide as a novel coating material.

7. Process intensication using SILM The combination of biocatalysed reactions with supported ionic liquid membranes has been shown to be a promising integrated reaction/separation process for the synthesis of ne-chemical and pharmaceutical products. One of the most interesting applications of these systems is the kinetic resolution of racemic alcohols, since these systems integrate the enantioselective catalytic action of the enzyme and the selective permeability of the compounds through the SILM, which allows the conversion and separation of the enantiomer in a single step. The rst example of process integration using SILMs was reported by Miyako et al. [104], who carried out

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no (R)-1-phenylethanol was detected. After 24 h of operation, the (S)-phenylethanol is nearly completely separated in the receiving phase. These results demonstrate that the coupling of lipases with an SILM provides a promising basis for the development of environmentally friendly methodologies for practical production of enantiomerically pure or enriched compounds. 8. Ionic liquids: green aspects During the last ve years great interest has been shown in the study of the toxicity of ionic liquids [107113]. Different degrees of toxicity have been reported from ILs, compared to that of chemicals currently used as solvent in chemical industry, which could be explained by the enormous variety of ionic liquids. The water content of an ionic liquid have also been found to affect the degree of toxicity of ionic liquid based on PF6 anions since this anion can degrade in the presence of water and form HF [114]. From the above studies, structural information has been obtained for a rational design of safer ILs. For instance, the toxicity of ionic liquid has been correlated directly with the length of the alkyl substituent in the cation while the anion has a low effect on this parameter [108,109]. On the other hand, it should be noted that, in contrast to conventional solvents, the negligible vapour pressure usually associated with ILs would result in lower emissions and consequently in a reduced exposure. Evaluations of the risk posed by ionic liquids to the environment, compared to traditional industrial solvents, must consider not only toxicity but also this presumably reduced exposure to ionic liquids. The reduced exposure to ionic liquids is not only due to the negligible vapour pressure of ionic liquid but also to the possible lower bioaccumulation of ionic liquid. Bioaccumulation, as the capability of penetration through the membranes and accumulation into organisms, could be measured by the octanolwater partition coefcient. The higher octanolwater partition coefcient a compound, the easier to cross thought organics membranes and accumulate in the hydrophobic tissues, like brain. This parameter has been measured from a wide range of ionic liquids and is signicantly lower than that from conventional organic solvents due to the ionic nature of ionic liquids [41]. Therefore, the adjustable nature of ionic liquids, and the structuretoxicity relationship found would allow the design of more environmentally friendly ionic liquids. Anyway, deeper investigations are necessary to evaluate further risk assessment. For that, a broader set of test methods should be applied, including studies focusing on exposition pathways as well as on bioaccumulation and degradation processes. 9. Summary Supported ionic liquid membranes (SILMs) have been applied to a wide range of separation processes in different elds of application due to the possibility of design suitable ionic liquids for specic separation problems. The emergence of a considerable number of new ILs, more and more currently task-specic ionic liquids, will open up new eld of application of these SILMs. Stability studies on SILMs have corroborated their high operational and structural stability in liquid/liquid and gas/gas separations, even at relatively high-temperature/high-pressure conditions (up to 300 C and 10 bar), which makes possible their industrial application. The use of this new technology in industrial processes could also lead to minimize waste generation and savings in energy consumption, while providing high product quality. As has been evidenced in this review, the supported ionic liquid membrane technologies have been incessantly progressing during the past ten years and no limit in the future progress is currently in sight. Some key challenges for

Fig. 9. Time courses for (R)-1-phenylethanol, (S)-1-phenylethanol, vinyl laurate, (R)-1-phenylethyl laurate and lauric acid in the feed and receiving phase using the Nylon membrane with [bmim+ ][BF4 ] when vinyl laurate were used as acyl donor (conditions: initial solute concentrations, 100 mM; amount of enzyme, 80 mg; temperature, 30 C; time, 72 h).

the lipase-facilitated transport of (S)-ibuprofen through an ionic liquid-based SLM. In this system, the feed phase contains (rac)ibuprofen and lipase from Candida rugosa and the enantioselective esterication takes places in this phase. Afterwards, esters selectively pass through the SLM to the receiving phase where they are further hydrolysed by lipase from porcine pancreas. More recently, others kinetic resolutions have been carried out using this reaction/separation process, for example, the kinetic resolutions of rac-2-pentanol [105] and rac-1-phenyletanol [106] by transesterication with a vinyl ester catalysed by a commercial immobilized Candida antarctica lipase B (CaLB). In this system, the enantioselective esterication takes place in the feed phase, and the non-reacted isomer of the alcohol diffuses through the receiving phase. Fig. 9 depicts the time course of the reaction/separation process in the feed and receiving phases in the case of the kinetic resolution of rac-phenylethanol using vinyl laurate as acylating agent. As can be seen from this gure, the (S)-1-phenylethanol isomer in the feed compartment did not react with vinyl laurate since (S)-1-phenylethyl laurate was not detected, so the enantioselectivity exhibited by the enzyme was very high (e.e.Product > 99.9%). Therefore, the (S)-1-phenylethanol diffused to the receiving phase until their equilibrium concentration was reached. In contrast, the (R)-1-phenylethanol reacted with the vinyl ester in the feed compartment to form (R)-1-phenylethyl laurate. In the early stage of the experiment the unreacted (R)-1-phenylethanol diffused to the receiving phase but, when the concentration of this substrate in the feed phase was lower than that in the receiving phase, the (R)-1-phenylethanol presented in the receiving phase returned to the feed phase, where it reacted with the vinyl laurate until

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L.J. Lozano et al. / Journal of Membrane Science 376 (2011) 114 [25] R. Sheldon, Catalytic reactions in ionic liquids, Chem. Commun. 23 (2001) 23992407. [26] M.J. Earle, K.R. Seddon, Ionic liquids. Green solvents for the future, Pure Appl. Chem. 72 (2000) 13911398. [27] K. Scott, N. Basov, R.J.J. Jachuck, N. Winterton, A. Cooper, C. Davies, Reactor studies of supported ionic liquids rhodium-catalysed hydrogenation of propene, Chem. Eng. Res. Des. 83 (2005) 11791185. [28] L.C. Branco, J.G. Grespo, C.A.M. Afonso, Studies on the selective transport of organic compounds by using ionic liquids as a novel supported liquid membranes, Chem. Eur. J. 8 (2002) 38653871. [29] P. Bonhote, A.-P. Dias, N. Papageourgio, K. Kalayanasundaram, M. Gratzel, Hydrophobic, highly conductive ambient-temperature molten salts, Inorg. Chem. 35 (1996) 11681178. [30] T. Welton, Room-temperature ionic liquids. Solvents for synthesis and catalysis, Chem. Rev. 99 (1999) 20712083. [31] K. 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commercial application of supported ionic liquid technology are (i) the design of modules of sufcient size for pilot and full scale implementation, (ii) the demonstration of the stability of these modules in full scale processes under real operating conditions, (iii) the better understanding of toxicity and potential environmental impact of ILs in order to design less toxic and biodegradable ILs for industrial applications and (iv) the study of the cost-benet and the economic and life-cycle analyses of processes.

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