Journal of Membrane Science 349 (2010) 611

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Journal of Membrane Science

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

Original paper

Gas separation properties of supported liquid membranes prepared with unconventional ionic liquids
Petra Cserjsi, Nndor Nemestthy, Katalin Bla-Bak
Research Institute of Chemical and Process Engineering, Pannon University, Egyetem u. 10., Veszprm 8200, Hungary

a r t i c l e

i n f o

a b s t r a c t
In this work rst supported liquid membranes (SLM) were prepared with twelve different types of ionic liquids (ILs). Then the permeability for H2 , N2 , CO2 and CH4 gases and the selectivity of the membranes were investigated in a self-designed membrane module. The effect of CO2 was also studied by measuring decrease in H2 permeability after the permeation of CO2 . Membranes with the best gas separation effectiveness were selected and the transmembrane pressure and temperature dependence of their permeability was determined applying H2 . Furthermore their stability was investigated by measuring the change in their H2 and N2 permeability and H2 /N2 selectivity as a function of time. It was found that the ILs that did not destroy the supporting membrane material, hence were suitable for membrane preparation showed adequate permeabilities and were highly selective for CO2 and CH4 . It was also shown that CO2 had an effect on each supported ionic liquid membranes (SILMs). However, the extent of the effect was slightly different in all cases. Experiments regarding the temperature and pressure dependence of membrane permeability indicated that the permeability decreased with the increase in pressure and increased with the increase in temperature. It can be stated that SILMs have adequate permeabilities, high selectivities and enhanced stability and therefore they could be successfully used in gas separation processes. 2009 Elsevier B.V. All rights reserved.

Article history: Received 18 September 2009 Received in revised form 16 October 2009 Accepted 23 October 2009 Available online 5 November 2009 Keywords: Ionic liquids Gas separation Carbon dioxide

1. Introduction Membrane gas separation is not only indispensable for certain industrial processes but it is also important from the environmental point of view. It can be used in industrial scale to separate hydrogen from ammonia purge gas [1], to sweeten natural gas [2] and to generate oxygen or inert gases [3]. Furthermore it could play an important role in environmental applications, such as VOC separation from gas streams [4] and hopefully in the very near future CO2 capture from ue gas [5] and the recovery and enrichment of biohydrogen [6]. Therefore the continuous improvement of gas separation membranes is essential. Polymeric membrane gas separation is well known for its ability to successfully separate gases and has several advantages compared to other processes, such as cryogenic distillation or absorption [7]. It is more energy efcient, easier to operate and results in higher quality products with lower environmental impact [8]. It also has disadvantages, since long-term stability of the ux and the membrane material is still not proved to be reliable [9] and there is a trade-off between permeability and selectivity, in

Corresponding author. Tel.: +36 88 624044; fax: +36 88 624038. E-mail address: bako@mukki.richem.hu (K. Bla-Bak). 0376-7388/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2009.10.044

most cases polymers have high permeabilities with relatively low selectivity values [10]. Improved selectivity and permeability hence better separation can be achieved by applying supported liquid membranes [11]. A supported (or immobilized) liquid membrane consists of two phases, a supporting porous membrane and a liquid phase, which is mostly an organic solvent and held in the pores by capillary forces [12]. The separation takes place in the liquid phase according to the solution diffusion model, in which the diffusion coefcient is at least threefour orders higher than in polymer membranes, so the permeability is expected to be much higher [13]. However, SLMs are not stable enough, they suffer from ux decline with time because the liquid phase evaporates or gets easily displaced from the pores due to transmembrane pressure difference [14,15]. The extension of SLM lifetime was attempted by liquid membrane gelation, surface modication and with the application of ionic liquids [16]. Ionic liquids are salts composed of organic cations and organic or inorganic anions. They are liquid at room temperature and by denition have low melting points [17]. They are chemically and thermally stable, have non-detectable vapour pressure and relatively high viscosity [18]. The replacement of the organic phase of a SLM with an IL consequently leads to a much more stable membrane, which is often referred to as supported ionic liquid membrane [19].

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Research on SILMs has just recently turned toward the direction of gas separation. Scovazzo et al. [20] investigated the permeation of CO2 , N2 and CH4 gases through SILMs prepared with ILs consisted of common [emim] cation and various water stable anions [NTf2 ], [CF3 SO3 ] and [dca]. They reported permeabilities in the range of 26257875 1018 m2 s1 Pa1 , 75382.5 1018 m2 s1 Pa1 and 232.5705 1018 m2 s1 Pa1 respectively and observed an interesting 50% increase in CO2 permeability in [emim][NTf2 ] with decreasing gas phase pressure from 19 kPa to 1.5 kPa. CO2 /CH4 and CO2 /N2 selectivities ranged from 4 to 20 and from 15 to as high as 61 at the upper bound of a CO2 /N2 Robeson plot of representative polymers. Gan et al. [21] studied the permeability of H2 , O2 , N2 , CO and CO2 through SILMs supported on nanoltration membranes applying ILs with a common [NTf2 ] anion and four different cations: [bmim], [omim], [N8881 ] and [C8 Py]. They reported permeability of 112.5 1018 m2 s1 Pa1 for H2 and a negligible value for CO at gas phase pressure of 3 105 Pa (3 bar).
Table 1 The ionic liquids used in this study. Short name Name Chemical structure

Neves et al. [22,23] examined O2 , N2 and CO2 permeability and CO2 /H2 , CO2 /N2 and H2 /N2 ideal selectivity for [bmim][PF6 ], [omim][PF6 ], [hmim][PF6 ] and [bmim][BF4 ] IL based SILMs. They observed that all SILMs had the highest permeability for CO2 and that the permeability was affected by the alkyl chain length of the IL cation and by the anion. 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. The objective of this work is to prepare SILMs with two well-known ILs ([bmim][BF4 ]), ([emim][CF3 SO3 ]) and with ten different types of commercially available novel ILs (AmmoengTM 100, EcoengTM 1111P, Cyphos 102, Cyphos 103, Cyphos 104, Cyphos 106, Cyphos 166, Cyphos 163, Cyphos 169 and [SEt3 ][NTf2 ]), applying hydrophobic porous PVDF at sheet membrane as a supporting phase, in order to compare their gas separation effectiveness with each other and to nd the SILM which can be successfully applied in gas separation processes. Therefore their permeability

Water content (w/w, %)

Purity

Source

[bmim][BF4 ]

1-Butyl-3-methylimidazolium tetrauoroborate

0.13

>97%

Solvent Innovation GmbH, Cologne, Germany

AmmoengTM 100

0.21

>95%

EcoengTM 1111P

1,3-Dimethylimidazolium dimethylphosphate

0.78

>98%

Cyphos 102

Trihexyltetradecylphosphonium bromide

0.04

>95%

Cyphos 103

Trihexyltetradecylphosphonium decanoate

4.68

>95%

IoLiTec GmbH & Co. KG, Germany

Cyphos 104

Trihexyltetradecylphosphonium bis(2,4,4trimethylpentyl)phosphinate

0.07

>95%

Cyphos 106

Triisobutylmethylphosphonium tosylate

1.22

>95%

Cyphos 166

Tetraoctylphosphonium bromide Tetrabutylphosphonium bromide Ethyltributylphosphonium diethyl phosphate

0.01

>95%

Cyphos 163

0.01

>95%

Cyphos 169

0.01

>97%

[emim][CF3 SO3 ]

1-Ethyl-3-methylimidazolium triate

0.83

>99%

[SEt3 ][NTf2 ]

Triethylsulfonium bis(triuoromethylsulfonyl) imide

0.32

>99%

P. Cserjsi et al. / Journal of Membrane Science 349 (2010) 611

and ideal selectivity were measured using H2 , N2 , CO2 and CH4 gases. The main advantage of the selected novel ILs is that they are commercially available in technical quantities for reasonable price and therefore represent an interesting new possibility in the eld of gas separation by supported liquid membranes. Furthermore Cyphos type ILs have strongly hydrophobic character hence they have high afnity to the supporting membrane. Since CO2 can cause unfavourable changes in the mechanical and chemical properties of the PVDF membranes used as the supporting phase due to plasticization [24] the effect of CO2 on the membranes was studied by measuring decrease in H2 permeability after the permeation of CO2 . Then membranes with the best permeability and selectivity values were selected and the effect of temperature on their gas separation effectiveness was determined by measuring the change in their H2 permeability under various temperatures. Moreover experiments were planned to determine how SILMs behave under various transmembrane pressures, since in case of SLMs there may be a pressure limitation, where the liquid is removed from the pores. Therefore it is important to study the effect of transmembrane pressure, as well. Furthermore the stability of these SILMs were investigated by detecting the alteration in their H2 and N2 permeability and H2 /N2 selectivity with time. Finding a SILM which has adequate permeability, selectivity and relatively high stability would be a remarkable breakthrough in the industrial scale application of liquid membranes in gas separation processes. 2. Experimental 2.1. Materials The used ILs, their name, chemical structure, water content, purity and their sources are listed in Table 1. The water content of the ILs was measured by KarlFischer titration and the values ranged between 0.01% and 4.68% (w/w) as shown in Table 1. After the 24 h long vacuum treatment all ILs contained less than 0.01% (w/w) water. To support the IL Durapore porous hydrophobic polyvinylidene uoride (PVDF) membrane was used. It has a pore size of 0.22 m, porosity of 75%, average thickness of 150 m and an air diffusion of 16 ml min1 cm2 (through a 23 C water-wet membrane) and was purchased from Millipore Corporation (USA). High purity nitrogen (N2 ), hydrogen (H2 ), carbon dioxide (CO2 ) and methane (CH4 ) gases (99.99%) were provided by Messer Industriegase GmbH (Germany). 2.2. Membrane preparation To prepare SILMs rst a membrane holder and conveyer equipment with the porous at sheet supporting membrane (D = 6 cm) and 1 ml of the vacuum treated IL in a Petri dish were placed in a desiccator under vacuum for 1 h in order to remove the air and water from the membrane pores. This way the hygroscopic IL could penetrate without any change in its physicochemical properties. After 1 h the membrane was conveyed into the IL and was maintained under vacuum for another 72 h. During this time the membrane became transparent since the IL penetrated into the membrane pores. Then the membrane was taken out of the desiccator and its surface was carefully dried with a soft tissue to remove excess IL. To determine the amount of immobilized IL the membrane was weighed before and after immobilization.

2.3. Experimental set-up The experimental set-up, which is shown in Fig. 1, is composed of the following parts: 1. gas feed, 2. membrane module, 3. pressure sensors, 4. interface, 5. computer and 6. voltage converter. The self-designed membrane module is built up of two stainless steel chambers separated by the SILM. Isolation is realized by o-rings and the effective membrane area is about 14.5 cm2 . Each chamber is connected to a Swagelock type pressure sensor, which measures the change in pressure with time. The data obtained through the interface can be stored in the computer and processed by the VI Logger program.

2.4. Gas permeability and selectivity measurements Permeability of all SILMs were determined for H2 , N2 , CO2 and CH4 with an initial driving force of 2 105 Pa (2 bar) and at constant temperature of 30 C, which was maintained with the help of a thermostat. The whole separation system was vacuumed before the feed gas entered the membrane module then the gas phase pressure was set and with opening one of the cells the gas permeation started. After 8 h of gas permeation from the pressure data the change in the gas volume was determined and permeability and ideal selectivity values were calculated.

2.5. Effect of CO2 permeation on permeability To determine the effect of CO2 on the permeability of the SILMs the change in H2 permeability and in CO2 /H2 selectivity was measured after the 8 h long permeation of CO2 at the same reaction conditions. The change in H2 permeability after the permeation of CO2 was compared to the change in H2 permeability after the permeation of H2 in order to prove that the change was caused by the CO2 and not by the aging of the membrane. 2.6. Effect of temperature and transmembrane pressure on permeability First SILMs with the best gas separation properties were selected with the help of an effectiveness factor, which was given as the average of the data calculated by multiplying CO2 permeability with CO2 /CH4 , CO2 /H2 and CO2 /H2 selectivity values. This way both permeability and selectivity results were taken into account. Then H2 permeability of these membranes was determined under various temperatures (20 C, 30 C, 40 C, 50 C, 60 C) and initial transmembrane pressures (1 105 Pa (1 bar), 2 105 Pa (2 bar), 3 105 Pa (3 bar), 4 105 Pa (4 bar), 5 105 Pa (5 bar)).

Fig. 1. Scheme of the experimental set-up.

P. Cserjsi et al. / Journal of Membrane Science 349 (2010) 611 Table 2 Permeability and selectivity results of the used supported ionic liquid membranes. IL Permeability (barrer) N2 [bmim][BF4 ] AMMOENGTM 100 ECOENGTM 1111P Cyphos 102 Cyphos 103 Cyphos 104 [emim][CF3 SO3 ] [SEt3 ][NTf2 ] 5.04 1.79 11.6 15.3 11.3 20.3 14.3 28.4 H2 32.2 11.9 19.9 92.6 86.6 124 37.2 112 CH4 20.3 5.76 15.6 76.5 65.1 113 21.1 81.2 CO2 93.9 93.9 127 637 487 642 486 747 Selectivity CO2 /N2 52.3 52.6 10.9 41.5 43.1 31.6 34.0 26.2 CO2 /H2 8.18 7.93 6.38 6.87 5.62 5.17 13.1 6.67 CO2 /CH4 12.9 16.3 8.12 8.32 7.49 5.66 23.1 9.20 H2 /N2 6.40 6.64 1.71 6.03 7.67 6.11 2.61 3.93 H2 /CH4 1.58 2.06 1.27 1.21 1.33 1.10 1.77 1.38 CH4 /N2 4.04 3.22 1.35 4.99 5.76 5.58 1.47 2.85

2.7. Stability measurements The operation stability of the selected SILMs was investigated for twenty-four cycles, twelve cycles of H2 and twelve cycles of N2 permeation in turn, where a single cycle was 12 h long, by detecting the alteration in their H2 and N2 permeability and H2 /N2 selectivity with time at 30 C and with an initial transmembrane pressure of 2 105 Pa (2 bar). 3. Results and discussion 3.1. Membrane preparation It was found that the Cyphos 106, Cyphos 163, Cyphos 166 and Cyphos 169 ILs were not suitable for membrane preparation because they destroyed the supporting membrane material. During impregnation the PVDF membrane discoloured and macroscopic splits were formed along its whole cross-section. 3.2. Gas permeability and selectivity Table 2 contains the N2 , H2 , CH4 and CO2 permeabilities and the selectivities of the investigated SILMs. All SILMs have the highest permeability values for CO2 and the lowest for N2 and the membrane permeabilities vary in the range of 37.5210 1018 m2 s1 Pa1 for N2 , 90840 1018 m2 s1 Pa1 for H2 , 45847.5 1018 m2 s1 Pa1 for CH4 and 7055602.5 1018 m2 s1 Pa1 for CO2 respectively. AMMOENGTM 100 has the lowest and [SEt3 ][NTf2 ] the highest permeability for the four gases tested. Although all of the SILMs are highly selective for CO2 over the other three gases, selective for H2 over N2 and CH4 and for CH4 over N2 there is a signicant variance in the ideal selectivity results. There is a 500% difference in CO2 /N2 , a 260% in CO2 /H2 , a 406% in CO2 /CH4 , a 388% in H2 /N2 , a 187% in H2 /CH4 and a 427% in CH4 /N2 selectivity. Comparing these preliminary selectivity results to the upper-bound values for the selectivity vs. permeability of polymer membranes for some common gas pairs (i.e. O2 /N2 , H2 /N2 , CO2 /CH4 ) given by Robeson [25] it can be concluded that most of these SILMs have better ideal-selection properties than the commonly used, industrial polymer membranes. The permeability and selectivity results of the SILM prepared with [emim][CF3 SO3 ] were compared to the data achieved by other scientists and it was found that the values are in high accordance. Scovazzo et al. [20] for example reported permeability of 26 barrers for N2 , 920 barrers for CO2 and an ideal CO2 /N2 selectivity of 35. 3.3. Effect of CO2 on permeability The change in H2 permeability after the permeation of CO2 and H2 is shown in Figs. 2 and 3, respectively. Fig. 4 represents the change in CO2 /H2 selectivity after CO2 permeation. It can be seen in Fig. 2 that apart from the SILM prepared with ECOENGTM 1111P

and [emim][CF3 SO3 ] the H2 permeability increased in all cases. The highest increase belongs to Cyphos 102 while the lowest one to AMMOENGTM 100. It is perceptible in Fig. 3 that after the permeation of H2 there is no signicant change in H2 permeability hence aging of the membrane does not play an important role in the change of H2 permeability.

Fig. 2. Change in H2 permeability after CO2 permeation.

Fig. 3. Change in H2 permeability after H2 permeation.

Fig. 4. Change in CO2 /H2 selectivity after CO2 permeation.

10 Table 3 Effectiveness factor of the tested SILMs. IL [bmim][BF4 ] AMMOENGTM 100 ECOENGTM 1111P Cyphos 102 Cyphos 103 Cyphos 104 [emim][CF3 SO3 ] [SEt3 ][NTf2 ]

P. Cserjsi et al. / Journal of Membrane Science 349 (2010) 611

Effectiveness factor 43.1 16.1 7.17 80.2 60.9 60.5 75.8 72.7

In accordance with the permeability change the CO2 /H2 selectivity was also affected by the CO2 permeation. In the case of ECOENGTM 1111P and [emim][CF3 SO3 ] it increased and in all other cases it decreased. Therefore it can be stated that CO2 mostly has an unfavourable effect on the permeability and selectivity of SILMs, probably due to the plasticization of the supporting polymer membrane. 3.4. Temperature and transmembrane pressure dependence of the permeability The effectiveness factor of the SILMs is reported in Table 3. The selected four ILs with the best values are: Cyphos 102, [emim][CF3 SO3 ], [SEt3 ][NTf2 ] and Cyphos 103. These ILs have relatively high permeabilities with high selectivities keeping in mind their trade-off relationship. The temperature and transmembrane pressure dependence of the selected SILMs are demonstrated in Figs. 5 and 6. It can be seen that the permeability increases with the increase in temperature and decreases with the increase in transmembrane pressure. The temperature has the most signicant effect on the permeability of Cyphos 103 increasing from

Fig. 7. Change in H2 and N2 permeability as a function of time.

5251387.5 1018 m2 s1 Pa1 and the smallest effect on [emim] [CF3 SO3 ] since here the change is less than 187.5 1018 m2 s1 Pa1 in the temperature range from 20 C to 60 C. It is not surprising taking into account the fact that IL viscosity decreases with the increase in temperature hence diffusion is enhanced. The transmembrane pressure affects also Cyphos 103 remarkably and has an almost negligible effect on [emim][CF3 SO3 ] in the range of 16 105 Pa (16 bar). It is interesting to note that with increasing transmembrane pressure the permeability should also increase since higher pressure corresponds to higher solubility therefore higher permeability. This reverse effect is mostly explained with the deformation of the shape and size of the supporting polymer membrane pores caused by elevated pressure. The deformation probably reduces the volume of the pores and the active separation area hence the permeability decreases. However, this is not proved so far and at this time we cannot give a particular explanation for the decreasing permeability. It is worth noticing that these SILMs are stable even at as high pressure as 5 105 Pa (5 bar) without a sudden increase in permeability hence without the IL being pushed out of the membrane pores. Exceeding 5 105 Pa (5 bar) the application of these SILMs would be pointless because of the low permeability values. Furthermore at 10 105 Pa (10 bar) a slight decrease in stability were observed, rst [emim][CF3 SO3 ] and [SEt3 ][NTf2 ], then at higher pressure the more hydrophobic Cyphos 102 and Cyphos 103 ILs were removed slowly from the smaller membrane pores making successful gas separation impossible. 3.5. Stability The multiple cycle H2 and N2 permeabilities and the H2 /N2 selectivity of the four previously selected SILMs are shown in

Fig. 5. Effect of temperature on H2 permeability.

Fig. 6. Effect of transmembrane pressure on H2 permeability.

Fig. 8. Change in H2 /N2 selectivity as a function of time.

P. Cserjsi et al. / Journal of Membrane Science 349 (2010) 611

11

Figs. 7 and 8. The H2 permeability values exhibited a signicant uctuation, especially in the case of Cyphos 103 and [SEt3 ][NTf2 ], where the permeability ranges from 72 barrers to 95 barrers and 78 barrers to 99 barrers, respectively. In the case of N2 the uctuation is much smaller, the change in permeability with time is less than 3 barrers regarding all SILMs. However, neither a denite increase nor a decrease can be observed in the permeability of these gases. The same can be noticed about the change of H2 /N2 selectivity since it uctuates with time, as well without a signicant alteration. Therefore it can be stated that the selected SILMs with the best effectiveness factors might be stable enough for long-term applications without a signicant change in their gas separation properties. 4. Conclusion Two well-known and ten novel types of ILs were tested for the preparation of SILMs applying hydrophobic PVDF membrane as the supporting phase. Some of the tested ILs were not suitable for membrane preparation because they destroyed the supporting membrane material. SILMs prepared with the rest of the ILs showed quite diverse but adequate H2 , N2 , CH4 , CO2 permeability and relatively high CO2 /N2 , CO2 /H2 , CO2 /CH4 , H2 /N2 , H2 /CH4 and CH4 /N2 selectivity, which were comparable to the permeability and selectivity of the polymeric membranes utilized in the industries. It was demonstrated that CO2 has an unfavourable effect on the separation properties of the studied SILMs, probably due to the plasticization of the supporting polymer membrane. After the permeation of CO2 the H2 permeability of most SILMs increased while their CO2 /H2 selectivity decreased. Four membranes with the best permeability and selectivity values were selected with the help of an effectiveness factor and the transmembrane pressure and temperature dependence of their permeability and their long-term stability were investigated. It was found that their permeability increased with the increase in temperature and decreased with the increase in transmembrane pressure. Furthermore they exhibited a relatively high long-term stability, their permeability did not show any signicant change during the experiments. Altogether it can be concluded that the SILMs have satisfying permeability and selectivity values and are stable enough to study their gas separation properties applying binary, ternary and quaternary gas mixtures in continuous and batch reactor systems in the near future. Acknowledgements The research work was supported by the Hungarian National Scientic Foundation for Fundamental Research (OTKA PD 72738) and the Czech-Hungarian Science and Technology Cooperation Programme, Grant No. CZ-8/08. References
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