Journal of Membrane Science 246 (2005) 7781

Selective separation of aromatic hydrocarbons through supported liquid membranes based on ionic liquids
Michiaki Matsumoto , Yasushi Inomoto, Kazuo Kondo
Department of Chemical Engineering and Materials Science, Doshisha University, Kyotanabe, Kyoto 610-0321, Japan Received 31 March 2004; received in revised form 25 June 2004; accepted 7 August 2004

Abstract Ionic liquids are emerging as alternative solvents for volatile organic compounds traditionally used in liquidliquid extraction and liquid membrane separation. In this paper, we examine whether room-temperature ionic liquids as a membrane solution can be utilized for hydrocarbon separation by using a supported liquid membrane. Aromatic hydrocarbons, benzene, toluene and p-xylene were successfully transported through the membrane based on the ionic liquids. Although the permeation rates through the membrane based on the ionic liquids were less than those of water, the selectivity of aromatic hydrocarbons was greatly improved. The maximum selectivity to heptane was obtained using benzene in the aromatic permeation and 1-n-butyl-3-methylimidazolium hexauorophosphate in the liquid membrane phase. 2004 Elsevier B.V. All rights reserved.
Keywords: Ionic liquids; Supported liquid membrane; Aromatic hydrocarbons; Green solvent

1. Introduction Such room-temperature ionic liquids (RTILs) as green solvents for separation processes have been extensively studied because they basically have no vapor pressure, which makes them logical replacements for volatile, conventional organic solvents used in solvent extraction and liquid membrane processes [1]. Recent studies report that the extractability and selectivity of lanthanide cations with an extractant dissolved in an ionic liquid can be greatly enhanced compared to that dissolved in conventional organic solvents [2]. RTILs have great potential as solvents with novel functions as well as replacements for volatile organic solvents. Supported liquid membranes (SLMs) are porous solids whose pores are lled with liquids. SLMs are promising because they combine the processes of extraction and stripping and the amount of solvent in the SLM process is also much less than that in the solvent extraction process. However, the

Corresponding author. Tel.: +81 774 65 6655; fax: +81 774 65 6655. E-mail address: mmatsumo@mail.doshisha.ac.jp (M. Matsumoto).

instability of SLMs has limited their commercial applications [3]. Scovazzo et al. [4] states that supported ionic liquid membranes have an advantage over conventional SLMs due to the negligible loss through vaporization of RTILs, which improves the membrane stability, and to the ability to modify selectively the properties of the membrane solvent. Recently, some researchers have reported that an SLM based on RTILs [47] achieved selective transport of organic compounds such as alcohol, ketones and amines [6,7]. In this paper, we examine whether RTILs as a membrane solution can be utilized for hydrocarbon separation by using a supported ionic liquid membrane without any carriers. Recently, there is a rapid development in the eld of separation of hydrocarbons focused on the isolation of aromatics from aliphatic hydrocarbons. Especially, the separation of benzene is one of the most important and most difcult processes in the petrochemical industry [8]. The separation of benzene from hexane or cyclohexane using aqueous based SLMs has been studied [911]. Silver nitrate and triethylene glycol were used as the carrier of benzene. Furthermore, the separation characteristics of SLMs based on ionic liquids were compared to those of water.

0376-7388/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2004.08.013

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Fig. 2. Experimental apparatus: (1) supported liquid membrane; (2) feed solution; (3) receiving solution; and (4) stirring bar.

2.3. Permeation through supported liquid membranes

Fig. 1. Ionic liquids used in this study.

2. Experimental 2.1. Reagents Imidazolium-based ionic liquids, the hexauorophosphates of 1-n-butyl-, 1-n-hexyl- and 1-n-octyl-3-methyl imidazolium, [Bmim][PF6 ], [Hmim][PF6 ], and [Omim][PF6 ] were prepared following the method of Laszlo and Compton [12]. Diethylmethyl(2-methoxyethyl)ammonium bis(triuoromethan sulfon) imido salt ([Et2 MeMeON] [Tf2 N]), which proved more hydrophobic than the above imidazolium-based ionic liquids, was kindly furnished by Nisshinbo Ind. Inc. (Tokyo, Japan). The structures of the ionic liquids used are shown in Fig. 1. All remaining reagents were of analytical grade and used without further purication. 2.2. Solubility of hydrocarbons to ionic liquids We roughly measured the solubility of hydrocarbons to ionic liquids by using a calibrated test tube. Five milliliters of hydrocarbon and ionic liquid were placed in a test tube and shaken at a constant temperature (303 K) to attain equilibrium. After 2 h, the volume of the ionic liquid phase was observed and measured. Solubility was dened as the volume of hydrocarbon dissolved into 100 ml of ionic liquid.
Table 1 Solubility of hydrocarbons in ionic liquidsa Hydrocarbon Benzene Toluene p-Xylene n-Heptane Hexadecane Methanol Acetonitrile Chloroform ET (30) [13] [Bmim][PF6 ] 90 36 19 Immiscible Immiscible Miscible Miscible 90 52.3 [Hmim][PF6 ] Miscible 72 36 Immiscible Immiscible Miscible Miscible 92

A membrane material, porous polyvinylidene uoride lm (Millipore, pore size 0.45 m), was used. The supported liquid membrane was prepared at room temperature by impregnating the porous lm with the ionic liquid or water. The feed solutions were a mixture of heptane and aromatic hydrocarbon. Hexadecane was used as a receiving solution. The experimental apparatus is shown in Fig. 2. A membrane with the effective area, A, of 20 cm2 was xed in the apparatus. The transport experiment was initiated by adding 100 ml of each solution at room temperature into their respective compartments. The stirring speed of the magnetic bar in each cell was controlled at 250 rpm. Samples of hydrocarbon were withdrawn at regular time intervals, and the concentrations were determined by GLC analysis with an internal standard method.

3. Results and discussion 3.1. Solubility of hydrocarbons to ionic liquids Table 1 lists the hydrocarbons examined in this study, observations of the solubility of the hydrocarbons in the ionic liquids, and the data on the solubility in water, based on the literature [13]. Values of solubility in the ionic liquids in Table 1 come from visible observations by using the calibrated test tubes. In Table 1, the ET(30) scale indicates the polarity of

[Omim][PF6 ] Miscible 86 60 Immiscible 6 Miscible Miscible Miscible 51.2

[Et2 MeMeON][Tf2 N] 38 56 36 Immiscible Not tested Miscible Miscible Miscible

Water [11]b 1800 540 170 2.9 Immiscible Miscible Miscible 7100 63.1

ET (30) [12] 34.3 33.9 33.1 31.1 55.4 45.6 39.1

a Solubility is dened as the dissolved volume of organic solvent into 100 ml of ionic liquid. These values were based on a visual evaluation. Therefore, immiscible means that the solubility is below 0.5 ml/100 ml of ionic liquid. b Solubility at 25 C is ppm, w/v.

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Fig. 3. Transport of benzene and heptane through SLMs based on Bmim and water, benzene-[Bmim][PF6 ] ( ), heptane-[Bmim][PF6 ] ( ), benzenewater ( ), and heptanewater ( ).

Fig. 4. Determination of overall mass transfer coefcient for benzene[Bmim] [PF6 ] ( ), heptane-[Bmim][PF6 ] ( ), benzenewater ( ), and heptanewater ( ).

each compound [14,15]. Generally, polar hydrocarbons have a high solubility in ionic liquids, and the tendency of solubility to ionic liquids is similar to that of water. These data suggest that ionic liquids as a membrane solution can be used for the selective separation of aromatic hydrocarbons from a mixture of aromatic and aliphatic hydrocarbons. 3.2. Permeation of hydrocarbons through supported liquid membranes Based on the data in Table 1, we attempted the selective transport of aromatic hydrocarbons from the mixture of aromatic hydrocarbon and heptane to hexadecane. Fig. 3 shows the transport of benzene and heptane through the SLMs based on [Bmim][PF6 ] and water. As is evident from Fig. 3, benzene selectively permeated through the SLM based on [Bmim][PF6 ]. The permeation rate of hydrocarbon, J, is dened in the following ux equation [16]: J = k Cf Kr Kf Cr , (1)

simplied to Eq. (2): J = V dCf = kCf , A dt A Cf ln 0 = kt, V Cf (2) (3)

where A, V, and t are the area of the membrane, the volume of the feed phase, and time, respectively. Superscript 0 denotes the initial state. Plots on the left hand side of Eq. (3) versus t are shown in Fig. 4, which gives a linear relationship in the initial period. In addition to the [Bmim][PF6 ]-benzene/heptane system, we investigated the transport of different aromatic hydrocarbons through the SLM based on various ionic liquids and listed the obtained overall mass transfer coefcients in Table 2. We calculated the selectivity of permeation of aromatic hydrocarbon from heptane, dened in the following equation and also listed in Table 2. Starget = ktarget . kheptane (4)

where k, C and K are the overall mass transfer coefcient, the concentration of hydrocarbon and the partition coefcient of hydrocarbon between the membrane and aqueous phases, respectively. Subscripts f and r denote feed and receiving phases, respectively. It can be assumed that Kf Kr based on the data in Table 1. Therefore, Eq. (1) is

Among hydrocarbons, the permeation rates increase in the order of heptane < toluene < p-xylene < benzene for the SLM based on ionic liquids; for the SLM based on water, the permeation rates increase in the order of toluene heptane < benzene < p-xylene. It was found that the selectivity was quite different between the ionic liquids and water, although the solubility of hydrocarbons

Table 2 Overall mass transfer coefcients, k (m/h), of hydrocarbon through SLM based on ionic liquids and water Hydrocarbon Benzene Toluene p-Xylene n-Heptane Sbenzene Stoluene Sxylene [Bmim][PF6 ] 9.9 105 1.5 104 9.3 106 67 11 16 6.2 104 [Hmim][PF6 ] 1.9 104 3.6 104 5.3 105 16 3.6 6.8 8.5 104 [Omim][PF6 ] 8.2 104 3.6 104 4.8 104 1.1 104 7.5 3.3 4.4 [Et2 MeMeON][Tf2 N] 1.3 103 2.8 104 7.4 104 1.8 104 7.2 1.6 4.1 Water 3.2 103 9.4 104 7.1 103 1.0 103 3.2 0.93 7.1

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decreased as the polarity of hydrocarbons increased for both the imidazolium-based ionic liquids and water, as shown in Table 1. The permeation rates through water membrane seem to be independent on the solubility of the components in the membrane solution. As described in our previous paper [16], because the apparatus used in this permeation experiments had a high diffusion resistance in the aqueous feed, the higher permeation rates obtained for water membrane is susceptible to the diffusion resistance, resulting in the decrease in selectivity. In liquid surfactant membrane processes, the enhancement of the selectivity of hydrocarbon in the presence of additives was explained by the relative difference in the change of activity coefcients in the aqueous membrane [17,18]. If true, then in this case the tendency of the solubility cannot be explained. This is an interesting behavior, but at present it is difcult to explain it fully. The solvent impregnated in the SLM is one of the most critical factors for determining the membrane function for the transport of hydrocarbons [19]. Hence we employed three ionic liquids, [Hmim][PF6 ], [Omim][PF6 ], and [Et2 MeMeON][Tf2 N], in addition to [Bmim][PF6 ] in the liquid membrane phase to examine the effect of the ionic liquids hydrophobicity on permeation and to compare the overall mass transfer coefcients of the hydrocarbons to those when using water. Generally, the permeation rates increase in the order of [Bmim][PF6 ] < [Hmim][PF6 ] < [Omim][PF6 ] < [Et2 MeMeON][Tf2 N], following the order of the increasing hydrophobicity of the ionic liquids. They were less than those through the SLM based on water because of the high viscosities of the ionic liquids [1]. Because the hydrophobic ionic liquids with high viscosities resulted in high permeation rates, it was assumed that the permeation rates were controlled by the distribution step from the feed solution to the membrane solution. As a result, the SLM impregnated with [Bmim][PF6 ] produced the highest selectivity for aromatic hydrocarbons, especially benzene.

Nomenclature A C J K k V S t contact area (m2 ) concentration (mol/dm3 ) permeation rate (mol/(m2 s)) distribution constant of hydrocarbons between the aqueous phase and ionic liquids overall mass transfer coefcient (m/h) volume of solution (m3 ) selectivity time (h)

Subscripts f feed solution r receiving solution Superscript 0 initial state

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4. Conclusion This study demonstrates that the use of RTILs as a membrane solvent enables the SLM operation to be used for the separation of aromatic hydrocarbons. Aromatic hydrocarbons were successfully transported through the membrane based on ionic liquids. Although the permeation rates through the membrane based on ionic liquids were less than when using water, the selectivity of aromatic compounds was greatly improved. The design of RTIL-supported membrane systems will further improve the selectivity in the future.

Acknowledgment The authors wish to thank Nisshinbo Ind. Inc. for providing ionic liquid [Et2 MeMeON][Tf2 N].

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