Journal of Membrane Science 297 (2007) 236242

Novel ploy(vinyl alcohol)/carbon nanotube hybrid membranes for pervaporation separation of benzene/cyclohexane mixtures
Fubing Peng a,b, , Changlai Hu b , Zhongyi Jiang b,
b

College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, PR China Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China Received 2 February 2007; received in revised form 24 March 2007; accepted 27 March 2007 Available online 31 March 2007

Abstract Novel ploy(vinyl alcohol)/carbon nanotube hybrid membranes were prepared and carbon nanotube was dispersed by using -cyclodextrin (CD). These hybrid membranes were characterized by TEM, SEM and DMA. Both pure PVA and -CD-CNT/PVA hybrid membranes are uniform and these hybrid membranes exhibited signicant improvement in Youngs modulus and thermal stability as compared to pure PVA and -CD/PVA membranes. These membranes were applied to pervaporation separation of benzene/cyclohexane mixtures, and showed excellent pervaporation properties. The permeation ux of benzene could be 61.0 g/(m2 h) and separation factor could be 41.2, which are above the upper bound trade-off curve summarized by Lue and Peng. The effects of -CD-CNT content, operating temperature and feed ow rate on pervaporation properties also were investigated. 2007 Elsevier B.V. All rights reserved.
Keywords: Pervaporation; Poly(vinyl alcohol); Carbon nanotube; Hybrid membrane; -Cyclodextrin

1. Introduction Organic mixtures have conventionally been separated by extractive distillation, extraction and adsorption processes; but there are high capital investment and energy consumption for these separation technologies. Recently, pervaporation, as an environment-benign and energy-saving technology, has gained much attention to separate organic mixtures due to its high separation efciencies coupled with energy savings, especially for the close boiling point and azeotropic mixtures [1,2]. Pervaporation is a very promising membrane technology for separation of organic/organic mixtures, among which separating benzene/cyclohexane mixture is one of the most important and most difcult processes. Organicinorganic hybrid membranes have attracted considerable recent attention as potential next generation membrane
Corresponding author at: College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, PR China. Tel.: +86 731 8872238; fax: +86 731 8872238. Corresponding author. Tel.: +86 22 27892143; fax: +86 22 27892143. E-mail addresses: fbpeng@gmail.com (F. Peng), zhyjiang@tju.edu.cn (Z. Jiang).

materials [35]. Such hybrid membranes are typically composed of polymeric and inorganic materials, and have both membrane-forming properties of a polymer and physicochemical stability of an inorganics [6,7]. Inorganic particles in organicinorganic hybrid membrane are usually silica, zeolite, metal oxide nanoparticle, nanotube and so on. More recently, there has been growing interest in exploring new applications of porous carbons because of their ability to interact with molecules not only at their surfaces but also within the bulk of the material [8]. In our previous paper, we had reported PDMS-carbon molecular sieve (CMS) [9], poly(vinyl alcohol) (PVA)CMS [10], and PVAgraphite composite or hybrid membranes [2,11] for removal of benzene from aqueous solution and separation of benzene/cyclohexane mixtures. Poly(vinyl alcohol) (PVA) is polar and hydrophilic, and is an ideal membrane material to separate benzene/cyclohexane mixture [12] due to the distinct preferential adsorption/solution of PVA toward benzene over cyclohexane since the solubility of benzene in water (1.8 g/L, 298 K [13]) is one order of magnitude larger than that of cyclohexane (0.0561 g/L, 298 K [20]). But because of the big difference of solubility parameters between benzene/cyclohexane and PVA, PVA often showed lower permeability to benzene and cyclohexane. Considering the superior

0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2007.03.048

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properties such as high exibility, low mass density, plus the effective stacking interaction between carbon nanotube and aromatic compounds [14,15], carbon nanotube (CNT) is speculated to be excellent candidate for substituting or complementing conventional nanollers in the fabrication of organicinorganic hybrid pervaporation membrane [1619]. To fully explore the potential of CNT, the serious aggregation of CNTs leads to difculties in their manipulation and incorporation into polymeric matrixes [20]. The dispersion and solubility behavior of CNT can be remarkably improved through incorporation of cyclodextrin [21,22]. In our previous study, we have found that incorporation of -CD into PVA matrix could considerably enhance the pervaporation performance of benzene and cyclohexane mixtures [23]. In this study, the pervaporation properties of poly(vinyl alcohol) (PVA) membranes lled with carbon nanotubes (CNT) dispersed by -CD for separation of benzene/cyclohexane mixtures were studied. The membrane structure and properties were characterized by TEM, SEM and DMA. The effects of -CDCNT content, operating temperature and feed ow rate on the pervaporation properties of these membranes were investigated. 2. Experimental 2.1. Materials Poly(vinyl alcohol) (the degree of polymerization was 1750 50, degree of hydrolysis was 95%) was supplied by Tianjin Yuanli Chemical Company (Tianjin, China), benzene and cyclohexane were purchased from Tianjin Jiangtian Chemicals Ltd., Tianjin, China. Multi-wall carbon nanotube was purchased from Tsinghua University, China. -CD was purchased from Sigma Co. All the chemicals were of analytical grade and were used without further purication. Double distilled water was used throughout the study. 2.2. Membrane preparation The CNT was dispersed by -CD, and the preparation procedure was in accordance with that outlined by Chen et al. [22] in which a mixture of -CD and CNT (in a 30:1 ratio) was ground in an agate mortar and pestle for approximately 2 h with the dropwise addition of ethanol (1 mL) over the rst 10 min, then dried for 24 h at 348 K. This procedure resulted in a ne homogeneous black powder (-CD-CNT). Poly(vinyl alcohol) (5 g) was dissolved in 45 g distilled water at 363 K. The hot solution was ltered and to the ltrate, a certain amount carbon nanotube dispersed by -CD and 2 mL cross-linker glutaraldehyde (25 wt.% aqueous solution) as well as 1 mL of concentrated HCl catalyst were added to initiate the cross-linking reaction. The solution was gently stirred for about 4 h at room temperature and the resulting homogeneous solution was cast onto a glass plate with the casting knife. The membranes were allowed to dry at room temperature for 12 days and the completely dried membranes were subsequently peeled off. Then, the membranes were heat-treated at 393 K for 13 h, and the membrane thickness was about 80 m. The mass ratio

of -CD-CNT to PVA was varied as 0.02, 0.04, 0.06, 0.08, 0.10, 0.20 and 0.30. 2.3. Membrane characterization The structures of the pristiline carbon nanotubes and carbon nanotubes dispersed by -CD were examined by a JEOLJEM-100CX transmission electron microscopy (TEM) with an acceleration voltage of 1.0 105 V. The cross-section morphologies of the membranes were investigated by scanning electron microscopy (SEM) (XL30ESEM, PHILIPS). The membrane samples were fractured in liquid nitrogen and then coated with gold. Dynamic mechanical data were obtained with a Perkin-Elmer DMA instrument. All samples were tested within the temperature range of 298500 K at a heating rate of 5 K/min, and a frequency of 1 Hz was selected for all the experiments. 2.4. Pervaporation experiment Pervaporation experiment apparatus is shown in Fig. 1. Pervaporation experiments were performed on the P-28 membrane module (CM-Celfa AG Company, Switzerland). The effective surface area of the membrane in contact with the feed mixture is 28.0 cm2 . The vacuum in the downstream side of the apparatus was maintained (1 kPa) using a vacuum pump. After a steady state (about 2 h) was attained, the permeate liquid was collected in cold traps immersed in the liquid nitrogen. The compositions of benzene and cyclohexane were estimated by gas chromatography (Agilent 6820, USA). The results from the permeation of benzene/cyclohexane mixtures during the pervaporation were reproducible, and the errors inherent in the pervaporation measurements were in the order of a few percent. From the pervaporation data, separation performances of the membranes can be assessed in terms of total ux (J) and separation factor (PV ), and they were calculated, respectively, using the following equations: J= W At PB /PC FB /FC (1) (2)

PV =

Here W is the mass of permeate (g), A the area of the membrane in contact with the feed mixture (m2 ), t the permeation time (h), PB and PC the weight fractions of benzene and cyclohexane in the permeate, respectively, and FB and FC are the respective weight fractions of benzene and cyclohexane in the feed. In this study, benzene/cyclohexane (50/50 wt.%) mixtures were used. 3. Results and discussion 3.1. Membrane characterization 3.1.1. Transmission electron microscopy (TEM) Transmission electron microscopy (TEM) was used to directly view the structure of the pristiline carbon nanotubes and

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Fig. 1. The schematic diagram of the PV experimental equipment. (1) Heater; (2) feed tank; (3) liquid level meter; (4) thermocouple; (5) feed pump; (6) membrane cell; (7) membrane, (8) rotameter, (9) permeate collection tube; (10) liquid nitrogen trap; (11) vacuum pump.

the carbon nanotubes dispersed by -CD to investigate the dispersion result. Typical TEM images were shown in Figs. 2 and 3. As shown in Fig. 3, the dispersion of CNT by -CD was very good. CNT and -CD do interact with each other in a fashion

similar to the originally suggested by Chen et al. [22], who proposed that -CD was absorbed at the surface of nanotube ropes by van der Waals forces. 3.1.2. Scanning electron microscopy (SEM) In order to investigate the membrane structure, SEM characterization of these membranes has been carried out. The SEM results of the cross-section of pure PVA and -CD-CNT/PVA hybrid membranes are shown in Fig. 4. Pure PVA and -CDCNT/PVA hybrid membranes were dense with no connected macroscopic voids and CNT dispersed uniformly within the PVA matrix. The aggregation of CNT was obviously improved by incorporation of -CD compared with pristine CNT, which was difcult to make a uniform membrane. The -CD-CNT was well adhesive with PVA due to the good compatibility between hydrophilic -CD and hydrophilic PVA. Therefore, no nonselective defects voids could be found at the interface between the PVA and CNT additives. 3.1.3. Dynamic mechanical analysis (DMA) Fig. 5 shows the dynamic mechanical behavior of pure PVA membrane, -CD/PVA and -CD-CNT/PVA hybrid membranes. The tan curves in the temperature range from 300 to 500 K of pure PVA, -CD/PVA, and -CD-CNT/PVA hybrid membranes are shown in Fig. 5(a). There are two peaks for pure PVA and -CD/PVA membrane, and the relaxation transitions are usually labeled by and with deceasing temperature. The highest transition, the relaxation, is the glass-to-rubber transition (Tg ). Tg was decreased from 375 K for pure PVA membrane to 340 K for -CD-CNT/PVA hybrid membrane, and Tg for -CD/PVA membrane was 468 K. Fig. 5(b) shows the Youngs modulus as a function of the temperature for pure PVA membrane, -CD/PVA and -CD-CNT/PVA hybrid membranes. Among all the test membranes, the Youngs modulus of pure PVA membrane was the lowest and that of -CD-CNT/PVA hybrid membrane was the largest, which indicated that incorporating with -CD and CNT both strengthened the mechanical properties of pure PVA membrane.

Fig. 2. The TEM photographs of the pristine carbon nanotubes.

Fig. 3. The TEM photographs of the carbon nanotubes dispersed by -CD.

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Fig. 4. The SEM photographs of the poly(vinyl alcohol) membrane: (a) pure PVA and (b) 8% -CD-CNT (30/1).

3.2. Effect of -CD/CNT content on permeation ux and separation factor Fig. 6 shows the effect of -CD-CNT content on the permeation ux and separation factor. The permeation ux of benzene and total permeation ux were increased when the -

CD-CNT content increased from 0 to 6 wt.%, and decreased when -CD-CNT content increased from 6 to 30 wt.%. Both total permeate ux and permeation ux of benzene reached the maximal value when -CD-CNT content was 6 wt.%. The reasons were, rstly, -CD-CNT could enhance sorption selectivity of PVA membrane to benzene compared with cyclohexane due to the interaction between CNT and benzene molecules; on the other hand, the distribution of -CD-CNT to interfere polymer chain packing in the membrane increased the transport resistance of benzene and cyclohexane molecules. The separation factor increased with the -CD-CNT content increasing. Comparing with these three different membranes, it could be seen that the permeation ux of benzene and separation factor of -CD-CNT/PVA hybrid membranes were higher than that of pure PVA membranes and -CD-PVA membranes, which was due to the special interaction between CNT and aromatic hydrocarbon compounds. There are a lot of bonds in the CNT and they have interaction with the bonds that benzene contains. This interaction could enhance the adsorption of benzene in the membrane surface and the diffusion in the membrane. When the -CD-CNT content is 6 wt.%, the permeation ux of benzene and separation factor are 42.3 g/(m2 h) and 36.4, respectively. 3.3. Effect of operating temperature on permeation ux and separation factor The effect of operating temperature on pervaporation properties of -CD-CNT/PVA hybrid membranes is shown in Fig. 7. It could be observed that both permeation ux and separation factor increased signicantly with operating temperature increasing from 303 to 333 K. It could be also seen that the relationship of permeation ux and separation factor obeyed the Arrhenius-type relationship from Fig. 7(a). When the operating temperature was 333 K, permeation ux of benzene could be 60.0 g/(m2 h) and separation factor could be 41.2. 3.4. Effect of feed ow rate on permeation ux and separation factor As shown in Fig. 8, both total permeation ux and benzene permeation ux increased with the increase of feed ow rate, whereas permeation ux of cyclohexane changed slightly.

Fig. 5. The dynamic mechanical properties results of PVA, -CD/PVA and CD-CNT/PVA (8% -CD-CNT) membranes.

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Fig. 6. The effect of -CD-CNT content on pervaporation properties of -CD-CNT/PVA hybrid membrane (feed temperature: 323 K, feed concentration: 50 wt.% benzene, feed ow rate: 50 mL/min).

Fig. 7. The effect of feed temperature on pervaporation properties of -CD-CNT/PVA hybrid membrane (-CD-CNT content: 8 wt.%, feed concentration: 50 wt.% benzene, feed ow rate: 50 mL/min).

Fig. 8. The effect of feed ow rate on the pervaporation properties of -CD-CNT/PVA hybrid membrane (feed temperature: 323 K, feed concentration: 50 wt.% benzene, -CD-CNT content: 8 wt.%).

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Meanwhile, separation factor increased with the increase of feed ow rate. With feed ow rate increasing, the turbulence of feed solution increased and the thickness of boundary layer decreased, i.e., the extent of concentration polarization on the upstream surface of membranes decreased. Therefore, mass transfer resistance of boundary layer on the upstream of membrane decreased, which led to the increase of total permeation ux correspondingly. Since permeation ux of benzene increased while permeation ux of cyclohexane decreased a little with increasing of feed ow rate, separation factor increased with feed ow rate increasing. When feed ow rate was 110 mL/min, the permeation ux of benzene could be 52.4 g/(m2 h) and separation factor could be 50.2. 3.5. Comparison of pervaporation properties of different membranes for separating benzene/cyclohexane mixtures The intrinsic trade-off between permeability and selectivity exists in polymeric membranes. Robeson [12] has summarized the upper bound trade-off curve for O2 /N2 , CO2 /CH4 , etc. gas separation polymeric membranes, which initiate the research of polymeric membrane with high permeability and selectivity. Lue and Peng [24] have collected the pervaporation results on benzene/cyclohexane separation using various membrane materials on 5060 wt.% benzene composition at an operating temperature of 2080 C and induced the relationship between benzene/cyclohexane selectivity and benzene ux to plot an upper bound trade-off curve shown in Fig. 9. According to this upper bound trade-off curve, in our experiment, the pervaporation properties of pure PVA and -CD/PVA membranes was obviously below this upper bound trade-off curve. By incorporating CNT into PVA membrane, pervaporation properties of -CD-CNT/PVA hybrid membranes are above the upper bound trade-off curve.

4. Conclusions Incorporation of carbon nanotube, which was dispersed with -CD by grinding method, into PVA membranes could increase the permeate ux and separation factor. The -CD-CNT/PVA hybrid membrane exhibited the highest benzene permeation ux of 61.0 g/(m2 h) with separation factor of 41.2 at 333 K for benzene/cyclohexane (50/50 wt.%) mixtures, which are above the upper bound trade-off curve summarized by Lue and Peng. The -CD-CNT/PVA membranes demonstrated much better mechanical strength properties, sorption and diffusion properties than pure PVA and -CD/PVA membranes. Acknowledgments We gratefully acknowledge nancial support from the CrossCentury Talent Raising Program (Ministry of Education, China), Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT), and SINOPEC Research Program (NO. X503029). References
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Fig. 9. Relationship between the benzene/cyclohexane selectivity and normalized permeation ux of different membranes. Normalized permeation ux (kg m/(m2 h)) = permeation ux (kg/(m2 h)) membrane thickness (80 m).

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