journal of MEMBRANE SCIENCE ELSEVIER

Journal of Membrane Science 132 (1997) 193-202

Permeation and separation of benzene/cyclohexane mixtures through cross-linked poly(alkyl methacrylate) membranes
Kuniaki Inui, Haruo Okumura, Takashi Miyata, Tadashi Uragaml
Chemical Branch, Faculty of Engineering, Kansai University, Suita, Osaka, 564-80, Japan
Received 7 November 1996; received in revised form 10 March 1997; accepted 10 March 1997
~

Abstract
Poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) which have strong affinity for benzene were selected as membrane materials and the characteristics of permeation and separation for the benzene/cyclohexane mixtures through these poly(alkyl methacrylate) cross-linked with ethylene glycol dimethacrylate (EGDM) membranes by pervaporation were investigated. The cross-linked poly(alkyl methacrylate) membranes exhibited a benzene permselectivity for the benzene/cyclohexane mixtures and the permeation rate increased with increasing benzene in the feed solution. The permselectivity of their membranes was strongly governed by the diffusion separation process depending on the difference of the molecular size between the benzene molecule and the cyclohexane molecule. The depression of swelling of those membranes with the increase of the cross-linker content in the benzene/cyclohexane mixtures enhanced the benzene permselectivity. This result was attributed to the increase of the selectivity in the sorption separation process with the depression of swelling of the membrane. Furthermore, the cross-linked copolymer (PMMA-PEMA-EGDM) membranes showed excellent benzene permselectivity. These results suggested that both, the increase of affinity of the membrane for benzene and depression of swelling of the membrane, were very important in the separation of the benzene/cyclohexane mixtures.

Keywords: Affinity for benzene; Benzene/cyclohexane mixtures; Cross-linked poly(alkyl methacrylate) membranes;
Depression of swelling; Pervaporation

1. Introduction
Separation of the benzene/cyclohexane mixtures is industrially significant. As cyclohexane is produced by the addition of hydrogen to benzene with Ni or Ptcatalyst [1], the removal of the unreactant, benzene, from the reaction solution is a very important process. However, the separation of the benzene/cyclohexane
*Corresponding author. Tel.: +81-6-368-0805; fax: +81-6-3303770; e-mail: uragami@ipcku.kansai-u.ac.jp. 0376-7388/97/$17.00 1997 Elsevier Science B.V. All rights reserved. PII S0376-7388(97)00069-0

mixtures, which are close-boiling point chemicals by distillation is very difficult. One of polymer membrane separation techniques, pervaporation (PV), is very useful for the separation of such liquid mixtures. The permselectivity mechanism in PV is based on the difference in the solubility and diffusivity of permeants in polymer membranes. In the separation of the benzene/cyclohexane mixtures by PV, many polymer membranes have been studied [2-11]. Shinohara et al. have reported that 2hydroxyethyl methacrylate-methyl acrylate graft

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K. Inui et al./Journal of Membrane Science 132 (1997) 193-202

copolymer membranes [2] and 2-hydroxy-3-(diethylamino)propyl methacrylate-styrene copolymer membranes with cyanuric chloride [3] exhibited excellent benzene permselectivity for the azeotropic mixture of benzene/cyclohexane. These membranes had a phase which preferentially dissolves and diffuses benzene. In order to depress the swelling of polymer membranes in the benzene/cyclohexane mixtures, the hydrophillic polymers which have a low affinity for hydrocarbons are used. Lee et al. have reported the separation of the benzene/cyclohexane mixtures by poly(vinyl alcohol)/poly(allyl amine) blend membranes [4] and Cabasso has done so by alloy membranes of cellulose acetate and various polyphosphonates [5]. On the other hand, Okamoto et al. have studied the hydrophobic copolymer membranes having polyimide structures which show good durability of organic solvents [6,7]. Furthermore, filling-polymerized membranes have been developed. Yamaguchi et al. have prepared filling-polymerized membranes which are modified by graft copolymerization of (methyl acrylate) pores in a porous highdensity polyethylene membrane [8] as membranes for the separation of hydrocarbons. Asaeda et al. have reported the effect of cross-linker length of polymer gel on the separation of the benzene/cyclohexane mixtures in the composite membranes having crosslinked dimethylaminoethyl methacrylate gel in pores of thin silica membranes [9]. These studies suggest that the difference of affinity for polymer membranes between benzene and cyclohexane and the depression of swelling of polymer membranes were very important in the separation of the benzene/cyclohexane mixtures.
CH 3 CI"I3 I I _(_CH2_ .C_)_~_CH2_ C n_)_ _ ~ I r CH 3 ' I
I

In this study, PMMA and PEMA having strong affinity for benzene were selected as membrane materials and the characteristics of permeation and separation in PV for the benzene/cyclohexane mixtures through their membranes which depressed the swelling by cross-linking were investigated.

2. Experimental

2.1. Materials
Methyl methacrylate (MMA) and ethyl methacrylate (EMA) were purified by distillation under reduced pressure. Benzoyl peroxide (BPO) which was supplied by Nacalai Tesque Inc., recrystallized from chloroform was used as an initiator. The cross-linker, ethylene glycol dimethacrylate (EGDM), and the other solvents supplied from Wako Pure Chemical Industries, Ltd., were used without further purification.

2.2. Preparation of cross-linked poly(alkyl methacrylate ) membranes

The cross-linked poly(alkyl methacrylate) (PMMA-EGDM), (PEMA-EGDM), (PMMAPEMA-EGDM) (see Scheme 1) membranes were prepared by the copolymerization of MMA or/and EMA with EGDM using BPO as an initiator in a mold of two glass plates at 80C for 8 h under a nitrogen atmosphere. In order to remove unreactants, the membranes were soaked in benzene for 24 h and dried at room temperature in vacuum.
CH3 , I
I

.CH3

.CH3

,CH3

C=O I O
I

C=O I O
I

C=O L O
CH2 CH3

C=O I O
CH21 CH 2

C=O I o
I

C=O I o
I

C=O I o

CH3

CH21 ICH2

CH3

CH2 CH3

,cH2 CH2
o I C=O
CH3

o
C=O CH 3 PMMA-EGDM PEMA-EGDM
I

o
C=O CH3 PMMA-PEMA-EGDM
[

Scheme 1. PMMA-EGDM, PEMA-EGDM and PMMA-PEMA-EGDM structures.

K. lnui et al./Journal of MembraneScience 132 (1997) 193-202 2.3. Composition of the PMMA-PEMA-EGDM membrane
The P M M A - P E M A - E G D M membranes were put on a boat of pyrolyzer (Shimadzu PYR-2A) and were depolymerized at 400C. The composition of these membranes was determined by the measurement of the vapor composition of the depolymerized M M A / E M A mixtures on a boat of pyrolyzer with gas chromatography (Shimadzu GC-14A) [12].

195

swollen in the benzene/cyclohexane mixtures and of the dried membrane, respectively.

2.6. Measurement of the composition of benzene/ cyclohexane in cross-linked poly(alkyl methacrylate ) membrane
A sample membrane prepared in a similar manner as the measurement of the degree of swelling of membranes was put on a boat of pyrolyzer. The composition of benzene/cyclohexane sorbed in the membrane was determined by measuring the vaporized mixtures on a boat of pyrolyzer with gas chromatography [13,14]. The sorption separation factor, ~sorp,B/C, was calculated from Eq. (3), asorp,a/c = (MB/Mc)/(FB/Fc) (3)

2.4. PV apparatus and measurements

The PV cell and PV apparatus have been described in a previous paper [13]. The effective membrane area was about 13.8 cm 2. The thickness of the cross-linked poly(alkyl methacrylate) membranes was about 5 0 g m . The PV experiments were carried out at 40C. The pressure at the downstream side was maintained at 0.01 torr. The benzene/cyclohexane mixtures were used as a feed solution. The permeate was collected in U tube at liquid nitrogen temperature. After the steady state was reached, the weight and benzene concentration of the permeate were measured. The benzene concentrations in the feed solution and permeate were determined by gas chromatography. The separation factor, %ep,B/c, was calculated from Eq. (1), OZsep,B/C= (PB/Pc)/(FB/Fc) (1)

where FB and Fc are the weight fractions of benzene and cyclohexane in the feed solution and MB and Mc are the membrane, respectively.

3. Results and discussion

3.1. Permeation and separation of benzene/cyclohexane mixtures through PMMAEGDM and PEMA-EGDM membranes
Fig. 1 shows the effect of benzene concentration in the feed solution on the benzene concentration in the permeate and normalized permeation rate (J) through the PMMA-EGDM and PEMA-EGDM membranes (the molar ratio, MMA or E M A / E G D M = 100/0.25) for the benzene/cyclohexane mixtures by PV. The benzene concentrations in the permeates in the PMMA-EGDM and PEMA-EGDM membranes were higher than those in the feed solution. These results suggest that their membranes were a benzene permselectivity for the benzene/cyclohexane mixtures. The permeation rates increased with increasing benzene in the feed solution. In order to closely investigate the permselectivity for the benzene/cyclohexane mixtures through the PMMA-EGDM and PEMA-EGDM membranes, the degree of swelling of these membranes in the benzene/cyclohexane mixtures and the composition of benzene/cyclohexane in these membranes were measured.

where FB and Fc are the weight fractions of benzene and cyclohexane in the feed solution and PB and Pc are the permeate, respectively.

2.5. Degree of swelling of cross-linked poly(alkyl methacrylate ) membrane

The dried cross-linked poly(alkyl methacrylate) membranes were immersed into the benzene/cyclohexane mixtures at 40C. After the weight of membranes was constant, a sample membrane was taken out of the vessel, wiped quickly with filter paper and weighed. The degree of swelling (DS) of the membrane was calculated from Eq. (2), DS = W~/Wd (2)

where Ws and Wd are the weights of the membrane

196

K. lnui et al./Journal of Membrane Science 132 (1997) 193-202

P M M A - E G D M membrane 100 P E M A - E G D M membrane 20 15 .~ 10
.= 40

f
." !,......'~"""

100 "~ 8O

j .,"/

20

8o

...."~
~ .E 40

2o
{? 0

~?""~, ..
././""""
20

~
80 0 100

.,," /

%
}
I I I

~
40 60

20
0 0

A"
20 40

60

80

0 100

Benzene in feed (wt%)

Benzene in feed (wt%)

Fig. 1. Effect of the benzene concentration in the feed solution on the benzene concentration in the permeate ( Q ) and normalized permeation rate (J: ) through the PMMA-EGDM and PEMA-EGDM membranes (MMA or EMA/EGDM = 100/0.25) for the benzene/cyclohexane mixtures by PV.

P M M A - E G D M membrane 4 20 4

P E M A - E G D M membrane ,20 '15 ~" 3 10

.~3
Q
~ 2

2 5
6 I 0 1

20

40

60

80

100

20

40

60

80

0 O0

Benzene in feed (wt%)

Benzene in feed (wt%)

Fig. 2. Effect of the benzene concentration in the feed solution on the degree of swelling of the PMMA-EGDM and PEMA-EGDM membranes (11) (MMA or EMA/EGDM = 100/0.25) and normalized permeation rate (J: O) through the PMMA-EGDM and PEMAEGDM membranes.

In Fig. 2, the degree of swelling of the P M M A EGDM and PEMA-EGDM membranes in the benzene/cyclohexane mixtures and the normalized permeation rate (J) are shown as a function of the benzene concentration in the feed solution. The degree of swelling of those membranes increases with increasing benzene in the feed solution. These results indicated that the PMMA-EGDM and PEMA-EGDM membranes had higher affinity for benzene than for

cyclohexane. In comparing the degree of swelling between the PEMA-EGDM membrane and the PMMA-EGDM membrane, the PEMA-EGDM membrane was strongly swollen in the benzene/cyclohexane mixtures than the PMMA-EGDM membrane. PEMA seems to have higher affinity for cyclohexane than PMMA, as PEMA which has the longer ester chain is more hydrophobic than PMMA. In general, the structure of polymer membranes

K. Inui et al./Journal of Membrane Science 132 (1997) 193-202

197

,00 / P M M A - E G D M membrane
80 ~
-- - ~ - __.~." ~ -t

]00, PEMA-EGDM membrane .... ,100

80
~

.~ 80 ~

.~

......

q 80
"~ 60 / .E

"

........~x'o ~"

""

J60

60 ~- ~ i f

q~,~.o.'. .........

,~,%~.~.-'~Y

i
= o

......... .......
o

20 40 60 80 100 Benzene in feed (wt%)

20 40 60 80 Benzene in feed (wt%)

100

Fig. 3. Relationship among the benzene concentrations in the feed solution, in the PMMA-EGDM and PEMA-EGDM membranes (MMA or EMA/EGDM = 100/0.25) (rq), and in the permeate (O) for the benzene/cyclohexane mixtures by PV.

becomes rough by the swelling of membranes. The swelling of membranes causes an increase in the permeation rate, as the diffusivity of the permeants in polymer membranes is enhanced due to the rough structure. Therefore, the increase of the permeation rate with increasing benzene in the feed solution is strongly attributed to the swelling of the PMMAEGDM and PEMA-EGDM membranes. Fig. 3 shows the relationship among the benzene concentrations in the feed solution, the PMMAEGDM and PEMA-EGDM membranes and the permeate for the benzene/cyclohexane mixtures. The benzene concentrations in the PMMA-EGDM membrane were slightly higher than those in feed solution. However, the difference in these benzene concentrations is small. Moreover, there is very little difference between the benzene concentrations in the PEMA-EGDM membrane and in the feed solution. These results support the thesis that the PMMAEGDM and PEMA-EGDM membranes do not have the sorption selectivity for the benzene/cyclohexane mixtures in PV. In general, the permselectivity mechanism of liquid mixtures through polymer membranes by PV is based on the difference of solubility of permeants between polymer membranes (the sorption separation process) and the diffusivity of permeants in polymer membranes (the diffusion separation process), namely, the solution--diffusion theory [ 13-15]. In this study, as can

be seen from a comparison between the benzene concentrations in the permeate and in the PMMAEGDM and PEMA-EGDM membranes in Fig. 3, the former is higher. These facts support the argument that the PMMA-EGDM and PEMA-EGDM membranes preferentially permeate benzene from the benzene/cyclohexane mixtures. In order to reveal in detail a mechanism in the benzene permselectivity of their membranes, the sorption and diffusion selectivity were analyzed by the solution-diffusion model. The sorption selectivity, asorp,B/c, could be determined by Eq. (3) and diffusion selectivity, adiff,B/C, could be calculated from the separation factor, C~sep,B/c, obtained by Eq. (1) and the sorption selectivity by Eq. (3), using Eq. (4) [13-15]:
OLdiff,B/C ~---OLsep,B/C/O~sorp,B/C

(4)

Fig. 4 shows the effect of the benzene concentration in the feed solution on the separation factor, OLsep,B/C, sorption, asorp,a/c, and diffusion selectivity, adiff,B/C, for the benzene/cyclohexane mixtures through the PMMA-EGDM and PEMA-EGDM membranes. The separation factors decreased with increasing benzene in the feed solution. As mentioned above, the increase of benzene in the feed solution leads to a rough structure of the membrane with the swelling of the membrane. Such a rough structure enhanced the permeation rate but lowered the separation factor. On the other hand, the diffusion selectivity was higher

198

K. Inui et al./Journal of Membrane Science 132 (1997) 193-202

P M M A - E G D M membrane 10

PEMA-EGDM membrane 10

9 O ~ O ~ d i f f ~ o~

~. diff

20 40 60 80 Benzene in feed (wt%)

100

20 40 60 80 Benzene in feed (wt%)

100

Fig. 4. Effect of the benzene concentration in the feed solution on the separation factor ([~), the sorption (O) and diffusion (O) selectivity for the benzene/cyclohexane mixtures through the PMMA-EGDM and PEMA-EGDM membranes (MMA or EMA/EGDM = 100/0.25).

than the sorption selectivity. In this system, the permselectivity mechanism is strongly governed by the diffusion separation process.

Table 1 Molar volume and solubility parameter (6) of permeants

Solvent Benzene Toluene Cyclohexane

Molar volume [cma/mol] 89.4 106.8 108.7

Solubility; 6 * [(cal/cm3)1/2] 9.2 8.9 8.2

3.2. Effect of molecular size of permeant

Some hydrophobic polymer membranes such as polystyrene [ 16], poly(vinyl chloride) [ 17,18], polly(vinyl p-tert-butylbenzoate) [19] membranes showed water permselectivity for aqueous ethanol and acetic acid solutions. The permselectivity mechanism for these aqueous solutions was strongly governed by the diffusion separation process depending upon the difference in the molecular size between the permeants. Huang et al. have reported that the molecular size of permeants has strongly influenced the permeation and separation of benzene/cyclohexane mixtures in PV [11]. In order to research the effect of the molecular size of permeants on the diffusion selectivity, toluene, which has a similar molecular size as cyclohexane (Table 1) [20], was selected as the permeant and the toluene/cyclohexane mixtures were examined through the PMMA-EGDM and P E M A EGDM membranes in PV. Table 2 shows the effect of the molecular size of the aromatic hydrocarbon on the degree of swelling of the PMMA-EGDM and PEMA-EGDM membranes, separation factor, sorption selectivity, diffusion selectivity and normalized permeation rate (J) of the aromatic hydrocarbons/cyclohexane mixtures through these membranes. The sorption selectivity for the

* 6pMMA and 6PEMA calculated by the group contribution method [21] are 9.0 and 8.9, respectively.

toluene/cyclohexane mixtures was higher than for the benzene/cyclohexane mixtures. The P M M A EGDM and PEMA-EGDM membranes seem to have a slightly higher affinity for toluene than for benzene, because A6 (t~PMMA--~toluene=0.1, t~PEMA--~toluene=0) between toluene and PMMA or PEMA is smaller than
A (~ (~PMMA -- ~benzene~-0"2, ~PEMA-- ~be. . . . . ~ 0 . 3 )

between benzene and PMMA or PEMA. However, the separation factors for the toluene/cyclohexane mixtures in both the membranes were lower than those for the benzene/cyclohexane mixtures. These results were caused by the drastic decrease of the diffusion selectivity with an increase in the molecular size of the aromatic hydrocarbon. The toluene molecule has lower diffusivity in the PMMA-EGDM and PEMA-EGDM membranes than the benzene molecule. The decrease of the separation factor for the toluene/cyclohexane mixtures is significantly dependent on a decrease of the diffusivity of the toluene molecule in the membrane.

K. lnui et al./Journal of Membrane Science 132 (1997) 193-202

199

Table 2 Effect of the molecular size of the aromatic hydrocarbonson the degree of swelling of membrane, separation factor, sorption selectivity, diffusion selectivity,and normalizedpermeationrate (J) for the benzene/cyclohexaneand toluene/cyclohexanemixtures throughthe PMMAEGDM and PEMA-EGDMmembranes by PV Membrane PMMA-EGDM B/C T/C PEMA-EGDM B/C T/C 1.40 1.39 6.71 4.44
1.34

Feed solution *

DS (g/g) 1.71 1.57

c~p

c~sorp

aaur

J X 10 6 (kg m/m2h) 55.1 14.5 8.69 4.94

3.88 3.46

1.18 2.48

3.28 1.40 5.01 2.40

1.85

*B/C: benzene/cyclohexane,T/C: toluene/cyclohexane.

Furthermore, the permeation rates for the toluene/cyclohexane mixtures through the P M M A EGDM and PEMA-EGDM membranes were lower than for the benzene/cyclohexane mixtures, The decrease of the diffusivity in the PMMA-EGDM and PEMA-EGDM membranes with increasing molecular size of the aromatic hydrocarbon strongly influenced on the permeation rate also. Consequently, the diffusion separation process in this system strongly depends on the difference of molecular size between the permeants. From the above results, the permselectivity mechanism of the benzene/cyclohexane mixtures through the PMMA-EGDM and PEMA-EGDM membranes is explained by a tentative model as shown in Fig. 5, which was already proposed by Binning et al. [22] and Neel et al. [23,24]. The feed solution side of the PMMA-EGDM and PEMA-EGDM membranes is swollen by the feed solution (swelling layer), while the permeation side of these membranes is in the dry state (dense layer). The permselectivity mechanism is mainly dominated by the effectively unplasticized and unswollen fraction of the membrane at the near end of the downstream membrane face. The permeation resistance provided by the diffusion through this part of the membrane presumably overshadows the less selective and less resistive swollen upper layer of the membrane. In the swelling layer the benzene permselectivity is low owing to the rough structure of membrane by the swelling. In the dense layer the benzene molecule, which is of smaller molecular size than the cyclohexane molecule, can predominantly diffuse.

Molarvolume [cm'/mol]

89.4

108.7

Sorption

Diffusion

B ,5
I Benzene

permselectivity I

Fig. 5. Model of the permselectivity mechanism for the benzene/cyclohexane mixtures through the PMMA-EGDM and PEMA-EGDMmembranes. Consequently, the benzene permselectivity exhibited by the PMMA-EGDM and PEMA-EGDM membranes strongly depended on the diffusion separation process in the dense layer based on the difference of molecular size between the benzene molecule and the cyclohexane molecule.
3.3. E f f e c t o f E G D M c o n t e n t a s c r o s s - l i n k e r

The extremely low sorption selectivity of the PMMA-EGDM and PEMA-EGDM membranes was caused by the remarkable swelling of their

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K. lnui et aL /Journal of Membrane Science 132 (1997) 193-202

membranes in the benzene/cyclohexane mixtures. Therefore, the depression of swelling of the PMMA-EGDM and PEMA-EGDM membranes is expected to enhance the sorption selectivity and leads to a high benzene permselectivity. Generally, the degree of swelling of the cross-linked polymers in the solvents decreases with an increase of the degree of cross-linking. In order to investigate the effect of the cross-linker content on the characteristics of permeation and separation of the cross-linked polymer membranes, the PMMA-EGDM and PEMA-EGDM membranes having various EGDM contents were applied to the separation of the benzene/cyclohexane mixtures in PV. Table 3 shows the effect of the EGDM content on the degree of swelling of the PMMA-EGDM and PEMA-EGDM membranes and characteristics of permeation and separation for the benzene/cyclohexane mixtures through these membranes. The degree of swelling of the PMMA-EGDM and PEMA-EGDM membranes in the benzene/cyclohexane mixtures decreased with increasing EGDM content. The sorption selectivity slightly increased with an increase of the cross-linker content. This slight increase in the sorption selectivity is attributed to the depression of swelling of these membranes as summarized in Table 3. Consequently, the slight increase in the sorption selectivity led to a high separation factor for these cross-linked membranes. On the other hand, the depression of swelling of the P M M A EGDM and PEMA-EGDM membranes decreased

the permeation rates of these membranes because the permeation resistance in the diffusion process was increased. From the above results, it was found that the increase of the EGDM content as a cross-linker resulted in the depression of the swelling of the PMMA-EGDM and PEMA-EGDM membranes for the benzene/cyclohexane mixtures and raised the benzene permselectivity.
3.4. P M M A - P E M A - E G D M copolymer membranes

The PMMA-EGDM membrane exhibited non-permeability for the benzene/cyclohexane mixtures in the low benzene concentration, while the PEMAEGDM membrane exhibited permeability. The PMMA-EGDM membrane was shrunk by cyclohexane which is non-solvent for PMMA. Therefore, if the MMA component is introduced to the PEMA-EGDM membrane, the increase of the benzene permselectivity for the benzene/cyclohexane mixtures with the shrinking of the MMA component is expected. In this study, PMMA-PEMA-EGDM membranes which have various MMA contents were prepared and the PV property for the benzene/cyclohexane mixtures through these membranes was tested. Table 4 shows the effect of the MMA content on the degree of swelling of the various P M M A - P E M A EGDM membranes and the characteristics of permeation and separation for a benzene/cyclohexane mixture of 10/90 (w/w) through these membranes (the

Table 3 Degree of swelling of membrane, separation factor, sorption selectivity, diffusion selectivity, and normalized permeation rate (J) for the benzene/cyclohexane mixtures through the PMMA-EGDMand PEMA-EGDMmembranesby PV Membrane PMMA-EGDM 100/0.25 100/1.0 100/2.5 100/5.0 PEMA-EGDM 100/0.25 100/1.0 100/2.5 100/5.0 1.40 1.36 1.32 1.26 6.71 7.51 8.57 9.35 1.34 1.49 1.70 2.04 5.01 5.04 5.04 4.58 8.69 4.99 3.37 1.56 1.55 1.45 1.37 1.17 3.99 4.29 4.65 5.98 1.22 1.46 1.70 2.21 3.27 2.94 2.74 2.71 33.7 26.6 8.79 4.56 Monomer/EGDM (molar ratio) DS (g/g) c~sep C~sorp a~iff J 106 (kg m/m2h)

K. Inui et al./Journal of Membrane Science 132 (1997) 193-202

201

Table 4 Effect of the MMA content on the degree of swelling of membrane, separation factor, sorption selectivity, diffusion selectivity, and normalized permeation rate (J) for a benzene/cyclohexane mixture through the PMMA-PEMA-EGDM membranes by PV MMA/EMA/EGDM (molar ratio) 0/100/0.25 30/70/0.25 50/50/0.25 70/30/0.25 DS (g/g) 1.40 1.28 1.22 1.16 C~sep 6.71 8.34 11.4 21.5 asorp 1.34 1.92 2.63 3.44 adife 5.01 4.34 4.33 6.25 J x 10s (kg m / m 2 h) 869 186 50.3 8.92

Feed solution: benzene/cyclohexane = 10/90 (w/w).

molar ratio, the alkyl methacrylate/EGDM = 100/0.25). The MMA/EMA ratio in the PMMAPEMA-EGDM membrane was the same as that in the feed. The separation factor drastically increased with increasing MMA content. Particularly, the PMMA-PEMA-EGDM membrane with MMA content of 70 mol% showed an excellent benzene permselectivity, O~sep,B/C : 21.5. The increase of a shrinking component (MMA) in the PMMA-PEMA-EGDM membranes led to the decrease of the degree of swelling of the membrane and increase of the sorption selectivity, C~so~p,B/C, and consequently gave a high benzene permselectivity. On the other hand, in comparing the PMMAPEMA-EGDM membranes, depressed by the swelling of membrane due to the introduction of the shrinking component (MMA), with the PEMAEGDM membranes having an increase of the cross-linker (EGDM), the former exhibited higher benzene permselectivity than the latter. In the separation of the benzene/cyclohexane mixtures, the copolymerization seems to be a more efficient membrane improvement than the cross-linking of the homopolymer.

4. Conclusions

swelling of the membrane for the benzene/ cyclohexane mixtures. 2. As the diffusion selectivity decreased with increasing molecular size of the aromatic hydrocarbon, the benzene permselectivity of the PMMAEGDM and PEMA-EGDM membranes in PV depended significantly on the diffusion separation process in the dense layer of membranes attributed to the difference of molecular size between the benzene molecule and the cyclohexane molecule. 3. The depression of swelling of the PMMAEGDM and PEMA-EGDM membranes with the increase of EGDM content as a cross-linker enhanced the benzene permselectivity. These results suggested that the difference of the affinity for polymer membranes between benzene and cyclohexane was very significant. 4. The PMMA-PEMA-EGDM membranes showed excellent benzene permselectivity. This improvement of benzene permselectivity was mainly caused by the depression of swelling of the membrane by a shrinking of the MMA component for which cyclohexane is non-solvent. If a component which has lower affinity for cyclohexane than MMA is introduced to the PEMA-EGDM membrane, it is expected that much higher benzene-permselective membranes will be developed.

I. The PMMA-EGDM and PEMA-EGDM membranes showed that benzene permselectivity and the permeation rate remarkably depended on the swelling of these membranes. The permselectivity for the benzene/cyclohexane mixtures through those membranes in PV was strongly governed by the diffusion selectivity in the dense layer of membranes because the sorption selectivity was lowered by the remarkable

References
[1] T. Asahara, N. Tokura, M. Okawara, J. Kumanotani and M. Senoo, Youzai Handbook, Koudansya, 1976, Chap. II, p. 219. [2] J. Terada, T. Hohjoh, S. Yoshimasu, M. Ikemi and I. Shinohara, Separation of benzene-cyclohexane azeotropic mixture through polymeric membranes with microphase separated structures, Polym. J., 14 (1982) 347.

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