Journal of Membrane Science 390–391 (2012) 175–181

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Journal of Membrane Science

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Separation of ethyl acetate (EA)/water by tubular silylated MCM-48 membranes

grafted with different alkyl chains
Shufeng Wu a,∗ , Jinqu Wang b , Guangli Liu a , Yue Yang a , Jinming Lu b
a
Lanzhou Petrochemical Research Center, PetroChina, Lanzhou 730060, China
b
Institute of Adsorption and Inorganic Membrane, Dalian University of Technology, Dalian 116012, China

a r t i c l e i n f o a b s t r a c t

Article history: The MCM-48 type materials and membranes had been successfully silylated with different alkyl chains
Received 7 July 2011 (methyl, propyl and n-octyl). The silylated MCM-48 membranes prepared on supports with pore size
Received in revised form of 1 ␮m had a good effect on separation of the ethyl acetate (EA)/water mixture. The materials were
14 November 2011
characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), IR spectroscopy, perva-
Accepted 19 November 2011
poration. These results showed that the silylated MCM-48 type materials could adsorb large amount
Available online 8 December 2011
of EA, about 145 mg/g for C8 H17 -MCM-48 at 7 kPa at the room temperature, which was ten times of
the Si-MCM-48 . Besides this, the C8 H17 -MCM-48 membranes had EA/H2 O separation factor of 251 at
Keywords:
Silylated MCM-48 membrane
room temperature and 123 at 50 ◦ C with the total flux 4.3 and 6.6 kg/(m2 h), respectively. The long-chain
Adsorption amount alkyl groups grafted in the membrane pore could enhance temperature tolerance of the membrane for
Pervaporation separating EA/H2 O. Under the same conditions, the CH3 - and C3 H7 -MCM-48 membranes had lower sepa-
Separation factor ration factor and larger total flux. The phenomenon in the separation experiments was controlled by the
solution-diffusion mechanism. EA molecules were firstly adsorbed in the silylated pores selectively and
made up a compact hydrophobic membrane, which could prevent the penetration of the water, resulting
in the high EA selectivity.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Ethyl acetate is a very important industrial chemical and excel-

Distillation is a main method for the separation of oil/water
mixture, which is important for the recycle of valuable organic
materials. But the method is not suitable for the purification of the
organic compounds with low concentration because of the high
energy consumption of the process. Recently, membrane-based
separation process had been proposed and the results showed
that it was a clear and energy saving unit operation for the
recovery of aimed products with low concentration [1,2]. The
membranes included hydrophilic membranes and hydrophobic
membranes. Hydrophilic membranes were appropriate to separate
water from water/organic mixtures with a low water concentra-
tion, for example, chitosan [3], polytetrafluoroethylene [4], and
zeolite NaA membranes [5–7] and so on. Hydrophobic mem-
branes were suitable for separating organic compounds from
organic/water mixtures with low organic concentrations. Mem-
branes made from polyethylene [8], polydimethylsiloxane and
polyolefin composites [9], polyvinylidene fluoride [10] and silicalite
[11–15] had all been studied for selective organic separations.
∗ Corresponding author. Tel.: +86 931 7961614.
E-mail address: wushufeng@petrochina.com.cn (S. Wu).
lent solvent, which is widely used in the production process of
coatings and paints. Ethyl acetate is slightly soluble in water. Now,
the industrial methods for the concentration of EA are almost
based on the extractive distillation, which process contained many
practical problems, such as high energy consumption, technology
complexity and so on. Thus an eco-friendly and concise separation
process has been in demanded.
In the early stage of the last decade a new family of mesoporous
materials designated as M41S [16,17] with narrow pore size dis-
tributions and tunable from 2 nm to 10 nm was discovered using
liquid crystal surfactant as templates. The materials included three
typical structures: MCM-41 which had two-dimension hexagonal
pores structure, MCM-50 with a laminar crystal that was not fit
for the transportation and MCM-48 which was the most promis-
ing material in the field of mesoporous inorganic membrane due
to their three-dimension (3D) pore structure and narrow pore size
distribution. Up to now, many studies have been reported on the
preparation of MCM-48 membrane on various supports, such as
glass [18], Al2 O3 plate with 100 nm pore size [19–22], tubes with
fine pores [23] and so on. Our team [24,25] had successfully syn-
thesized the MCM-48 membranes on the large pore ␣-Al2 O3 tubes
which are more available in industry. But the pure MCM-48 mem-
brane was only mesoporous separation membrane, which had no

0376-7388/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.11.034
176 S. Wu et al. / Journal of Membrane Science 390–391 (2012) 175–181

affinity for a particular species. Besides this, the materials had poor
hydrothermal stability because the Si–O–Si bond in the mesopore
walls could be easily hydrolyzed under the hydrothermal condition.
For this purpose, Nishiyama [22] synthesized the silylated MCM-
48 membranes on the Al2 O3 plates with pore size about 100 nm
and used the membrane in the separation of oil/water mixture.
Kumar [26] prepared the NH2 -MCM-48 membrane and used it in
the separation of CO2 . At presence of the other groups grafted in the
membrane pores, the membrane materials not only were protected
from the collapse of the pore walls, but also had special affinity for
particular species.
In this work, we reported the successful preparation of sily-
MCM-48 membranes with different length alkyl chains on large
pore supports. Moreover, the separation of EA/water mixtures was
carried out to test the sily-MCM-48 membranes. The effect of
temperature and pressure on the separation performance was sys-
tematically investigated and the separation mechanism was also
discussed.

2. Experimental

2.1. Preparation of MCM-48 membranes

The MCM-48 membrane was prepared on outer surface of
large pore supports by vacuum coating method [25]. The tubu-
lar ␣-Al2 O3 supports (11.5 mm in outer diameter, 8 mm in
inner diameter, 13 cm in length, about 1 ␮m pore diameter,
∼38% porosity) were seeded with MCM-48 powders with size
about 1 ␮m by vacuum coating. The MCM-48 powders were
prepared by the method of Ref. [25]. The final molar composi-
tion of the synthesis sol for preparation of MCM-48 membrane
was 1TEOS:0.25Na2 O:0.45CTAB:62H2 O. The reactants used in the
research were all analytical grade reagents. The pre-coated tube,
each end of which was sealed with teflon cap was placed perpen-
dicularly at the bottom of the stainless steel autoclave, which was
statically heated for 72 h at 373 K after synthesis sol was added.
Then the autoclave was quenched with tap water and the tube
was washed with deionized water, finally was dried at 333 K for
24 h. The membranes were calcined in air at 823 K for 6 h after
the final hydrothermal synthesis with heating and cooling rates
of 0.25 K/min and 1.0 K/min, respectively.
2.2. Silylation of the MCM-48 powders and the membranes
The coupling reagents (triethoxymethylsilane, propyltri-
ethoxysilane, n-octyltriethoxysilane) were industrial products.
0.1 mol/L coupling agent solution was prepared in toluene, in
which process H2 O avoided touching the coupling reagent. The
tubular MCM-48 membranes were placed perpendicularly at the
bottom of the autoclave. The coupling reagent solution was then
added into the autoclave. The autoclave was statically heated for
10 h at 333 K. Then the membranes were washed with toluene and
tetrahydrofuran twice, respectively, finally were dried at 323 K for
24 h.
2.3. Separation of EA/water mixtures
The separation of the EA/water mixture with 5 wt% EA was
carried out with the different silylated MCM-48 membranes by per-
vaporation (PV). Fig. 1 shows the flow chart of the pervaporation
with vacuum method. By PV performance, the permeation amount
of EA was much more than that of H2 O in permeation side. Because
ethyl acetate/water was not completely miscible, the mixture pre-
sented two layers. The quantity of organic compound and water
passing through the membrane was calculated by measuring the
total quantity and the volume of the two phases. In the PV system,
Fig. 1. Flow chart of enrichment of EA by pervaporation with vacuum method. 1,
Feed solution; 2, feed pump; 3, heater; 4, membrane separator; 5, cold trap; 6,
vacuum pump.
the cool trap was immersed in liquid nitrogen, which condensation
temperature was −196 ◦ C. At this temperature, the saturation vapor
pressure of water and EA is less 1.2 Pa and 100 Pa. According to the
actual situation of experiments, the pressure across the membrane
was selected 0.02–0.08 MPa. The pressure difference was produced
by vacuum pump (as shown in Fig. 1) in permeate side, while the
pressure of feed side was atmospheric pressure. The liquid flow rate
was selected 150 ml/min.
2.4. Characterization
The MCM-48 powders and membrane were simultaneously
obtained after the hydrothermal synthesis. The mesostructure of
the MCM-48 powders and membrane were studied by low angle
diffraction with Cu K␣ radiation at 40 kV and 50 mA. The morphol-
ogy of the cross-section of MCM-48 membranes was observed by
SEM in a KYKY-2800B scanning electron microscope. The IR of the
silylated MCM-48 type materials was carried out on the Bruker
EQUINOX55 spectrometer and the adsorption of organic gas on the
Cahn-2000 electrobalance.
3. Results and discussion
3.1. Characterization of the MCM-48 membranes
Fig. 2 presented the SEM images of the surface and the cross-
section of the calcined Si-MCM-48 membrane that was synthesized
on vacuumed supports [25]. Apparently, both the surface and the
cross section were continuous and crack-free. At the presence of
coated MCM-48 layer on the surface of porous support, few MCM-
48 granules were seen in the depth of the support and a continuous
membrane with thickness about 4 ␮m was obtained, indicating
that the penetration of the synthesis sol could be effectively pre-
vented from penetrating into the inner support. The formation of
MCM-48 membrane was self-assembly of SiO2 and liquid crystal
template. Not like the growth of ZSM-5 membrane, the strength of
self-assembly was weak. The vacuumed MCM-48 materials could
not change the self-assembly balance between support and syn-
thetic solution in the interface. So it was superior to form a good
 S. Wu et al. / Journal of Membrane Science 390–391 (2012) 175–181 177

14

Permeance/[10 mol/(Pa.s.m )]
2
12

-8
10 CH3 -MCM-48 membrane
C3H7 -MCM-48 membrane
C8H17 -MCM-48 membrane

8
0.6 0.8 1.0 1.2 1.4 1.6 1.8
ΔP/Bar

Fig. 3. N2 permeation of the silylated MCM-48 membranes.

211

220

Intensity

(a)

(b)
2 4 6 8 10
Fig. 2. SEM images of the calcined MCM-48 membrane, (a) surface; and (b) cross
2theta/(deg.)
section.

Fig. 4. XRD pattern of the MCM-48 membranes. (a) Calcined MCM-48 membrane;
and (b) MCM-48 membrane used in pervaporation system for 1 h.
membrane on the support surface. The membranes possessed the
features that a compact inorganic membrane should have, such
as thin functional separation layer and large pore supports. The
(d)
permeance of the calcined membranes prepared in this work was
evaluated by a soap-films flow meter at room temperature. The (c)
results showed that the membrane had a permeance of about (b)
1.9 × 10−7 mol m−2 s−1 Pa−1 for N2 , and relatively high ideal sepa-
(a)
Ttansmittance

ration factor for H2 /N2 3.33. Besides this, the Knudsen contribution
to the total flux for N2 permeation of the membrane was about
97.8%, indicating that there were only about 2% defects exiting in
the membrane. Fig. 3 shows the N2 permeation of the CH3 -, C3 H7 -
and C8 H17 -MCM-48 membranes. As shown, the N2 permeance of
the silylated MCM-48 membranes was all lower than calcined ones,
indicating that the pore volume of MCM-48 materials could be
occupied by alkyl groups. Especially, the C8 H17 -MCM-48 mem-
brane had about one half of the permeance of calcined membrane.
Fig. 4a shows the XRD patterns of the calcined MCM-48 mem- 500 1000 1500 2000 2500 3000 3500 4000
brane that prepared on the pretreated support. As noted, they were Wave numbers / cm
-1

all compatible with the cubic Ia3d space group and represented
the 3D mesoporous MCM-48 membrane materials. The cubic struc- Fig. 5. IR spectra of MCM-48 zeolites, (a) Si-MCM-48; (b) CH3 -MCM-48; (c) C3 H7 -
ture of the mesoporous phase was confirmed by the distinct (2 1 1), MCM-48; and (d) n-C8 H17 -MCM-48.

(2 2 0) reflections, suggesting that it was superior to form a good

structure at presence of the diadochic coating layer.
3.2. Alkylation and adsorption of the MCM-48 powders
Fig. 5 was the IR spectra of the Si-MCM-48 and silylated MCM-
48 powders. The absorption peak of 1080 cm−1 and 802 cm−1 were
caused by the stretching vibration of Si–O–Si bond in the MCM-
48 skeleton. The absorption peak of 456 cm−1 was corresponding
to the bending vibration of Si–O–Si bond. The absorption peak of
956 cm−1 was the characteristic absorption of silica mesoporous
zeolites caused by the symmetry stretching vibration of end-group
of Si–OH. After alkylation of the MCM-48, the absorption peak of
178 S. Wu et al. / Journal of Membrane Science 390–391 (2012) 175–181
150
120
Adsorption amount / (mg/g)
90 CH3-MCM-48
C3H7-MCM-48
60 C8H17-MCM-48
Si-MCM-48
30
0 0
1 2 3 4 5 6
P / kPa
Fig. 6. Adsorption isotherms curve of ethyl acetate on MCM-48 materials.
956 cm−1 was disappeared as shown in Fig. 5b–d, indicating that
the Si–OH group in the surface of mesopores were connected with
the coupling reagent, in other words, the alkyls were successfully
grafted in the mesopores of MCM-48 materials. The relatively broad
absorption peak located at 3200–3600 cm−1 was attributed to the
hydrogen bonds of Si–OH and H2 O in the surface of mesopores and
the absorption peak at 1650 cm−1 was corresponding to adsorbed
water peak in the pores. The intensity of these peaks had a signifi-
cant reduction after the alkylation, also suggesting that the surface
of mesopores were covered by the alkyl chains. The intensity of
the broad peak of n-octyl-MCM-48 was the smallest among these
samples, since the most space of internal channels was occupied
by n-octyl groups. Furthermore, the direct evidence to the intro-
duction of alkyl groups was the absorption characteristics near
2900 cm−1 caused by the –CH3 and –CH2 –. With the growth of alkyl
chain length, the absorption peak intensity increased gradually at
this position.
Fig. 6 was the adsorption equilibrium curve of ethyl acetate for
MCM-48 materials at room temperature. The saturated vapor pres-
sure of EA is 13.3 kPa at room temperature. In order to protect the
adsorption apparatus, the highest adsorption pressure was selected
at 7 kPa. As shown in Fig. 6, the adsorption amount of unmodi-
fied MCM-48 for EA was smallest. By contrast, the adsorption of EA
for MCM-48 modified by three different alkyl chains had a great
increment. Among the three samples, adsorption amount of EA
for CH3 -MCM-48 was relatively smallest. The carrier could only
reach about 130 mg/g. The C3 H7 -MCM-48 and C8 H17 -MCM-48 had
almost the same adsorption for EA, about 140 mg/g. The reason was
that although the pure Si-MCM-48 had the large surface area, the
nature of the surface was neutral, which could not adsorb some
species selectively. After the alkylation of the materials, the pore
surface of the material was covered by the hydrophobic alkyl chain.
The alkyl chains changed the nature of surface to hydrophobic and
therefore could enhance the adsorption amount of the hydrophobic
molecules, such as EA. As for C3 H7 -MCM-48 and C8 H17 -MCM-48,
they had same adsorption amount for EA, the possible reason was
that the C8 H17 – groups grafted in the MCM-48 pores could take
more pore volume, which prevented more adsorption amount in
the pores. According to the different separation results of the two
membranes, it indicated that the amount of EA adsorbed tightly
on the pore surface of C8 H17 -MCM-48 membrane was more than
that of C3 H7 -MCM-48 membrane. In contrast with the adsorption
results of ethyl acetate, the adsorption isotherms curve of H2 O on
the silylated MCM-48 materials was shown in Fig. 7. As shown, the
adsorption amount of these materials for H2 O was in the range of
5–12 mg/g, which was about one tenth of that for EA, indicating
14
12
Adsorption amount / (mg/g)
10
8
6
C8H17-MCM-48
4
C3H7-MCM-48
2 CH3-MCM-48
7 1 2 3 4 5 6 7
P / kPa
Fig. 7. Adsorption isotherms curve of water on MCM-48 materials.
that the hydrophobic of MCM-48 membrane was highly enhanced
by grafting hydrophobic groups. Among the three materials, the
C8 H17 -MCM-48 had the biggest change of hydrophobic property,
while the CH3 -MCM-48 had the least.
3.3. Effect of the feed temperature on the separation performance
The pure MCM-48 membrane had no selectivity for ethyl acetate
(EA) and water, so there was no effective separation for EA/water
with pure MCM-48 membrane. Besides this, the 220 X-diffraction
peak of MCM-48 membranes was disappeared in an hour at 308 K in
this experimental system (as shown in Fig. 4b), also indicating the
bad hydrothermal stability of MCM-48 materials, which reason was
that H2 O touching the pore wall could prompt the decomposition
of the Si–O–Si bond in the pore wall. By comparison, Fig. 8 shows
the curves of the flux for ethyl acetate (EA) and water with different
feed temperature at permeation pressure difference of 0.02 MPa. As
shown, the EA and water flux of three membranes all had a rising
trend with increasing feed temperature, while the separation factor
for EA/H2 O was gradually reduced. As the feed temperature rising
in PV performance, the activity level of hydrophobic groups grafted
in the mesopores would increase, resulting in the weak adsorp-
tion strength between the hydrophobic groups and EA molecules.
Although the grafted hydrophobic groups could not be washed
away, the EA molecules adsorbed tightly in the traps of alkyl chains
would be partly loss, which caused the increase of effective pore
size of membrane and the decrease of hydrophobic property of sep-
aration membranes. This was the possible reason why the flux of EA
and H2 O was increase, while the separation factor was decreased
as the feed temperature rising. In addition, with the growth of alkyl
chain length from CH3 – (Fig. 8a) to C8 H17 – (Fig. 8c), the flux through
the membranes decreased gradually, while the separation factor
was increased correspondingly. At room temperature, the separa-
tion factor of CH3 -MCM-48 membrane for EA/water was 126, and
that of the C8 H17 -MCM-48 membrane was up to 251. These results
showed that there had a closely relationship with the modifica-
tion extent of the mesopores with the different alkyl chains. The
density of hydrophobic groups in the pore surface of CH3 -MCM-
48 membrane was less than that of the other two, which could
be proved by the difference adsorption amount of the correspond-
ing materials for EA. Longer hydrophobic chains could reduce the
pore size by a larger extent, so a more compact hydrophobic mem-
brane was formed by adsorbing the EA molecules, which allowed
the presence of higher separation factor for EA/H2 O. In order to
clear the separation mechanism, the PV performance of the sily-
lated MCM-48 membranes for H2 O at the same condition for the
 S. Wu et al. / Journal of Membrane Science 390–391 (2012) 175–181 179

7 (a) H2O 16
120
6

Separation factor of EA/water

14

Flux / (kg.m .h )
5

-1
100
Flux / (kg.m .h )
-1

12

-2
-2

80 10
3

2 8 CH3-MCM-48 membrane
EA
60 C3H7-MCM-48 membrane
1
6 C8H17-MCM-48 membrane
20 25 30 35 40 45 50 55
o
Feed temp. / C 20 30 40 50
o
Feed temp. / C
7
(b) H2O
180 Fig. 9. PV performance of the silylated MCM-48 membranes for H2 O at permeation
6 pressure difference of 0.02 MPa.

Separation factor of EA/water

5 160
Flux / (kg.m .h )

6.0 270
-1
-2

4 140 240

Separation factor of EA/water

5.6
3
210

Flux / ( kg.m .h )
-1
120
5.2
2 -2
180
EA 100
1 4.8
150

0 80 120
20 25 30 35 40 45 50 55 4.4
o
Feed temp. / C
90
4.0
6 260
60
(c) H2O 0.02 0.04 0.06 0.08
5 240
Δ P/ (MPa)
Separation factor of EA/water

220
4 Fig. 10. Effect of permeate pressure on vapor permeation performance of EA/H2 O.
Flux / (kg.m .h )
-1

200
-2

3
2 brane pores had stronger strength to restrain the activity of EA
1 EA
0 120
20 25 30 35 40
o
Feed temp. / C
Fig. 8. Effect of feed temperature on separation factor of the silylated MCM-48
membrane for EA/H2 O system, (a) methyl, (b) propyl, and (c) octyl.
EA/H2 O system was shown in Fig. 9. As shown, the total flux was
larger than that of EA/H2 O system, indicating that water could eas-
ily go through the membrane at pressure difference of 0.02 MPa
without EA. These results proved that the presence of hydropho-
bic molecules in the separation system had an important role in
enhancing the hydrophobic property of membrane.
Table 1 shows the comparison of performance date of mem-
branes in this work and in the Ref. [22]. As shown, the
(CH3 )3 -MCM-48 membrane had separation factor of 351 at 30 ◦ C.
But when the temperature was up to 50 ◦ C, the separation factor
was down to 100. In this work, although the C8 H17 -MCM-48 mem-
brane had lower separation factor 251 at 25 ◦ C, there had a higher
separation factor 123 than (CH3 )3 -MCM-48 at 50 ◦ C. These results
indicated that the temperature tolerance for separating EA/H2 O
of MCM-48 membrane was enhanced by grafted long-chain alkyl
180
groups. The probable reason was that long chains in MCM-48 mem-
160
molecules. The separation factor for EA/H2 O in the work of Ref.
140 [22] was higher than that in this work at low temperature, because
the MCM-48 membrane on fine pore plate had better compactness
than that on large pore tubular support. But at high temperature the
45 50 55
trends turned over, which reason was relation with the difference
of the alkyl chain length. In the limited pore volume of MCM-48
materials, more EA molecules could be tightly adsorbed in the traps
of the C8 H17 – groups on the pore surface than that in the traps of
the (CH3 )3 – groups. The EA molecules adsorbed tightly on the pore
surface were difficult to escape from the traps when rising up the
temperature. By contrast, with shot chains the EA molecules were
adsorbed on pore surface layer by layer, which was easy to escape
from there when temperature was high.
3.4. Effect of vacuum in the permeate side on the separation
performance
Fig. 10 shows the curves of the EA flux and the separation factor
through the C8 H17 -MCM-48 membrane with different permeate
pressure difference at 25 ◦ C. As shown from the curves, the flux of
EA was increased gradually with increasing the permeate pressure
difference, mainly duo to the increment of driving forces across the
membrane. But under high driving forces, H2 O molecules were also
forced to penetrate through the membrane, resulting in reducing
180 S. Wu et al. / Journal of Membrane Science 390–391 (2012) 175–181
Table 1
Comparison of the separation data for different MCM-48 membranes.
Membrane Temp (◦ C) Flux (kg/m−2 h−1 )
EA
25 6.12
CH3 -MCM-48
50 7.06
25 5.61
C3 H7 -MCM-48
50 6.87
25 4.05
C8 H17 -MCM-48
50 5.78
(CH3 )3 -MCM- 30 5.8
48 50 – –
Fig. 11. Separation mechanism of the EA/H2 O system by silylated membrane.
the separation factors of the system. As shown, the separation fac-
tors was 251 at the permeate pressure difference of 0.02 MPa, while
there remained 89 at the permeate pressure difference of 0.08 MPa.
With further decreased the permeate pressure difference, more
water was forced to penetrate to the permeate side and the sep-
aration factor was decreased dramatically, which was unfavorable
for the energy saving.
3.5. Mechanism of the separation of EA/H2 O by silylated MCM-48
membranes
As we all known, Si-MCM-48 membrane had no selectivity for
the separation of liquid mixtures. With the pore size of several
nanometers, the membrane could only reject the large molecules
from its solution. Nishiyama [27] investigated the reject molecu-
lar weight of polyethylene glycol with MCM-48 membrane and
concluded that the reject molecular weight was about 3800. For
the separation of gases, the mechanism followed the Kudsen diffu-
sion. However, all the pores surface of the materials was covered
with Si–OH group which could be grafted by other functional
groups to change the surface property. In this work, the meso-
pores surface of MCM-48 was grafted by different alkyl groups
which made the pore surface hydrophobic. The silylated MCM-
48 showed a good adsorption performance for EA, which carrier
could be up to 145 mg/g. From the separation performance of the
silylated MCM-48 membranes, it could be seen that hydropho-
bic groups in pores had an important role in the separation of
EA. The Fig. 11 shows the separation mechanism of the EA/H2 O
by the silylated MCM-48 membranes. The hydrophobic surface
could adsorb the hydrophobic molecules strongly, especially at
the lower temperature, resulting in the reduction of pore size.
In other words, a compact hydrophobic membrane consisted of
Separation factor Ref.
Water (EA/water)
0.92 126
In this work
2.34 57
0.58 182
In this work
1.54 84
0.30 251
In this work
0.89 123
0.39 351
[22]
100
the grafted functional groups and the adsorbed EA molecules. The
separation process followed the solution-diffusion mechanism. As
shown in the Fig. 11, the EA molecules could be dissolved in the
pores selectively, and penetrated the membrane by driving forces
of concentration difference. As for H2 O molecules, they could not
be dissolved in the hydrophobic pores and be prevented in the feed
side. But the membrane was not stabile at relatively high temper-
ature. The adsorbed molecules and adsorbed site on the surface
would be more active at the higher temperature, resulting in des-
orption of the EA molecules from the hydrophobic surface and
penetration of H2 O molecules.
4. Conclusions
The silylated MCM-48 type materials and membranes were suc-
cessfully prepared by reaction with the silane coupling reagent.
The hydrophobic groups grafted in the pores made the materials
possess a large adsorption amount of EA, about 145 mg/g for C8 H17 -
MCM-48 materials at 7 kPa at room temperature, which was ten
times of that for Si-MCM-48. Because of the good selectivity for EA,
the silylated MCM-48 membranes showed a good separation per-
formance for EA/water system. The C8 H17 -MCM-48 membrane had
a separation factor of 251 at room temperature with the total flux of
4.5 kg/(m2 h). Under the same conditions, the CH3 - and C3 H7 -MCM-
48 membranes had the separation factor of 126 and 182, the total
flux of 7.0 and 6.2 kg/(m2 h), respectively. These results suggested
that the separation process was controlled by the solution-diffusion
mechanism. Besides this, long-chain alkyl groups grafted in the
membrane pore could enhance temperature tolerance of the mem-
brane for separating EA/H2 O. The compact hydrophobic MCM-48
membrane consisted of the grafted groups and the adsorbed EA
molecules, which could permit EA molecule penetrating the mem-
brane by driving force of concentration difference and prevent the
penetration of H2 O molecules.
Acknowledgment
The authors gratefully acknowledge Dalian Institute of Chemical
Physics for the donation of ␣-Al2 O3 supports.
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