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Chinese Science Bulletin

© 2008 SCIENCE IN CHINA PRESS

Springer

Synthesis and pervaporation performance of

high-reproducibility silicalite-1 membranes
CHEN HongLiang1,2†, LI YanShuo2, Zhu GuangQi2, LIU Jie2 & YANG WeiShen2
1
Key Laboratory of Eco-remediation of Contaminated Environment and Resources Reuse of Ministry of Education, Shenyang Uni-
versity, Shenyang 110044, China;
2
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

High-reproducibility silicalite-1 membranes were synthesized on silica tubes by in-situ hydrothermal

synthesis, and the relative standard deviation (R.S.D.) of average separation factor for eight mem-
branes was only 7.5%. By using an effective method called “solution-filling (SF)”, the average flux of
membranes prepared with SF method was improved by about 49% compared to membranes prepared
without SF method, and the highest flux of membrane prepared with SF method towards ethanol/H2O
mixture at 80℃ was 1.49 kg/(m2·h). Pervaporation experiments showed that the fluxes of silicalite-1
membranes at 60℃ were 2.63, 0.87, 0.24, and 0.20 kg/(m2·h) towards methanol/H2O, ethanol/H2O,
2-propanol/H2O, and 1-propanol/H2O mixtures, respectively, and the corresponding separation factors
were 22, 69, 81, and159, respectively.

silicalite-1 membrane, solution-filling, reproducibility, silica tube

Zeolite membranes have enormous potential applica-
tions to gas separation, pervaporation, and membrane
reactors, especially MFI (silicalite-1 and ZSM-5) mem-
branes[1 3]. Compared with conventional separation
―
methods (including distillation, extraction, and sorption),
membrane pervaporation needs lower energy because
only a fraction of a mixture can pass the membrane as
vapor at lower temperature. In addition, membranes are
operated continuously without requiring the regeneration
of the sorbent, and they are modular, which allows de-
sign flexibility. These advantages make membrane
silicalite-1 membrane was only synthesized and applied
within the laboratories, no commercial modules have
come into operation until now. Before evaluating the
separation performance of the as-synthesized silicalite-1
membranes, calcination should be carried out in order to
remove the templates embedded in the channels of zeo-
lite crystals, and this may cause the formation of cracks
because of the different thermal expansion coefficients
between the supports and zeolite layers, which decreases
the separation performance and reproducibility of sili-
calite-1 membranes.
INORGANIC CHEMISTRY

processes or hybrid processes exhibit more attractive in
many industrial applications.
With the improvement of preparation and characteri-
zation, the separation performance of zeolite membranes
was improved significantly, and the first commercial
plant made up of 16 modules of zeolite A tubular mem-
brane was built up in 2001[4]. For hydrophobic sili-
calite-1 membrane, one important application is to ex-
tract ethanol from fermentation broth[5] or other organics
from low concentration aqueous solutions[6,7], but the
It is well known that the poor reproducibility of zeo-
lite membrane is a common problem, which raises the
preparation cost of zeolite membranes and influences the
application of zeolite membranes in large scale. For
example, Van de Graaf et al. reported that only 4 out of
Received July 18, 2008; accepted September 17, 2008
doi: 10.1007/s11434-008-0481-4
†
Corresponding author (email: chl@dicp.ac.cn)
Supported by the National Advanced Materials Committee of China (Grant No.
2003AA328010) and the Ministry of Science and Technology of China (Grant No.
G2003CB615802)

www.scichina.com | csb.scichina.com | www.springerlink.com Chinese Science Bulletin | November 2008 | vol. 53 | no. 22 | 3505-3510
12 silicalite-1 membranes had acceptable quality[8] and
the reproducibility was much lower. In 2002, Noack
group[9] reported the preparation of MFI membranes
with high reproducibility, and the reproducibility (five
times the Knudsen factor) was increased to 70%. In
2000, Lin group[10] synthesized high performance and
high reproducible silicalite-1 membranes on mullite
supports, and all the membranes showed high separation
performance towards ethanol/water mixture. These re-
sults further suggest that suitable support is useful to
improve the separation performance and reproducibility
of silicalite-1 membranes.
Considering the practical applications, preparation of
reproducible and high performance silicalite-1 mem-
branes on cheaper porous tubular supports at a large
scale is still a challenge[10,11]. In this report, high-repro-
ducibility silicalite-1 membranes were successfully syn-
thesized on porous silica tubes, and the separation per-
formance towards different alcohols/water mixtures was
also investigated briefly.
1 Experimental
1.1 Synthesis of silicalite-1 membranes
Two types of porous tubes were used as supports, the
silica tubes were prepared by casting method and the
α-alumina tubes were prepared by extrusion method.
The silica tubes were 11 mm in OD, 7 mm in ID, 90 mm
in length, 0.3 μm in pore diameter, with the porosity
being 45%. The α-alumina tubes were 14 mm in OD, 10
mm in ID, 160 mm in length, 0.3 μm in pore diameter,
with the porosity being 40%. Before hydrothermal syn-
thesis, all the tubes were polished with sand paper,
washed with deionized water in ultrasonic apparatus,
and calcined at 500℃ for 5 h to remove organics ad-
sorbed on the surface.
Two-step in-situ hydrothermal synthesis was used to
synthesize silicalite-1 membranes on the outside sur-
faces of porous α-alumina tubes and silica tubes. Syn-
thesis solutions were prepared by mixing NaOH, TPABr,
silica sol (26 wt% SiO2), and deionized water at room
temperature. The molar composition of synthesis solu-
tions was TPABr:Na2O:SiO2:H2O=1:0.25:10:X (so-
lution 1: X = 800; solution 2: X=1000). Before each
hydrothermal synthesis, two α-alumina tubes and eight
silica tubes were filled with viscous mixed solution
(containing water and glycerol), and two silica tubes as
3506 CHEN HongLiang et al. Chinese Science Bulletin | November 2008 | vol. 53 | no. 22 | 3505-3510
comparison were used without solution-filling (SF). Af-
ter the synthesis solution was added, the autoclaves were
put into an air oven and aged at 60℃ for 12 h, and then
the oven temperature was increased to 180℃. The first
crystallization with solution 1 was carried out for 22 h
and the second crystallization with solution 2 was car-
ried out for 10 h. After each crystallization, the sili-
calite-1 membranes were washed with deionized water,
and dried at 80℃ overnight, and then the silicalite-1
membranes were calcined at 500℃ for 12 h to remove
the templates.
1.2 Membrane characterization
The top view and the cross section of silicalite-1 mem-
branes were detected by scanning electron microscopy
(SEM, Quanta 200 FEG) and SEM was also used to ob-
tain the images of the inner surface of silica tubes. The
surface Si/Al ratio of silicalite-1 membranes synthesized
on silica tubes and α-alumina tubes was determined by
energy dispersive X-ray detector (EDX, Quanta 200
FEG).
1.3 Pervaporation performance
The pervaporation performance of the as-synthesized
silicalite-1 membranes was evaluated by separating al-
cohols/water mixtures on a standard pervaporation ap-
paratus. A centrifugal pump circulated the feed through
the system to reduce the influence of concentration po-
larization. The permeate and feed concentrations of al-
cohols and water were measured by off-line gas-chro-
matography (GC, HP 5890). The total flux was calcu-
lated by weighting the condensed permeate. The separa-
tion factor was determined as αA/W= (YA/YW)/(XA/XW),
where XA, XW, YA, and YW denote the mass fractions of
components A (alcohol) and W (water) on the feed and
permeate sides, respectively.
2 Results and discussion
2.1 Effects of filling solution
Figure 1 shows the SEM images of silicalite-1 mem-
branes synthesized on silica tubes. After filling the silica
tubes with mixed solution, the thickness of the sili-
calite-1 membrane (Figure 1(b)) became only about 40
μm, while for membrane (Figure 1(d)) without filling,
the thickness turned to about 60 μm, and the membrane
thickness decreased by about 20 μm after filling the sil-
ica tubes. By comparing the membranes synthesized by

using SF method (Figure 1(a)) with the membrane syn-
thesized without using SF method (Figure 1(c)), it can
be seen that the surface of the former was more compact
than that of the latter. Therefore, it can be deduced that a
higher flux and a higher separation factor should be ob-
tained after filling the silica tubes, which resulted from
the decrease of membrane thickness and the improve-
ment of surface compactness, which was further verified
by pervaporation experiments, as shown in Table 1.
ARTICLES
In order to protect the porous supports from the inva-
sion of synthesis solution, Hedlund et al.[12] masked the
porous discs with high-melting-point polyethylene wax,
and the flux was one or two orders of magnitude higher
than those in the literature. In this work, a suitable
mixed solution composed of high boiling point solvent
glycerol (bp: 290℃) and water was used to fill the silica
tubes and α-alumina tubes. After filling the silica tubes,
all the membranes showed high separation performance

Figure 1 SEM images of silicalite-1 membranes synthesized on silica tubes. (a) top view and (b) cross section of membrane with SF; (c) top view and (d)
cross section of membrane without SF.

Table 1 Separation performances of silicalite-1 membranes prepared on silica and alunina tubesa)
EtOH/H2O (3 wt% EtOH)
Membr. No. Aging temperature (℃) Crystallization Time (h) Filling
Flux (kg/(m2·h)) Separation factor RSDb)
SS-1 60+60 22+10 Yes 0.78 70
SS-2 60+60 22+10 Yes 1.06 59
INORGANIC CHEMISTRY
SS-3 60+60 22+10 Yes 1.49 66
SS-4 60+60 22+10 Yes 0.99 67
7.5%
SS-5 60+60 22+10 Yes 0.97 62
SS-6 60+60 22+10 Yes 1.20 72
SS-7 60+60 22+10 Yes 1.09 58
SS-8 60+60 22+10 Yes 0.88 61
SS-9 60+60 22+10 No 0.68 61
SS-10 60+60 22+10 No 0.74 64
AA-1 60+60 22+10 Yes 0.35 33
AA-2 60+60 22+10 Yes 0.47 32
a) Feed temperature: 80℃; SS: silica tubes; AA: α-alumina tubes; b) RSD was calculated with STDEVP/average.

CHEN HongLiang et al. Chinese Science Bulletin | November 2008 | vol. 53 | no. 22 | 3505-3510 3507
towards ethanol/water mixtures, and the membrane
(SS-3) with the highest flux of 1.49 kg/(m2·h) and sepa-
ration factor of 66 was obtained, and these results were
higher than those reported in ref. [13], while for mem-
brane (SS-9) without filling, the lowest flux of 0.68
kg/(m2·h) and separation factor of 61 were obtained. By
using the SF method, the average flux and the average
separation factor of eight membranes were 1.06
kg/(m2·h) and 64, respectively. By comparing the per-
vaporation data, it can be seen that the average flux can
be improved by 49% while the higher separation factor
was kept, and this result was similar to that reported by
our group previously[14].
During hydrothermal synthesis, the penetration of
synthesis solution into support pores is inevitable, and
this will result in the formation of zeolite crystals in the
support pores, which enhances the pervaporation resis-
tance and decreases membrane flux. After filling the
tubes with viscous mixed solution, the penetration of
synthesis solution into support pores will be decreased
because of protection of SF method, especially after the
first hydrothermal synthesis, the penetration of synthesis
solution will be further reduced because of the protec-
tion of filling solution and silicalite-1 film formed on the
outer surfaces of silica tubes. Furthermore, an evidence
to reduce the penetration of synthesis solution was that
zeolite crystals were collected within the tubes without
using SF method, while almost no zeolite crystals were
collected within the tubes with SF method. Another evi-
dence was that only a few large zeolite crystals were
formed on the inner surfaces of silica tubes, as shown in
Figure 2(a), so it can be deduced that the formation of
zeolite crystals in the supports pores will be restrained;
Figure 2 SEM images of the inner surface of silica tubes. (a) Tube with SF; (b) tube without SF.
3508 CHEN HongLiang et al. Chinese Science Bulletin | November 2008 | vol. 53 | no. 22 | 3505-3510
for membranes synthesized without filling, nearly a
layer of film shown in Figure 2(b) was formed, which
will increase the effective thickness of silicalite-1 mem-
brane and decrease the flux, which was further verified
by pervaporation data shown in Table 1.
2.2 Influence of the chemical compositions of dif-
ferent supports
Decreasing the Si/Al ratio will result in the formation of
silicalite-1 membranes with lower hydrophobicity,
which will decrease the separation performance of sili-
calite-1 membranes. As shown in Table 1, at the same
synthesis conditions, membranes synthesized on
α-alumina tubes showed much lower separation per-
formance towards ethanol/water mixtures compared
with membranes synthesized on silica tubes, and the
average flux and separation factor for two membranes
were only 0.41 kg/(m2·h) and 33, respectively. The poor
separation performance may be caused by the decrease
of hydrophobicity resulting from the dissolution of alu-
mina tubes during hydrothermal synthesis. After ana-
lyzing the surface Si/Al ratio of membranes by EDX, it
can be seen that the surface Si/Al ratio of membranes
synthesized on silica tubes was 100 and the Al atoms
came from the clays added to the slurry, which was
much higher than Si/Al ratio (about 34) of membranes
synthesized on α-alumina tubes. For the separation of
ethanol/water mixtures, the capability of adsorbing or-
ganics will determine the separation performance of
silicalite-1 membranes, so decreasing or avoiding the
introduction of aluminum is significant for improving
the hydrophobicity of silicalite-1 membranes, and this
was verified by the ref. [2].

2.3 Separation performance towards different al-
cohols/water mixtures
Table 2 shows the separation performance of membrane
SS-3 (Table 1) for 3 wt% alcohols/water mixtures from
this work, including methanol/water, ethanol/water,
2-propanol/water, and 1-propanol/water mixtures. As
seen from Table 2, methanol showed the highest flux
and lowest separation factor, which were 2.63 kg/(m2·h)
and 22, respectively. Compared with methanol, 1-pro-
panol showed the lowest flux 0.20 kg/(m2·h) and high-
est separation factor 159. With the increase of carbon
number, the alcohol molecules became more difficult to
leave the membrane surface, so the flux decreased in the
sequence of methanol, ethanol, and 1-propanol, while
the separation factors increase in this sequence. The
trend of flux and separation factor changed in accor-
dance with that obtained by Bowen in 2003[15].
Table 2 Pervaporation performance of silicalite-1 membrane twards
alcohols/H2O mixturesa)
Alcohols/H2O (3wt% alcohol)
Alcohols
Total flux(kg/(m2·h)) Separation factor
methanol 2.63 22
ethanol 0.87 69
2-propanol 0.24 81
1-propanol 0.20 159
a) Feed temperature: 60℃; Membrane: SS-3.
Figure 3 shows the influence of feed temperature on
the separation performance of silicalite-1 membrane. With
the increase of feed temperature from 30℃ to 80℃, the
flux also increased from 0.32 kg/(m 2 ·h) to 1.49
kg/(m2·h) due to the higher vapor pressure of compo-
nents of the feed, but the separation factor changed
Figure 3 Influence of feed temperature on the separation performance of
silicalite-1 membrane.
CHEN HongLiang et al. Chinese Science Bulletin | November 2008 | vol. 53 | no. 22 | 3505-3510
ARTICLES
slightly with increasing temperature. According to Ar-
rhenius equation, membrane flux, f = Ae−Ea/RT, the rela-
tionship between flux ln(f) and temperature 1/T is linear.
As shown in Figure 4, nearly two parallel lines were
obtained, and the apparent activation energy Ea of etha-
nol and water were 28.8 and 26.8 kJ/mol, respectively.
Because the apparent activation energy Ea of ethanol
was similar to that of water in ethanol/water mixtures,
which resulted in slight decrease of separation factor
when the feed temperature was increased. The influence
of feed temperature on flux and separation factor in this
work was similar to that obtained by other research-
ers[2,7].
Figure 4 The relationship between flux ln(f) and feed temperature 1/T.
2.4 Reproducibility of silicalite-1 membranes
An important aspect of a successful method for zeolite
membranes is reproducibility. As is known, improving
the reproducibility of tubular membranes is more diffi-
cult than that of membranes synthesized on discs. In this
work, the pervaporation experiments were carried out to
test the reproducibility of silicalite-1 membranes. As
shown in Table 1, all the membranes synthesized on sil-
ica tubes, including membranes synthesized with filling INORGANIC CHEMISTRY
or without filling, showed high separation performance
towards ethanol/water mixtures. From SS-1 to SS-8, the
relative standard deviation (R.S.D.) of average separa-
tion factor was only 7.5%, showing high reproducibility.
The high-reproducibility may be caused by the follow-
ing two reasons: one was the similar properties between
silica supports and zeolite crystals, which decreased or
eliminated the formation of cracks during calcinations,
and Lai et al.[16] found that the presence of the silica
layer eliminated the formation of stress-induced cracks
during calcinations; the other was decreasing the forma-
3509
tion of zeolite crystals in the support pores because of
the protection of SF method, which may destroy the
supports or membranes during calcinations. However, in
order to fully evaluate the reason of high-reproducibility
for silicalite-1 membranes synthesized on silica tubes,
further experiments should be carried out.
3 Conclusions
High-reproducibility silicalite-1 membranes were syn-
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thesized on silica tubes, and all the membranes showed
high separation performance towards ethanol/water mix-
tures. However, membranes synthesized on α-alumina
tubes showed much lower separation performance than
that of membranes on silica tubes, which was caused by
the decrease of hydrophobicity resulting from the disso-
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