TS-1 Molecular Sieves Filled Polydimethylsiloxane Membranes
for Ethanol/Water Separation via Pervaporation
Xiaolong Han,1 Xingmei Zhang,2 Xiaoxun Ma,1 Jiding Li3
1
School of Chemical Engineering, Northwest University, Xi’an, Shaanxi 710069, China
2
School of Chemical Engineering, Xi’an University, Xi’an, Shaanxi 710065, China
3
Department of Chemical Engineering, The State Key Laboratory of Chemical Engineering, Tsinghua University,
Beijing 100084, China
TS-1 molecular sieves were synthesized and characterized
by Fourier transform infrared spectroscopy, X-ray diffraction,
scanning electron microscopy, thermogravimetric analysis,
and UV–Vis spectroscopy. Results showed that the morphol-
ogy, crystallinity, and purity of TS-1 were closely related to
the Ti/Si ratio, crystallization time, crystallization temperature,
and calcination time. The TS-1 particles were incorporated
into polydimethylsiloxane to form mixed matrix membranes
(MMMs), and these MMMs were first used to separate etha-
nol/water mixtures via pervaporation. The MMMs with 50
wt% TS-1 (Ti/Si ratio of 0.02) loading showed the highest
separation factor of 14.1 for 5 wt% ethanol feed concentra-
tion at 508C. POLYM. ENG. SCI., 56:583–589, 2016. V C 2016 Society
of Plastics Engineers
INTRODUCTION
Pervaporation is a clean, environmentally friendly, and
energy-efficient separation technology. It has been used to sepa-
rate close boiling liquids and azeotropic mixtures, which are
difficult to separate using conventional separation processes,
such as distillation [1–4]. Recently, heteroatomic zeolites have
been used to prepare inorganic membrane or mixed matrix
membranes (MMMs) for pervaporation. For example, a series of
transition metal (Ag, Cu, and Ni ions) ion-exchanged NaY zeo-
lites were filled into polymer membranes to produce MMMs for
pervaporation desulfurization [5–7]. Both flux and enrichment
factor were increased because of the p-complexation between
thiophene molecules and transitional metal ions. Li et al. pre-
pared Ge-substituted ZSM-5 membrane and used the Ge-ZSM-5
membrane to separate acetic acid from acetic acid/water mix-
tures, producing higher selectivity than silicallite-1 membrane
[8]. Chen et al. prepared the titanium-substituted silicalite-1
(TS-1) membranes on the surface of tubular mullite support, and
the TS-1 membrane showed high ethanol selectivity for ethanol/
water mixtures [9].
The selective removal of ethanol from fermentation broths
via pervaporation (PV) has drawn more and more attention
[10–12]. A previous work showed that the hydrophobicity of the
Correspondence to: X. Han; e-mail: hanxl@nwu.edu.cn or X. Ma; e-mail:
maxym@nwu.edu.cn
Contract grant sponsor: State Key Laboratory of Chemical Engineering; con-
tract grant number: SKL-ChE-12A01; contract grant sponsor: The Postdoctor
Science Foundation of China; contract grant number: 2014M560802; con-
tract grant sponsor: Natural Science Foundation of Xi’an City; contract grant
number: CXY1531WL31; contract grant sponsor: NWU Scientific Research
Foundation; contract grant number: PR13022, NG14028.
DOI 10.1002/pen.24283
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2016 Society of Plastics Engineers
V were dispersed into the solution with vigorous stirring. Next, the
POLYMER ENGINEERING AND SCIENCE—2016
zeolites strongly influenced the pervaporation performance of the
membrane for ethanol/water separation [13]. Zeolite particles with
hydrophobic surfaces could increase the strength of interfacial
adhesion between zeolites and polydimethylsiloxane (PDMS)
matrix, and the hydrophobic outer surfaces of the zeolite particles
guarantee that ethanol molecules preferentially permeate through
zeolite pores, while water molecules have to permeate the path-
way between zeolites and PDMS. In this way, the membrane’s
selectivity for ethanol can be improved. The incorporation of Ti
into the molecular sieve framework can increase the hydrophobic-
ity of the zeolite. Therefore, TS-1 zeolites may be excellent candi-
date filler for the preparation of MMMs for ethanol-selective
removal from ethanol/water mixtures.
In this paper, titanium-substituted silicalite-1 (TS-1) molecu-
lar sieves were synthesized, and the TS-1 particles were incor-
porated into polydimethylsiloxane (PDMS) to form MMMs. The
MMMs were first used to separate ethanol/water mixtures via
pervaporation. Additionally, the effects of the Ti/Si ratio, feed
temperature, and TS-1 loading on the membrane performance
were carefully investigated.
EXPERIMENTAL
Materials
Polydimethylsiloxane (PDMS) was purchased from Beijing
Chemical Reagents Corp., China. Tween 40, tetrabutyl orthotita-
nate (TBOT), tetraethyl orthosilicate (TEOS), and tetrapropyl
ammonium hydroxide (TPAOH) were obtained from Sinopharm
Chemical Regent, China. N-heptane, ethanol, isopropyl alcohol,
and dibutyltin dilaurate (DBTL) (Beijing Jingyi Chemical
Reagents Corp., China) were used without further purification.
Synthesis of TS-1 Zeolites
TS-1 zeolites were prepared according to the modified hydro-
thermal synthesis method described previously [14, 15]. Then, 4 g
of Tween 40 and 60 g of aqueous TPAOH solution was added to
330 g of deionized water with stirring. Then, 62.4 g of TEOS was
dropped slowly into the above solution under vigorously stirring.
After clarification, TBOT dissolved in 18 g of isopropyl alcohol
was added in drops and stirred for 3 h. Then the mixture was
poured into a Teflon autoclave and crystallized at 160–2008C for
20–60 h. Then, the mixture was washed with distilled water and
calcined at 5508C in air for 6–10 h at heating rates of 18C/min.
Preparation of TS-1 Filled PDMS MMMs
PDMS was dissolved in n-heptane with magnetic stirring until
a homogeneous suspension was obtained. Then TS-1 particles
 FIG. 1. FT-IR spectra of TS-1 zeolites prepared under different conditions [(a) Ti/Si 5 0.02, T 5 1808C; (b)
Ti/Si 5 0.02, t 5 40 h; (c, d) T 5 1808C, t 5 40 h]. [Color figure can be viewed in the online issue, which is available
at wileyonlinelibrary.com.]
resulting mixture was placed in ultrasonic water bath for 30 min
and subsequently agitated for 1 h. After the treatment, TEOS and
DBTL were added to the mixture. Once the suspension became
highly viscous, it was immediately cast on a polyvinylidene fluo-
ride (PVDF) supporting membrane (self-made in our lab) and
dried at room temperature for 12 h. The membrane was then
cross-linked for 5 h at 808C.
Physicochemical Characterizations
Fourier Transform Infrared (FT-IR). The FT-IR spectra of the
TS-1 particles were obtained from a Nicolet IR 560 spectrome-
ter measuring in the range of 4000–500 cm21.
X-ray Diffraction (XRD). The crystal structure of the prepared
TS-1 particles was examined by XRD using an X-ray diffrac-
tometer (Rigaku D/max-2550X, Japan). The diffractograms were
measured at a scanning speed of 48/min in the 2h range of 6–
708 using Cu Ka radiation (k 5 0.154 nm). The anode was oper-
ated at 40 kV and 40 mA.
Scanning Electron Microscopy (SEM). The morphology of the
TS-1 particles and the surface and cross section of the MMMs were
observed by a scanning electron microscope (SEM, JSM-6301F).
These samples were coated with a conductive layer of sputtered gold.
584 POLYMER ENGINEERING AND SCIENCE—2016
Thermogravimetric Analysis (TGA). The thermal stability of TS-1
particles was examined with a TGA thermalanalyzer (TA Instru-
ments, Q-500). Temperature programs were run from room tem-
perature to 8008C at a heating rate of 108C min21 in a nitrogen
atmosphere.
Ultroviolet–Visible Spectra (UV–Vis). The UV–Vis spectra of TS-
1 particles were measured using a Shimadzu UV-3600 spectro-
photometer equipped with an integration sphere.
Pervaporation Experiments
The pervaporation apparatus and experiments were reported in
a previously published paper [16]. The compositions of the feed
solution and permeate were analyzed by gas chromatography
(SHIMADZU, GC-14C). Membrane separation performance was
evaluated on the basis of the total flux and the separation factor.
The permeate total flux J was determined by measuring the
weight of permeate collected in the cold trap divided by time
and the membrane’s surface area as shown in Eq. 1
W
J5 (1)
At
Here, W represents the mass of permeate, A is the effective
membrane area, and t is the permeation time. Then the selectiv-
ity of a membrane in a binary system is obtained as follows:
DOI 10.1002/pen

FIG. 2. XRD patterns of the TS-1 zeolites prepared under different condi-
tions [(a) Ti/Si 5 0.02, T 5 1808C; (b) Ti/Si 5 0.02, t 5 40 h; (c) T 5 1808C,
t 5 40 h]. [Color figure can be viewed in the online issue, which is available
at wileyonlinelibrary.com.]
yETH =yW
a5 (2)
xETH =xW
Here a is separation factor; x and y represent the weight frac-
tions of corresponding solute in feed and permeate, respectively;
subscripts ETH and W denote ethanol and water, respectively.
DOI 10.1002/pen
RESULTS AND DISCUSSION
Characterization of TS-1 Zeolites
Fourier Transform Infrared (FT-IR). The FT-IR spectra of
TS-1 zeolites prepared under different conditions are given in
Fig. 1. The adsorption peaks at 1230, 1100, 800, 550, 450 cm21
are attributed to the characteristic bands for MFI zeolite [17].
The signal at 1230 cm21 is not observed in the spectrum of
TS-1 zeolites prepared at 2008C (Fig. 1b) and with Ti/Si ratio of
0.01 and 0.03 (Fig. 1c), the results indicate that the topology
structure of TS-1 zeolites prepared under these conditions are
not perfect. The band at 960 cm21 is observed in the spectrum
of all TS-1 samples, which is often taken as indication of tita-
nium substitution in the framework of TS-1 zeolite [18, 19].
The results indicated that all the samples prepared under all sets
of conditions were TS-1 particles. As shown in Fig. 1d, the
maximum of I960/I800 is observed at Ti/Si ratio of 0.02, so the
actual titanium content of the corresponding TS-1 sample was
the highest [17].
X-ray Diffraction (XRD). Figure 2 shows the XRD patterns of
the TS-1 zeolites prepared at different conditions. The character-
istic peaks at 2h 5 7.98, 8.98, 23.18, 23.98, and 24.48 correspond-
ing to the diffraction of MFI zeolites are observed in all XRD
patterns [18]. However, the peaks intensity of the samples pre-
pared at a series of conditions are different. As shown in
Fig. 2a, as the duration of synthesis increased from 20 to 40 h,
the crystallinity of the TS-1 particles also increased. As the
synthesis time reaches 60 h, on the contrary, the crystallinity of
the TS-1 particles is decreased. A similar phenomenon, observed
as the temperature of synthesis was increased, is shown in Fig.
2b, the crystallinity of the TS-1 particles prepared at 1808C
peaked. Figure 2c shows that the structure of TS-1 samples was
perfect at a synthesis composition of Ti/Si 5 0.02.
Scanning Electron Microscopy (SEM). Figure 3 presents the
morphology of TS-1 zeolites prepared under different conditions.
As shown in Fig. 3a, most of the morphology of the TS-1 samples
synthesized with Ti/Si ratio of 0.02 at 1808C for 20 h was ellip-
soid, but some smaller particles were clearly observable in the
samples. As the duration of synthesis extended to 40 and 60 h
(Fig. 3b and c), these smaller particles disappeared. All the TS-1
particles were ellipsoidal in shape and approximately 100–200 nm
in size. As indicated by the SEM images shown in Fig. 3e, when
the temperature of synthesis reached 2008C, the size distribution
of the TS-1 particles was not uniform. This indicated that the ideal
hydrothermal treatment temperature is 160–1808C.
Ultroviolet–Visible Spectra (UV–Vis). UV–Vis spectra of TS-1
samples are presented in Fig. 4. All samples show an adsorption
peak near 210 nm, which indicate that tetrahedral Ti41 was
present in the TS-1 samples [17]. Moreover, there were no
adsorption signals near 330 nm, which would have been attrib-
uted to TiO2 in the framework of TS-1 zeolites. This indicates
that none of the TS-1 samples synthesized at different Ti/Si
ratios at 1808C for 40 h contained anatase-like oxide species
inside the channels.
Thermogravimetric Analysis (TGA). The remnants of template can
block the pores and reduce the hydrophobicity of zeolites, which
POLYMER ENGINEERING AND SCIENCE—2016 585
 FIG. 3. SEM of the TS-1 zeolites prepared under different conditions (a) Ti/Si 5 0.02, T 5 180 h, t 5 20 h;
(b) Ti/Si 5 0.02, T 5 1808C, t 5 40 h; (c) Ti/Si 5 0.02, T 5 1808C, t 5 60 h; (d) Ti/Si 5 0.02, t 5 40 h, T 5 1608C;
(e) Ti/Si 5 0.02, t 5 60 h, T 5 2008C.

may affect the separation performance of zeolite-filled mem-

branes. For ethanol/water separation, even traces of template
can reduce the permeability and ethanol selectivity of zeolite-
filled membranes [20]. Thermal gravimetric curves of TS-1
samples synthesized with different Ti/Si ratios at 1808C for 40 h
are shown in Fig. 5. As shown in Fig. 5a, weight loss below
2008C was attributed to the water adsorption in the surface and
inner pores of TS-1 samples. In addition, obvious weight loss
was observed between 200 and 5008C. It was attributed to
decomposition of the template. This indicates that the template
cannot be clearly removed by calcination at 5508C for 6 h.
However, only about 1 wt% weight loss below 2008C was
observed and there was almost no weight loss between 200 and
8008C in Fig. 5b. This indicated that there was little template in
the pores of TS-1 particles by calcination at 5508C for 10 h.

FIG. 4. UV–Vis spectra of TS-1 zeolites synthesized at different Ti/Si FIG. 5. Thermal gravimetric curves of TS-1 samples synthesized with
ratios at 1808C for 40 h. [Color figure can be viewed in the online issue, different Ti/Si ratio at 1808C for 40 h. [Color figure can be viewed in the
which is available at wileyonlinelibrary.com.] online issue, which is available at wileyonlinelibrary.com.]

586 POLYMER ENGINEERING AND SCIENCE—2016 DOI 10.1002/pen

 FIG. 6. Cross-sectional morphology of (a) PDMS and TS-1 filled PDMS MMMs with different TS-1 contents:
(b) 50 wt%, (c) 60 wt%.

Characterization and Pervaporation Performance of MMMs
Scanning Electron Microscopy (SEM) of MMMs. Figure 6
shows the cross-sectional morphology of PDMS and TS-1-filled
PDMS MMMs. As shown in Fig. 6a and b, the top layers and
the PVDF supports combined tightly and properly. When the
TS-1 particle loading reached 60 wt%, some pinholes and
microcracks were observed in Fig. 6c, which may have resulted
in the decline of performance of MMMs.
titanium content; the Ti/Si ratio of the 0.03 TS-1 particles was
lower than that of the Ti/Si ratio of 0.02 TS-1 particles, as indicated
by FTIR spectra of Fig. 1d.
Effect of Feed Concentration. The effect of ethanol content in
the feed on pervaporation performance of TS-1 particles filled
PDMS MMMS with 50% TS-1 loading at 508C are depicted in
Fig. 9. It can be seen that the total flux increased while the

Effect of TS-1 Particles Loading. Figure 7 depicts the effect of

TS-1 content on the pervaporation performance of TS-1 particles
filled PDMS MMMs for 5 wt% ethanol/water mixtures at 508C.
As shown in Fig. 7a, the total flux of TS-1 filled PDMS MMMs
decreased with increasing TS-1 content. This can be ascribed to
the following two factors, the membrane swelling and plasticiza-
tion were restricted because of the introduction of TS-1 particles
to the PDMS matrix [21]. However, the crystallization of the
PDMS membranes increased as TS-1 loading increased. This
reduces the free volume of PDMS membranes and reduces the
pathway for ethanol/water permeation [22]. As shown in Fig.
7b, the separation factor of TS-1 particles filled PDMS mem-
brane increased steadily as TS-1 particle content increased. It
peaked at 50% TS-1 filling. As the zeolite loading reached
60%, the separation factor decreased. This was mainly attributed
to the fact that the excess TS-1 particles produced small defects
in the PDMS matrix, which can be confirmed by SEM imaging,
as shown in Fig. 6c. Water molecules may preferentially perme-
ate through the defects than ethanol molecules, leading to the
decline of separation factor.

Effect of Operation Temperature. In order to investigate the

effect of temperature on pervaporation of TS-1 particles filled
PDMS MMMS, TS-1 particles synthesized with different Ti/Si
ratios at 1808C for 40 h were incorporated into PDMS at a loading
of 50 wt%, these MMMs were used to separate 5 wt% ethanol/
water mixtures. The results are shown in Fig. 8. As shown in Fig.
8a. As temperature increased, the total flux of TS-1 particles with
different Ti/Si ratio filled MMMs all increased, but not very much.
As shown in Fig. 8b, the separation factor increased as temperature
increased, peaking at 508C. In addition, the separation factor
increased with the Ti/Si ratio, peaking at 14.1 for Ti/Si ratio of FIG. 7. Effect of TS-1 loading on pervaporation performance of TS-1 par-
0.02 at 508C. However, the separation factor of Ti/Si ratio of 0.03 ticles (prepared at 1808C for 40 h) filled PDMS MMMs. (a) Total flux,
TS-1-filled PDMS MMMs was lower than that of Ti/Si ratio of (b) separation factor. [Color figure can be viewed in the online issue, which
0.02 TS-1-filled PDMS MMMs. This can be attributed to the actual is available at wileyonlinelibrary.com.]

DOI 10.1002/pen POLYMER ENGINEERING AND SCIENCE—2016 587

FIG. 8. Effect of temperature on pervaporation performance of TS-1 par- FIG. 9. Effect of feed concentration on pervaporation performance of TS-1
ticles (prepared at 1808C for 40 h) filled PDMS MMMs. (a) Total flux, (b) particles filled PDMS MMMs. (a) Total flux, (b) separation factor. [Color fig-
separation factor. [Color figure can be viewed in the online issue, which is ure can be viewed in the online issue, which is available at wileyonlinelibrary.
available at wileyonlinelibrary.com.] com.]

separation factor decreased with increasing ethanol concentra- TS-1 particles filled PDMS MMMS with 50% TS-1 loading at
tion. This phenomenon was similar to the literature [11, [21]. 508C was shown in Fig. 10. It can be seen that the total flux
According to the solution–diffusion theory [23], the permselec- and separation factor of the MMMs were remained relatively
tivity of liquid mixtures through polymer membranes by perva- constant during the 24 h operation. This indicated that the mem-
poration depends on both the differences in the solubility brane was stable and has potential industrial application.
process and the diffusion process of the permeant molecules in
the polymer membranes. As the ethanol content in the feed
increased, the swelling degree of the membrane increased due to
the strong affinity of ethanol for the membrane. Thus the free
volume and chain mobility of PDMS increased, resulting in the
diffusion of ethanol and water more easily. Therefore, the total
flux increased with increasing ethanol content in feed [16].
However, the increase in the water diffusivity was much larger
than that of ethanol diffusivity in the diffusion process, science
the molecular size of water was smaller than that of ethanol. In
this case, the increase of diffusivity difference played a more
important role than that of the solubility process. As a result,
increasing ethanol content led to a higher total flux and lower
separation factor.

Effect of Operation Time. It is well known that the stability of

FIG. 10. Effect of operation time on pervaporation performance of TS-1
membrane performance is very important for pervaporation particles (Ti/Si ratio of 0.02) filled PDMS MMMs with 50% TS-1 loading at
industrial application. To investigate the stability of the mem- 508C. [Color figure can be viewed in the online issue, which is available at
branes performance, a long time pervaporation experiment of wileyonlinelibrary.com.]

588 POLYMER ENGINEERING AND SCIENCE—2016 DOI 10.1002/pen

CONCLUSIONS
In this work, TS-1 molecular sieves were synthesized and
examined using FT-IR, SEM, TGA, XRD, and UV–Vis. The
effect of the Ti/Si ratio, crystallization time, crystallization tem-
perature, and calcination time on the morphology, crystallinity,
and purity of TS-1 were investigated carefully. The optimal syn-
thetic parameters are the Ti/Si molar ratio of 0.2 at 1808C for
40 h with hydrothermal treatment. The TS-1 particles were
incorporated into PDMS to form MMMs. These membranes
were used here to remove ethanol from dilute ethanol solutions
by pervaporation. The MMMs prepared with 50 wt% zeolite
loading showed highest separation factor, 14.1, for 5 wt% etha-
nol feed concentration at 508C.
REFERENCES
1. L. Wang, X.L. Han, J.D. Li, L. Qin, and D.J. Zheng, Powder
Technol., 231, 63 (2006).
2. G. Genduso, H. Farrokhzad, Y. Latre, S. Darvishmanesh,
P. Luis, and B.V. Bruggen, J. Membr. Sci., 482, 128 (2015).
3. D.Y. Liu, G.P. Liu, L. Men, Z. Dong, K. Huang, and W.Q. Jin,
Sep. Purif. Technol., 146, 24 (2015).
4. T. Wu, N.X. Wang, J. Li, L. Wang, W. Zhang, G.J. Zhang, and
S.L. Ji, J. Membr. Sci., 486, 1 (2015).
5. R. Qi, Y. Wang, J. Chen, J.D. Li, and S.L. Zhu, J. Membr. Sci.,
295, 114 (2007).
6. B. Li, D. Xu, Z.Y. Jiang, X.F. Zhang, W.P. Liu, and D. Xiao,
J. Membr. Sci., 322, 293 (2008).
7. L. Lin, Y. Zhang, and H. Li, J. Colloid Interface Sci., 350, 355
(2010).
DOI 10.1002/pen
8. S.G. Li, V.A. Tuan, R.D. Nobel, and J.L. Falconer, Indus. Eng.
Chem. Res., 40, 6165 (2001).
9. X.S. Chen, P. Chen, and H. Kita, Microporous Mesoporous
Mater., 115, 164 (2009).
10. N.X. Wang, J.D. Liu, J. Li, J. Gao, S.L. Ji, and J.R. Li, Micro-
porous Mesoporous Mater., 201, 35 (2015).
11. S.L. Yi, Y. Su, and Y.H. Wan, J. Membr. Sci., 360, 341 (2010).
12. W. Wei, S.S. Xia, G.P. Liu, X.L. Dong, W.Q. Jin, and N.P. Xu,
J. Membr. Sci., 375, 334 (2011).
13. X. Zhan, J.D. Li, C. Fan, and X.L. Han, Chin. J. Polym. Sci.,
28, 625 (2010).
14. R. Khomane, B. Kulkarni, and A. Paraskar, Mater. Chem.
Phys., 76, 99 (2002).
15. L.Q. Wang, X. Wang, X. Guo, G. Li, and Y.Y. Chen, Chin. J.
Catal., 24, 161 (2003).
16. X.L. Han, L. Wang, J.D. Li, X. Zhan, J. Chen, and J.C. Yang,
J. Appl. Polym. Sci., 119, 3413 (2011).
17. X.B. Wang, X.F. Xiong, X. H. Liu, K.L. Yeung, and J.Q.
Wang, Chem. Eng. J., 156, 562 (2010).,
18. J.Z. Lin, F. Xin, L.B. Yang, and Z. Zhuang, Catal. Commun.,
45, 104 (2014).
19. G. Ricchiardi, A. Damin, S. Bordiga, C. Lamberti, G. Spano, F.
Rivetti, and A. Zecchina, J. Am. Chem. Soc., 123, 11409 (2001).
20. L.M. Vane, V.V. Namboodiri, and T.C. Bowen, J. Membr. Sci.,
308, 230 (2008).
21. L. Wang, X.L. Han, J.D. Li, L. Qin, and D.J. Zheng, J. Appl.
Polym. Sci, 127, 4662 (2013).
22. L. Liu, Z. Jiang, and F. Pan, J. Membr. Sci, 279, 111 (2006).
23. J. Wijmans and R. Baker, J. Membr. Sci., 107, 1 (1995).
POLYMER ENGINEERING AND SCIENCE—2016 589