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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 zeolites strongly influenced the pervaporation performance of the
by Fourier transform infrared spectroscopy, X-ray diffraction, membrane for ethanol/water separation [13]. Zeolite particles with
scanning electron microscopy, thermogravimetric analysis, hydrophobic surfaces could increase the strength of interfacial
and UV–Vis spectroscopy. Results showed that the morphol- adhesion between zeolites and polydimethylsiloxane (PDMS)
ogy, crystallinity, and purity of TS-1 were closely related to matrix, and the hydrophobic outer surfaces of the zeolite particles
the Ti/Si ratio, crystallization time, crystallization temperature,
and calcination time. The TS-1 particles were incorporated guarantee that ethanol molecules preferentially permeate through
into polydimethylsiloxane to form mixed matrix membranes zeolite pores, while water molecules have to permeate the path-
(MMMs), and these MMMs were first used to separate etha- way between zeolites and PDMS. In this way, the membrane’s
nol/water mixtures via pervaporation. The MMMs with 50 selectivity for ethanol can be improved. The incorporation of Ti
wt% TS-1 (Ti/Si ratio of 0.02) loading showed the highest into the molecular sieve framework can increase the hydrophobic-
separation factor of 14.1 for 5 wt% ethanol feed concentra- ity of the zeolite. Therefore, TS-1 zeolites may be excellent candi-
tion at 508C. POLYM. ENG. SCI., 56:583–589, 2016. V C 2016 Society
date filler for the preparation of MMMs for ethanol-selective
of Plastics Engineers
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-
INTRODUCTION
porated into polydimethylsiloxane (PDMS) to form MMMs. The
Pervaporation is a clean, environmentally friendly, and MMMs were first used to separate ethanol/water mixtures via
energy-efficient separation technology. It has been used to sepa- pervaporation. Additionally, the effects of the Ti/Si ratio, feed
rate close boiling liquids and azeotropic mixtures, which are temperature, and TS-1 loading on the membrane performance
difficult to separate using conventional separation processes, were carefully investigated.
such as distillation [1–4]. Recently, heteroatomic zeolites have
been used to prepare inorganic membrane or mixed matrix EXPERIMENTAL
membranes (MMMs) for pervaporation. For example, a series of
Materials
transition metal (Ag, Cu, and Ni ions) ion-exchanged NaY zeo-
lites were filled into polymer membranes to produce MMMs for Polydimethylsiloxane (PDMS) was purchased from Beijing
pervaporation desulfurization [5–7]. Both flux and enrichment Chemical Reagents Corp., China. Tween 40, tetrabutyl orthotita-
factor were increased because of the p-complexation between nate (TBOT), tetraethyl orthosilicate (TEOS), and tetrapropyl
thiophene molecules and transitional metal ions. Li et al. pre- ammonium hydroxide (TPAOH) were obtained from Sinopharm
pared Ge-substituted ZSM-5 membrane and used the Ge-ZSM-5 Chemical Regent, China. N-heptane, ethanol, isopropyl alcohol,
membrane to separate acetic acid from acetic acid/water mix- and dibutyltin dilaurate (DBTL) (Beijing Jingyi Chemical
tures, producing higher selectivity than silicallite-1 membrane Reagents Corp., China) were used without further purification.
[8]. Chen et al. prepared the titanium-substituted silicalite-1
(TS-1) membranes on the surface of tubular mullite support, and Synthesis of TS-1 Zeolites
the TS-1 membrane showed high ethanol selectivity for ethanol/ TS-1 zeolites were prepared according to the modified hydro-
water mixtures [9]. thermal synthesis method described previously [14, 15]. Then, 4 g
The selective removal of ethanol from fermentation broths of Tween 40 and 60 g of aqueous TPAOH solution was added to
via pervaporation (PV) has drawn more and more attention 330 g of deionized water with stirring. Then, 62.4 g of TEOS was
[10–12]. A previous work showed that the hydrophobicity of the dropped slowly into the above solution under vigorously stirring.
After clarification, TBOT dissolved in 18 g of isopropyl alcohol
Correspondence to: X. Han; e-mail: hanxl@nwu.edu.cn or X. Ma; e-mail: was added in drops and stirred for 3 h. Then the mixture was
maxym@nwu.edu.cn poured into a Teflon autoclave and crystallized at 160–2008C for
Contract grant sponsor: State Key Laboratory of Chemical Engineering; con-
20–60 h. Then, the mixture was washed with distilled water and
tract grant number: SKL-ChE-12A01; contract grant sponsor: The Postdoctor
Science Foundation of China; contract grant number: 2014M560802; con- calcined at 5508C in air for 6–10 h at heating rates of 18C/min.
tract grant sponsor: Natural Science Foundation of Xi’an City; contract grant
number: CXY1531WL31; contract grant sponsor: NWU Scientific Research Preparation of TS-1 Filled PDMS MMMs
Foundation; contract grant number: PR13022, NG14028.
DOI 10.1002/pen.24283 PDMS was dissolved in n-heptane with magnetic stirring until
Published online in Wiley Online Library (wileyonlinelibrary.com). a homogeneous suspension was obtained. Then TS-1 particles
C 2016 Society of Plastics Engineers
V were dispersed into the solution with vigorous stirring. Next, the

POLYMER ENGINEERING AND SCIENCE—2016


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 Thermogravimetric Analysis (TGA). The thermal stability of TS-1
and subsequently agitated for 1 h. After the treatment, TEOS and particles was examined with a TGA thermalanalyzer (TA Instru-
DBTL were added to the mixture. Once the suspension became ments, Q-500). Temperature programs were run from room tem-
highly viscous, it was immediately cast on a polyvinylidene fluo- perature to 8008C at a heating rate of 108C min21 in a nitrogen
ride (PVDF) supporting membrane (self-made in our lab) and atmosphere.
dried at room temperature for 12 h. The membrane was then
cross-linked for 5 h at 808C. 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.
Physicochemical Characterizations
Fourier Transform Infrared (FT-IR). The FT-IR spectra of the
TS-1 particles were obtained from a Nicolet IR 560 spectrome- Pervaporation Experiments
ter measuring in the range of 4000–500 cm21. 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
X-ray Diffraction (XRD). The crystal structure of the prepared
(SHIMADZU, GC-14C). Membrane separation performance was
TS-1 particles was examined by XRD using an X-ray diffrac-
evaluated on the basis of the total flux and the separation factor.
tometer (Rigaku D/max-2550X, Japan). The diffractograms were The permeate total flux J was determined by measuring the
measured at a scanning speed of 48/min in the 2h range of 6– weight of permeate collected in the cold trap divided by time
708 using Cu Ka radiation (k 5 0.154 nm). The anode was oper- and the membrane’s surface area as shown in Eq. 1
ated at 40 kV and 40 mA.
W
J5 (1)
At
Scanning Electron Microscopy (SEM). The morphology of the
TS-1 particles and the surface and cross section of the MMMs were Here, W represents the mass of permeate, A is the effective
observed by a scanning electron microscope (SEM, JSM-6301F). membrane area, and t is the permeation time. Then the selectiv-
These samples were coated with a conductive layer of sputtered gold. ity of a membrane in a binary system is obtained as follows:

584 POLYMER ENGINEERING AND SCIENCE—2016 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


FIG. 2. XRD patterns of the TS-1 zeolites prepared under different condi-
samples are presented in Fig. 4. All samples show an adsorption
tions [(a) Ti/Si 5 0.02, T 5 1808C; (b) Ti/Si 5 0.02, t 5 40 h; (c) T 5 1808C, peak near 210 nm, which indicate that tetrahedral Ti41 was
t 5 40 h]. [Color figure can be viewed in the online issue, which is available present in the TS-1 samples [17]. Moreover, there were no
at wileyonlinelibrary.com.] adsorption signals near 330 nm, which would have been attrib-
uted to TiO2 in the framework of TS-1 zeolites. This indicates
yETH =yW that none of the TS-1 samples synthesized at different Ti/Si
a5 (2) ratios at 1808C for 40 h contained anatase-like oxide species
xETH =xW
inside the channels.
Here a is separation factor; x and y represent the weight frac-
tions of corresponding solute in feed and permeate, respectively; Thermogravimetric Analysis (TGA). The remnants of template can
subscripts ETH and W denote ethanol and water, respectively. block the pores and reduce the hydrophobicity of zeolites, which

DOI 10.1002/pen 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 titanium content; the Ti/Si ratio of the 0.03 TS-1 particles was
Scanning Electron Microscopy (SEM) of MMMs. Figure 6 lower than that of the Ti/Si ratio of 0.02 TS-1 particles, as indicated
shows the cross-sectional morphology of PDMS and TS-1-filled by FTIR spectra of Fig. 1d.
PDMS MMMs. As shown in Fig. 6a and b, the top layers and
the PVDF supports combined tightly and properly. When the Effect of Feed Concentration. The effect of ethanol content in
TS-1 particle loading reached 60 wt%, some pinholes and the feed on pervaporation performance of TS-1 particles filled
microcracks were observed in Fig. 6c, which may have resulted PDMS MMMS with 50% TS-1 loading at 508C are depicted in
in the decline of performance of MMMs. 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 8. S.G. Li, V.A. Tuan, R.D. Nobel, and J.L. Falconer, Indus. Eng.
In this work, TS-1 molecular sieves were synthesized and Chem. Res., 40, 6165 (2001).
examined using FT-IR, SEM, TGA, XRD, and UV–Vis. The 9. X.S. Chen, P. Chen, and H. Kita, Microporous Mesoporous
effect of the Ti/Si ratio, crystallization time, crystallization tem- Mater., 115, 164 (2009).
perature, and calcination time on the morphology, crystallinity, 10. N.X. Wang, J.D. Liu, J. Li, J. Gao, S.L. Ji, and J.R. Li, Micro-
and purity of TS-1 were investigated carefully. The optimal syn- porous Mesoporous Mater., 201, 35 (2015).
thetic parameters are the Ti/Si molar ratio of 0.2 at 1808C for 11. S.L. Yi, Y. Su, and Y.H. Wan, J. Membr. Sci., 360, 341 (2010).
40 h with hydrothermal treatment. The TS-1 particles were 12. W. Wei, S.S. Xia, G.P. Liu, X.L. Dong, W.Q. Jin, and N.P. Xu,
incorporated into PDMS to form MMMs. These membranes J. Membr. Sci., 375, 334 (2011).
were used here to remove ethanol from dilute ethanol solutions 13. X. Zhan, J.D. Li, C. Fan, and X.L. Han, Chin. J. Polym. Sci.,
by pervaporation. The MMMs prepared with 50 wt% zeolite 28, 625 (2010).
loading showed highest separation factor, 14.1, for 5 wt% etha- 14. R. Khomane, B. Kulkarni, and A. Paraskar, Mater. Chem.
nol feed concentration at 508C. Phys., 76, 99 (2002).
15. L.Q. Wang, X. Wang, X. Guo, G. Li, and Y.Y. Chen, Chin. J.
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