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NUS Graduate School for Integrative Science and Engineering, National University of Singapore, Singapore 117456, Singapore
Department of Chemical & Biomolecular Engineering, National University of Singapore, Singapore 117585, Singapore
art ic l e i nf o
a b s t r a c t
Article history:
Received 21 May 2014
Received in revised form
17 July 2014
Accepted 26 July 2014
Available online 14 August 2014
For the rst time, this paper reports the fabrication of novel thin-lm composite tri-bore hollow ber
(TFC TbHF) membranes for pervaporation dehydration of isopropanol (IPA). The interfacial polymerization conditions were rst optimized using the conventional single-bore hollow ber (SbHF) substrate.
Then, the effects of spinning parameters such as bore uid composition, bore uid ow rate, air gap and
dope ow rate on TFC TbHF membranes' geometry, morphology and pervaporation performance were
systematically investigated. It was found that the bore uid composition is the most critical factor.
Moreover, ne TFC TbHF membranes with an outer diameter of approximately 1 mm exhibit better
separation performance for IPA dehydration than thick TFC TbHF membranes with an outer diameter of
approximately 2 mm. The optimal TFC TbHF membrane shows a ux of 2.65 kg m 2 h 1 with a
separation factor (water/IPA) of 261 for the dehydration of an IPA/water (85/15 wt%) mixture at 50 1C.
Most importantly, the newly designed TFC TbHF membrane not only shows enhanced separation
performance and mechanical strengths as compared with the conventional TFC SbHF spun from the
identical spinning conditions, but also exhibits satisfying long-term stability, suggesting its a great
potential for pervaporation applications.
& 2014 Elsevier B.V. All rights reserved.
Keywords:
Multi-bore hollow ber (MbHF)
Tri-bore hollow ber (TbHF)
Thin lm composite (TFC)
Isopropanol
Pervaporation
1. Introduction
Alcohols are of great importance in industry because they are
widely used as good solvents, cleaning agents, raw materials or
chemical intermediates for organic synthesis, and potentially clean
liquid fuels [17]. Accordingly, the dehydration of alcohol/water
mixtures is a critical issue in the production and recycle of
alcohols. However, the alcohol (ethanol, isopropanol, or butanol)
and water can form an azeotropic mixture, rendering the purication of alcohols by conventional methods such as distillation
inefcient and uneconomic. Considering the requirements for
energy-saving and environmentally friendly processes in the
chemical industry nowadays, the pervaporation process is of
considerable interest due to its high separation efciency, ability
to break azeotropes, lower energy consumption, as well as exible
process control and module fabrication [710].
The pervaporation membrane is the heart of pervaporation
processes. Based on its conguration, it can be categorized as at
sheet, hollow ber (HF) or tubular membrane. Among them, the
polymeric HF membrane has been widely applied in various
n
Corresponding author at: National University of Singapore, Department of
Chemical and Biomolecular Engineering, 10 Kent Ridge Crescent, Singapore
117585, Singapore. Tel.: 65 6516 6645; fax: 65 6779 1936.
E-mail address: chencts@nus.edu.sg (T.-S. Chung).
http://dx.doi.org/10.1016/j.memsci.2014.07.059
0376-7388/& 2014 Elsevier B.V. All rights reserved.
156
were fully explored. Their MbHFs for MD not only showed high
permeation uxes and energy efciency but also possess superior
stability and robustness. In addition, TFC MbHFs for FO were
fabricated via a spinning process followed by interfacial polymerization. These bers showed comparable separation performance with
other FO membranes. Spruck et al. also fabricated TFC seven-bore HF
membranes which showed good mechanical strengths and acceptable performance in nanoltration for desalination and water softening applications [43].
In view of the aforementioned advantages of MbHF membranes
and TFC membranes, we aim to design and explore thin-lm
composite tri-bore hollow ber (TFC TbHF) membranes for the
application of IPA dehydration. To our best knowledge, this is a
pioneering work to fabricate polymeric outer-selective TFC TbHF
membranes for pervaporation dehydration. Firstly, the effects of
interfacial polymerization conditions on pervaporation performance of TFC HF membranes were studied by using conventional
SbHF substrates. A most suitable procedure for the subsequent
fabrication of TFC TbHF membranes was then identied based on
the aforementioned study. Afterwards, the effects of spinning
conditions on membrane morphology of the TbHF substrates and
their TFC TbHF performance for pervaporation dehydration of IPA
were systematically investigated. The outcome of this study may
Fig. 1. The scheme of fabricating TFC HF with different methods: (1) the central red solid line box: the interfacial polymerization process; (2) the green dashed line box: precoating HPEI and then interfacial polymerization; (3) the blue dotted line box: post-PDMS coating after the interfacial polymerization. (For interpretation of the references to
color in this gure legend, the reader is referred to the web version of this article.)
Fig. 2. The parameters (right) for describing the conguration of the TbHF substrate (left).
2. Experimental methods
157
Table 1
Effects of amine solution composition on IPA dehydration performance of TFC SbHF a.
Condition Composition of the Total ux
Water
(g m 2 h 1) concentration at
aqueous amine
solution
the permeate (wt
%)
Separation
factor
(Water/IPA)
2.1. Materials
A commercial poly (ether imide) known as Ultems 1010 was
supplied by SABIC Innovative Plastics. N-methyl-2-pyrrolidone
(NMP, analytical grade, Merck) and ethanol (analytical grade,
Fisher) were acquired as the solvent and non-solvent respectively
to prepare the spinning solution, while NMP, 1-butanol (BuOH,
analytical grade, Fisher) as well as deionized water were used to
prepare the bore uids. A hyper-branched polyethyleneimine
(HPEI, 50 wt% in aqueous solutions, Sigma-Aldrich) with a molecular weight of 60 kg/mol was used to prepare the surface coating
solution. Sylgards184 silicone elastomer and its curing agent for
polydimethylsiloxane (PDMS) coating were purchased from Dow
Corning Singapore Pte. Ltd. The reaction monomers for the
interfacial polymerization, namely, m-phenylenediamine (MPD,
reagent grade, Tokyo Chemical Industry Co., Ltd.) and trimesoyl
chloride (TMC, reagent grade, Sigma-Aldrich) were dissolved in
aqueous and organic phases, respectively. In addition, sodium
dodecyl sulfate (SDS, reagent grade, Fluka), triethylamine (TEA,
reagent grade, Sigma-Aldrich), and cetyltrimethylammonium
bromide (CTAB, reagent grade, Sigma-Aldrich) were procured as
additives for the interfacial polymerization. Moreover, methanol
(reagent grade, Merck) and n-hexane (analytical grade, Fisher)
were employed as solvents in this study. Isopropanol (IPA, reagent
grade, Fisher) and deionized water were used to prepare the feed
mixture for pervaporation studies. All chemicals were used as
received.
Substrate Nil
1
MPD (2 wt%)
2
MPD(2 wt%) SDS
(0.1 wt%)b
3
MPD (2 wt%)
CTAB(0.1 wt%)b
61727 404
2682 7 37
25017 61
37.3 7 2.6
90.4 7 0.3
84.17 1.0
3.4 7 0.4
51.2 7 1.4
307 2.1
26377 38
83.0 7 1.0
287 2.0
a
Substrate spinning conditions: bore uid composition: NMP/H2O (95/5 wt%),
bore uid ow rate: 5 ml/min, air gap: 2.5 cm, dope ow rate: 5 ml/min.
b
TEA was used as the base source with a weight amount of 0.5 wt%.
end sealed by epoxy were immersed into the aqueous solution for
3 min at room temperature. They were then blotted with tissue
paper and dipped into the organic solution for 1 min for the
interfacial polymerization. Finally, the resultant bers were
annealed at 65 1C for 15 min to stabilize the selective TFC layer.
In the case of applying HPEI as the pre-treatment (referred to as
HPEI-TFC), the substrate was rst immersed into an aqueous 1 wt%
HPEI solution for 2 min, and then dried at 65 1C for 10 min.
Thereafter, the polyamide selective layer was synthesized as
described above. The resultant sample is referred to as HPEI-TFC.
In the case of PDMS post-treatment (referred to as TFC-PDMS), the
TFC-HF was immersed into a 3 wt% PDMS/hexane solution for
1 min and then the coated ber was cured for at least 24 h in air.
The scheme of all methods to fabricate TFC-HF membranes is
illustrated in Fig. 1.
2.4. The fabrication of HF modules
158
Fig. 3. FESEM images of SbHF outer surfaces made from different amine solutions, (a) substrate, (b) 1st amine solution, (c) 2nd amine solution, (d) 3rd amine solution.
Fig. 4. FESEM images of cross-section and outer surface of TFC SbHFs: (a) substrate, (b) only TFC, (c) TFC-PDMS, (d) HPEI-TFC. (The spinning conditions of the SbHF substrate:
bore uid composition: NMP/H2O (95/5 wt%), bore uid ow rate: 5 ml/min, air gap: 2.5 cm, dope ow rate: 5 ml/min.).
mixture (85/15 wt%) was circulated through the shell side of the
module with a ow rate of 30 L/h at a feed temperature of 50 1C,
while the lumen side (permeate side) of the module was
vacuumed at a pressure below 1 mbar throughout the experiments. The system was stabilized for 2 h before the sample
collection. Thereafter, permeate samples were collected by a cold
trap immersed in liquid nitrogen. The samples were then weighted
and their compositions were analyzed by gas chromatography
(HewlettPackard GC 7890, HP-INNOWAX column, thermal
Q
At
ywi =ywj
xwi =xwj
wherein, P~ i and Pi are the mole-based permeance and permeability of component i, respectively. l is the membrane thickness,
Ji, Mi, i, and psat
are the ux, molecular weight, activity coefcient,
i
and the saturated vapor pressure of component i, respectively,
xi and yi are the mole fractions of component i in the feed and
permeate, pp is the total pressure at the permeate side, which
could be assumed as zero due to the vacuum condition. Both of i
Table 2
The IPA dehydration performance of TFC SbHF membranes with different treatments a.
Coating
conditions
Total ux
Water concentration at
(g m 2 h 1) the
permeate (wt%)
Separation
factor
(Water/IPA)
Nil (substrate)
TFC (condition 1)
TFC-PDMS
HPEI-TFC
61727 404
2682 7 37
2480 7 57
23567 26
37.3 7 2.6
90.4 7 0.3
90.8 7 0.5
97.17 0.2
3.4 7 0.4
51.2 7 1.4
55.9 7 3.6
192.2 7 12.1
a
Substrate spinning conditions: bore uid composition: NMP/H2O (95/5 wt%),
bore uid ow rate: 5 ml/min, air gap: 2.5 cm, dope ow rate: 5 ml/min.
159
and psat
were determined by the Wilson equation and the Antoine
i
equation, respectively, with the aid of the AspenTech Process
Modeling software (version 7.2). Then, the mole-based selectivity
of the membrane () was dened as the ratio of the permeability
of components i and j:
P~ i =P~ j
Fig. 5. 3-D AFM images and mean surface roughness of SbHF outer surfaces (10 10 m2) prepared under different coating methods (a) substrate (b) only TFC (c) TFCPDMS
(d) only HPEI; (e) HPEI-TFC. (The spinning conditions of the SbHF substrate: bore uid composition: NMP/H2O (95/5 wt%), bore uid ow rate: 5 ml/min, air gap: 2.5 cm,
dope ow rate: 5 ml/min.).
160
Fig. 6. The cross-section, outer surface as well as inner surface morphologies of TbHF substrates spun from the bore uid compositions of NMP/H2O (80/20 wt%), NMP/H2O
(95/5 wt%), NMP/BuOH (80/20 wt%), NMP/BuOH (95/5 wt%). Other spinning conditions: bore uid ow rate: 5 ml/min , air gap: 0.5 cm, dope ow rate: 5 ml/min.
Fig. 7. Schematic representation of the concept of phase inversion processes for the formation of thick and ne TbHF substrates.
NMP/H2O
(80/20 wt%)
NMP/H2O
(95/5 wt%)
NMP/BuOH
(80/20 wt%)
NMP/BuOH
(95/5 wt%)
Total ux
(g m 2 h 1)
Water
concentration
at the permeate
(wt%)
Separation factor
(Water/IPA)
943 7 11
77.8 7 0.5
20.17 0.6
24757 80
97.1 7 0.2
197.0 7 14.6
27307 47
95.1 7 0.3
113.0 7 6.5
3080 7 112
98.0 7 0.3
274.0 7 40.5
a
Other spinning conditions: bore uid ow rate: 5 ml/min, air gap: 0.5 cm,
dope ow rate: 5 ml/min.
161
Table 4
R parameters, TFC layer thicknesses and positron lifetime results of the ne and thick TFC TbHF membranes a.
Sample
R1
L1 (nm)
3 (ns)
I3 (%)
R ()
FFV (%)
Thick TbHF
Fine TbHF
0.4194 70.0004
0.4190 70.0003
199 712
101 74
2.234 70.025
1.595 70.037
12.85 70.12
10.53 70.27
3.067 0.02
2.45 7 0.04
2.78 7 0.07
1.177 0.08
a
The TbHF substrates for the thick and ne TFC TbHFs were spun from bore uids of NMP/H2O (80/20 wt%) and NMP/H2O (95/5 wt%), respectively. R1 is the R parameter
obtained from VEPFIT; L1 is the thickness of the top selective layer obtained from VEPFIT; 3 is the o-Ps lifetime obtained from PALS; I3 is the intensity of 3 obtained from
PALS; R is the mean free volume radius obtained from PALS; FFV is the fractional free volume obtained from PALS.
162
Fig. 8. (a) The cross-section, outer surface as well as inner surface morphologies of TbHF substrates spun from the bore uid ow rates of 3, 4 and 5 ml/min when using
NMP/H2O 95/5 wt% as the bore uid. Other spinning conditions: air gap: 0.5 cm, dope ow rate: 5 ml/min. (b) The cross-section, outer surface as well as inner surface
morphologies of TbHF substrates spun from the bore uid ow rates of 3, 4 and 5 ml/min when using NMP/BuOH 95/5 wt% as the bore uid. Other spinning conditions: air
gap: 0.5 cm, dope ow rate: 5 ml/min.
163
Table 5
Effects of bore uid rate on IPA dehydration performance of TFC TbHF membranesa.
Bore uid composition
Total ux (g m 2 h 1)
3
4
5
3
4
5
20757 34
2348 7 29
24757 80
2099 7 54
25157 74
3080 7 112
88.9 7 0.5
95.17 0.2
97.17 0.2
95.4 7 0.3
97.6 7 0.4
98.0 7 0.3
45.4 72.2
110.7 73.8
197.0 714.6
120.7 78.2
233.6739.1
274.0 740.5
Other spinning conditions: air gap: 0.5 cm, dope ow rate: 5 ml/min.
Fig. 9. The cross-section, outer surface as well as inner surface morphologies of TbHF substrates spun at the air gap distances of 0.5, 2.5 and 5.0 cm. Other spinning
conditions: bore uid composition: NMP/H2O (95/5 wt%), bore uid ow rate: 5 ml/min, dope ow rate: 5 ml/min.
Table 6
Effects of air gap on IPA dehydration performance of TFC TbHF membranesa.
Air gap
(cm)
Total ux
(g m 2 h 1)
Separation factor
(Water/IPA)
0.5
2.5
5
2475 780
2647 749
2877 7110
97.1 70.2
97.8 70.2
96.9 70.3
197.0 714.6
260.7 726.9
180 719.4
a
Other spinning conditions: bore uid composition: NMP/H2O (95/5 wt%),
bore uid ow rate: 5 ml/min, dope ow rate: 5 ml/min.
(104 74 vs. 199 712 nm), thus the former has a higher ux than
the latter.
Since the o-Ps lifetime 3 and its intensity I3 obtained from
PALS analyses correspond to the free volume size and concentration, respectively, the mean free volume radius (R) and fractional
free volume (FFV) can be calculated according to established semiempirical correlation equations from the pick-off annihilation [58
60]. Table 4 shows the calculated results and indicates that the ne
TFC TbHF have a smaller R and FFV than the thick TFC TbHF. The
smaller R implies that the ne TFC TbHF has a higher rejection
against IPA than the thick TFC TbHF. In addition, the smaller FFV
does not affect the ne TFC TbHF because it has a thinner selective
layer. As a result, the ne TbHF substrates spun from weak bore
uids were more preferred for fabricating TFC membranes with
good overall pervaporation performance.
164
Fig. 10. The cross-section, outer surface as well as inner surface morphologies of TbHF substrates spun from dope ow rate of 5, 6 and 7 ml/min. Other spinning conditions:
bore uid composition: NMP/H2O (95/5 wt%), bore uid ow rate: 5 ml/min , air gap: 2.5 cm.
Table 7
Effects of dope ow rate on IPA dehydration performance of TFC TbHF membranesa.
Dope ow rate Total ux
(ml/min)
(g m 2 h 1)
5
6
7
97.8 7 0.2
93.6 7 0.5
90.8 7 0.3
26477 49
23347 81
2081 7 75
260.7 7 26.9
81.8 7 7.5
55.5 7 2.1
a
Other spinning conditions: bore uid composition: NMP/H2O (95/5 wt%),
bore uid ow rate: 5 ml/min, air gap: 2.5 cm.
former has weaker or more bended spokes than the latter because
H2O is a much stronger coagulant than BuOH. As a result, the TbHF
substrate spun from the bore uid of NMP/H2O (95/5 wt%) at a
ow rate of 5 ml/min is preferred.
3.2.3. Air gap
Fig. 9 shows the effects of air gap on cross-section, outer and
inner skin morphologies of the TbHF substrates. The increase in air
gap results in TbHFs with a smaller outer diameter and a thinner
wall due to the elongational stretch induced by the gravitational
force [14,52]. The spokes of TbHF become severely deformed at the
air gap of 5 cm possibly due to unbalanced ow stresses and slow
phase inversion. Nevertheless, a dense outer layer and a porous
inner layer are observed for all the TbHFs.
As shown in Table 6, the ux of the TFC TbHF continuously
increases at a higher air gap due to the decrease of wall thickness
and consequently reduced transport resistance. The up and down
trend of separation factor with air gap distance is caused by two
competing factors: the elongational stress induced by the gravity
may bring about molecular orientation at the skin (i.e., selective)
layer and enhance the separation factor, while a large air gap may
overstretch the skin and create defects that favor ux but impair
the separation factor [14,52,63]. Therefore, the TbHF substrate
spun from an air gap distance of 2.5 cm is selected for the
subsequent studies considering its separation performance and
morphology in maintaining the mechanical integrity of the TbHFs.
3.2.4. Dope ow rate
The dope ow rate also inuences the TbHF morphology as
demonstrated in Fig. 10. The thicknesses of both wall and spokes
increase with an increase in dope ow rate. At the optimum air
gap of 2.5 cm, the spokes of all TbHFs are able to maintain their
geometry. However, a higher dope ow rate results in a less
porous inner surface because a thick wall may retard non-solvent
intrusion from the outer surface. As a consequence, the ux of the
165
Table 8
Comparisons of mechanical properties and pervaporation performance of TFC SbHF and TFC TbHF membranesa.
Comparisons
Geometries
Mechanical properties
PV performance
SbHF
thick TbHF
ne TbHF
0.33
1.00
42.8 72.8
11.8 70.5
350.5 7 9.0
2356 726
192.2 7 12.1
1.53
2.18
42.7 73.2
14.9 7 0.3
411.4 710.8
10087 56
22 70.6
0.30
1.02
50.0 7 2.9
15.0 70.7
426.2 7 9.1
26477 49
260.7 7 26.9
a
Spinning conditions: dope ow rate: 5 mL min 1; bore uid ow rate: 5 mL min 1; air gap: 2.5 cm; coagulant bath: water; bore uid composition NMP/H2O (95/5 wt
%) for the SbHF and ne TbHF and NMP/H2O (80/20 wt%) for the thick TbHF; take up speed: free fall.
Table 9
Performance benchmark of the ne TFC TbHF with other polymeric membranes for IPA pervaporative dehydration.
Membrane
T/oC Feed
(IPA
wt%)
Flux/
Separation factor
g m 2 h 1 (water/IPA)
mole-based selectivity
(water/IPA)
Ref.
25
60
60
25
60
80
60
60
25
50
50
50
70
90
85
85
90
85
84
85
85
95
85
85
85
70
186
883
570
145
1000
1800
765
480
4.4
1374
1980
3519
1720
1116
10585
125
2991
185
132
1944
2332
94981
53
349
278
177
5.5
3.4
2.1
4.3
3.8
2.7
3.0
1.8
0.2
7.8
12.3
21.8
3.5
1022
13227
145
2739
216
155
2275
2750
66731
62
407
324
364
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[24]
[24]
[23]
[70]
70
25
70
90
340
213
1150
105
0.7
5.8
2394
96
[71]
[72]
16
90
140
40
11.0
59
[73]
50
85
2647
261
15.8
294
This
work
Fig. 11. Long-term pervaporation performance of the ne TFC TbHF for the
dehydration of aqueous IPA (IPA/water 85/15 wt%) at 50 1C.
166
4. Conclusions
We have molecularly designed TFC TbHF membranes with
excellent pervaporation performance for IPA dehydration and
superior mechanical strength to traditional SbHF membranes.
The optimal TFC TbHF membrane shows a ux of 2.65 kg m 2 h 1
with a separation factor of 246 for water/IPA separation at 50 1C
using 85/15 wt% IPA/water as the feed. The following conclusions
can be drawn from this study:
(1) The interfacial polymerization conditions play important roles
in determining the morphology of the TFC layer and its
performance for pervaporation dehydration. The pretreatment of HPEI on substrates not only smoothens the
substrate surface but also produces the TCF layer with fewer
defects.
(2) The effects of spinning conditions on the geometry and
morphology of TbHFs have been determined. Bore uid
composition plays the most important role. To prepare highperformance TFC TbHFs for pervaporation dehydration of IPA,
the preferred conditions to prepare TbHF substrates are as
follows: spinning from a dope made of Ultems/ethanol/NMP
(23/5/72 wt%) with a bore uid composition of NMP/H2O (95/
5 wt%), a bore uid ow rate of 5 ml/min, an air gap of 2.5 cm,
and a dope ow rate of 5 ml/min.
(3) In comparison with the TFC SbHF with a similar outer
diameter, the ne TFC TbHF shows superior pervaporation
performance and mechanical strength.
(4) The newly developed ne TFC TbHF shows both satisfactory
separation performance and long-term stability. It may have
potential for the industrial IPA dehydration application.
Acknowledgments
The authors are grateful to National Research Foundation,
Prime Minister's Ofce, Singapore for funding this research under
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