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Hydrophilic and organophilic pervaporation of

Cite this: RSC Adv., 2021, 11, 9274
industrially important a,b and a,u-diols†
Open Access Article. Published on 01 March 2021. Downloaded on 4/13/2024 5:37:11 PM.
Shivshankar Chaudhari,a HyeonTae Shin,a SeoungYong Choi,a KieYong Cho, *a

MinYoung Shon, *a SeungEun Namb and YouIn Parkb
The distillation-based purification of a,b and a,u-diols is energy and resource intensive, as well as time
consuming. Pervaporation separation is considered to be a remarkable energy efficient membrane
technology for purification of diols. Thus, as a core pervaporation process, hydrophilic polyvinyl alcohol
(PVA) membranes for the removal of water from 1,2-hexanediol (1,2-HDO) and organophilic
polydimethylsiloxane–polysulfone (PDMS–PSF) membranes for the removal of isopropanol from 1,5
pentanediol (1,5-PDO) were employed. For 1,2-HDO/water separation using a feed having a 1 : 4 weight
ratio of 1,2-HDO/water, the membrane prepared using 4 vol% glutaraldehyde (GA4) showed the best
performance, yielding a flux of 0.59 kg m2 h1 and a separation factor of 175 at 40 C. In the
organophilic pervaporation separation of the 1,5-PDO/IPA feed having a 9 : 1 weight ratio of
components, the PDMS membrane prepared with a molar ratio of TEOS alkoxy groups to PDMS hydroxyl
groups of 70 yielded a flux of 0.12 kg m2 h1 and separation factor of 17 638 at 40 C. Long term
Received 19th January 2021
Accepted 16th February 2021
stability analysis found that both hydrophilic (PVA) and organophilic (PDMS) membranes retained
excellent pervaporation output over 18 days' continuous exposure to the feed. Both the hydrophilic and
DOI: 10.1039/d1ra00467k
organophilic membranes exhibited promising separation performance at elevated operating conditions,
rsc.li/rsc-advances showing their great potential for purification of a,b and a,u-diols.
The hydrogenation of the ecofriendly bio-product furfural

Introduction produces furfural alcohol. Further hydrogenation of furfural
Diols contain two hydroxyl groups per molecule and are very alcohol, for which isopropyl alcohol (IPA) is used as the solvent,
important industrial chemicals because they can be synthesized produces both 1,2- and 1,5-PDO.8 In contrast, 1,2-HDO is
from bio-resources such as lignin, making them promising synthesized by the dehydrogenization of hexane to 1-hexene,
renewable materials.1,2 a,u-Diols have a broad range of appli- followed by further oxidation of the double bond in 1-hexene by
cations in various industries, for example, as monomers for hydrogen peroxide, yielding 1,2-HDO.9
polymer synthesis, such as polyester and polyurethane, bio- Both 1,2-HDO and 1,5-PDO are essential in the manufac-
fuels, in pharmaceuticals as solvents, and as moisturizer ture of cosmetics and dermatological pharmaceutical formu-
components in cosmetics.3–6 The worldwide value of the lations.4,10–12 In the syntheses of both 1,2-HDO and 1,5-PDO by
cosmetic market was US$ 507.8 billion in 2018 and is projected the above methods, the last stages of the process involve
to increase to US$ 758.4 billion by 2025. Two important diols in separation, purication, and concentration; however, these
cosmetics are 1,5-pentanediol (1,5-PDO) and 1,2-hexanediol processes are very complicated, typically requiring large
(1,2-HDO). Thus, these diols have huge market potential. In facilities and being energy intensive. The gas–liquid separa-
fact, the global market for 1,2-HDO is expected to reach US$ 54 tion method has been used to remove the IPA solvent from 1,5-
million by 2024 from US$ 40 million in 2019. 1,5-PDO is used in PDO. However, as the concentration of the solution increases,
place of 1,6-hexanediol and 1,4-butanediol and also has a huge separation becomes increasingly difficult, and trace amounts
market potential, which is projected to reach a compound of IPA remain in the product. Therefore, multi-stage distilla-
annual growth rate (CAGR) of 5.5% between 2017 and 2021.3–7 tion is oen used, but this is also an energy intensive tech-
nique. In contrast, for the production of 1,2-HDO, vacuum
a
distillation is used to remove excess water. Again, this process
Department of Industrial Chemistry, Pukyong National University, San 100,
Yongdang-Dong, Nam-Gu, Busan 608-739, Korea. E-mail: [email protected];
is challenging, particularly because of the formation of
[email protected]; Fax: +82 51 629 6429; Tel: +82 51 629 6440 bubbles in the mixture. Thus, when standard distillation
b
Center for Membranes, Korea Research Institute of Chemical Technology, 141 methods are used, a large amount of energy is consumed and
Gajeong-ro, Yuseong-gu, Daejeon 305-600, Korea a large amount of time is required.
† Electronic supplementary information (ESI) available. See DOI:
10.1039/d1ra00467k
9274 | RSC Adv., 2021, 11, 9274–9284 © 2021 The Author(s). Published by the Royal Society of Chemistry
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As an alternative to distillation, pervaporation is becoming industries is expanding day by days. In the beginning it was
popular. The pervaporation process requires less space and less started from the dehydration of various alcohol, now it applied
energy than traditional distillation methods.13–15 for recovery of bio fuel,14,28 treatment of effluent treatment in
Pervaporation operates on the solution diffusion principle,16 pharmaceutical industries.29 Therefore, to expand the applica-
in which the selective adsorption and diffusion of the target tions of pervaporation to the production of important raw
occur. Pervaporation separation can be achieved by creating materials in the cosmetics industry, we examined the potential
a potential gradient across a membrane by applying a pressure of PVA- and PDMS-based pervaporation membranes for the
difference over the membrane.16,17 removal of excess water from 1,2-HDO (hydrophilic approach)
Polysulfone (PSF) is one of the most widely used and trace amounts of IPA from 1,5-PDO (organophilic
membrane materials, and membranes fabricated from PSF approach), respectively, with low energy consumption. For both
have excellent mechanical properties, heat aging resistance, hydrophilic and organophilic separation, the synthetic and
and chemical stability.18 Additionally, PSF exhibits inherent operating conditions were varied to optimize the pervaporation
hydrophobicity and high biocompatibility. Poly- output of both membranes. To date, there have been no reports
dimethylsiloxane (PDMS) is another widely used membrane of the pervaporation separation of 1,2-HDO and water and that
material, having applications in the recovery of various of IPA and 1,5-PDO.
solvents because of its excellent hydrophobicity (organo-
philicity), low permeation resistance because of its amor-
phous nature, and excellent biocompatibility.19,20 Commercial Experimental
PDMS is an oligomer and does not have membrane proper- Materials
ties. Therefore, to form a membrane, the PDMS oligomers PSF (Ultrason 3010, 55 000 g mol1) granules were purchased
must be crosslinked.21 Tetraethyl orthosilicate (TEOS) has from BASF Korea. Hydroxyl-terminated PDMS (OH-PDMS,
four crosslinkable alkoxide groups and can be used for this 110 000 g mol1) was procured from Sigma-Aldrich (USA).
purpose. Aer crosslinking, the TEOS occupies a very small Dibutyltin dilaurate (DBDA, 95%) and TEOS (99.5%) were
fraction of material bulk but has a signicant effect on the purchased from Aldrich (USA). 1,5-PDO (95%), 1,2-HDO (97%),
membrane structure and performance.22 Aer crosslinking and PVA (98–99% hydrolyzed, 8800–97 000) were purchased
with TEOS, the mobility of the PDMS polymer chains can be from Alfa Aesar (USA). All other chemicals, such as glutaralde-
controlled by increasing or decreasing the crosslinking hyde (25% aqueous solution), hydrochloric acid (36%), IPA
density. Thus, PSF and PDMS membranes have excellent (99.5%), n-hexane, and N-methyl pyrrolidone, were procured
inherent hydrophobic (organophilic) properties and are from Dae-Jung Chemicals & Metal Co., Korea.
compatible, and it is possible to use PSF as a support and
PDMS as an active layer to fabricate a PDMS-coated PSF
composite membrane with enhanced performance.23 In the Membrane preparation
pervaporation separation of 1,5-PDO and IPA, the amorphous Preparation of PVA membrane. Homogeneous PVA
PDMS membrane allows a higher ux of IPA with less diffu- membranes were prepared by dissolving PVA (7 g) powder in
sion resistance because the IPA molecules are much smaller water (93 g) with continuous stirring at 80 C for 5 h. The
than those of 1,5-PDO. Additionally, the hydrophobic nature resultant polymer solution was ltered to remove any residual
of PDMS is likely to have a higher affinity for IPA than 1,5- undissolved particles. The solution was then le to stand
PDO. overnight to allow any air bubbles to leave the solution.
For the pervaporation separation of 1,2-HDO, a hydrophilic Following the resting period, the solution was cast on a glass
membrane is required. Poly(vinyl alcohol) (PVA) is a semi- plate using a casting applicator and dried at room temperature.
crystalline, aliphatic material frequently used as a base mate- The thickness of the wet membrane was 1.5 mm. Subsequently,
rial for the preparation of hydrophilic membranes, making it the membrane was pulled away from the glass plate, and the
a good candidate material.24,25 The large number of hydroxyl lms were crosslinked in a crosslinking bath containing 90/10/
groups in the polymer main chain give PVA an inherently (1–4)/1 (v/v) IPA/water/GA solution/catalytic HCl at 60 C for 1 h.
hydrophilic nature. Furthermore, membranes prepared from The thicknesses of the resulting membranes were 70–80 mm.
PVA are robust, exhibiting excellent chemical and mechanical The membrane prepared in the crosslinking bath containing
stability. However, in aqueous feed mixtures, PVA membranes 90/10/1/1 (v/v) IPA/water/glutaraldehyde/HCl solution showed
undergo excessive swelling. Therefore, membranes prepared a very low mechanical strength (ESI, Fig. S3†). Therefore, it was
with PVA must be post crosslinked using agents such as not used for the pervaporation tests. The membranes are
glutaraldehyde at relatively low temperatures.26,27 Because the denoted by the volume percentage of GA use, i.e., GA1–GA4.
molecular size of water is much less than that of 1,2-HDO and Preparation of PDMS–PSF composite membrane. Details of
because of the hydrophilic nature of PVA, it is likely to have the preparation of the PSF support are provided in the ESI.†
a higher affinity (via hydrogen bonds and dipole–dipole inter- The PDMS–PSF composite membrane was prepared by
actions) for water than 1,2-HDO. mixing OH-PDMS (6.11 g) oligomer in n-hexane (40 mL) with
As pervaporation is profound technique for saving an energy stirring. Thereaer, different amounts of TEOS (0.058, 0.23,
against energy consuming traditional distillation process, 0.405, and 0.58 g equivalent to molar ratios of the alkoxy groups
therefore application of pervaporation process in various in TEOS to hydroxyl groups in OH-PDMS of 10, 40, 70, and 100,
© 2021 The Author(s). Published by the Royal Society of Chemistry RSC Adv., 2021, 11, 9274–9284 | 9275
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respectively) and 0.1 g of DBDA catalyst were added. The PDMS- strength of GA2 to GA5 membrane samples were calculated
doped crosslinking solution was then stirred at a constant using Shimadzu AGX-X Universal Testing Machine (UTM)
speed for 30 min at room temperature. Meanwhile, the PSF equipped with Trapezium soware. Previously dried samples
support was xed to a glass plate with tape, and the crosslinking (vacuum oven at 25 C for 24 h) were cut in 25 100 mm and
solution was cast on the PSF support using a casting applicator UTM test was performed at room temperature.
(casting thickness set to 300 mm). Aer drying at room
temperature for 3 h to remove residual solvent, the lm was Pervaporation experiment set-up
transferred to an oven preheated to 75 C and thermally cured
The pervaporation experiments were conducted using a PV
for 20 h. Later, the fabricated membranes were cut into circles.
apparatus, as shown schematically in Fig. 1. The membrane cell
The thicknesses of the PDMS active layers of the membranes
was divided into two parts: one joined to the feed tank and the
ranged from 16 to 20 mm (ESI, Fig. S5b†). The membranes are
other connected to the downstream side. A round membrane

labeled with respect to the molar ratio of alkoxy groups in TEOS
sample (PDMS or PVA) was affixed to the membrane cell, and
to hydroxyl groups in PDMS in the membrane (i.e., 10 M, 40 M,
the feed side membrane was wetted by the feed solution (HDO/
70 M, and 100 M).
water or 1,5-PDO/IPA) by dynamic circulation (70 g min1) by
a circulation pump (Cole Palmer, USA). Based on the design of
Membrane characterization the cell, the effective area of the membrane was 0.0019643 m2.
Porometry (Porolux 100 (IB-FT GmbH)) was used to measure the The permeated vapor was collected in a tube and dipped in
pore size distribution in the PSF support. Using the capillary a cylinder of liquid nitrogen. A vacuum pump (Edwards, RV8)
Porometry method, the pore size distribution in the PSF was was used to maintain the pressure and create a driving force for
determined. The structural characteristics of PVA and PDMS the experiment. For all experiments, the pressure on the
were analyzed by attenuated total reection Fourier transform downstream was less than 1 torr, as measured by a digital
infrared spectroscopy (ATR FT-IR, Nicolet iS10, USA). All the pressure gauge (Super Bee, Instrutech Inc.). On the feed side,
spectra were recorded between 400 and 4000 cm1 by accu- the temperatures of the feed solution were maintained at 30–50
mulating 32 scans at 2 cm1 resolution frequency. Thermog- and 50–70 C for the PVA and PDMS membranes, respectively.
ravimetric analysis (TGA) of the PVA and PVA–glutaraldehyde The collected permeate samples were then weighed with an
crosslinked membranes was performed using a TGA 7 device electronic balance (Sartorius BA210S). For each type of
(TA Instruments, Perkin Elmer, USA). The membrane samples membrane specimen, three successive tests were carried out,
were heated from 25 to 600 C at a heating rate of 10 C min1. and the average value of ux with a relative standard deviation
The surface and cross-sectional morphology of the PSF supports less than 5% was obtained. The feed mixtures were varied from
and PDMS and PVA membranes were examined by eld- 10 wt% to 20 wt% IPA and 25 wt% to 15 wt% 1,2-HDO for the
emission scanning electron microscopy (FE-SEM, Vega II, Tes- IPA- and water-containing feeds, respectively. These feed
can, Czech Republic). The membrane specimens were coated compositions were selected because the separation of diols in
with silver before analysis to make the lm conductive. Tensile feeds of this range is energetically costly. The separation factor
Fig. 1 Schematic diagram of pervaporation apparatus: (a) water bath (b) feed tank (c) temperature indicator (d) circulation pump (e) membrane
cell, (f) vacuum gauge (g, h) cold trap + liquid nitrogen (i) vacuum pump.
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was calculated based on the exact concentrations of 1,5-PDO, Results and discussion
1,2-HDO, and IPA in the feed and permeate, which were
measured using gas chromatography (DS Sci. DS7200 equipped Details of the characterization of both PDMS and PVA
with a ame ionization detector (FID)). membranes are given in the ESI (Fig. S1–S8†).
Eqn (1)–(3) were used to evaluate the membrane perfor-

mance based on the pervaporation ux (J), separation factor (a),
Pervaporation of a,u-diol feed mixtures
and ux of individual components (Ji) for each membrane.
The separation performances of the PVA and PDMS membranes
J ¼ Q/(At) (1) developed in this study were optimized by measuring the uxes
and separation factors of these membranes for the pervapora-
here, J is the permeation ux (kg m2 h1), Q is the mass of the tion of 1,2-HDO/water and 1,5-PDO/IPA feed mixtures, respec-
permeated solution collected in the cold trap (kg) with respect tively. To achieve this, a range of experimental conditions were
to the effective area (A, m2) and time (t, h). applied, and the results are given below.
In this study, the target components for removal were water
(for hydrophilic 1,2-HDO separation) and IPA (for organophilic
Effect of crosslinker concentration
1,5-PDO separation). Therefore, the separation factors (a) were
calculated for water and IPA with respect to 1,2-HDO and 1,5- Pervaporation tests were carried out to evaluate the effect of the
PDO, respectively. GA crosslinker concentration on the ux and separation factor
on the dehydration of the 1,2-HDO/water system. Fig. 2 shows
PI =PJ
a¼ (2) the effect of the GA concentration on the ux and separation
FI =FJ
factor with a 25 : 75 (wt%) 1,2-HDO/water feed composition at
here, PI, PJ, FI, and FJ are the weight fractions of water or IPA and 40 C. As in the swelling degree study (Fig. S8†), the ux fol-
1,2-HDO or 1,5-PDO in the permeate and feed solutions, lowed a similar trend, decreasing from 1.27 to 0.51 kg m2 h1
respectively. for the membranes prepared with GA concentrations from 2 to
JPi 5 vol%. In contrast, the separation factor increased from 59 to
Ji ¼ (3) 196, and the water content of the permeate solution also
100
increased from 99.43 to 99.83 wt%. As it can be seen from the
here, Ji is the ux of component i (kg m2 h1), and Pi is the FTIR analysis, in the crosslinking reaction, the hydroxyl moie-
weight fraction of component i water, IPA, 1,2-HDO, or 1,5-PDO ties in PVA and GA react, leading to the formation of hydro-
in the permeate solution. phobic ether linkages in the membrane structure.30 This results
The pervaporation separation index (PSI) is given by eqn (4). in increased membrane compactness and reduced membrane
swelling, as well as the reduced free volume of the membrane.31
PSI ¼ Ja (4)
As shown in Fig. S3† the lower content of GA in the PVA
here, J is the total ux (kg m2 h1), and a is the separation produced loose polymer network of membrane and vice versa.
factor calculated from eqn (2). Therefore, there is less space for the permeation of water and
1,2-HDO through the membrane. However, there are abundant
Fig. 2 Effect of GA concentration in crosslinking solution on flux and separation factor, feed solution 25/75 (1,2-HDO/water, w/w, %) at 40 C.
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Fig. 3 Effect of alkoxy to hydroxyl ratio on flux and separation factor, feed 80/20 1,5-PDO/IPA, w/w, %, temperature 50 C.
hydroxyl functional groups in the PVA that can form hydrogen performance. In addition, the affinity of the PDMS layer for IPA
bonds with water and 1,2-HDO. The Hansen solubility param- (hydrophobic) is higher than that for 1,5-PDO (hydrophilic).
eters of PVA (15.9 MPa1/2), water (15.5 MPa1/2), and 1,2-HDO Thus, all membranes exhibited excellent separation perfor-
(16.31 MPa1/2) are comparable.32,33 Therefore, PVA, 1,2-HDO, mance. Because the PSF support is also hydrophobic in nature,
and water are likely to form polar–polar and hydrogen-bonding pervaporation tests were also performed using a PSF membrane
interactions. Conversely, the separation factor increased with alone under the same conditions to determine the effect of the
increase in crosslinking agent concentration, possibly because PDMS coating layer; the results are shown in Fig. 3. In the initial
of the intermolecular crosslinking of PVA chains, which reduces 2 h of PV test the PSF membrane also exhibited excellent
the gap between polymer chains and prohibits the passage of performance (J ¼ 0.25 kg m2 h1 and a ¼ 1996) for IPA/1,5-
the larger 1,2-HDO molecules but not that of the small water PDO separation. However, as the pervaporation operation
molecules. Therefore, improvement in separation was achieved time was extended beyond 3 h, the membrane began to leak and
when using a higher crosslinking agent concentration. performance dropped. This is due to, as shown in Fig. S1,† the
Recently, Cai et al. have developed for PVA-modied by PS membrane has thin skin layer followed by nger like con-
TiC2Tx membrane for the pervaporation dehydration of ethanol, nected macro void structure and porous in nature. Therefore,
where TiC2Tx acted as crosslinker and reported that, the ux overall, the PDMS coating layer slightly affected the separation
decreased and separation factor increased with increased of performance of the IPA/PDO feed mixture system; however, it is
TiC2Tx attributed to decline in the hydrophilicity of the necessary to cover the defects (pore) in the PSF support
membrane by crosslinking.34 membrane.
For the organophilic approach for the separation of the IPA/ Because the GA4 and 70 M membranes were comparatively
1,5-PDO mixture, pervaporation tests were carried out to eval- robust, they were selected for further testing for the optimiza-
uate the effect of the alkoxy-to-hydroxyl ratio in the PDMS tion of the operating conditions.
casting solution on the ux and separation of a 80 : 20 (wt%)
1,5-PDO/IPA feed at 50 C. The results are shown in Fig. 3. The
Effect of operating conditions
ux and separation factor were not signicantly inuenced by
the crosslinking density. The ux dropped from 0.22 to 0.19 kg Fig. 4 shows the effect of the feed concentration on membrane
m2 h1, the separation factor increased from 2206 to 3072, and performance. The 1,2-HDO concentration was varied from 15 to
the IPA content in the permeate increased from 99.82 to 25 wt% at 40 C. In general, more water in the feed increases the
99.87 wt% with increase in the hydroxyl-to-alkoxy molar ratio in plasticization of PVA, leading to polymer chain loosening. This
the crosslinking solution from 10 to 100, respectively. This is the reason for the decrease in ux (1.0 to 0.59 kg m2 h1).34
means that the pervaporation performance of all membranes In addition, the plasticization of the membrane results in the
only varied marginally with the crosslinking density. This is formation of a large gap between the polymer chains in the
because the PDMS membrane is amorphous elastomeric poly- membrane structure, which promotes the permeation of water,
mer and the glass transition temperature of PDMS is below as well as that of the larger 1,2-HDO molecules, thus reducing
25 C.35 Therefore, the PDMS membrane has a large free volume the separation factor (175 to 167). Additionally, the PSI values
to penetrate small IPA as well as big 1,5-PDO molecules through calculated from eqn (4) are also decreased (167, 133, and
it, and only the hydrophobicity of PDMS affects the membrane 103 kg m2 h1) on increasing the 1,2-HDO concentration from
15 to 25 wt%, respectively, at 40 C.36 Nevertheless, the water
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Fig. 4 Effect of feed concentration on flux and separation factor, temperature 40 C, membrane: GA4.
content in the permeate (99.80 0.009 wt%) was negligibly typically, as the content of the target component selective to the
affected by the changes in the feed composition. Thus, the PVA membrane in the feed increases, the driving force for its
membrane shows excellent performance in this feed range; in permeation also increases.16,22 PDMS is IPA-selective (hydro-
contrast, the separation of water and 1,2-HDO by vacuum phobic in nature); therefore, as the IPA concentration in the
distillation is challenging in this range of feed compositions feed increased, the ux increased from 0.10 to 0.23 kg m2 h1.
because the large amount of water in the solution results in the However, because a high IPA concentration in the feed induces
formation of many bubbles. Thus, pervaporation separation is membrane swelling, the separation factor decreased. Similar
more efficient than vacuum distillation. trends of pervaporation out put through PDMS membrane for n-
Next, the effect of the feed composition on the performance butanol and ethanol aqueous solution have reported by the
of the 70 M membrane for the separation of 1,5-PDO from IPA at Cheng et al.28 and Li et al.37 respectively. Despite this, the IPA
50 C in terms of ux and separation factor is discussed. The content in the permeate was only reduced from 99.93 to
IPA concentration in the feed was varied from 10 to 30 wt%, and 99.86 wt%, and the PSI values were 1342, 481, and 377 kg m2
the results are shown in Fig. 5. In pervaporation separation, h1 as the IPA content of the feed was varied from 10 to 30 wt%,
Fig. 5 Effect of feed concentration on flux and separation factor, membrane 70 M, temperature – 50 C.
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Fig. 6 Effect of operating temperature on flux and separation factor, feed: 25/75 (1,2-HDO/water, w/w, %) membrane: GA4.
respectively. The PSI value is very high at a feed composition of that of the permeate side remains the same. These two factors
10 : 90 IPA/1,5-PDO (wt%) for the 70 M PDMS membrane, sug- increase the driving force for the permeation of both compo-
gesting that it has excellent potential for processing high-IPA nents; therefore, the ux increases and the separation factor
feed mixtures. In contrast, conventional multi-stage distilla- decreases.17,38,39
tion and liquid–gas separation are costly and require large-scale The effect of temperature on the pervaporation ux and
equipment, making the pervaporation separation of high-IPA- separation factor using the 70 M PDMS membrane with
content IPA/1,5-PDO feeds using the PDMS membrane very a 10 : 90 (wt%) IPA/PDO feed was examined, and the results are
attractive. shown in Fig. 7. As is common in pervaporation separation, the
Fig. 6 shows the effect of the operating temperature on the ux increased with increase in temperature. However, the IPA
ux and separation factor of the GA4 membrane with a feed content in the permeate and separation factor also increased
containing 25 : 75 (wt%) 1,2-HDO/water. As oen observed in with temperature. This is because of the large difference in the
pervaporation separation, the polymer membrane ux boiling points of IPA and 1,5-PDO (82 and 238 C, respectively).
increased with increase in temperature, whereas the separation As a result, as the temperature increased, the saturated pressure
factor decreased. This occurs because an increase in the of the mixture increased because IPA is a lower boiling liquid;
temperature of the feed solution increases (1) the polymer free (Boiling Point ¼ 82.5 C) therefore, the driving force for IPA
volume because of the increased thermal motion of the polymer permeation was greater than that of 1,5-PDO (Boiling Point ¼
chains and the (2) vapor pressure on the feed side increases but 242 C). Thus, at higher temperatures, ux was enhanced
Fig. 7 Effect of feed temperature on flux and separation factor, membrane – 70 M, feed 10/90 IPA/PDO, w/w, % solution.
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Fig. 8 Plot of log of individual fluxes of water and 1,2-HDO versus 1000/temperature, feed: 25/75 (1,2-HDO/water, w/w, %) membrane: GA4.
without affecting the IPA content in the permeate. Similar increased free volume in the membrane resulted in the
behavior has been reported for the pervaporation separation of permeation of both components across the membrane; there-
ethylene glycol/water and n-butanol/water mixtures.40,41 Li et al. fore, the ux increased and the separation factor decreased.34,42
developed, PDMS membrane with self-assembled monolayers The temperature dependence of ux can be expressed by the
for ethanol/water pervaporation separation, with increased of Arrhenius-type relationship show in eqn (5).39,43
feed temperature they have found to be increased both ux and
separation factor attributed to the increased diffusion rate of Ji ¼ Ap eEp/RT (5)
ethanol than water by temperature.37 Nevertheless, this
phenomenon was not observed for 1,2-HDO/water separation, here, as before, Ji is the ux of component i (i.e., water, 1,2-HDO,
possibly because PVA is hydrophilic and has affinity for both 1,5-PDO, or IPA) (kg m2 h1), T (K) is the absolute temperature
1,2-HDO and water. On increasing the temperature, the (K); R is the universal gas constant (J mol1 K1) (kJ mol1 K1);
Fig. 9 Plot of log of individual fluxes of IPA and 1,5-PDO versus 1000/temperature, membrane – 70 M, feed 10/90 IPA/PDO, w/w, % solution.
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and Ap (kg m2 h1) and Ep (kJ mol1) are the pre-exponential side of the membrane. At intervals, pervaporation tests were
factor and the apparent activation energy for permeation, carried out, and the pervaporation ux and water content of the
respectively. permeate solution were determined. In total, the membrane
To calculate the apparent activation energy for permeation, operation stability tests were carried out for 18 days. Fig. 10
the log of both sides of eqn (5) is taken (eqn (6)). shows the effect of long-term pervaporation on membrane
Ep performance. As shown in the gure, the ux only slightly
lnðJi Þ ¼ ln Ap (6) increased (0.56 to 0.62), and the water content of the permeate
RT
solution marginally decreased (99.81 to 99.63 wt%) from 1 to 18
here, R ¼ 8.3145 103 kJ mol1 K1, so eqn (6) can be written days. This suggests that the PVA GA4 membrane has potential
as eqn (7). for the long-term separation of water from 1,2-HDO.
Ep 1000 For the organophilic approach, the long-term stability of the
lnðJi Þ ¼ ln Ap ; (7)
8:3145 T PDMS–PSF membrane (70 M) with a feed containing 10 : 90
(wt%) IPA/1,5-PDO was continuously circulated on either side of
Thus, by plotting ln Ji versus 1000/T, Ep can be obtained. The the membrane at 60 C. Again, at intervals, pervaporation tests
logarithmic plots for both hydrophilic and organophilic perva- were carried out to evaluate the pervaporation ux and amount
poration separation are shown in Fig. 8 and 9. The Ep values for of IPA in the permeate solution. In this case, the membrane
water, 1,2-HDO, IPA, and 1,5-PDO are 22.45, 62.15, 18.68, and stability tests were carried out for 18 days. The effect of long-
20.05 kJ mol1, respectively. In the case of 1,2-HDO/water term pervaporation on membrane performance is shown in
pervaporation, the higher Ep of 1,2-HDO compared that of Fig. 11. As shown, the ux decreased initially by a small amount
water indicates that the permeation of 1,2-HDO is more sensi- (from 0.12 to 0.09 kg m2 h1) but subsequently remained
tive to temperature.43,44 On the other hand, for IPA/PDO sepa- almost constant until the end of the tests (day 18). Further, the
ration, the positive value of Ep for IPA suggests that the ux of IPA content of the permeate remained 99.9 0.1 wt% during
IPA increases with temperature, whereas the negative value of the whole test period.
Ep of 1,5-PDO suggests that the ux of 1,5-PDO decreases with Thus, on the basis of the stability evaluation, both hydro-
increasing temperature of the feed solution.45 philic (PVA-based) and organophilic (PDMS-based) separation
membranes have tremendous potential for use in the low-cost,
low-energy industrial pervaporation of a,b and a,u-diols
Long-term pervaporation operation stability of membranes mixtures. Additionally, although this was a laboratory-scale
The performance of both the hydrophilic and organophilic study accordingly free-standing at PVA sheets and a PDMS–
membranes for a,b and a,u-diol production can only be PSF composite membrane were used, the pervaporation output
considered efficient if they exhibit constant long-term separa- could be scaled up by (1) changing the membrane module
tion output. conguration from a at sheet to a hollow ber module system,
Therefore, to examine the long-term stability of the PVA and (2) reducing the active layer membrane thickness from the
membrane (GA4), a feed containing 25 : 75 (wt%) 1,2-HDO/ micrometer to nanometer range.
water at 40 C was continuously circulated through the feed
Fig. 10 Long term stability evaluation in 25/75 (HDO/water, w/w, %) feed mixture of GA4 membrane at 40 C.
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Fig. 11 Long term stability evaluation, membrane – 70 M, feed 10/90 IPA/PDO, w/w, % solution at 60 C.
Conclusions decreased from 13 423 to 1641, and the IPA content of the
permeate increased slightly from 99.93% to 99.96%. In the long-
From an energy-saving perspective, the use of hydrophilic (PVA- term stability evaluation of the PDMS membrane, the 70 M
based membrane) and organophilic (PDMS-based membrane) membrane showed excellent stability with only slightly
pervaporation separation for a,u-diol production were exam- decreased ux, and the IPA content in the permeated solution
ined. As a result of our evaluation, the following conclusions was approximately 99.9% throughout the study. Overall, it can
were drawn. be concluded from the stability evaluation that both hydrophilic
For the pervaporation dehydration of water/1,2-HDO feeds, (PVA) and organophilic (PDMS) membranes have tremendous
a free-standing glutaraldehyde-crosslinked PVA membrane was potential for processing water/1,2-HDO and IPA/1,5-PDO,
developed. The membrane thickness was around 70 mm. For the respectively, mixtures. Crucially, these systems require less
pervaporation separation of a feed containing a 25 : 75 weight energy than traditional distillation-based processes and, thus,
ratio of 1,2-HDO and water at 40 C, the membranes showed will help increase the economics of industrial a,u-diol
decreased membrane swelling and ux (1.27 to 0.51 kg m2 h1) production.
but increased separation factor (59 to 196) with increase in GA
crosslinker contents from 2 to 5 wt%, respectively. Using the
same feed conditions but with the temperature varied from 30 Conflicts of interest
to 60 C, the ux increased from 0.56 to 1.08 kg m2 h1 and the There are no conicts to declare.
separation factor decreased from 178 to 41. In the long-term
stability evaluation of the GA4 membrane with the 25 : 75
(wt%) 1,2-HDO/water feed at 40 C, the hydrophilic membrane Acknowledgements
exhibited excellent performance with only a slight increase in
ux and no signicant reduction in the water content of the This work was supported by the (1) Korea Institute of Energy
permeate. Technology Evaluation and Planning (KETEP) and the Ministry
For the pervaporation separation of 1,5-PDO and IPA feeds, of Trade, Industry & Energy (MOTIE) of the Republic of Korea
a PDMS–PSF membrane was developed. The amount of TEOS (No. 20194010201840) (2) Korea Institute of Energy Technology
crosslinker used for membrane preparation had no effect on the Evaluation and Planning (KETEP) grant funded by the Korea
membrane ux but had a slight effect on the separation factor. government (MOTIE) (20202020800330, Development and
For the 70 M membrane, a ux of approximately 0.20 kg m2 demonstration of energy efficient reaction–separa-
h1 and separation factor of 2406 were obtained using a 20 : 80 tion$purication process for ne chemical industry).
(wt%) IPA/1,5-PDO feed at 50 C. In addition, using the same
membrane, the effect of the feed composition was studied by Notes and references
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