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Salt transport in polymeric pervaporation membrane

Dihua Wu, Aoran Gao, Xianshe Feng

PII: S1004-9541(19)30927-9
DOI: https://doi.org/10.1016/j.cjche.2019.11.009
Reference: CJCHE 1589

To appear in: Chinese Journal of Chemical Engineering

Received date: 24 June 2019

Revised date: 7 November 2019
Accepted date: 21 November 2019

Please cite this article as: D. Wu, A. Gao and X. Feng, Salt transport in polymeric
pervaporation membrane, Chinese Journal of Chemical Engineering(2019),
https://doi.org/10.1016/j.cjche.2019.11.009

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© 2019 Published by Elsevier.

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Dihua Wu1,2 a, Aoran Gao2 a, Xianshe Feng2*

Salt transport in polymeric pervaporation membrane

Abstract

The salt transport in a PEBA membrane used in pervaporative desalination was studied. The

of
concentration profile of salt in the membrane during pervaporation was investigated

ro
experimentally using a multilayer membrane. The salt was found to be sorbed in the membrane

-p
but was not removed during the pervaporative desalination process, and the salt concentration in
re
the membrane varied linearly with position. High purity water was obtained as the permeate as

long as the permeate side was kept dry under vacuum. The accumulated salt uptake in the
lP

membrane follows the order of MgCl2 > NaCl > Na2SO4. The solubility of salt in the membrane
na

follows the order of MgCl2 > NaCl > Na2SO4. Both the permeability and diffusivity of salt in the

membrane follow the order of NaCl > MgCl2 > Na2SO4. The permeability of salt in the
ur

membrane is not influenced by the feed salt concentration. It is mainly determined by the
Jo

diffusion coefficients.

Key words: Concentration profile, Pervaporative desalination, Salt transport

1
Dr. Dihua Wu, College of Materials and Environmental Engineering, Hangzhou Dianzi University, Xiasha Higher
Education Zone, Hangzhou, 310018, Zhejiang Province, China
2
Dr. Dihua Wu, Aoran Gao, Prof. Dr. Xianshe Feng, Department of Chemical Engineering, University of Waterloo,
200 University Avenue West, Waterloo, N2L 3G1, Ontario, Canada
a
The two authors contributed equally to this paper.
*Corresponding author. Tel.: +1 519 888 4567; E-mail: xfeng@uwaterloo.ca (X.Feng).

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Highlights

 The salt concentration profile in the membrane was determined experimentally

 The salt was found to be sorbed into the membrane but would not be removed during the
pervaporative desalination
 The permeability coefficient of the salt was determined by the mass balance method
 The permeation of the salt in the membrane is mainly determined by the diffusion

of
ro
-p
re
lP
na
ur
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1. Introduction

Desalination is one of the most important technologies for obtaining fresh water from

seawater and brackish water. Currently, reverse osmosis (RO) is still the dominant membrane-

based technology for the treatment of seawater and brackish water and accounts for 60% of

desalination plants. However, the main limitation for RO is the high osmotic pressure caused by

the salinity of the solution. Pervaporative desalination and membrane distillation (MD) have

been considered as alternative technologies for the production of ultrapure water. Both these two

of
processes are energy-saving as they do not have the concern about the high osmotic pressure.

ro
Pervaporative desalination is generally performed by a dense and hydrophilic membrane. Water

-p
molecules adsorbed onto the membrane surface diffuse through the membrane and vaporize on
re
the permeate side. Pervaporative desalination is driven by the partial pressure differences of
lP

water on the two sides. On the contrary, MD is carried out by a hydrophobic microporous

membrane as a barrier for the liquid water while allowing vaporous water to pass through the
na

pores. The salt rejection can be achieved at nearly 100% in both these two processes regardless

of salinity. MD has a higher flux than pervaporation desalination. However, membrane fouling
ur

and wetting are main problems in MD [1], which causes the decline of water flux and salt
Jo

rejection, even the damage and degradation of the membrane materials [2]. Such problems can

be mitigated in pervaporation desalination because it uses hydrophilic materials.

The electrical energy required for pumping the feed and permeate for pervaporative

desalination is generally 2 kWh.m-3 [3], which is the lowest value RO can achieve now [3]. The

water flux of pervaporative desalination can be enhanced to a comparable value of RO about 40

kg.m-2.h-1 by increasing the feed temperature and tailoring the membrane materials [4]. The

energy needed for elevating the feed temperature for pervaporative desalination can be helped by

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the renewable solar energy, though the capacity is small. Therefore, pervaporative desalination is

a promising candidate for desalination in terms of energy consumption, especially for the small-

scale processes.

Different hydrophilic materials have been used for pervaporative desalination. Zeolite [5]

and silica [6] are the two main inorganic materials, and poly(vinyl alcohol) (PVA) [7,8] is an

excellent organic material for pervaporative desalination. Recently, two-dimensional materials,

such as graphene oxide [9] and MXene nanosheets [10], have been employed as new materials

of
for pervaporative desalination. Many studies have focused on developing new membrane

ro
materials and tailoring the membrane properties to obtain a better separation performance. Little

-p
attention has been paid to the intrinsic transport of salt through the membrane. Salt is almost
re
fully retained by the membrane in the pervaporation process due to its nonvolatility. However,

this does not mean that the membrane is fully impermeable to salt. Therefore, determining the
lP

permeability and diffusivity of salt in the membrane is significantly meaningful for insight into
na

salt transport in the membrane during the pervaporative desalination process.

A mass balance is the most general method for evaluating these permeabilities based on the
ur

concentration variations of salt in the donator and receiver sides of the membrane [11,12]. This
Jo

method is minimally restricted by the experimental conditions. The basic hypotheses of this

method are as follows: (1) the amount of permeant remaining in the membrane is negligible, and

(2) the permeant is receipted on the receiver side immediately after leaving the donator side. In

some circumstances, such as gas permeation [13] and drug release [14] through polymeric films,

a transient permeation happens in the beginning stage of the diffusion and causes a “time-lag

(θ)”, during which a concentration profile in the membrane is established. After the transient

permeation elapses, the diffusion reaches the pseudo-steady state as soon as difference of the

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transmembrane concentration is constant. Then, an unsteady state appears when the

concentration on the receiver side is high enough, and the permeation stops when there is no

concentration difference across the membrane. However, in the mass balance method, the

“transient” stage of permeation is neglected, and the data at the initial stage, which are

significantly influenced by the “transient” permeation, are excluded. Apparently, the accuracy of

the kinetic parameter so determined is compromised.

A new approach that considers the characteristics of both the mass balance and time lag was

of
developed to determine the permeability and diffusivity coefficients [15]. In this method, the

ro
permeation data in short time are evaluated by the time-lag method, and the permeation data in

-p
long time are evaluated by the mass balance technique. The modified method for determination
re
of permeability coefficient is briefly described in the Supporting Information.

In view of the above, the concentration profile of salt in the membrane during the
lP

pervaporative desalination process was investigated. To our knowledge, this is the first time that
na

the concentration profile of salt in the membrane was determined experimentally. The

permeability and diffusivity coefficients of salts in the polymeric membrane were evaluated by
ur

the modified method. A poly(ether-block-amide) (PEBA) membrane was used for pervaporative
Jo

desalination [16] due to its hydrophilicity.

2. Experimental

2.1 Membrane preparation and characterization

The PEBA copolymer was kindly provided by Specialty Polymers, Arkema Inc.

(Philadelphia, PA). The solution-casting method was used to prepare the homogeneous

membranes with specific thicknesses, and the details have been described before [16].

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The surface charge property of the PEBA membrane was studied by means of streaming

potential. The measurements were taken by an Anton Paar zeta potential analysis meter (Austria).

A membrane sample was placed in the measuring cell and the KCl solution with a concentration

of 0.001 M, at pH=2-9 and temperature of 25 °C was circulated through the cell at. The average

values based on at least three repeated tests are presented.

2.2 Pervaporation with multilayer membranes

of
The experimental setup for pervaporative desalination is similar to that in our previous

ro
study [16]. To determine the concentration profile of salts in the membrane, multilayer

-p
membranes were used for pervaporative desalination. Five sheets of membranes with the same
re
thickness and area (40 µm and 22.05 cm2) were laminated tightly and placed together in the
lP

membrane cell, and the total membrane thickness was approximately 200 µm. Pervaporative

desalination was conducted using feed solutions with various salt concentrations (from 2 to 20
na

wt%) at 25 °C continuously for 10 h. After the pervaporation process, these five membrane

sheets were separated immediately, and each membrane was put into 100 mL of deionized water
ur

to extract the salt from the membrane. The amount of salt dissolved in the membrane equals that
Jo

dissolved in the water. It was determined by measuring the salt concentration in water using a

conductivity meter. This procedure is shown in Fig. S1 for a clear illustration.

2.3 Sorption/desorption

Sorption and desorption experiments were carried out to investigate the solubility of water

and salt in the membrane. The dried membranes with a thickness of 56 μm were immersed in

aqueous solutions of NaCl, MgCl2 and Na2SO4 at concentrations of 1, 5, 10, 15, and 20 wt%.

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The membrane samples were submerged in these solutions at 25 °C for 24 h to reach the sorption

equilibrium. The total sorption weights of water and salt in the membrane was calculated from:

(1)

where and are the weights of the membrane sample before and after sorption,

respectively, and is the total weight of water and salt sorbed in the membrane.

To calculate the respective weights of water and salt in the membrane, the membrane

of
sample after sorption was placed in a vacuum oven at 60 °C for 24 h to achieve complete

ro
desorption of water from the membrane. Thus, the sorption uptake of water can be calculated as:

-p (2)
re
where is the weight of water sorbed in the membrane, and is the weight of the dry
lP

membrane sample after water desorption, Mw is the molecular weight of water. Then, the

sorption uptake of salt can be expressed as:

na
ur

(3)
Jo

where is the weight of the salt sorbed in the membrane, Ms is the molecular weight of salt.

Each experiment was repeated at least twice.

2.4 Swelling

The membrane swelling experiments were carried out using membrane samples with sizes

of 3 cm × 3 cm. By measuring the thickness, length and width of the membrane, the volume of

the membrane can thus be determined. The membrane swelling was expressed as:

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(4)

where and are the volume of the membrane before and after the sorption experiment,

respectively.

2.5 Diffusion/permeation

The diffusivity and permeability of salts in the membrane were investigated by permeation

of
experiments. Fig. S2 shows the experimental apparatus, which comprises a compartment with a

ro
capacity of 100 ml as the donor and a compartment with a capacity of 1500 ml as the receiver.

the
-p
The membrane was fixed at the bottom of the donor compartment and suspended on the top of

receipting compartment. Stirrers were equipped in both the source and receiving
re
compartments to eliminate the boundary layer effect. Before the experiment started, 950 ml
lP

deionized water filled in the receiver compartment, and then 50 ml salt solution at a certain
na

concentration (i.e., 1, 5, 10, 15, or 20 wt%) filled in the donator compartment to induce salt

diffusion and permeation through the membrane. The salt concentration in the receiving
ur

compartment was measured by the conductivity meter in real time. The membrane thickness
Jo

used in this study was the same as that used in the sorption/desorption experiments (i.e., 56 μm),

and the effective membrane area for permeation was 11.34 cm2. The experiment was carried out

at 25 °C.

3. Results and discussion

3.1 Concentration profile of salts in membrane during pervaporation

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The concentration profile of salts in the membrane during the pervaporation process was

determined using five sheet membranes that were laminated together. The salt contents in every

sheet and the accumulative sorption amount are shown in Fig. 1 for NaCl, Figs. S3 and S4 for

MgCl2 and Na2SO4, respectively. The salt amount in the membrane decreases from the first layer

of the membrane (i.e., the layer nearest to the feed side) to the last layer (i.e., the layer furthest

from the feed side). The accumulative salt in the laminated membrane sheets increases, but the

increase becomes less significant along the direction from feed to permeate side. By increasing

of
in the salt concentration, the uptake of salt in every single membrane sheet increases, and the

ro
accumulative amount of salt uptake in the membrane sheets also increases. The accumulative

-p
amount of salt uptake in the membrane accounts for only 0.036 - 0.24% of the total salt in the
re
feed solution.
lP

1.2
(a) NaCl (wt%)
na

20%
Salt in membrane / 10-3 mol.g-1

1.0 10%
2%
ur

0.8
Jo

0.6

0.4

0.2

0.0
Feed 20 60 100 140 180 Permeate
side side
Position measured from feed side /m

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3.5
(b)

Accumulated mass of salts in membrane

3.0 NaCl (wt%)
2%
10%
2.5
20%
363
-1

2.0 0.00
/ 10 mol.g

3X +
6
2 + 0.01
-5 X
-3

1.5 10
1 
44
= -3.3 63
1.0
Y
7 61 X + 0.009
0.00

of
-5 2
1 4  1 0 X +
46
Y = -1.
0.5 + 0.0068
X + 0.002791X

ro
-5 2
Y = -6.4799  10
0.0
0 20 40 60 80
-p 100 120

Total membrane thickness / m

140 160 180 200
re
Fig. 1 Amount of NaCl in each membrane sheet (a) and the accumulated amount of salt in the laminated
lP

membranes at different positions (b).

na

It may be hypothesized that the salts are sorbed in the membrane by the following possible

mechanisms: (1) Under the pressure difference applied across the membrane during
ur

pervaporation, both water molecules and salt ions were dragged into the membrane. (2)
Jo

Following the solution-diffusion model, both the water and the salt molecules diffuse into the

membrane. Regardless of how the salts enter the membrane, they are left at a local position

because of their nonvolatility while the water molecules permeate through the membrane.

The accumulated salt amounts in the membrane as a function of position (Fig. 1, Figs. S3

and S4) were found to be well represented mathematically by a polynomial function, and a

differential was taken with respect to the position, which is shown in Fig. 2, depicting the

concentration profile of the salts in the membrane. Here, l is the total thickness of the five sheets

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membranes laminated together, x is the thickness of the membrane at a certain point of the five

sheets. The following observations can be made: (1) The amount of salt in the membrane varies

linearly with the local position. Note that in pervaporation, where the permeate side is under

vacuum, it is expected that the membrane gradually becomes dryer in the direction of

pervaporation mass transport. The linear relationship over the entire membrane thickness

indicates that the change in membrane “wetness” across membrane thickness has no effect on

salt distribution in the local positions in the membrane. (2) An increase in salt concentration in

of
the feed results in a higher salt content in the membrane, as well as a higher salt concentration

ro
gradient across the membrane. The high salt concentration gradient across the membrane means

-p
an enhanced driving force for salt transport, which is unfavorable for the permeation of water
re
molecules. This further explains the decreased water flux by increasing the feed salt

concentration. (3) The accumulated salt uptake in the membrane follows the order of MgCl2 >
lP

NaCl > Na2SO4. However, in our previous study [16], the water permeability followed the trend
na

of NaCl solution > MgCl2 solution > Na2SO4 solution. These results indicate that the water

permeability in the membrane may be influenced by other factors. Thus, the transport of salts in
ur

the membrane, including solubility, diffusivity and permeability, will be investigated in detail
Jo

below.

The flux and salt rejection of multilayer membranes for feed solutions with different

concentrations are shown in Table 1 The details about the pervaporation performance (e.g., the

effects of feed salt concentration, operating temperature and membrane thickness on flux and salt

rejection) can be obtained in our previous study [16].

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Table 1 Flux and salt rejection of multilayer membranes (temperature: 25 °C, total thickness:100
μm)

Salt solution Concentration, % Water flux, [g/(m2.h)] Salt rejection, %

2 278.2
NaCl 10 208.3
20 108.4
2 276.4
MgCl2 10 200.2 > 99.9
20 103.8
2 275.2

of
Na2SO4 10 190.5
20 98.5

ro
0.025
-p
Salt uptake in membrane / 10-3 mol.g-1

re
NaCl
0.020 MgCl2 20 %
lP

Na2SO4
0.015
na

20 %
ur

0.010
Jo

10 %
10 %
0.005
20 %
2%
10 %
2%
2%

0.000
0 0.25 0.5 0.75 1.0
-1
x.l / -
Fig. 2 Concentration profiles of NaCl, MgCl2 and Na2SO4 in the membrane. Temperature: 25 °C.

3.2 Solubility of salts in membrane

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Fig. 3 shows the salt and water uptake in the membrane as a function of salt concentration

in the liquid solution. It should be mentioned that the salt uptake in membrane was calculated

according to the volume of the membrane sample and its unit is “kmol.m-3” here in order to

obtain the non-dimensional solubility coefficients. Within the range of feed concentrations

investigated, salt sorption is proportional to the salt concentration in the feed, a relationship that

is similar to Henry’s law, which has been observed for aroma sorption in membranes relevant to

aroma enrichment [17]. The salt uptake in the membrane follows the order of MgCl2 > NaCl >

of
Na2SO4, which is in the same order as their accumulated uptake in the membrane during the

ro
pervaporation process in Sect 3.1. The solubility coefficients can be calculated from the slopes of

-p
the straight lines, which are 1.05, 0.421 and 0.315, in units (mol/m3 membrane)/(mol/m3
re
solution), for MgCl2, NaCl and Na2SO4, respectively. By testing the surface zeta potential of the

PEBA membrane under different pH values (shown in Fig. 4), the membrane appears
lP

significantly negatively charged around pH=7. Thus, it is not surprising that the membrane
na

shows the highest affinity to the divalent cation Mg2+ while the greatest repulsion to the divalent

anion SO42-.
ur

The water uptake in the membranes decreases with increasing salt content in the solution
Jo

due to the decreased water activity and osmotic deswelling [18]. The swelling degree of the

membrane in different salt solutions is shown in Fig. 5. It was found that the water uptake in the

membrane and the membrane swelling degree follow the same order of NaCl solution > MgCl2

solution > Na2SO4 solution, which is the same as the order of water permeability in the

membrane during the pervaporative desalination process [16]. This further confirms that the

osmotic pressure of the salt solution is an important factor influencing the transport of water

molecules in the membrane. The osmotic pressure of the salt solution can be calculated as:

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Π = фΠ* = фibRT [19]

(5)

where Π*(=ibRT) is the osmotic pressure for an ideal solution, ф is the osmotic coefficient, i is

the total number of ions given by one mole of salt, b is the solute molality, R is the gas constant,

and T is the temperature. Table 2 shows the osmotic coefficient and osmotic pressure for 1

mol/m3 salt solutions at 298 K. The NaCl solution shows the smallest osmotic pressure and thus

has the least effect on membrane deswelling. The osmotic pressure of the MgCl2 solution is the

of
highest, but the Na2SO4 solution shows the most significant effect on membrane deswelling as

ro
well as water uptake and water permeability in the membrane. Hence, in addition to the Donnan

-p
effects and osmotic pressure, the water transport of different salt solutions in the membrane is
re
probably influenced by another factor.

2.5
lP

(a)
MgCl2
Salt uptake in membrane / kmol.m-3

2
na

1.5 NaC
ur

l
Jo

0.5 Na2SO4

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25
(b)

Water uptake in membrane / kmol.m -3

20

15

10 NaC
Na2SO4 MgCl l
2

of
ro
0
0 1 2 3 4

-p
Salt concentration / kmol.m-3
re
Fig. 3 Sorption uptake of (a) salts and (b) water in the membrane under different salt concentrations. at
25 °C.
lP

10
na

0
ur
Zeta potential / MV

-10
Jo

-20

-30

-40
1 2 3 4 5 6 7 8 9 10 11 12
pH / -

Fig. 4 Surface zeta potential of PEBA membrane (Tested with 0.001 M KCl at 25 °C).

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45
NaCl
40 MgCl2
35 Na2SO4
Swelling degree / %
30

25

20

of
15

10

ro
5

0
0.0 0.5 1.0 1.5
-p 2.0 2.5 3.0 3.5 4.0
re
-3
Salt concentration / kmol.m
lP

Fig. 5 Swelling degree of the membrane under different salt concentrations at 25 °C.
na

Table 2 Osmotic coefficient and osmotic pressure for 1 (mol/m3) salt solution at 298 K

NaCl MgCl2 Na2SO4

ur

i 2 3 3
Jo

ф 0.8945 [20] 1.1096 [21] 0.7063 [20]

Π [Pa] 4432.38 8247.34 5249.73

It is known that the presence of electrolytes in aqueous solutions disrupts the neighboring

structure of water molecular [22]. Hofmeister ranked a series of ions according to the

interactions between ions and water. The ions are known as structure makers or kosmotropes

when the interactions between ion-water is stronger than water-water, whereas ions are known as

structure breakers or chaotropes when the opposite effect exsits [23]. In the Hofmeister series

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[24], SO42- is a typical kosmotropic anion, and Na+ is also classified as a kosmotropic cation.

Thus, Na2SO4 has the strongest interaction with water among the three electrolytes. It is

understandable that the membrane in the Na2SO4 solution has the lowest swelling degree and

water uptake because the water is likely to be “locked” by SO42- and Na+. This effect also

explains the lowest water permeability of the Na2SO4 solution during pervaporative desalination

in our previous study [16].

of
3.3 Permeability and diffusivity of salts in membrane

ro
Fig. 6 shows the change in the salt concentration in the receipting compartment as a

-p
function of time through a membrane with the thickness of 56 μm at various initial salt
re
concentrations. It was found that the time lag in diffusion was not significant. Thus, the salt

diffusivity in the membrane cannot be evaluated from the time-lag method. Nonetheless, the
lP

permeability coefficients can still be evaluated using the mass balance method in quasi-steady
na

state permeation. The F(t)1 -t plots of the three salts are shown in Fig. 7, and no nonlinear part

was found even when using t0 = 0, which further confirms that the time-lag method is not able to
ur

determine the salt diffusivity in the membrane. This is probably because the transient permeation
Jo

of salt in the membrane is very quick, the diffusion reaches the pseudo-steady state immediately

after the salt leaves the liquid solution, and the time lag is too short to be detected accurately by

the technique used in this study.

1
F(t) = -ln[(mT-VTCR)/(mT-VTa)], see the details in Supporting Information

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100
90
(a) NaCl

Concentration of NaCl / mg.L-1

80
70
1%
60
5%
50
10%
40
15%
30
20%
20
10
0

of
100
(b) MgCl2
90

ro
Concentration of MgCl2 mg.L-1

80
70
60
50
-p
re
40
30
lP

20
10
0
na

3
(c) Na2SO4
ur Concentration of Na2SO4 / mg.L-1

2.5
Jo

1.5

0.5

0
0 2 4 6 8 10 12 14 16 18 20 22
Time / min

Fig. 6 Concentration of (a) NaCl, (b) MgCl2 and (c) Na2SO4 in the receipting compartment as a function
of time. Membrane thickness: 56 μm.

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0.01
(a) NaCl

0.008

0.006 1%

F(t)
5%
10%
0.004
15%
20%
0.002

of
0.01
(b)

ro
0.008

0.006
-p
F(t)

re
0.004
lP

0.002
na

0
ur
Jo

Fig. 7 F(t) vs t curves for (a) NaCl, (b) MgCl2 and (c) Na2SO4 diffusion. Membrane thickness: 56 μm.

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The permeability coefficients of the salts determined from the slope of the F(t)-t plots are

shown in Fig. 8. It can be seen that: (1) For the same salt, the feed concentration has little

influence on the permeability of the salt over the salt concentration range investigated here. (2)

The salt permeability is related to the salt type and follows the order of NaCl > MgCl2 > Na2SO4.

It is not surprising that NaCl has the highest permeability because it is the smallest salt (effective

size of 0.15 nm [25]) among the three. MgCl2 and Na2SO4 have a similar effective molecular size

of 0.2 nm [25]; however, the repulsion between the negatively charged membrane and SO 42-

of
resulted in the lowest permeability of Na2SO4 in the membrane. Please note that such

ro
permeability coefficients measure the ability of the salt to pass through the membrane under a

concentration gradient across the membrane. These coefficients have dimensions of [(mol-
-p
salt).(m-membrane thickness)]/[(m2-membrane area).(s-time)/[(mol-salt)/(m3-solution volume)]
re
or [m2.s-1], which is commonly used in the literature.
lP

2.0
na
Permeability coefficient / 10 -11 m2.s-1

1.5 NaC
ur

MgCl2
Jo

1.0

0.5

Na2SO4
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24

Salt concentration / wt%

Fig. 8 Permeability coefficient of salt in the membrane as determined from the diffusion experiments.

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When the diffusion coefficient and solubility coefficient are independent of salt

concentration, the permeability coefficient P will be equal to the product of the diffusion and

solubility coefficients, that is, P=D∙S. The diffusivity coefficient can be estimated from D=P/S,

and the results are shown in Fig. 9. Note that the solubility coefficient measures how much salt is

sorbed in the membrane at a given salt concentration in the solution, and the diffusion coefficient

measures how fast the salt diffuses through the membrane under a concentration gradient across

the membrane. The diffusivity of the three salts in the membrane also follows the order of NaCl >

of
MgCl2 > Na2SO4. Therefore, it may be concluded that the permeability of the salts in the

ro
membrane is mainly determined by the diffusion coefficients.

5.0
-p
re
4.0
lP

NaCl
Diffusivity / 10 -11 m2.s-1

3.0
na
ur

2.0
Jo

MgCl2
1.0

Na2SO
0.0 4
0 2 4 6 8 10 12 14 16 18 20 22 24

Salt concentration / wt%

Fig. 9 Salt diffusivity in the membrane estimated from the solubility and permeability coefficients.

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A comparison of salt transport properties of different membranes is illustrated in Table 3.

The PEBA membrane studied in this work shows a medium-low salt permeability comparing

with other polymeric membranes, which is favorable for desalination applications.

Table 3 A comparison of salt transport properties

S D P
Membrane Salt Ref
(dimensionless) (10-11 m2.s-1) (10-11 m2.s-1)
PEBA NaCl 0.421±0.02 3.85±0.05 1.55±0.05 This study

PEBA MgCl2 1.05±0.03 1.20±0.01 1.15±0.05 This study

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PEBA Na2SO4 0.315±0.02 0.35±0.03 0.15±0.01 This study

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Disulfonated Poly 0.018±0.001 0.029±0.006 0.00058±0.00007
(arylene ether NaCl [11]
sulfone)

TRP-BP
- 0.116±0.005
0.050±0.008
-p - 4.78±0.21
1.2±0.2
- 0.554±0.0178
0.058±0.001
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NaCl [12]
- 0.159±0.020 - 12±2 - 1.99±0.06
Hybrid
[26]
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NaCl 0.43 - 1.93 4.5- 49.6 1.9 - 95.4

PVA/MA/TEOS
Poly(ethylene oxide) 0.067±0.002 2.4±0.2 0.16±0.01
NaCl [27]
hydrogels - 0.791±0.036 - 44±4 - 27±3
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4. Conclusions
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The salt transport in the PEBA membrane used in pervaporative desalination was studied.
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The concentration profile of salts in the membrane during pervaporation was investigated

experimentally using a multilayer membrane. The solubility, diffusivity and permeability of salts

in the membrane were determined. The following conclusions can be drawn:

(1) The salt was found to be sorbed in the membrane but was not removed during the

pervaporative desalination process, and the salt concentration in the membrane varied linearly

with position. The accumulated salt uptake in the membrane follows the order of MgCl2 > NaCl >

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Na2SO4. High purity water was obtained as the permeate as long as the permeate side was kept

dry under vacuum.

(2) The solubility of salt in the membrane follows the order of MgCl2 > NaCl > Na2SO4.

(3) Both the permeability and diffusivity of salts in the membrane follow the order of NaCl >

MgCl2 > Na2SO4. The permeability of the salts in the membrane is not influenced by the feed salt

concentration. It is mainly determined by the diffusion coefficients.

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Acknowledgement

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Research support from the Natural Sciences and Engineering Research Council (NSERC) of

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Canada is gratefully acknowledged. We also wish to acknowledge Arkema Inc. for generously
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supplying the polymer used in making the membranes.
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Conflict of interest statement: None

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Symbols used

b [mol.kg-1] molality
D [m2.s-1] diffusion coefficient
F(t) [-] function of t
i [-] total number of ions given by one mole of salt
l [μm] total thickness of membrane
-1
M [kg.mol ] molecular weight

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m0 [kg] weight of membrane sample before sorption

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m1 [kg] total weight of water and salt sorbed in the membrane
m2 [kg]
m3 [kg] -p
weight of membrane sample after sorption
weight of dry membrane sample after water desorption
re
2 -1
P [m .s ] permeability coefficient
3 -1 -1
R [m ·Pa·mol ·K ] gas constant
lP

S [-] solubility coefficients

T [K]
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temperature
t [min] time
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-3
U [kmol.m ] uptake
3
V1 [m ] volume of membrane before sorption
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3
V2 [m ] volume of membrane after sorption
x [μm] thickness of membrane at a certain point

Subscripts
s salt
w water

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Greek letters
Π [Pa] osmotic pressure of the salt solution
Π* [Pa] osmotic pressure for an ideal solution
ф [-] osmotic coefficient
θ [min] time lag

Abbreviations
MA maleic acid

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MD membrane distillation
PVA poly(vinyl alcohol)

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PEBAX poly(ether-block-amide)
RO
TEOS
reverse osmosis
tetraethyl orthosilicate
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TRP-BP triptycene-containing sulfonated polysulfone
lP
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Figure legends

Fig. 1 Amount of NaCl in each membrane sheet (a) and the accumulated amount of salt in the
laminated membranes at different positions (b).

Fig. 2 Concentration profiles of NaCl, MgCl2 and Na2SO4 in the membrane. Temperature: 25 °C.

Fig. 3 Sorption uptake of (a) salts and (b) water in the membrane under different salt
concentrations. at 25 °C.

Fig. 4 Surface zeta potential of PEBA membrane (Tested with 0.001 M KCl at 25 °C).

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Fig. 5 Swelling degree of the membrane under different salt concentrations at 25 °C.

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Fig. 6 Concentration of (a) NaCl, (b) MgCl2 and (c) Na2SO4 in the receipting compartment as a
function of time. Membrane thickness: 56 μm.

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Fig. 7 F(t) vs t curves for (a) NaCl, (b) MgCl2 and (c) Na2SO4 diffusion. Membrane thickness: 56
μm.
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Fig. 8 Permeability coefficient of salt in the membrane as determined from the diffusion
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experiments.

Fig. 9 Salt diffusivity in the membrane estimated from the solubility and permeability
coefficients.
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