Article

Experimental and Theoretical Analysis of Lead Pb2+

and Cd2+ Retention from a Single Salt Using a Hollow
Fiber PES Membrane
Salwa Hadi 1, Ahmed A. Mohammed 2, Sama M. Al-Jubouri 3, Mahmood F. Abd 4,
Hasan Shaker Majdi 5, Qusay F. Alsalhy 6,*, Khalid T. Rashid 6, Salah S. Ibrahim 6,
Issam K. Salih 5 and Alberto Figoli 7
1 Environment Engineering Department, College of Engineering, University of Tikrit, 34001 Tikrit, Iraq;
[email protected]
2 Environment Engineering Department, College of Engineering, University of Baghdad, 10071 Baghdad,

Iraq; [email protected]
3 Department of Chemical Engineering, College of Engineering, University of Baghdad, 10071 Baghdad, Iraq;

[email protected]
4 Environment Geology Department, College of Science, University of Tikrit, 34001 Tikrit, Iraq;

[email protected]
5 Department of Chemical Engineering and Petroleum Industries, AlMustaqbal University College, Babylon

51001, Iraq; [email protected] (H.S.M.); [email protected] (I.K.S.)

6 Membrane Technology Research Unit, Chemical Engineering Department, University of Technology, 10066

Baghdad, Iraq; [email protected] (K.T.R.); [email protected] (S.S.I.)

7 Institute on Membrane Technology, National Research Council (ITM-CNR), 87030 Rende (CS), Italy;

[email protected]
* Correspondence: [email protected]

Received: 6 June 2020; Accepted: 28 June 2020; Published: 30 June 2020

Abstract: The present work reports the performance of three types of polyethersulfone (PES)
membrane in the removal of highly polluting and toxic lead Pb2+ and cadmium Cd2+ ions from a
single salt. This study investigated the effect of operating variables, including pH, types of PES
membrane, and feed concentration, on the separation process. The transport parameters and mass
transfer coefficient (k) of the membranes were estimated using the combined film
theory-solution-diffusion (CFSD), combined film theory-Spiegler-Kedem (CFSK), and combined
film theory-finely-porous (CFFP) membrane transport models. Various parameters were used to
estimate the enrichment factors, concentration polarization modulus, and Péclet number. The pH
values significantly affected the permeation flux of the Pb2+ solution but only had a slight effect on
the Cd2+ solution. However, Cd2+ rejection was highly improved by increasing the pH value. The
rejection of the PES membranes increased greatly as the heavy metal concentration rose, while the
heavy metal concentration moderately affected the permeation flux. The maximum rejection of Pb2+
in a single-salt solution was 99%, 97.5%, and 98% for a feed solution containing 10 mg Pb/L at pH 6,
6.2, and 5.7, for PES1, PES2, and PES3, respectively. The maximum rejection of Cd2+ in single-salt
solutions was 78%, 50.2%, and 44% for a feed solution containing 10 mg Cd/L at pH 6.5, 6.2, and 6.5,
for PES1, PES2, and PES3, respectively. The analysis of the experimental data using the CFSD,
CFSK, and CFFP models showed a good agreement between the theoretical and experimental
results. The effective membrane thickness and active skin layer thickness were evaluated using the
CFFP model, indicating that the Péclet number is important for determining the mechanism of
separation by diffusion.

Keywords: hollow fiber membrane; CFSK model; CFSD model; CFFP model; wastewater
treatment; heavy metals

Membranes 2020, 10, 136; doi:10.3390/membranes10070136 www.mdpi.com/journal/membranes

Membranes 2020, 10, 136 2 of 25

1. Introduction
In the past few years, attention has been concentrated on the removal of heavy metal ions from
wastewater due to their toxicity, and thus, their impact on human health. Therefore, according to
environmental regulations, all of the heavy metals from wastewater of various industries must be
removed, meaning that wastewater requires total control prior to its discharge into the environment
[1]. Various traditional processes have been employed to remove heavy metals from effluents, such
as chemical precipitation, electrocoagulation, solvent extraction, ion exchange, and adsorption on
various sorbents, etc. Most of these above-mentioned processes suffer from economic limitations
and other disadvantages. For example, both adsorption and ion exchange are inexpensive and
highly effective for treating low concentrations of heavy metals; however, they generate hazardous
sludge that requires regeneration or additional treatment, such as solidification. Furthermore, in the
adsorption process, some adsorbents have limited capacities, low selectivity, require a long
adsorption contact time, and show slow adsorption kinetics, even as most of the adsorbents,
especially the synthetic nanoparticles, are expensive. Also, solvent extraction and chemical
precipitation are considered to be polluting processes themselves [2–12].
Membrane separation processes have been found to be efficient, economic, and green
(non-polluting) separation processes in comparison with the traditional and polluting methods
mentioned above. Membrane separation processes have achieved wide use in treating various
industrial wastewaters, with some used to remove heavy metals from wastewaters, such as reverse
osmosis (RO), nanofiltration (NF), and ultrafiltration (UF) [13–18]. Nanofiltration membranes have
mainly been used in various industries for the removal of heavy metals, compared with UF and RO
processes, due to the high removal efficiency of NF and its ability to work at moderate pressure [18–
20]. Separation by membranes generates concentrate/retentate that requires special attention before
discharge into the environment. Also, the concentrate can accumulate at the membrane surface and
reduce the water flow rate at a given transmembrane pressure. The literature shows that the method
used to deal with concentrate mainly depends on its contents. The concentrate resultant from
treating oily water can be reused for soap production. Also, the concentrate containing fructose,
glucose, etc., can be used for the synthesis of beverages, while the concentrate resultant from treating
wastewater containing heavy metals can be recycled for filling up the electroplating bath and rinsing
purposes [21].
Much research has been conducted using the NF membrane process to remove heavy metal
ions from wastewater, such as nickel, zinc, copper, arsenic, lead, cadmium, and chromium. Despite
the efficient use of NF membranes in the removal of heavy metals, several factors have been found to
determine the performance of NF membranes, including the membrane type, metal solution pH,
metal ions, and metal concentration [19–31]. The literature rarely discusses the preparation of hollow
fiber membranes with optimum specifications in the range located between NF and UF membranes
that were applied for highly efficient heavy metal removal with high permeate flux. It is obvious that
the main factors controlling the flow rate and the separation factor across the membrane are the
characteristics of the membrane, such as the porosity, pore size, pore size distribution, and
membrane thickness. Therefore, competition for the ability to manufacture hollow fibers has the best
specifications, which makes the hollow fiber highly efficient for separation of solutes and mass
production with approximately low costs. Because of the fact that the use of NF membrane in the
process of removing heavy metals is common and the fact that NF membranes require high
operating pressures compared to ultrafiltration membranes, three types of membranes whose
specifications are between NF and UF have been prepared in this study. It is assumed that the
efficiency of these hollow fibers is higher in terms of mass production and the removal rate of the
heavy metals with those commercially manufactured membranes.
However, only a few studies have reported on highly concentrated solutions. Moreover, the
investigation of various heavy metals using the same hollow fiber, at the similar operating
conditions, provides important information about the appropriateness of the hollow fiber for a
particular heavy metal under various conditions. Therefore, this work investigates the effective
removal of two heavy metals (i.e., Cd2+ and Pb2+) from simulated aqueous solutions using three
Membranes 2020, 10, 136 3 of 25

polyethersulfone (PES) membranes prepared for this purpose. These two heavy metals were selected
due to their severe side effects on human health, whereas the removal efficiency of other heavy
metals (e.g., Co2+) was studied in our previous work [32]. This research studies the effect of the
operating conditions on the membrane separation performance, including pressure (1 bar), initial
feed concentration (10–250) ppm, and pH solution (5.5–6.5). The literature dedicated to describing
the concentration polarization and transport phenomena through hollow fiber membranes is not
extensive. Therefore, this work aims to address this gap. So far, the membrane transport parameters
and mass transfer coefficient have not been extensively studied using the following models: film
theory, combined film theory-Spiegler-Kedem (CFSK), combined film theory-solution-diffusion
(CFSD), combined film theory-finely-porous (CFFP) models, calculated concentration polarization
model (CPM), enrichment factor (Eo), and Péclet number (Pe). In previous literature, the membrane
transport parameters and mass transfer coefficient were studied for only one membrane using a
single selected model. But, this work will compare the membrane transport parameters, mass
transfer coefficient, and the experimental results of the three different membranes using several
selected models.

2. Experimental Work

2.1. Materials and Methods

Simulated wastewater was prepared by adding cadmium nitrate (Cd(NO3)2·4H2O) and lead
nitrate (Pb(NO3)2) to distilled water. Several solutions were prepared with different concentrations
of 10 to 250 ppm and pH values of 5.5 to 6.5. Three types of polyethersulfone (PES) membranes (PES
type Radel) were provided by Solvay Advanced Polymers (Solvay, Brussels, Belgium), which were
prepared using a dry/wet phase inversion method coded as PES1, PES2, and PES3 for heavy metal
removal. The surface morphology and all the specifications of the PES membranes are summarized
in Table 1, and details of the preparation method and measurement of the characteristics of the PES
hollow fibers are presented elsewhere [33–35]. The reason behind selected different PES hollow
fibers was to find the optimum specifications of the hollow fibers (e.g., pore size, porosity, and
thickness) in the range located between NF and UF membranes that was applied for highly efficient
heavy metal removal with high permeate flux. The pH values were measured using a calibrated pH
meter (HQ411d, pH/mv, HACH Company, Loveland, CO, USA), whereas the concentrations of the
metal ions in the simulated and treated solutions were measured using an AA-6200 atomic
absorption flam emission spectrophotometer (Shimadzu Corporation, Kyoto, Japan) that was
calibrated regularly, with the calibration curve verified before each sample set. The membrane
surface charge depends on the pH value, with the membrane surface charge being negative for
solution pH values higher than 5 and positive when pH values are less than 4 [30–36].

Table 1. Characteristics of the polyethersulfone (PES) membranes.

Average Pore size Outer Inner

Membrane Membrane Porosity Thickness
Pore Size Distribution Diameter Diameter
Code Material (%) (µm)
(nm) (nm) (µm) (µm)
PES1 PES (29%) 52.04 25–100 52.5 1012 620 196
PES2 PES (27%) 58.11 35–130 67.6 958.4 576 191.2
PES3 PES (27%) 47.75 20–115 58.1 1005 603.6 200.7

2.2. Membrane Filtration and Heavy Metal Rejection

The experiments testing the permeation flux of distilled water and heavy metal solutions as
well as the rejection of heavy metals using PES1, PES2, and PES3 hollow fibers were achieved by
module cross-flow pattern filtration. Two hollow fiber membrane modules composed of five fibers
of the same membrane for each PES type were tested. Membrane experiments were conducted at a
transmembrane pressure of 1 bar, heavy metal solution temperature of 25 °C, and metal solution
concentration of 1000 ppm, using the PES hollow fiber membrane experimental setup shown in
Figure 1. The effect of the pH and heavy metal concentration on the performance of three PES hollow
Membranes 2020, 10, 136 4 of 25

fibers was studied extensively, and Table 2 shows the operating conditions of the membrane
experiments. Permeation flux (JV) and heavy metal rejection (R%) were obtained from Equations (1)
and (2), respectively:

Jv = V/t·A (1)

R (%) = [1 − Cp/Cf] × 100 (2)

where V is the permeate volume (l), t is the collected permeate time (h), A is the membrane surface
area (m2), Cp is the concentration of the solute in the permeate, and Cb is an average bulk
concentration of the solute in the feed (Cf) plus what is in the concentrate/retentate (Cr), estimated
using Equation (3):
C + C
C = (3)
2
After each set of experiments for a given feed concentration, the setup was rinsed with distilled
water for 1 h at 4 bar pressure to clean the NF membrane experimental system. This was followed by
measuring the pure water permeation flux with distilled water to ensure that the initial membrane
flux was restored. Moreover, the pH value was adjusted using 1 M NaOH or 1 M HCl. By plotting
the membrane flux (Jv) versus the different applied pressures (ΔP), the membrane permeability
(pure water permeability, Lp) can be obtained from the slope of the line given by Equation (4):
J
L = (4)
∆P

Figure 1. A schematic diagram of the membrane filtration test system.

Table 2. Operating conditions of the hollow fiber membrane separation process.

Metal Salts pH metal Cmetal (ppm) Pressure

Pb(NO3)2 5.5, 5.7, 6, 6.2, 6.5 10, 50, 100, 200, 250 1 bar
Cd(NO3)2·4H2O 5.5, 5.7, 6, 6.2, 6.5 10, 50, 100, 200, 250 1 bar
Pb(NO3)2 + Cd(NO3)2·4H2O 6 ± 0.2 10 + 50, 50 + 10, 50 + 50 1 bar
Membranes 2020, 10, 136 5 of 25

2.3. Models of Membrane Transport

2.3.1. Film Theory

The concentration polarization (CP) phenomenon is known as the solute concentration
accumulation at the surface of the membrane throughout the separation process. The solute is
transferred by convection into the boundary layer and back by diffusion to the bulk solution [37,38].
Figure 2 shows that the flux of the solute within the PES membranes decreased because of the
CP phenomenon, where a gel layer formed on the membrane surface due to the retained solutes,
resulting in an increase in osmotic pressure. From the basic principle of mass balance, the solute
transfer at any point across the boundary layer can be described by Equation (5) [39]:
dc
(C − Cp)J = D (5)
dx
where D is the diffusivity of the solute, C is the concentration of the solute in the boundary layer, x is
the distance from the membrane layer, and Cp is the concentration of the solute in the permeate
solution. Equation (5) can be integrated with respect to the following boundary conditions to obtain
Equation (6), based on the following:
C = Cm (at x = 0), C = Cb (at x = 𝛿)

where Cm is the concentration of the solute at the surface of the membrane/water interface, Cb is the
solute in the bulk solution, and 𝛿 is the edge of the mass transfer boundary layer,
C − C J
= exp( ) (6)
C − C k

where k is the coefficient of mass transfer and is expressed as k = , and Dab is the diffusivity of
solute a in water (solvent) b (cm /s).
2

The typical expressions of the observed Ro and actual solute R are the rejections by a
membrane given by Equations (7) and (8), respectively [40]:
C
R =1− (7)
C
C
R=1− (8)
C
Using Equations (7) and (8), Equation (6) can be rewritten in the following form [37]:
1−R 1
ln = J + ln(P ) (9)
R k
where P = .
By plotting ln versus J based on the experimental data, the overall permeability
coefficient (Ps) and the coefficient of mass transfer (k) can be calculated from the intercept of the line
on the y-axis and the slope, respectively.
Membranes 2020, 10, 136 6 of 25

Figure 2. Schematic diagram of concentration polarization phenomenon in hollow fiber.

2.3.2. Combined Film Theory/Solution-Diffusion Model (CFSD)

This model depicts the transfer mechanism, where the solute and solvent dissolve in the
nonporous and homogeneous membrane surface, expressed by Equations (10) and (11) [41]:
J = L (∆P − ∆π) (10)

D K
J = C − C (11)
δ
where Lp is the water (solvent) permeability parameter that can be calculated from measurements
of the Pure water permeation flux (PWP), and where is considered to be a single parameter,
namely, the solute transfer variable or parameter.
R J −J
= exp (12)
1−R D K/δ k
Therefore, in the current study, the CFSD model will be described by Equation (12). The
parameter and the coefficient of mass transfer (k) can be calculated numerically by inserting
(Ro) versus (J) data.

2.3.3. Combined Film Theory-Spiegler-Kedem Model (CFSK)

An irreversible thermodynamics (IT) model can be applied in the absence of electrostatic
interaction between the membrane and solute to explain the transfer of a single solute and solvent
within a PES membrane, as reported by Kedem et al. [42]. The process is the sum of convective and
diffusive fluxes, where these fluxes are due to the difference in pressure and to the concentration
gradient at the membrane surface, respectively. In IT, the membrane is considered to be a black box.
Therefore, the physicochemical properties of the membrane and solution system are considered as
model parameters. The working equations of the nonlinear Spiegler-Kedem model [38,42] are as
follows:
J = − L (∆p − σ∆π) (13)
Js= - PM∆𝐶 + (1 − 𝜎)𝐶 𝐽 (14)
Assuming the constant coefficients and constant fluxes PM and 𝜎, Equation (14) is integrated
within the thickness of the membrane. The Spiegler-Kedem equation, which relates the retention of
the solute (R, given by Equation (15)) with the volumetric flux of the water (solvent) and the
permeability of the solute, results in the following:
Membranes 2020, 10, 136 7 of 25

σ(1 − F)
R= (14)
1 − σF

where F = exp[−J a2] (15)

1−σ
and a2 = (16)
P
where 𝜎, the reflection coefficient that assimilates the membrane rejection (e.g., 𝜎 = 0), refers to a
rejection with 0% and 𝜎 = 1 denotes a solute rejection of 100%, 𝑃 is the permeability of the salt
(L/m2·h), and Lp is the membrane hydraulic permeability coefficient. F represents the flow
parameter given by Equation (16). Additionally, Equation (15) can be rearranged to give Equation
(18):
𝑅
= 𝑎1(1 − 𝐹) (17)
1−𝑅
𝜎
where 𝑎1 = (18)
1−𝜎
Equation (20), shown below, is the result of substituting Equation (18) into Equation (9):
Ro −J
= a1[1 − exp (−Ja2)] exp ( ) (20)
1 − Ro k
Equation (20) represents the CFSK model. The membrane σ, the P , and the coefficient of mass
transfer (k) can be calculated by using a nonlinear parameter estimation method (SPSS version 22),
where at different conditions, Ro versus J serve as inputs into the model [43].

2.3.4. Combined Film Theory-Finely-Porous Model (CFFP)

The combined film theory-finely-porous model (CFFP) merges the effect of friction between
the membrane pore wall and the solute molecules. The friction impact is taken into account as
factor b. Equation (21) represents the working equation [44]:
1 bε k−b ε τε
= + exp −J (19)
1−R k k εb D
where bf is a factor measuring the friction between the membrane pore wall and the solute
molecules, which is calculated from bf = 1+ fsm/ fsw, where fsm is the coefficient of friction between the
membrane and the solute, whereas fsw is the coefficient of friction between the solvent (water) and
the solute.
The substitution of Equation (21) into Equation (9) results in Equation (22):
R bε τδ J
= −1 1 − exp −J exp − (20)
1−R k εbD k
where
bε
b1 = −1 (21)
k
τδ
b2 = (22)
εbD
Equation (22) represents the CFFP model. A nonlinear parameter estimation method (SPSS
version 22) can be used to calculate the membrane parameters and k by supplying, at various
conditions, the data for Ro versus J for each set.

2.3.5. Concentration Polarization Model (CPM) and the Enrichment Factor (Eo)
Concentration polarization (CP) is commonly characterized using the film theory model,
where it is described by the boundary layer thickness across which the counter diffusion takes
place. Here, the terms of the concentration in Equation (6) are substituted by the enrichment factors
Membranes 2020, 10, 136 8 of 25

E (e.g., Cp/Cb) and Eo (e.g., Cp/Cm). Also, the CP in Equation (6) can be expressed by the Péclet
number Pe (known as J/k), which produces Equation (24) [45]:
1/E − 1
= exp(P ) (23)
1/E − 1
Any increase or decrease in the concentration of the solute at the surface of the membrane
compared to the bulk solution concentration determines the effect or range of the CP. The ratio
Cm/Cb represents the concentration polarization model (CPM) and is a perfect indication of the
effect or range of the CP. No CP takes place when CPM ≤ 1. On the other hand, the model becomes
increasingly neutralized when CPM > 1, at which point the CP’s impact on the selectivity and flux
of the membrane becomes critical. Based on the definition of Eo and E, the CPM is equivalent to Eo
and E, and using Equations (6) and (10), Equation (26) can be generated [43,45]:
E C exp (𝑃 )
= = (24)
E C 1 + 𝑃 [exp(𝑃 ) − 1]
Also, Equation (27) can be obtained by rearranging Equation (25) to calculate Cm, as shown
below [46]:

= (1-Ro)+Ro exp(J/k) (25)

where, Ro = 1 − Cp/Cm.
The CP modulus can be lower or higher than 1, depending on the hollow fiber enrichment
code Eo. Equation (26) presents the parameters used to calculate the CP value: the boundary layer
thickness δ, the hollow fiber enrichment Eo, the volumetric flow rate through the hollow fiber J, and
the coefficient of solute diffusion throughout the boundary layer fluid D. The boundary layer
thickness δ is the most significant parameter that affects the CP. When δ decreases, Equation (26)
indicates that the CP modulus is exponentially low. Thus, the optimal method for reducing the CP
is to decrease δ by accelerating the turbulence around the surface of the hollow fiber [47]. Also, the
CP is affected by the actual enrichment (Eo) of the hollow fiber. For example, Eo equals 1 if the
hollow fiber is completely unselective. The concentration gradient in the boundary layer does not
take place unless there are changes in the species concentrations of the permeating solution across
the hollow fiber. Moreover, when the difference in the permeability of the species increases, the
actual enrichment Eo of the fiber is enhanced, and the concentration gradient formed at the
boundary layer increases. Another significant characteristic of Equation (26) is that the Eo created by
the fiber, not the actual selectivity α, determines the CP modulus and the fiber separation
performance. Equation (26) demonstrates that increasing the total volumetric flowrate J within the
hollow fiber increases the CP exponentially.

2.3.6. Comparison of the Experimental Results (S2) and Model Predictions

This study investigated the models’ validity and the type of fitting used by calculating the
nonlinear parameters expressed by Equation (28) [46]:
S2 = ∑ (Rexp – Rth)2/Rth (26)
where Rexp and Rth are the experimental and theoretical rejection of the solute respectively, as
estimated by the models. If Rexp > Rth, S2 will be large, while if Rexp ≤ Rth, S2 will be small.

2.3.7. Calculation of the Péclet Number (Pe)

In the study of transport phenomena in fluid flows, the Péclet number (Pe) (defined as a
dimensionless number) is considered to be a significant parameter. It corresponds to the ratio
between the convective transfer J of a physical quantity and the flow and diffusive transfer k (Dab/𝛿)
of the similar quantity driven by a proper difference. By Equation (29), the Pe is defined as follows:
Membranes 2020, 10, 136 9 of 25

advective transport rate J

P = i. e., P = (27)
diffusive transport rate k
where k denotes the coefficient of mass transfer from the CFSK model [43].

3. Results and Discussion

3.1. Effect of the Feed pH on the Membrane Performance

Figures 3 and 4 show the effect of the feed pH value on the permeation flux of the three types of
PES membranes (i.e., PES1, PES2, and PES3) for 100 ppm lead and cadmium solutions at a
transmembrane pressure of 1 bar and temperature of 25 °C. The permeation flux of the Pb2+ solution
decreased from 14.1 to 12.1 (L/m2·h) when increasing the feed pH value from 5.5 to 6.0 using PES1,
while no significant decrease in the permeation flux was observed when increasing the pH value to
6.5, as shown in Figure 2. Using PES2, the permeation flux for the Pb2+ solution decreased from 32.1
(L/m2·h) at a feed pH of 5.5, to 30.3 (L/m2·h) at a feed pH of 6.5, as shown in Figure 3. Moreover, a
similar trend was obtained using PES3 to separate the Pb2+ solutions, as shown in Figure 3. The
permeation flux slightly and gradually decreased from 15.5 to 14.1 (L/m2·h) with increases in the pH
of the Pb2+ solution from 5.5 to 6.5. Regarding the Cd2+ solution, a trend similar to that of Pb2+ was
observed for Cd2+, as shown in Figure 4, where the permeation flux slightly decreased from 10.2 to
9.8 (L/m2·h) as the pH value rose from 5.5 to 6.5 using PES1. In contrast, the permeation flux at pH
5.5 was 28.4 (L/m2·h), and it decreased slightly to 27.5 (L/m2·h) at a feed pH of 6.5 using the PES2
membrane, as shown in Figure 3. For PES3, the permeation flux decreased from 14.2 to 13 (L/m2·h) as
the Cd2+ solution pH rose from 5.5 to 6.5, as shown in Figure 4. From the above results, it can be
concluded that the pH value has a similar effect on the permeation flux of all membrane types at
various pH values. This phenomenon is mainly attributed to the charge of the membrane surface.
From a pH of 5.5 to 6.5, the charge of the membrane becomes more negative due to the increase in
OH-; therefore, the adsorption of heavy metal ions occurs at the surface of the hollow fiber
membrane because of the electrostatic attraction, which in turn led to a decrease in pore size of the
membrane, thus decreasing the permeation flux and increasing the heavy metal rejection. The
variations in the permeation flux as a result of changing the pore size of the hollow fiber with pH
may be attributed to three reasons, first: expansion or contraction associated with a network of
polymer membrane, second: electric-viscous effect, and third: net driving force higher than the
osmotic pressure on the membrane surface [48]. Another explanation is due to shrinkage of the
membrane layer as a result of differences in the hydration of membrane-ionized groups [26]. The
same behavior was found by Tanninen et al. [30].
Membranes 2020, 10, 136 10 of 25

35

30

PES1 PES2 PES3

Flux (l/m2 h)

25

20

15

10
5.4 5.6 5.8 6 6.2 6.4 6.6
pH value

Figure 3. Effect of feed pH value on final permeate flux of PES1, PES2, and PES3 membranes for Pb2+
(experimental conditions: Pb2+ concentration of 100 ppm, transmembrane pressure of 1 bar).

35

30

25 PES1 PES2 PES3

Flux (l/m2 h)

20

15

10

5
5.4 5.6 5.8 6 6.2 6.4 6.6
pH Value

Figure 4. Effect of feed pH value on final permeate flux of PES1, PES2, and PES3 membranes,
(experimental conditions: Cd2+ concentration of 100 ppm, transmembrane pressure of 1 bar).

Figures 5 and 6 show the effect of the feed pH on the Pb2+ and Cd2+ rejection of the three
membranes (i.e., PES1, PES2, and PES3) for solutions containing 100 ppm of lead and cadmium ions
at a transmembrane pressure of 1 bar and temperature of 25 °C. In Figure 5, the rejection of the Pb2+
solution using PES1 increased from 62.4 ± 1.1% at a pH of 5.5 to 81.2 ± 2.2% at a pH of 6. In contrast,
the rejection of Pb2+ decreased significantly with a further increase in the pH value to 6.5. Figure 5
shows that the Pb2+ rejection using PES2 increased from 62.45 ± 1.05% to 64.6 ± 0.6% when increasing
the pH value from 5.5 to 5.7. However, there was no significant change in the Pb2+ rejection with
further increases in the pH value from 5.7 to 6.5, and the maximum Pb2+ rejection was 65.2 ± 0.6% at a
pH of 6.5. For PES3, there was no significant change in the Pb2+ rejection when increasing the pH
Membranes 2020, 10, 136 11 of 25

value from 5.5 to 6.2. A further increase in the pH value decreased the Pb2+ rejection from 67.65 ±
0.35% at a pH of 6.2 and to 38.4 ± 1.8% at a pH of 6.5, as shown in Figure 5.
In Figure 6, it can be observed that the Cd2+ rejection increased from 22.5 ± 0.5% to 63 ± 3% after
increasing the pH from 5.5 to 6.5. Using PES2, the Cd2+ rejection increased significantly from 21 ± 3%
to 44.25 ± 0.25% after increasing the pH value from 5.5 to 6.2. With a further increase in the pH value
(i.e., to 6.5), the Cd2+ rejection decreased. For PES3, the Cd2+ rejection increased from 11.3 ± 0.3% at a
pH of 5.5 to 30.5 ± 0.5% at a pH of 6.5, as shown in Figure 6. These results demonstrated that heavy
metal rejection increased with rising pH values mainly due to the intensification of the negative
charge on the membrane surface, which increased the attraction between the lead and cadmium ions
and the membrane surface. Consequently, this enhanced the membrane separation performance
[1,30]. Moreover, as pH increased from 5.5 to 6.5, the fiber surface charge became more negative
because of the increasing OH-; therefore, precipitation of heavy metal ions occurs at the fiber surface
because of the electrostatic attraction and forms a solid layer at the surface of the fiber. This solid
layer can significantly affect the separation characteristics of the fiber by changing the rejection of
ion metals. In this effort, it may be seen that at pH 5.5, the hollow fiber iso-electric point (IEP) is
recommended. Where IEP refers to the pH value, which resulted in a less rejection of the ion. PES1,
PES2, and PES3 showed normal behavior, acting as positively charged fibers at pH less than IEP and
as negatively charged fibers at pH greater than IEP. Increase of rejection with increasing pH above
the IEP is due to the fact that the surface of fiber becomes more negatively charged because of the
increment of OH-. Therefore, adsorption of heavy metal ions occurs at the hollow fiber surface
because of the electrostatic attraction, which in turn leads to an increase in rejection. Gherasim et al.
[38] also recommended the IEP for their PES membrane for rejection of Cd2+. Also, rejection of Pb2+
was higher than Cd2+ for PES1, rejection of Pb2+ was higher than Cd2+ for PES2, and rejection of Pb2+
was higher than Cd2+ for PES3 at pH > 5.5. This can be explained due to normalized volume charge
density (known as the ratio of the effective volume charge density of the membrane to the total
concentration of charge in solution, expressed in equivalents of charge per volume unit).
85

80 PES1
PES2
Rejection (R%)

75 PES3

70

65

60
5.4 5.6 5.8 6 6.2 6.4 6.6
pH value

Figure 5. Effect of feed pH value on pb2+ rejection of PES1, PES2, and PES3 membranes (experimental
conditions: pb2+concentration of 100 ppm, transmembrane pressure of 1 bar).
Membranes 2020, 10, 136 12 of 25

70

60 PES1
PES2
Rejection (R%) 50
PES3
40

30

20

10

0
5.4 5.6 5.8 6 6.2 6.4 6.6
pH Value

Figure 6. Effect of feed pH on Cd2+ rejection of PES1, PES2, and PES3 membranes (experimental
conditions: Cd2+ concentration of 100 ppm, and transmembrane pressure of 1 bar).

3.2. Effect of Heavy Metal Concentration on the PES Hollow Fiber Performance
Figures 7 and 8 show the effect of heavy metal concentration on the permeation flux for three
types of PES membranes at a feed temperature of 25 °C, pH = 6 ± 0.2, and transmembrane pressure of
1 bar. The permeation flux using PES1 did not change significantly when increasing the Pb2+
concentration from 10 to 100 ppm, whereas a 13.34% reduction in the permeation flux was observed
when increasing the Pb2+ concentration to either 200 or 250 ppm, as illustrated in Figure 7. Moreover,
Figure 8 shows that the permeation flux of only PES2 and PES3 decreased slightly after increasing
the Pb2+ concentration to 200 or 250 ppm. In general, the permeate flux and separation factor mainly
depend on the characteristics of the hollow fiber, such as pore size, distribution of the pore size at the
fiber surface, and porosity, as well as the wall thickness of the fiber. Therefore, from the results of the
PES membranes, it can be seen that PES2 has higher permeation flux than PES1 and PES3 due to the
higher pore size and porosity and lower hollow fiber thickness, as well as wider pore size
distribution, as shown in Table 1. Accordingly, it can be concluded that the performance of the
hollow fiber strongly depends on the membrane properties.
Regarding the effect of Cd2+ concentration on the performance of all membrane types, Figure 8
shows a minor effect of the Cd2+ concentration on the permeation flux of PES1 and PES3. Using PES2,
the permeation flux decreased from 28 to 27.5 (L/m2·h) with increasing Cd2+ concentration from 10 to
100. While sharp decreases in the permeation flux were observed from 27.5 to 23.7 when increasing
the Cd2+ concentration from 100 to 200, these values decreased from 23.7 to 22.1 when the Cd2+
concentration increased from 200 and 250 ppm, as shown in Figure 8. This decline in the permeation
flux of the three types of PES fibers can be attributed to an increase in the deposition of metals on the
membrane surface with increases in the heavy metal concentration. The deposition or adsorption of
heavy metals on the surface of the hollow fiber resulted in a reduction of the effective pore size of the
fiber.
The effect of various lead and cadmium concentrations (i.e., 10, 50, 100, 200, and 250 ppm) on
the rejection of three PES membranes is shown in Figures 9 and 10. Using the PES1 membrane, the
rejection of Pb2+ was 98.9 ± 0.1% at 10 ppm and sharply decreased to 45.3 ± 2.25% at a concentration
of 250 ppm, as shown in Figure 9. Using PES2, the rejection of Pb2+ was approximately constant at 95
± 2% for the 10 and 50 ppm Pb2+ concentrations, whereas further increases in the Pb2+ concentration
resulted in a sharp decrease in the Pb2+ rejection (i.e., 44 ± 1%), with similar behavior observed for
PES3. For Cd2+, using PES1, the rejection at 10 ppm was 73 ± 3%, and it gradually decreased to 59.75 ±
0.4% when the Cd2+ concentration was reduced to 200 ppm, while using a Cd2+ concentration of 250
Membranes 2020, 10, 136 13 of 25

ppm, the rejection of the Cd2+ sharply decreased to 41.8 ± 0.2%, as shown in Figure 10. Rejection of
Cd2+ using PES2 was 49.6 ± 0.6% at 10 ppm, while at 250 ppm, the Cd2+ rejection greatly decreased to
28.75 ± 1.25%. The rejection of Cd2+ using PES3 was 43 ± 0.9% at 10 ppm, while at 250 ppm, the Cd2+
rejection greatly decreased to 27 ± 0.7%, as displayed in Figure 10.
Also, the Cd2+ exhibited more fouling on the membrane surface compared with the Pb2+. The
ionic radius of the Pb2+ cation (i.e., 133 pm) was larger than that of the Cd2+ cation (i.e., 97 pm),
meaning that the Pb2+ cation possessed a smaller hydration radius than the Cd2+ cation [49]. Thus, the
Cd2+ cations had more of a tendency than the Pb2+ cations to attach to water molecules, stay in the
solution, and pass through the membrane pores with water molecules in the permeate.

35
30
25
Flux (L/m2 h)

20 PES1 PES2 PES3

15
10
5
0
0 50 100 150 200 250 300
Pb2+ concentration (ppm)

Figure 7. Effect of Pb2+ initial concentration on permeate flux of PES1, PES2, and PES3 membranes
(experimental conditions: pH = 6 ± 0.2, transmembrane pressure of 1 bar).

30

25

20
Flux (l/m2 h)

PES1 PES2 PES3

15

10

0
0 50 100 150 200 250 300
Cd2+ concentration (ppm)

Figure 8. Effect of Cd2+ initial concentration on permeate flux of PES1, PES2, and PES3 membranes
(experimental conditions: pH = 6 ± 0.2, transmembrane pressure of 1 bar).
Membranes 2020, 10, 136 14 of 25

110
100
Pb2+ Rejection (R%) PES1 PES2 PES3
90
80
70
60
50
40
30
0 50 100 150 200 250 300
Pb2+ concentration (ppm)

Figure 9. Effect of initial Pb2+concentration on Pb2+ rejection using PES1, PES2, and PES3 membranes
(experimental conditions: pH = 6 ± 0.2, transmembrane pressure of 1 bar).

80
PES1 PES2 PES3
70
Cd2+ Rejection (R%)

60

50

40

30

20
0 50 100 150 200 250 300
Cd2+ concentration (ppm)

Figure 10. Effect of initial Cd2+ concentration on Cd2+ rejection using PES1, PES2, and PES3
membranes (experimental conditions: pH = 6 ± 0.2, transmembrane pressure of 1 bar).

3.3. Estimating Parameters for the Membrane and Coefficient of Mass Transfer
According to the Levenberg–Marquardt method [50], the experimental data were analyzed
using the SPSS version 22 nonlinear parameter estimation program, where the observed rejection
(Ro) and permeate flux (J) were calculated at conditions in which various parameters were altered
(i.e., feed pH, PES membrane type, and initial ion concentration) for each dataset. The parameters
estimated by applying the different models expressed by Equations (12), (20), and (22) were
employed to calculate the PES membrane transport parameters and mass transfer coefficients
according to their respective relations. To obtain the Ro of the PES membrane for different J values,
these parameters were subsequently used according to the specification of each individual model, as
presented in Tables 3 and 4. PES3 was arbitrarily chosen to compare the experimental data and
theoretical data of the CFSD model for Pb2+, while PES1 was arbitrarily chosen to compare the
experimental data and theoretical data of the CFSD model Cd2+, as shown in Figures 11 and 12. This
Membranes 2020, 10, 136 15 of 25

can also be discerned through the values of the nonlinear parameters (S2) presented in Tables 3 and
4, where the experimental results were substituted into the theoretical equations, and the values of
the parameters were calculated. Then, these parameters were substituted again into the equations to
find the second values of efficiency and J by applying a statistical program using a trial and error
method. Both outputs confirmed that all of the results were equally fitted. Moreover, the
model-predicted ion concentrations for specific rejection values were in good agreement with the
experimental results.
 Membranes 2020, 10, 136 16 of 25

Table 3. Parameter estimated for various modules by a nonlinear estimated program (Pb2+).

Feed Conc. CFSD Model CFSK Model CFFP Model

Type of Membrane No. of Set pH
(ppm) Dam Kb/ δ × 104(cm/s) ka × 103 (cm/s) σ PM × 105 (cm/s) ka × 103 (cm/s) S2 ε/ka εDab/𝝉𝜹 × 104
1 6.0 10 2.45 4.5 0.9101 5.53 20.72 0.007 7.72 9.45
2 6.0 50 2.48 4.33 0.9080 5.97 20.53 0.009 7.79 9.27
PES1 3 6.0 100 2.51 4.25 0.9004 6.21 20.21 0.016 7.92 9.55
4 6.0 200 2.42 4.11 0.8864 7.84 19.73 0.032 8.11 9.8
5 6.0 250 2.38 4.03 0.8795 8.44 19.43 0.043 8.23 10.21
6 6.5 10 2.64 4.68 0.9211 6.33 21.12 0.024 7.58 9.75
7 6.5 50 2.58 4.55 0.9156 6.67 21.01 0.018 7.62 9.62
PES2 8 6.5 100 2.47 4.46 0.9111 6.91 20.61 0.019 7.76 9.85
9 6.5 200 2.38 4.43 0.8981 7.44 20.41 0.035 7.84 9.83
10 6.5 250 2.39 4.23 0.8895 7.84 19.73 0.042 8.11 10.11
11 6.2 10 2.44 4.88 0.9255 6.43 20.92 0.00025 7.65 9.65
12 6.2 50 2.68 4.73 0.9246 6.58 20.71 0.00049 7.73 9.41
PES3 13 6.2 100 2.57 4.58 0.9201 6.84 20.11 0.0021 7.96 9.55
14 6.2 200 2.78 4.54 0.9181 7.14 19.71 0.007 8.12 9.91
15 6.2 250 2.88 4.43 0.9095 7.74 19.13 0.0059 8.36 10.31
a value of mass transfer coefficient of CFSD, CFSK, and CFFP models. b Solute partition coefficient.

Table 4. Parameter estimated for various modules by a nonlinear estimated program (Cd2+).

CFSD Model CFSK Model CFFP Model

Type of Membrane No. of Set pH Feed Conc. (ppm)
Dam Kb/ δ × 104(cm/s) ka × 103 (cm/s) σ PM × 105 (cm/s) ka × 103 (cm/s) S2 ε/ka εDab/𝝉𝜹 × 104
1 6.5 10 2.87 4.77 0.9227 5.58 20.98 0.048 7.63 10.23
2 6.5 50 2.76 4.65 0.9219 6.11 20.61 0.029 7.76 10.56
PES1 3 6.5 100 2.81 4.63 0.9205 6.54 20.33 0.057 7.87 10.66
4 6.5 200 2.66 4.58 0.9198 7.23 20.01 0.053 8.00 10.98
5 6.5 250 2.57 4.55 0.9187 8.67 19.88 0.074 8.05 11.32
6 6.2 10 2.97 4.87 0.9223 6.78 21.88 0.042 7.31 10.28
7 6.2 50 2.88 4.81 0.9119 7.11 20.91 0.04 7.65 10.38
PES2 8 6.2 100 2.84 4.67 0.9122 7.45 20.73 0.048 7.72 10.76
9 6.2 200 2.76 4.61 0.9089 8.13 20.91 0.134 7.65 10.86
10 6.2 250 2.51 4.53 0.9087 8.77 19.73 0.185 8.11 11.12
11 6.5 10 2.67 4.89 0.9263 6.68 20.08 0.051 7.59 10.27
12 6.5 50 2.79 4.78 0.9219 6.01 20.95 0.112 7.64 10.67
PES3 13 6.5 100 2.82 4.69 0.9202 7.15 20.43 0.184 7.83 10.69
14 6.5 200 2.86 4.71 0.9189 8.03 20.11 0.254 7.96 11.58
15 6.5 250 2.91 4.83 0.9127 8.25 19.83 0.082 8.07 11.82
a value of mass transfer coefficient of CFSD, CFSK model and CFFP model; b Solute partition coefficient.
 Membranes 2020, 10, 136 17 of 25

Table 3. Parameter estimated for various modules by a nonlinear estimated program (Pb2+).

Feed Conc. CFSD Model CFSK Model CFFP Model

Type of Membrane No. of Set pH
(ppm) Dam Kb/ δ × 104(cm/s) ka × 103 (cm/s) σ PM × 105 (cm/s) ka × 103 (cm/s) S2 ε/ka εDab/𝝉𝜹 × 104
1 6.0 10 2.45 4.5 0.9101 5.53 20.72 0.007 7.72 9.45
2 6.0 50 2.48 4.33 0.9080 5.97 20.53 0.009 7.79 9.27
PES1 3 6.0 100 2.51 4.25 0.9004 6.21 20.21 0.016 7.92 9.55
4 6.0 200 2.42 4.11 0.8864 7.84 19.73 0.032 8.11 9.8
5 6.0 250 2.38 4.03 0.8795 8.44 19.43 0.043 8.23 10.21
6 6.5 10 2.64 4.68 0.9211 6.33 21.12 0.024 7.58 9.75
7 6.5 50 2.58 4.55 0.9156 6.67 21.01 0.018 7.62 9.62
PES2 8 6.5 100 2.47 4.46 0.9111 6.91 20.61 0.019 7.76 9.85
9 6.5 200 2.38 4.43 0.8981 7.44 20.41 0.035 7.84 9.83
10 6.5 250 2.39 4.23 0.8895 7.84 19.73 0.042 8.11 10.11
11 6.2 10 2.44 4.88 0.9255 6.43 20.92 0.00025 7.65 9.65
12 6.2 50 2.68 4.73 0.9246 6.58 20.71 0.00049 7.73 9.41
PES3 13 6.2 100 2.57 4.58 0.9201 6.84 20.11 0.0021 7.96 9.55
14 6.2 200 2.78 4.54 0.9181 7.14 19.71 0.007 8.12 9.91
15 6.2 250 2.88 4.43 0.9095 7.74 19.13 0.0059 8.36 10.31
a value of mass transfer coefficient of CFSD, CFSK, and CFFP models. b Solute partition coefficient.

Table 4. Parameter estimated for various modules by a nonlinear estimated program (Cd2+).

Type of No. of Feed Conc. CFSD Model CFSK Model CFFP Model
pH
Membrane Set (ppm) Dam Kb/ δ × 104(cm/s) ka × 103 (cm/s) σ PM × 105 (cm/s) ka × 103 (cm/s) S2 ε/ka εDab/𝝉𝜹 × 104
1 6.5 10 2.87 4.77 0.9227 5.58 20.98 0.048 7.63 10.23
2 6.5 50 2.76 4.65 0.9219 6.11 20.61 0.029 7.76 10.56
PES1 3 6.5 100 2.81 4.63 0.9205 6.54 20.33 0.057 7.87 10.66
4 6.5 200 2.66 4.58 0.9198 7.23 20.01 0.053 8.00 10.98
5 6.5 250 2.57 4.55 0.9187 8.67 19.88 0.074 8.05 11.32
6 6.2 10 2.97 4.87 0.9223 6.78 21.88 0.042 7.31 10.28
7 6.2 50 2.88 4.81 0.9119 7.11 20.91 0.04 7.65 10.38
PES2 8 6.2 100 2.84 4.67 0.9122 7.45 20.73 0.048 7.72 10.76
9 6.2 200 2.76 4.61 0.9089 8.13 20.91 0.134 7.65 10.86
10 6.2 250 2.51 4.53 0.9087 8.77 19.73 0.185 8.11 11.12
11 6.5 10 2.67 4.89 0.9263 6.68 20.08 0.051 7.59 10.27
12 6.5 50 2.79 4.78 0.9219 6.01 20.95 0.112 7.64 10.67
PES3 13 6.5 100 2.82 4.69 0.9202 7.15 20.43 0.184 7.83 10.69
14 6.5 200 2.86 4.71 0.9189 8.03 20.11 0.254 7.96 11.58
15 6.5 250 2.91 4.83 0.9127 8.25 19.83 0.082 8.07 11.82
a value of mass transfer coefficient of CFSD, CFSK model and CFFP model; b Solute partition coefficient.
Membranes 2020, 10, 136 18 of 25

The combined film theory-Spiegler-Kedem (CFSK) model showed a high degree of accuracy
when applied to the experimental rejection data for all initial metal concentrations and PES
membrane types. In sum, very high reflection coefficients ( 𝜎) and very low values of the
permeability solute (Ps) were obtained by fitting the CFSK model to the experimental data. As these
parameters were based on the initial metal concentrations, the Ps increased as the initial metal
concentration increased due to the high solute amount crossing through the membrane. On the other
hand, a gradual decrease in the solute rejection reduction was observed with different 𝜎, as was also
found by Al-Zoubi [51]. It can be concluded that for a wide range of single-salts concentrations (e.g.,
10 to 250 ppm), the model is still valid.
These results explicate the transport mechanism of solutes in these processes by the same
remarks. At low pressure, a high solute transport by diffusion was expected for low rejection. At
high pressure, the convective solute transport is more critical; however, this effect was not observed
in the current work because the rejection was high even at low pressures. Thus, the convective
transport seemed to be dominant in the rejection processes under study. Moreover, σ, a measure of
the extent of the convective solute transport in the PES membranes, was almost serially hindered
[52]. Therefore, the Spiegler-Kedem parameter values proved that the previous results reflected the
membrane structure. Ballet et al. [26] examined the impact of Pb2+ and Cd2+ ion characteristics on the
solute rejection and reported that the reflection coefficient (𝜎) for each solute increased with an
increase in the Pb2+ and Cd2+ ion valence, while the Ps decreased. Similar results were obtained by
Wang et al. [53]. For the CFFP model, the effective membrane thickness (𝜏𝛿/𝜀) can be determined
from the average value of the parameter b2, which was previously calculated as 255 µm [54]. If the
values of the membrane void fraction (𝜀) and tortuosity (𝜏) are assumed to be 0.16 and 3
respectively [55], the thickness of the boundary layer (𝛿) will be 14, which is a reasonable value with
regard to the data submitted by the supplier.

110
10 ppm pb, %Rexp.
100
10 ppm Pb, %Rth.
Rejection (R %)

90 50 ppm pb, %Rexp.

50 ppm Pb, %Rth.
80
100 ppm pb, %Rexp.
70 100 ppm Pb, %Rth.
200 ppm pb, %Rexp.
60
200 ppm Pb, %Rth.
50 250 ppm pb, %Rexp.
250 ppm pb, %Rth.
40
0.3 0.35 0.4 0.45
Flux, J ×103 (cm/sec)

Figure 11. Results of CFSD model for the dataset of the PES3 membrane for Pb(NO3)2.
Membranes 2020, 10, 136 19 of 25

85
80 10 ppm Cd, %Rexp.
75 10 ppm Cd, %Rth.
Rejection (R %)

50 ppm Cd, %Rexp.

70
50 ppm Cd, %Rth.
65 100 ppm Cd, %Rexp.
60 100 ppm Cd, %Rth.

55 200 ppm Cd, %Rexp.

200 ppm Cd, %Rth.
50
250 ppm Cd, %Rexp.
45 250 ppm Cd, %Rth.
40
0.5 0.6 0.7 0.8
Flux, J×103 (cm/s)

Figure 12. Results of CFFP model for the dataset of the PES1 membrane for Cd (NO3)2.

3.4. Estimation of the Concentration Polarization Model (CPM), Enrichment Factors (Eo and E), and Péclet
Number (Pe)
To calculate the true rejection using the membrane transport model, which depends on the
concentration polarization, Equation (25) was applied, as it includes the factors that impact
concentration polarization, namely the permeate volume flux, diffusion coefficient of the solute in
the thickness of the boundary layer (𝛿), and membrane enrichment factor (which depends on the
Cp/Cb ratio). In Tables 5 and 6, the enrichment factors Eo and E for the three types of PES membranes
and the solutes’ (i.e., Pb2+and Cd2+) ions are given. The concentration of the solute at the membrane
surface ranged from 1.0072 to 1.0163, from 1.0177 to 1.0423, and from 1.0102 to 1.0210 times greater
for Pb2+ and from 1.0055 to 1.0104, from 1.0076 to 1.0178, and from 1.0048 to 1.0081 times greater for
Cd2+ than in the absence of any concentration polarization, for PES1, PES2, and PES3, respectively.
With respect to reverse osmosis, the concentration polarization models are usually about 1.1 and 1.5
[52], while the Eo ranges from 0.0100 to 0.5100, from 0.025 to 0.57, and from 0.02 to 0.51 for Pb2+, and
from 0.2200 to 0.5800, from 0.5 to 0.74, and from 0.56 to 0.722 for Cd2+ for PES1, PES2, and PES3,
respectively. Regarding reverse osmosis, the enrichment factors are usually about 0.01 [52] due to
the membrane solute rejection capability being about 100% [43].
The comparison between the concentration polarization and Péclet number for the PES1, PES2,
and PES3 membranes at different Pb2+ and Cd2+ ion concentrations is shown in Tables 5 and 6. When
the Péclet number is large (J >> k), the convective flux through the membrane cannot be easily
stabilized by diffusion in the boundary layer, and concentration polarization models will be large.
On the other hand, when the Péclet number is small (J << k), the convective flux through the
membrane can be easily stabilized by diffusion in the boundary layer, and concentration
polarization models are close to unity [41]. The Péclet number values of the Pb2+ ion ranged from
0.0149 to 0.0174 for PES1, from 0.0408 to 0.0425 for PES2, and from 0.0218 to 0.0212 for PES3, and the
Péclet number values for the Cd2+ ion ranged from 0.0131 to 0.0132 for PES1, from 0.0327 to 0.0366 for
PES2, and from 0.0177 to 0.0183 for PES3. Therefore, the Péclet number is a key factor in determining
the mechanism of separation by diffusion [55]. Borisov et al. [56] suggested a novel model to
evaluate the impact of concentration polarization on pervaporation. They found that the intrinsic
enrichment factor can be directly estimated from the experimental data. The method is also practical
compared to the approaches evaluating the intrinsic membrane properties by altering the thickness
of the membrane or the driving force. The influence of process parameters such as concentration of
organic component, temperature, and velocity of feed solution on the membrane separation
performance was studied. They found that the intrinsic enrichment factor value noticeably alters
when the process parameters are changed. This change is one of the key factors affecting the value of
 Membranes 2020, 10, 136 20 of 25

concentration polarization modulus throughout the pervaporation process. The suggested approach
provides a procedure to minimize the effect of concentration polarization on the pervaporation
separation process under suitable conditions.

Table 5. Summary of CPM, enrichment factors (Eo and E), and Péclet number (Pb2+).

Feed Enrichment
Type of No. of CPM ka × 103 Permeate Flux Péclet Number
pH Conc. Factors
membrane set (cm/s) (×103) (cm/s) (J/ka)
(ppm) E Eo Cm/Cb
1 6.0 10 0.0098 0.0100 1.0163 20.72 0.361 0.0174
2 6.0 50 0.0433 0.0440 1.0154 20.53 0.358 0.0175
PES1 3 6.0 100 0.1648 0.1670 1.0135 20.21 0.353 0.0175
4 6.0 200 0.4864 0.4900 1.0075 19.73 0.292 0.0148
5 6.0 250 0.5063 0.5100 1.0072 19.43 0.289 0.0149
6 6.5 10 0.0240 0.025 1.0423 21.12 0.8972 0.0425
7 6.5 50 0.0538 0.056 1.0402 21.01 0.8778 0.0418
PES2 8 6.5 100 0.3585 0.368 1.0264 20.61 0.8528 0.0414
9 6.5 200 0.5301 0.540 1.0186 20.41 0.8194 0.0401
10 6.5 250 0.5601 0.57 1.0177 19.73 0.8056 0.0408
11 6.2 10 0.0196 0.02 1.0210 20.92 0.4444 0.0212
12 6.2 50 0.0824 0.084 1.0196 20.71 0.4389 0.0212
PES3 13 6.2 100 0.3493 0.354 1.0135 20.11 0.4333 0.0215
14 6.2 200 0.4749 0.48 1.0108 19.71 0.4222 0.0214
15 6.2 250 0.5049 0.51 1.0102 19.13 0.4167 0.0218
a value of mass transfer coefficient of the CFSK and CFFP models.

Table 6. Summary of CPM, enrichment factors (Eo and E), and Péclet number (Cd2+).

Feed Enrichment
Type of No. of CPM ka × 103 Permeate Flux Péclet Number
pH Conc. Factors
Membrane Set (cm/s) (×103) (cm/s) (J/ka)
(ppm) E Eo Cm/Cb
1 6.5 10 0.2177 0.2200 1.0104 20.98 0.278 0.0132
2 6.5 50 0.2674 0.2700 1.0097 20.61 0.275 0.0133
PES1 3 6.5 100 0.3968 0.4000 1.0080 20.33 0.272 0.0134
4 6.5 200 0.3868 0.3900 1.0082 20.01 0.264 0.0132
5 6.5 250 0.5769 0.5800 1.0055 19.88 0.261 0.0131
6 6.2 10 0.4913 0.500 1.0178 21.88 0.8000 0.0366
7 6.2 50 0.5171 0.526 1.0173 20.91 0.7806 0.0373
PES2 8 6.2 100 0.5461 0.555 1.0163 20.73 0.7667 0.0370
9 6.2 200 0.6735 0.680 1.0097 20.91 0.6833 0.0327
10 6.2 250 0.7344 0.740 1.0076 19.73 0.6444 0.0327
11 6.5 10 0.5555 0.560 1.0081 21.08 0.3861 0.0183
12 6.5 50 0.6057 0.610 1.0070 20.95 0.3806 0.0182
PES3 13 6.5 100 0.6761 0.680 1.0058 20.43 0.3722 0.0182
14 6.5 200 0.6963 0.700 1.0054 20.11 0.3639 0.0181
15 6.5 250 0.7185 0.722 1.0048 19.83 0.3500 0.0177
a value of mass transfer coefficient of the CFSK and CFFP models; Conc.: Concentration

3.5. Comparative Study of PES Membranes

Table 7 depicts a comparison study between the performance of the three types of PES
membranes used in the current study with the separation performance of the various types of NF
membranes found in the literature. The most significant operating variables such as pH of the feed
solution, feed solution concentration, and trans-membrane pressure are also presented in Table 7. It
can be noticed that the three types of PES membranes’ performance in the current experimental
work have excellent Pb2+ rejection values in comparison with most NF membranes presented in the
literature. Also, it can be observed from Table 7 that the separation performance of the three types of
PES membranes used in this study have a reasonable rejection of Cd2+ in comparison with the
separation performance of most NF membranes found in the literature.
Membranes 2020, 10, 136 21 of 25

Table 7. Comparison between the performances of the current study and types of NF membranes
presented in the literature.

Type of Material Removed

Module pH Con. ppm Pressure Rejection % Ref.
Membrane (Aqueous Solution)
Cd = 99%
2+
NF270 Flat sheet Pb(NO3)2/Cd(NO3)2 1.5–5 100–2000 3–5 bar [27]
Pb2+ = 74%
Na2Cr2O7 4.74 Cr2O7− = 98%
Dual-layer NF hollow fiber CdCl2 5.45 1000 1 bar Cd2+ = 95% [28]
pb(NO3)2 5.03 Pb2+ = 93%
polyamide Cd2+ = 80%
TFC-NF300 CdCl2; NiSO4 5 5–150 2–20 atm [43]
thin film Ni2+ = 97%
polyamide
ESNA1-4040 pbCl2 1–12 20 4–16 Mpa pb2+ = 93.3% [57]
thin film
Polyamide
5.8 bar for Pb2+ = 86%
flat sheet, Pb(NO3)2
NF (JCM) 3–4 1 pb2+ Ni2+ = 93% [58]
spiral NiSO4
6 for Ni2+
wound
(PEI) cross
hollow fiber pb(NO3)2 12 1000 13 bar pb2+ = 91.05% [59]
linked P84
PVDF/APTES
Cu2+, Cd2+ and Cr6+
functionalized Flat sheet 5.5 5 5 bar Cd2+ = 44.2% [60]
homogeneous solution
halloysite
Poly/PIP PA
layer
5.0– Cd2+ = 97%
modified PEI Flat sheet Pb2+, and Cd2+ solution 100 5 bar [61]
7.0 Pb2+ = 99%
substrate:
PES/Ag
cellulose
acetate (CA) Flat sheet Cd(NO3)2 2–12 0.001 mol/l 9 bar Cd2+ = 84% [62]
NF-23
Pb2+ = 99%;
PES1; PES2; (Cd(NO3)2·4H2O); 5.5– 97.5%; 98% This
hollow fiber 10–250 1 bar
PES3 (Pb(NO3)2) 6.5 Cd2+ = 78%; study
49.2%; 44%

4. Conclusions
In the present study, three types of PES membranes, symbolized by PES1, PES2, and PES3, were
used to remove the highly polluting and toxic Pb2+ and Cd2+ ions from wastewater. The performance
of the membranes with single Pb2+ and Cd2+ ions, similar to those found in a real mining effluent, was
evaluated. Different operating conditions were used for the removal of heavy metal ions to treat
wastewater prior to discharge into the environment. It can be concluded that the permeation flux
and rejection of Pb2+ were higher than that of Cd2+ at various pH values and heavy metal ions’
concentration, and that PES2 was a very efficient hollow fiber for the removal of heavy metal ions.
The separation performance of the hollow fiber PES membranes strongly depends on the membrane
properties, such as mean pore size, pore size distribution, and thickness. Analysis of the
experimental data using CFSD, CFSK, and CFFP models showed good agreement between the
theoretical and experimental results. Moreover, the active skin layer thickness and the effective
membrane thickness were predicted by the CFFP model. According to the value of the Péclet
number, the mechanism of separation was due to diffusion. The PES membranes’ performance in the
current experimental work has excellent Pb2+ rejection values in comparison with most NF
membranes presented in the literature.

Nomenclature
A = Membrane surface area, m2
bf = Factor measure of friction between the solute molecules and the membrane pore wall, calculated
from bf = 1+ fsm/ fsw
C = Solute concentration in the boundary layer, g/m3
Membranes 2020, 10, 136 22 of 25

Cb = Average bulk concentration, g/m3

Cf = Concentration of solute in the feed, g/m3
CFFP = Combined film theory-finely-porous model
CFSD = Combined film theory-solution-diffusion model
CFSK = Combined film theory-Spiegler-Kedem model
Cm = Solute concentration at the membrane surface/water (solvent) interface, g/m3
CP = Concentration Polarization
Cp = Concentration of solute in permeate, g/m3
CPM = Concentration Polarization Model
Cr = Concentration of solute in retentate, g/m3
Dam K/𝛿 = Solute transport parameter, cm/s
D = Diffusion coefficient, cm2/s
Dab = Diffusivity of solute a in solvent b, cm2/s
Dam = Diffusivity of salt a on surface membrane, cm2/ s
Eo = Enrichment Factor, known as Cp/Cm
F = Flow parameter defined in Equation (15)
fsm = Friction coefficient between solute and membrane
fsw = Friction coefficient between solute and solvent (water)
JS = Solute flux through membrane, m3/m2s
Jv = Convective + Diffusive mass transfer rate, m3/m2s
K = Solute partition coefficient
k = Mass transfer coefficient, expressed as k =
Pe = Péclet number (a dimensionless number)
PES = Polyethersulfone
PM = Salt permeability, L/m2·h
Ps = Overall permeability coefficient
PWP = Pure water permeability
R = True solute rejections
Rexp = Experimental rejection
Ro = Observed rejection
Rth= Theoretical rejection
t = Collected permeate time, h
TMP = Transmembrane pressure, bar
V = Permeate volume, L
x = Distance from the membrane layer, m

Greek letters
ε = Membrane void fraction
τ = Tortuosity
𝛿 = Layer thickness; thickness of the boundary layer, m
= Effective membrane thickness
∆𝑃 = Transmembrane pressure, bar
∆𝜋 = Osmotic pressure difference, bar

Author Contributions: Conceptualization, Q.F.A., S.H., A.A.M. and A.F.; methodology, Q.F.A., S.M.A., K.T.R.,
and M.F.A., software, S.S.I.; validation, Q.F.A., A.A.M., A.F. and S.H.; formal analysis, Q.F.A., H.S.M. and
S.M.A.; investigation, Q.F.A., A.F. and S.S.I.; resources, H.S.M. and I.K.S.; data curation, K.T.R. and S.H.;
writing—original draft preparation, Q.F.A., S.H., S.M.A and K.T.R.; writing—review and editing, Q.F.A., S.H.,
S.M.A, and I.K.S.; visualization, Q.F.A. and A.F.; supervision, Q.F.A., A.A.M. and A.F.; All authors have read
and agreed to the published version of the manuscript.

Funding: This research received no external funding

Conflicts of Interest: The authors declare no conflict of interest.

Membranes 2020, 10, 136 23 of 25

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