Journal of Water Process Engineering 39 (2021) 101718

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Journal of Water Process Engineering

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Phenol and ammonia removal in petroleum refinery wastewater using a

poly(vinyl) alcohol coated polysulfone nanohybrid membrane
Tutuk Djoko Kusworo a, b, *, Andri Cahyo Kumoro a, Dani Puji Utomo a
a
Department of Chemical Engineering, Faculty of Engineering, University of Diponegoro, Semarang, Indonesia
b
Membrane Research Center (Mer-C), University of Diponegoro, Semarang, Indonesia

A R T I C L E I N F O A B S T R A C T

Keywords: Petroleum refinery wastewater (PRW) contains high concentrations of phenolic compounds and ammonia that
Ammonia are noxious and harmful to the environment, especially to human health. The improper treatment of PRW could
Membrane cause serious problems. In this study, a membrane with a polyvinyl alcohol (PVA) coating was fabricated to
Petroleum
improve PRW treatment for phenolic compounds and ammonia removal. The fabricated membranes were
Phenol
Polyvinyl alcohol
investigated using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), water
Wastewater contact angle, mechanical strength, permeability, pollutant rejection, and foulant resistance. The coated mem­
branes exhibited improved surface properties and mechanical strength compared to that of uncoated pristine
polysulfone (PSf) membranes. The membranes also showed excellent phenol and ammonia removal up to 82.68
% and 92.42 %, respectively. Although the permeate flux decreased with increasing PVA concentration, the
antifouling behavior of the membrane was significantly improved. Therefore, the fabricated membranes showed
great potential for petroleum wastewater treatment.

1. Introduction
The large quantity of polluted wastewater generated by petroleum
refineries requires treatment technologies to remove hazardous con­
taminants [1]. In general, the refinery industry generates a wastewater
volume that is about 0.4–1.6 times greater than that of the volume of
refined oil [2]. Petroleum refinery wastewater (PRW) usually contains a
high concentration of contaminants, such as dissolved oil, organics,
hydrocarbon derivatives, heavy metals, phenolic compounds, ammonia,
and a high concentration of chemical oxygen demand (COD) [3,4]. As
reported in many studies, PRW generally contains dissolved oil and
grease at 500–3000 mg.L− 1, chemical oxygen demand (COD) and
biochemical oxygen demand (BOD) at 750–1600 mg.L− 1 and 300 − 1000
mg.L− 1, respectively [5]. Toxic organics, such as phenolic compounds,
are found in PRW at approximately 950 mg.L− 1, and ammonia and
sulfide are typically at 20–80 mg.L− 1 and 13–17 mg.L− 1, respectively
[6]. In some cases, heavy metals and radioactive materials are observed
in refinery wastewaters [7]. Existing PRW treatments usually only
reduce the total solids and major organic pollutants; however, this
treated wastewater still contains phenolic compounds and ammonia at
high concentrations. Phenolic compounds are identified as priority
contaminants as they are highly toxic and corrosive even at a low con­
centration [8]. The sources of phenolic compounds in PRW are usually
from the tank water drain, multiphase separator, desalter water effluent,
and neutralized spent caustic waste. In Pertamina Ltd. Indonesia, the
primary source of the phenols, is the residual fluid catalytic cracking
(RFCC) waste stream with an average phenol concentration of 960 mg.
L− 1 [6]. In recent years, phenol and its derivatives have warranted more
attention in the field of industrial wastewater because of their toxicity
and contamination in wastewater production. Phenolic compounds
discharged into the environment remain for long periods and harm the
ecosystem, especially humans [9,10]. Phenolic compounds that are
commonly found in PRW are phenol, m-p-cresol, o-cresol, tri and tetra
chlorophenols, and 4-chloro-3-cresol [11], as shown in Fig. 1.
The US Environmental Protection Agency (EPA) has labeled phenolic
derivatives as a priority contaminant in water. The limited concentra­
tion of phenol in wastewater discharge was set strictly to avoid envi­
ronmental damage. The toxicity level of phenol derivatives is usually in
the range of 9–25 mg.L− 1 for both humans and aquatic life [12].
Long-term exposure to phenol can lead to a serious health problem such
as diarrhea, vertigo, salivation, tremors, coma, and respiratory failure
for humans exposed to lethal doses. Therefore, industries that produce

* Corresponding author.
E-mail address: tdkusworo@che.undip.ac.id (T.D. Kusworo).

https://doi.org/10.1016/j.jwpe.2020.101718
Received 2 July 2020; Received in revised form 23 September 2020; Accepted 25 September 2020
Available online 6 October 2020
2214-7144/© 2020 Elsevier Ltd. All rights reserved.
T.D. Kusworo et al.
Fig. 1. Molecular structure of the phenol derivatives (a) phenol, (b) p-cresol,
(c) m-cresol, (d) o-cresol, (e) trichloro phenol, and (f) 4-chloro-3-cresol.
phenol-contaminated wastewater, such as petroleum refineries, must
pay attention to the treatment of wastewater to meet quality standards
of wastewater discharge.
Another pollutant in petroleum refinery wastewater and petro­
chemicals that becomes a serious issue is ammonia. Ammonia in
wastewater is usually generated from the degradation of nitrogen
components. Excessive ammonia in wastewater is highly toxic and
harmful to the environment and human health; moreover, ammonia is
associated with the malodor problem of wastewater [13]. Generally, the
ammonia–nitrogen content in refinery wastewater is in the range of
20–80 mg.L− 1 [14]. Treatment using chemical and biological methods
are unable to nitrify the ammonia content to the desired level. Ammonia
in wastewater is generated from the degradation process of
nitrogen-containing compounds. Ammonia is toxic to aquatic life and
human health at very low concentrations. The common maximum
permitted level of ammonia in discharged wastewater is 0.7 mg.L− 1
[15]. Ammonia in water can be in an equilibrium state of dissolved
ammonia and ammonium ions or bound as organic amine (R-NH2), as
shown in Eq. 1.
NH3 + H2O → NH+
4 + OH
−
(1)
Wastewater from food processing plants is nutritious enough to
enrich the nitrification bacteria by converting ammonium ions to nitrate
ions. However, in petroleum wastewater treatment, nitrifying bacteria
are seldom observed because of poor nutritional content. Therefore, it is
highly important to develop an effective method for phenolic com­
pounds and ammonia removal or neutralization, given their serious
environmental threat.
In recent decades, many attempts have been made to eliminate
contaminants in PRW, such as the advanced oxidation process (AOP),
coagulation, absorption, adsorption, chemical, and biological treat­
ments [16–18]. Such methods effectively remove a variety of organic
compounds. However, membrane separation is considered a faster and
more efficient process than other physically-driven and
equilibrium-driven processes. Conventional size exclusion based sepa­
rations such as Ultrafiltration is unable to remove phenolic compounds
or ammonia with high separation efficiency [19]. Hence, a dense
membrane, such as reverse osmosis or nanofiltration membrane, is
required, resulting in high energy consumption [20] and faster fouling
formation. A hybrid process, such as the adsorption prior to membrane
separation, has been previously reported [21] using activated carbon
2
Journal of Water Process Engineering 39 (2021) 101718
followed by an ultrafiltration membrane. This process effectively
reduced energy consumption. However, the process is complex as it
requires more than one stage. In the past few years, the membrane
research is dominated by the development of mixed matrix membranes
(MMMs) that combine the molecular sieving mechanism and adsorption
of inorganic filler; furthermore, the introduction of inorganic material
significantly increases the surface properties, mechanical strength, and
perm-selectivity of the fabricated membrane [22]. Polymeric mem­
branes with an embedded microsized inorganic filler have shown
excellent performance in removing various organic compounds during
water treatment, and the membrane’s hydrophilic property can be
significantly improved. However, the incorporation of inorganic filler at
normal size (micron scale) into polymeric membranes has the risk of
producing defective membranes. A defect membrane might be caused by
the formation unselective void as the result of the de-attachment be­
tween the polymer and the particle surface [23]. Recent developments
include the incorporation of nanosized inorganic particles because of
their higher surface area, high shape uniformity, and excellent affinity
with a polymer matrix [24]. Many researchers have reported that the
incorporation of nanosized inorganic materials and functionalized metal
oxides into a polymeric membrane significantly enhance the perme­
ability, structural properties, surface hydrophilicity, antifouling
behavior, and separation properties [25,26]. However, in some cases of
wastewater with a high organic level, such as PRW, the utilization of the
nanohybrid membrane has a short lifetime because of surface fouling
[27]. Moreover, the membrane with a smaller pore size that is used to
remove molecular pollutants leads to low permeability.
In this study, a nanohybrid PSf membrane was used as a support
membrane, and a polyvinyl alcohol (PVA) layer was added to improve
the membrane surface properties. PVA is a low-cost polymer that pos­
sesses good chemical and mechanical stability, excellent hydrophilicity,
and film-forming ability, which is widely used as the coating material.
PVA can be used to produce a stable membrane with good mechanical
properties and selective permeability to water by crosslinking, grafting,
or other modification reactions. The objectives of introducing PVA on
the PSf membrane were to enhance the removal efficiency of phenol and
ammonia in petroleum wastewater and to improve the membrane me­
chanical properties as well as to minimize the membrane fouling during
operation. Furthermore, the removal efficiency and permeability were
studied using untreated petroleum refinery wastewater effluent to
explore the industrial applicability of this technique.
2. Experimental methods
2.1. Materials
Polysulfone (Udel® PSU P1700NT) polymer granules were pur­
chased from Solvay, USA, and used as the main polymer of the mem­
brane preparation. N-methyl-2-pyrrolidone (NMP) solvent and sulfuric
acid were supplied from Merck, USA. Polyvinyl alcohol (PVA, 86 %–88
% hydrolyzed, Mw 130,000 Da), polyethylene glycol (PEG) with a mo­
lecular weight of 4000 Da as a pore-forming agent and glutaraldehyde
(GA) as a crosslinking agent were purchased from Sigma-Aldrich, Ger­
many. Nanosized ZnO powder (±350 nm) was obtained from Nano
Center Indonesia, Indonesia. PRW (sedimentation-coagulation effluent)
was obtained from Pertamina, Ltd., and the characteristics of the
Table 1
Characteristics of the petroleum refinery wastewater from Pertamina, Ltd.
Parameter Average value
pH 8.6
Total dissolved solids (mg.L− 1) 1503
Chemical oxygen demand (mg.L− 1) 3134
Total N-NH3 (mg.L− 1) 335.09
Total phenolic compounds (mg.L− 1) 855
T.D. Kusworo et al.
wastewater are presented in Table 1.
2.2. Preparation of the nanohybrid PSf-ZnO membrane
Nanohybrid PSf-ZnO membranes were fabricated via a non-solvent
induced phase separation (NIPS) method adapted from a previous
study [28]. ZnO nanoparticles were dispersed in NMP at various total
solid concentrations, as shown in Table 2, and the mixture was ultra­
sonicated for 30 min. PSf and PEG were dissolved in NMP at the polymer
concentrations listed in Table 2 and stirred for 8 h. The ZnO suspensions
and polymer solutions were blended and homogenized. The polymer
solution was then cast using a manual casting machine with an outlet
gap thickness of 150 μm. The polymer film was evaporated for 60 s to
form a selective layer and was subsequently immersed in pure water for
24 h at room temperature for complete phase separation. The wet
membranes were placed between filter papers and dried at 50 ◦ C for 24
h.
2.3. PVA coating of the PSf-ZnO membrane surface
According to the previous work [29], the addition of ZnO in polymer
matrix significantly improved the permeate flux and mechanical
strength of the membrane but risks on creating unselective gap. Coating
procedure using PVA polymer on the fabricated nanohybrid membrane
one of which aims to help overcoming the aforementioned issue. The
PVA coating was prepared by dip-coating the top surface of the mem­
brane to provide a selectivity property [30]. PVA solutions were pre­
pared with the concentrations in Table 2. An appropriate amount of PVA
granules was dissolved in deionized water at 85 ◦ C under constant
stirring for 8 h. The top side of the membrane was dipped into the PVA
solution, and the excess solution on the membrane surface was wiped off
using filter paper. The coated membranes were crosslinked using a
crosslink-agent containing 5 wt% glutaraldehyde and 0.5 wt% sulfuric
acid as the catalyst. The coated membranes were rinsed to remove the
residual chemicals. A schematic illustration of the membrane coating
using PVA is shown in Fig. 2.
2.4. Membrane characterization by SEM and FT-IR
The morphology of both the surface and internal structure of the
fabricated membranes were evaluated using scanning electron micro­
scopy (SEM, JEOL Series JSM-6510-LA, Japan). The morphological
structure of the membrane was observed at low and high magnification
(1000x and 20,000x). Fourier-transform infrared spectroscopy (FT-IR,
Perkin Elmer Frontier, USA) was used for the investigation of the change
in the chemical groups as a result of the modification treatment. The FT-
IR spectra of the fabricated membranes were recorded in the wave­
number range of 4000–400 cm− 1.
2.5. Water contact angle and mechanical strength test
Water contact angle (WCA) measurements were performed via a
sessile-drop method with 25 ◦ C pure water used as the probe liquid. The
static angle of the water droplet on the membrane surface was measured
using an angle-meter (RASE Angle-meter, Japan) at six different points.
Table 2
Composition of the prepared membranes.
Membrane PSf (wt Nano-ZnO PEG (wt PVA coating agent
%) (wt%) %) (wt%)
M1 (neat PSf) 19 0 2 0
M2 (uncoated 19 0.5 2 0
nanohybrid)
M3 19 0.5 2 1
M4 19 0.5 2 2
M5 19 0.5 2 3
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Journal of Water Process Engineering 39 (2021) 101718
The membrane mechanical strength was studied by measuring the ten­
sile strength and elongation percentage at break using a testing machine
(UTS H001, China). The membrane sample (5cm × 1cm) was clamped
and stretched at a rate of 20 mm.min− 1 until the break poin. The me­
chanical strength test was repeated three times for each membrane type.
2.6. Permeation and rejection performance of the membranes
The membrane performance in terms of the pure water permeability
(PWP), water flux using untreated PRW, and contaminant removal (total
phenols, ammonia, TDS, COD, and turbidity) were performed using a
cross-flow filtration setup as shown in Fig. 3. The tested membrane (with
an effective area of 15.90 cm2) was compacted using pure water at 5 bar
for 30 min before PWP measurement. The PWP was recorded every 0.5 h
at a constant pressure of 5 bar. For untreated refinery wastewater
filtration, the pure water was replaced with untreated wastewater. The
PWP (Jw) and wastewater permeate flux (Ji) were calculated using Eq. 2
[31].
V
J= (2)
A.t
Where J is the permeate flux, L. m− 2 h− 1; V is the permeate volume, L; A
is the effective membrane area, m2; and t is the permeation time (h).
Pollutant rejections were calculated using Eq. 3 as follows [32]:
( )
Cp
R= 1− × 100% (3)
Cf
Where Cp and Cf are the pollutant concentration in the permeate and
feed solution, respectively. The ammonia and total phenol concentration
were analyzed using spectrophotometric measurements. Other pollutant
rejections such as TDS, COD, and turbidity were determined using a
conductivity meter, spectrophotometer, and nephelometer,
respectively.
2.7. Fouling evaluation for refinery wastewater treatment
Fouling properties of the membrane in the refinery wastewater
filtration were evaluated using a series model of cake resistance mea­
surements [33,34]. The membrane resistance during filtration is
contributed to by the intrinsic membrane itself, absorbed foulant com­
pound (irreversible fouling), and cake of the foulant deposition on the
membrane surface (reversible fouling). The clean membrane was used in
the pure water permeation test and using Eq. 4 to evaluate the intrinsic
membrane resistance. To obtain the value of the irreversible fouling
resistance, the fouled membrane was rinsed using deionized (DI) water
to remove the foulant deposition on the membrane surface. The fouled
membrane was used for the DI water permeation test, and the irre­
versible fouling resistance was evaluated using Eq. 5. The cake resis­
tance was assessed using the total fouled membrane for a DI water
permeation test. The cake resistance was determined using Eq. 6.
ΔP
Rm = (4)
μ × J0
ΔP
Ra = − Rm (5)
μ × Ja
ΔP
Rc = − Rm − Ra (6)
μ × Jt
Rt = R m + R a + R c (7)
Where Rm, Ra, and Rc are the resistance of the clean membrane, absorbed
foulant, and cake of the deposited foulant, respectively (m− 1). J0, Ja, and
Jt are the constant permeate flux of pure water using clean membrane,
internal fouled membrane, and total fouled membrane, respectively (m3.
T.D. Kusworo et al. Journal of Water Process Engineering 39 (2021) 101718

Fig. 2. Schematic illustration of the PVA coating on the fabricated membrane surface.

s− 1); μ is the viscosity of water at 25 ◦ C (8.9 × 10− 4

Pa.s); ΔP is the
transmembrane pressure (Pa).

3. Results and discussion

3.1. Membrane morphology characterization

An investigation of the structure is necessary to evaluate the perm-

Fig. 3. A schematic representation of the membrane filtration system.
selectivity performance of the membrane. The surface and cross-
sectional morphologies of the PSf-ZnO and PVA-coated PSf-ZnO mem­
branes are shown in Fig. 4. A clear surface morphological difference is
observed in Figs. 4A and 4B. The membrane surface of the uncoated
membrane is rough, with many visible pores. This morphology was
affected by the addition of PEG, which is a known pore-forming agent in
the membrane fabrication process [35]. The porous structure of the

Fig. 4. Surface and cross-sectional images of the (A) & (C) PSf-ZnO nanohybrid membrane and (B) & (D) PSf-ZnO/crosslinked PVA coating morphologies.

4
T.D. Kusworo et al.
support membrane is beneficial as it provides better permeation in the
filtration process. The enhanced surface porosity might occur with the
addition of a hydrophilic polymer (PEG), which dissolves in a
non-solvent. When the casting film was soaked in DI water, the exchange
of the solvent/non-solvent was followed by the migration of PEG into
the water, thus inducing the formation of more pores. In Fig. 4B, the
surface is smooth, and no pores were observed even at a magnification of
20,000x, indicating that the surface layer is dense and suitable for mo­
lecular separation. The smooth and dense layer might have resulted
from the coating of the crosslinked PVA. A membrane with a smoother
surface tends to have better antifouling properties.
Finger-like micropore structures were observed the cross-sections of
all membranes. The shape and micropore size of the finger-like struc­
tures were similar for all membranes because the membrane support
materials have the same composition. The structural properties of the
membrane sublayer were attributed to the polymer solution composi­
tion. The viscosity and hydrophilicity of the polymer solution play an
important role in determining the micropore structural properties. The
high concentration of the incorporated nanoparticles leads to larger
finger-like micropores. Closer observation of the membrane top-layer
revealed that the thickness of the dense layer of the membrane is
different. The PVA-coated membrane has a thicker layer than the un­
coated membrane. The average dense layer thickness of the uncoated
and PVA-coated membranes based on SEM analysis are 1.62 ± 0.30 μm
and 3.47 ± 0.41 μm, respectively. A thicker dense layer resulted from
the PVA coating on the selective layer of the membrane. With focused
observation at the selective layer, it can be noticed the different char­
acteristic layer can be ascertained as PVA layer. The denser selective
layer may improve the molecular separation; however, it also decreases
the water flux [36].
3.2. FT-IR spectra of the fabricated membrane
The functional groups of the fabricated membrane were inspected
using FT-IR spectra analysis. The FT-IR spectra of the uncoated nano­
hybrid PSf-ZnO and PVA-coated membranes are shown in Fig. 5. The FT-
IR spectra of the uncoated membrane (PSf-ZnO) show characteristic
peaks at around 1582 cm− 1 representing the aromatic ring of the PSf
backbone. Methyl and sulfone groups were observed by the appearance
of a single sharp peak at 1487 cm− 1 and double peaks at around 1297
cm− 1, respectively. The peak at 2969 cm− 1 also indicates the stretching
of C–H from the methyl in PSf. The presence of ZnO in the membrane
was observed by the weak stretching of the absorbed hydroxyl at 450
cm− 1. The weak broad peak from 3700–3000 cm− 1 represented the vi­
bration of− OH absorbed by ZnO nanoparticles, which indicates that the
incorporation of ZnO nanoparticles improved the hydrophilicity of the
Fig. 5. FT-IR spectra of uncoated and PVA-coated PSf-ZnO nano­
hybrid membranes.
5
Journal of Water Process Engineering 39 (2021) 101718
polysulfone membrane.
The PVA-coated PSf-ZnO membrane shows a stronger, broad peak
around 3312 cm− 1, which is typical for the hydroxyl vibration of the
PVA molecule. The stronger peak also appears at 2937 cm− 1, which is
analogous to the peak at 2969 cm− 1 of the uncoated PSf-ZnO membrane.
The peak shift from 2969 to 2937 cm− 1 shows the presence of C–H
stretching from the vinyl group in PVA. The absorption band at 1146
cm− 1 was observed in the PVA-coated membrane spectra, which is
related to the stretching of acetal ester groups as a result of the cross­
linking reaction between PVA and GA. Besides, the C–O stretching at
1151 cm− 1 in the uncoated membrane is replaced by a stronger ab­
sorption band at 1098 cm− 1 that can be attributed to the ether (C–O)
group formed by the crosslinking reaction. A strong peak at 1733 cm− 1
was observed at the PVA-coated membrane, but it does not appear in the
spectra of the uncoated membrane. This peak belongs to the C– –O
stretching of the aldehyde from GA. The result explains that the alde­
hyde group of GA did not completely react with the hydroxyl group in
PVA [37]. Given the presence of the strong− OH stretching in the
PVA-coated PSf-ZnO membrane, the PVA coating significantly improved
the hydrophilicity of the membrane surface. The improved hydrophilic
property of the membrane surface improves the water flux and anti­
fouling behavior.
3.3. Contact angle value and pure water permeability of the membrane
surface
The WCA of the membrane surface is influenced by several factors,
including surface tension, hydrophilic property, and surface roughness.
Membrane hydrophilicity is attributed to the water permeation rate
through the membrane barrier in the filtration process. As shown in
Fig. 6, the static WCA of the neat PSf membrane shows the highest value,
i.e., 61.75◦ . This result shows that polysulfone has a slight hydrophobic
nature. With the addition of 0.5 wt% ZnO nanoparticles, the WCA de­
creases from 61.75◦ to 46.00◦ ; the ZnO nanoparticles enhance the hy­
drophilic property of the PSf membrane surface. This result is supported
by the FT-IR spectra analysis, where the addition of ZnO resulted in the
presence of absorbed− OH, thus the membrane becomes more
hydrophilic.
The PVA layer on the membrane surface significantly decreases the
WCA from 46.00◦ to 31.17◦ at a PVA concentration of 1 wt%. The
improvement of the surface hydrophilicity might come from the pres­
ence of hydroxyl groups in the PVA. This explanation is supported by the
FT-IR analysis, where the hydroxyl vibration band increases signifi­
cantly. Moreover, the presence of PVA as a selective skin layer decreases
the surface roughness of the membrane, as shown in Fig. 3. The previous
study conducted by Woo and co-workers also revealed that a rougher
Fig. 6. Water contact angle results of the fabricated membranes.
T.D. Kusworo et al. Journal of Water Process Engineering 39 (2021) 101718

membrane surface had a higher WCA value [38]. The higher concen­ Table 3
tration of the PVA slightly decreasing the contact angle might be due to Tensile strength and elongation at break of the fabricated membranes.
the increase in PVA in the coating solution resulting in a denser skin Tensile strength (MPa) Elongation at break (%)
top-layer. The denser skin layer slightly increased the surface tension; Membrane Thickness (μm)
average error average error
therefore, increasing the PVA concentration in the coating solution is not
linearly proportional to the decrease in the WCA. M1 60 4.90 0.10 12.03 0.25
M2 65 5.67 0.29 11.50 0.30
A PWP experiment was conducted to evaluate the water transport M3 70 7.70 0.30 14.00 0.30
properties of the prepared membranes. The PWP results at different M4 70 8.43 0.15 15.50 0.30
operating pressures are shown in Fig. 7. It is shown that the permeate M5 70 8.80 0.10 15.70 0.30
flux of pure water for all types of the membrane (M1-M4) increased
proportionally with the operating pressure (5–9 bar) from the feed side.
structure. The coating of PVA also affected the membrane thickness, as
This result indicates that the permeation of the membranes is a pressure-
shown by the increase in the membrane skin layer thickness in the SEM
driven filtration. The pristine PSf membrane seems to have a relatively
analysis. However, the increase in PVA concentration did not signifi­
low PWP value due to its slightly hydrophobic nature. The PWP of the
cantly increase the thickness of the membrane. The tensile strength
nanohybrid membrane increased by about 1.33 times with the incor­
values of the modified membranes were higher than the neat PSf
poration of 0.5 wt% ZnO nanoparticles. The PWP enhancement might be
membrane. The incorporated nanoparticles in the membrane help
from the improved structural properties with the incorporation of the
absorb the energy applied to the membrane during the mechanical test.
nanoparticles. As reported in a previous study, the membrane blended
Hence, the membrane is not easily broken, despite higher applied en­
with inorganic nanoparticles had improved membrane porosity, average
ergy. However, the elongation at breakpoint decreases from 12.03%–
pore radius, and surface hydrophilicity, which leads to a permeate flux
11.50 % as ZnO is added as the ZnO nanoparticles restrict the chain
enhancement [39]. This result is also supported by the SEM image
mobility of the PSf matrix to a certain extent.
analysis, where the nanohybrid membrane was shown to have a porous
The PVA deposition on the PSf-ZnO membrane improves both the
surface. However, the PVA layer addition on the membrane surface
tensile strength and elongation at break. This phenomenon is attributed
significantly decreases the PWP by as much as 0.71 times at 1 wt% PVA.
to the PVA coating on the membrane surface. PVA naturally has excel­
The thicker dense top layer of the membrane due to PVA deposition may
lent tensile strength, flexibility, and adhesive properties. The presence of
increase the membrane resistance. According to Darcy’s law of fluid
PVA provides enhancement of the support membrane mechanical
transport through porous media, the higher resistance of the membrane
strength. The adhesive and flexibility properties of PVA contributed to
would decrease the permeate flux. The PWP value continuously de­
the tensile strength and elongation at break of the whole membrane. The
creases with an increase in PVA concentration from 1 wt% to 3 wt%.
PVA coating significantly enhanced the membrane mechanical strength,
Although the PVA coating enhances the surface hydrophilicity, the
extending the membrane life span.
increased density of the coating layer with increasing PVA decreases the
mass transfer rate of the water.
3.5. Performance evaluation using refinery wastewater treatment
3.4. Mechanical strength evaluation of the fabricated membranes
Untreated petroleum wastewater filtration experiments in a cross-
The individual structural components contribute to the mechanical flow system were performed to evaluate the separation performance
properties of the overall membrane. According to the SEM images, the of the prepared membranes. The wastewater was obtained from the
overall membrane thickness increases when ZnO nanoparticles are physical-chemical waste treatment output of Pertamina, Ltd., Indonesia.
incorporated, and the membrane is coated with PVA. The nanoparticles The characteristics of the wastewater were 1800 mg.L− 1 total dissolved
change the rheological properties of the polymer solution that influences solid, 671.68 mg.L− 1 COD, 143 mg.L− 1 NH3, 75 mg.L− 1 total phenol,
the formation of the membrane structure during the phase separation and 32 NTU turbidity. As shown in Fig. 8, the initial flux of PSf was
process. Table 3 presents the thickness, tensile strength, and elongation slightly enhanced from 1.68 to 1.82 L.m− 2. h− 1 by the membrane with
at break of the prepared membranes. The thickness of the membrane 0.5 wt% ZnO nanoparticles. However, the PVA coating caused a decline
increased with the modifications in this study. The nanohybrid PSf-ZnO in the initial flux to 1.23 L.m− 2 h− 1, 0.84 L.m− 2 h− 1, and 0.69 L.m− 2 h− 1
membrane has a thicker membrane compared with the neat PSf mem­ for PVA concentrations of 1, 2, and 3 wt%, respectively. The
brane due to the impregnation of nanoparticles into the polymer

Fig. 8. Membrane performance evaluation in terms of the permeation flux for

Fig. 7. Pure water permeability of the fabricated membranes. the PRW treatment.

6
T.D. Kusworo et al.
enhancement of the permeate flux may be related to the improvements
in the membrane porosity and hydrophilicity by the addition of nano-
ZnO nanoparticles in the PSf membrane. The decline of the initial
permeate flux might be due to the increase in skin layer thickness as a
result of the PVA coating that also increased the resistance.
Over the operating time for each membrane, decreases in the
permeation fluxes were observed. The significant decline in the first 60
min might be due to external fouling caused by particulate attachment
on the membrane surface. After 90 min of filtration time, the flux pro­
files showed a pseudo-steady-state due to foulant adsorption and con­
centration polarization. Although the initial flux of the PVA-coated
membranes was less than the pristine PSf membrane, the permeate flux
decline of the pristine PSf membrane yields a serious decline during the
PRW treatment. Higher-level pseudo-steady-states was achieved by the
membrane with a PVA coating. This phenomenon indicates that the
foulant deposition on the PVA-coated membranes was less than that on
the neat uncoated membrane. The PVA coating was proven to improve
the antifouling behavior of the membrane during the filtration process.
However, with a higher concentration of PVA in the coating solution, the
pseudo-steady-state of the permeate flux declines by 0.5–0.6 times,
which might be due to a higher density of the membrane skin layer with
the higher PVA concentration as the coating agent. The sharp flux
decline of the neat PSf membrane was consistent with a previous study
[40]. It might be ascribed to the hydrophobic nature of the PSf polymer
that attracts oil droplets from the wastewater to form a waterproof layer
on the membrane surface and internal body of the membrane.
Another parameter in the membrane performance evaluation was
pollutant rejection. In this study, phenol and ammonia are the pollutants
focused on removal from wastewater. Phenol and ammonia levels
become an issue in PRW treatment using conventional techniques. As
shown in Fig. 9, all fabricated membranes exhibited a phenol removal
efficiency greater than 51 %, and the ammonia removal efficiency
greater than 82 %. The removal efficiency obtained from this study was
greater than a previous study [41] that reached 25 %– 50 % removal
efficiency. This lower efficiency may be due to the effect of other con­
taminants in the untreated wastewater. Ammonia (NH3) in wastewater
is in the equilibrium state with ammonium ions (NH+ 4 ), which can be
absorbed by other contaminants, such as colloids and suspended solids,
that are easier to remove using a membrane. Hence, the pH plays an
essential role in the separation efficiency, where the pH of the feed
determines the equilibrium state between NH3 and NH+ 4 ions. The
presence of the PVA layer improves the selectivity performance of the
membrane by enhancing the phenol and ammonia removal efficiency
from 51.52%–82.68% and 82.89%–92.42%, respectively. The enhanced
Fig. 9. Removal efficiency of phenol and ammonia in PRW treatment using the
fabricated membranes in this study.
7
Journal of Water Process Engineering 39 (2021) 101718
removal efficiency may be due to charge exclusion.
As reported by Li and co-workers, the PVA polymer is a negatively-
charged polymer over the whole pH region that repels negatively-
charged molecules [42]. In the alkaline environment of PRW (pH =
8.6), the form of the dissolved NH3 in water is the dominating NH+4 form.
Since NH3 is a Lewis base, the NH3 molecules were rejected via Donnan’s
exclusion mechanism by the PVA surface. Phenolic compounds have
hydroxyls linked to the benzene ring with a delocalized electron cloud.
The electron-withdrawing groups (electrophilic functional group) can
interfere with the electron cloud and create a partial positive charge in
the aromatic ring [43]. Electronegative oxygen in phenolic compounds
creates a negative charge on the benzene ring in the pH range of 8–12,
where the hydrogen is attracted to form a phenolate anion that is
negatively charged. Ammonia experiences a stronger electrostatic
repelling force than phenolic compounds, given its stronger negative
charge. However, phenol and N-NH3 concentrations in the permeate are
still relatively high at 148.09 mg.L− 1 (82.68 % removal) and 25.40 mg.
L− 1 (92.42 % removal), respectively. According to the low removal ef­
ficiency of N-NH3, another process, such as advanced oxidation pro­
cesses (Electrochemical oxidation, Fenton oxidation, etc.) [44,45],
should be integrated with the membrane separation to achieve the
higher quality of treated water.
Other pollutants, such as TDS, COD, and turbidity, were also evalu­
ated to investigate the membrane performance for contaminant removal
efficiency. The TDS level represents the concentration of dissolved
solids, such as minerals. The COD level indicates the concentration of
organic compounds in the PRW, while turbidity is a measure of the
micro-particulates present in the PRW. As presented in Fig. 10, the TDS
removal increases with the addition of ZnO nanoparticles and PVA
coating. However, the higher concentration of PVA in the coating so­
lution does not have a significant effect on TDS rejection. The TDS
removal efficiency of all membranes was in the range of 18.33 %–38.25
%. In general, the rejection of TDS was relatively low, which might be
because the membrane was unable to reject monovalent ions such as
Na+, K+, and Cl− . Thus, the monovalent ions experienced weak size
exclusion and Donnan’s exclusion effects. The enhancement of TDS
rejection by the PVA-coated membrane might be attributed to by the
electrostatic repulsion. The positively-charged membrane surface pro­
vided a stronger repulsion force against cations. The PVA coating ex­
hibits an obvious enhancement in the COD removal efficiency. Organics
compounds were excluded due to both the size exclusion effect and
charge exclusion effect due to their larger molecular size and functional
groups. Many organic contaminants in PRW are hydrocarbon and ben­
zene derivatives that have strong repulsion forces with hydrophilic
Fig. 10. Contaminant rejection in PRW treatment using the fabri­
cated membrane.
T.D. Kusworo et al.
surfaces such as that produced by the PVA coating. Turbidity removal
efficiencies were excellent for all membrane types, where the removal
efficiencies are in the range of 97 %–99 %. The turbidity in PRW was
caused by particulates with a micro-scale size. Since the membrane
pores are nanoscale, the particulates in PRW were rejected via size
exclusion mechanism.
3.6. Membrane fouling analysis
The main issue in membrane separation applications for wastewater
treatment is fouling during operation. Fouling in the membrane gradu­
ally decreases the permeation flux and also reduces the lifespan of the
membrane; therefore, the membrane application is not economically
feasible. In this work, the PVA coating was used to enhance the mem­
brane hydrophilicity to improve the antifouling behavior of the mem­
brane. The examination of the fouling can be performed by qualitative
and quantitative analyses. Qualitative analysis can be performed
through a fouling autopsy to indicate the foulant deposition on the
membrane [46]. In this study, a quantitative approach was conducted to
evaluate how much the membrane modification can mitigate the fouling
formation during PRW treatment. A series model of the resistance
equation derived from Darcy’s law was used to examine the resistance
created by the foulant. The resistance in the membrane separation was
contributed to by the membrane structure itself, absorbed foulant, and
cake formation of the foulant deposition on the membrane surface. The
resistance of the fabricated membranes during a 150-min PRW filtration
experiment are shown in Table 4.
The value of Rm decreases slightly with the addition of ZnO nano­
particles, possible because the incorporation of ZnO nanoparticles im­
proves the porosity and hydrophilicity. However, the Rm of the
membrane increases as the PVA coating is applied. This increase in Rm
might be because the PVA coating decreased the size of the surface pores
on the membrane, forming a denser membrane. Alternatively, the PVA
addition increases the selective layer thickness, thus increasing the
resistance. The lowest resistance from the absorbed foulant was shown
by the membrane with a 2 wt% PVA coating. The highest cake resistance
was shown by a neat PSf membrane that has a slightly hydrophobic
surface and unrepaired properties. As shown in Table 4, the PVA in the
selective layer can reduce pollutant deposition on the membrane wall
despite the significant increase in the intrinsic membrane resistance. The
PVA coating improves the antifouling behavior of the membrane.
4. Conclusion
Nanohybrid membranes of PSf-ZnO with crosslinked PVA were
successfully fabricated with a dense and smooth surface using a non-
solvent induced phase separation (NIPS) method. The PVA coating can
significantly repair the porous surface of the nanohybrid membrane, as
shown in SEM images. The FT-IR spectra analysis also revealed that the
addition of ZnO nanoparticles and a PVA coating significantly improved
the hydrophilicity by introducing− OH functional groups. These results
were supported by WCA measurement. The membrane also exhibited a
distinct improvement in the surface charge, mechanical strength,
pollutant removal efficiency, and antifouling behavior. The modifica­
tion made in this study significantly enhanced the phenol and ammonia
removal efficiency from 51.52%–82.68% and 82.89%–92.42%, respec­
tively. The fouling evaluation also showed that the PVA coating provides
lower cake and absorbed foulant resistance during PRW treatment.
Declaration of Competing Interest
We wish to confirm that there are no known conflicts of interest
associated with this publication and there has been no significant
financial support for this work that could have influenced its outcome.
We confirm that the manuscript has been read and approved by all
named authors and that there are no other persons who satisfied the
8
Journal of Water Process Engineering 39 (2021) 101718
Table 4
The resistance of the membrane and fouled membrane during filtration.
Membrane Rm x 10− 17
Ra x 10− 17
Rc x 10− 17
RT x 10− 17
(m− 1) (m− 1) (m− 1) (m− 1)
M1 5.4265 1.4491 1.0837 7.9594
M2 4.4055 1.3763 0.6298 6.4116
M3 6.4165 0.7296 0.4132 7.5592
M4 9.7234 0.2923 0.4039 10.4196
M5 11.6502 1.3294 0.4065 13.3861
criteria for authorship but are not listed. We further confirm that the
order of authors listed in the manuscript has been approved by all of us.
We confirm that we have given due consideration to the protection of
intellectual property associated with this work and that there are no
impediments to publication, including the timing of publication, with
respect to intellectual property. In so doing we confirm that we have
followed the regulations of our institutions concerning intellectual
property.
We understand that the Corresponding Author is the sole contact for
the Editorial process (including Editorial Manager and direct commu­
nications with the office). He/she is responsible for communicating with
the other authors about progress, submissions of revisions and final
approval of proofs. We confirm that we have provided a current, correct
email address which is accessible by the Corresponding Author and
which has been configured to accept email from tdkusworo@che.undip.
ac.id
Acknowledgments
This research was financially supported by the grant from the Min­
istry of Indonesia Research, Technology, and Higher Education under
the PTUPT research scheme. The authors also would like to thank the
Department of Chemical Engineering at Diponegoro University for the
use of the supporting facilities.
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