Journal of Food Engineering 166 (2015) 165–173

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Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

Deacidification of crude palm oil using PVA-crosslinked PVDF

membrane
R.A. Azmi a, P.S. Goh a,⇑, A.F. Ismail a, W.J. Lau a, B.C. Ng a, N.H. Othman a,b, A.M. Noor b, M.S.A. Yusoff b
a
Advanced Membrane Technology Research Centre (AMTEC), Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor Darul Takzim, Malaysia
b
Sime Darby R&D Centre Downstream, Lot 2664, Jalan Pulau Carey, 42960 Pulau Carey, Selangor, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Over recent years, there has been an explosive growth of interest in the development of alternative
Received 5 November 2014 approaches for crude palm oil (CPO) refining. During a typical refinery process, free fatty acid (FFA) is
Received in revised form 8 April 2015 one of the key objectionable impurities that need to be reduced if not completely removed from CPO
Accepted 1 June 2015
in order to minimize their detrimental effects on the oil quality. Polyvinylidene fluoride (PVDF) mem-
Available online 3 June 2015
brane shows great potential in removing FFA from CPO owing to its hydrophobic properties, high
mechanical strength and good thermal stability. However, low concentration of FFA in CPO, which is nor-
Keywords:
mally ranging from 3% to 5%, has hindered the capability of the membranes to separate the trace amount
Crude palm oil
Free fatty acids
of FFA from the bulk. Thus, modification of PVDF membrane is essential to enhance the interaction
Polyvinyl alcohol between the membrane surface and FFA molecules, facilitating efficient FFA removal. In order to achieve
Membrane this purpose in the present study, the outer surface of PVDF hollow fiber membranes was crosslinked
Polyvinylidene fluoride with polyvinyl alcohol (PVA). Glutaraldehyde (GA) was used as a crosslinking agent to avoid the PVA dis-
solution. Despite the negligible morphological change observed in the resultant membranes upon PVA
crosslinking, the contact angle has been significantly reduced in proportional to the concentration of
PVA used for the crosslinking, suggesting the decrease in membrane hydrophobicity. Additionally, the
average roughness of the crosslinked PVDF membranes increased with the increasing PVA concentration.
The results obtained suggested that the PVDF hollow fiber crosslinked with 100 ppm PVA exhibited the
highest FFA rejection of 5.93% after 3 h of operation. In addition, the membrane also showed good result
in reducing the content of phosphorus in the permeate and partial reduction of its color intensity. This
study served as the first attempt of CPO deacidification through UF membrane system without the addi-
tion of any chemical during the filtration process.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Oil palm industry is vital for the social and economic growth of
countries such as Malaysia and Indonesia which serve as the
world’s two biggest producers. In industry, CPO has been conven-
tionally refined through physical and chemical means to partially
or completely remove the impurities. The multiple stages involved
in the refining process have inevitably resulted in unfavorable oil
and nutrient loss, use of huge amounts of water and chemicals,
high energy consumption and generation of heavily polluted
wastewater (Arora et al., 2006; Cui and Muralidhara, 2010; Iyuke
et al., 2004). Furthermore, conventional refining techniques nor-
mally require the addition of chemicals which has also unavoid-
ably created several problems originated from the chemical
⇑ Corresponding author.
E-mail address: peisean@petroleum.utm.my (P.S. Goh).
reactions involved. For instance, the CPO treatment with sodium
hydroxide during the chemical refining process is known to create
emulsion and oil occlusion in the soap stock whereas the saponifi-
cation reaction is deemed to contribute to the oil loss and conse-
quently reduction in overall profit (Young, 1981).
One of the new approaches to overcome the major drawbacks of
conventional processes is membrane-based refining process. The
feasibility of using membrane technology in oil industry has been
widely reported in the literature (Alicieo et al., 2002; Arora et al.,
2006; de Morais Coutinho et al., 2009; Hafidi et al., 2005;
Manjula et al., 2011; Ochoa et al., 2001; Pagliero et al., 2007;
Pioch and Largue, 1998; Raman et al., 1996). Membrane-based
technology can be favorably operated at ambient temperature
without undergoing phase changes. This technology can also be
used to simultaneously concentrate, fractionate and purify prod-
ucts (Hwang, 2010; Raman et al., 1996). Owing to its versatility,
membrane technology can be applied in almost all the stages of

http://dx.doi.org/10.1016/j.jfoodeng.2015.06.001
0260-8774/Ó 2015 Elsevier Ltd. All rights reserved.
166 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173
oil processing (Kale et al., 1999). The main advantages of using
membranes in edible oil industry are low energy consumption,
preservation of desirable components in the oil and elimination
of wastewater treatment. In the technological and nutritional point
of view, reduction of energy cost as well as the retention of nutri-
ents are highly desired in the oil processing industry (Cui and
Muralidhara, 2010). Most importantly, membrane technology
offers an attractive refining route where the usage of chemicals
such as sodium hydroxide can be avoided throughout the process.
During CPO refining, impurities such as phospholipids, FFA,
trace metals, oxidation products and sterols must be minimized,
if not completely removed, to ensure the quality of the CPO as an
acceptable edible commodity. Of all the impurities mentioned,
removal of FFA greatly affects the further steps in CPO processing.
Ineffectiveness in the deacidification stage will result in huge oil
loss in the subsequent processing steps (Cui and Muralidhara,
2010). On the other hand, the components with nutritional values,
such as tocopherol, tocotrienol and carotene, should be retained as
they act as natural antioxidants that protect the oil from oxidation
while serving as the natural source of vitamin E.
Despite the considerable research efforts pursued in the last few
decades, only a few commercial applications of membrane tech-
nology for edible oil processing have been reported. Various
attempts made on the deacidification and degumming of edible
oils using membrane technology are summarized in Table 1.
Undeniably, despite showing potential in removing the undesired
phosphatides content from the vegetable oil, membrane separation
was insufficient to effectively remove FFA from the edible oil. In
fact, it has been generally presumed that addition of alkali is essen-
tial to successfully deacidify the oil (Bhosle and Subramanian,
2005). The limitation encountered in this aspect has stumbled
the further development of membrane technology in edible refin-
ing process.
Although membranes have been commonly known for their
separation principle which based on size exclusion mechanism,
the understandably ineffectiveness of membrane separation for
deacidification of CPO is primarily ascribed to the small molecular
weight difference between the triglycerides (oil molecules) and
FFAs, which has in turn upset the capability of membrane separa-
tion. To further complicate the issue, the low concentration of FFA
in CPO, which is normally in the range of 3–5%, is also found to
hamper the capability of membrane to separate the trace amount
of FFA from the bulk. In order to combat the identified shadow side,
membranes with precise selectivity toward FFA are highly desired
to perform the deacidification process. In this context, it is impor-
tant to develop highly selective membranes to render strong inter-
actions between the membrane surface and FFA molecules.
Since FFA is a carboxyl derivative, material with hydroxyl (–OH)
containing groups is expected to show high affinity and selectivity
Table 1
Deacidification of edible oil using membrane technology.
Membrane Vegetable oil Target(s)
Polysulfone Soybean oil FFA, soap and phosphorus
removal
Cellulose Sunflower and FFA, soap and phosphorus
rapeseed oil removal
Polyamide Model fatty acid FFA removal
solution
Zirconia Crude palm oil FFA, phosphorus and iron
(ceramic) removal
a
R = rejection, FFA = free fatty acid and PHO: phosphorus.
b
PL = phospholipids.
toward the FFA based on the interaction established between the
hydroxyl and carboxyl groups. Polyvinyl alcohol (PVA) which pos-
sesses abundant amount of –OH groups is a suitable candidate to
increase the affinity of FFA toward membrane. In this study,
PVDF membranes have been crosslinked with PVA of various con-
centrations. Modification of PVDF with PVA has been practiced by
several methods which include blending, surface coating by solid–
vapor interfacial crosslinking and PVA grafting by immersion.
However, PVA crosslink accomplished through direct dipping of
the membranes into PVA solution is by far the most facile and con-
venient way to introduce –OH molecules onto the membrane sur-
face. To avoid its dissolution during deacidification process,
glutaraldehyde (GA) has been used as the crosslinking agent
(Barbari and Li, 1995; Dai and Barbari, 2000; Djennad et al.,
2003; Du et al., 2009; Plieva et al., 2006; Wang et al., 2006;
Yeom and Lee, 1996). GA reacts with different PVA chains to yield
intermolecular crosslinking and intra-polymer network as shown
in Fig. 1. Since PVDF membrane has been extensively applied in
many separation processes, and serves as a potential candidate in
CPO refining, it is important to apply a mild modification on
PVDF membrane to retain the desired separation properties while
optimizing the crosslinking condition in removing FFA from CPO.
It is important to emphasize that, no chemical was added dur-
ing the pressure-driven deacidification process conducted in this
study. Up to date, no similar effort has been reported for the
deacidification of CPO. Low concentration of dilute PVA (100–
5000 ppm) was used for the crosslinking to allow the formation
of thin coating layer that is sufficient to induce strong affinity
toward FFA in CPO. The separation performance of the resultant
hollow fiber membranes in terms of the oil flux and FFA rejection
was investigated through the membrane-based UF system.
2. Material and methods
2.1. Materials
Commercial PVDF pellets (Kynar 760) was used as main compo-
nent in membrane formation. N-methyl-2-pyrrolidone (NMP) and
ethylene glycol (EG) were used as solvent and additive, respec-
tively during dope solution preparation. Polyvinyl alcohol (PVA)
with molecular weight of 31,000–50,000 g/mol and 98–99% hydro-
lyzed was used to crosslink with glutaraldehyde (GA) solution
(Grade II, 25%). All chemicals used in this work were used as
received without further treatment.
2.2. Preparation of dope solution
Membranes used in this study were spun with a dope formula-
tion of 18% PVDF/76% NMP/6% EG (wt.%). PVDF pellets were first
a b
Results Drawback(s) Refs.
RFFA = 34.39% Incomplete removal of PLs and soap Alicieo et al.
RPHO = 73.37% (2002)
Rsoap = 85.81%
Results varied depending on Chemicals are needed to produce good Pioch and Largue
chemicals used oil permeate (1998)
Fouling is severe in dead-end filtration
RFFA = 75–84% Methanol is required to extract FFA Raman et al.
Low solvent stability of membrane (1996)
against alcohol
RPHO = 78.1% Incomplete rejection of PLs Iyuke et al. (2004)
Riron = 59.7% No selectivity of FFA
 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173
Fig. 1. Structure of crosslinked PVA: (a) intermolecular crosslinking and (b) intramolecular crosslinking (Du et al., 2009).
dried in an oven at 100 °C for 5 h to remove the moisture contents.
The dried PVDF was then added slowly into NMP solution in flange
reaction flask and mixed using mechanical stirrer at 60 °C. EG solu-
tion which acted as an additive was added slowly when a homoge-
nous solution of PVDF and NMP was obtained. In the final step, the
formulated dope solution was ultrasonicated for 24 h in order to
remove the microbubbles in the dope.
2.3. PVDF hollow fiber membrane preparation
The hollow fiber membranes were prepared using dry–jet wet
spinning method. Water was used as the internal (in lumen side
of membrane) and external coagulation bath and the air gap were
set at 10 cm. The as-spun membranes were then immersed in a
water bath at room temperature for 24 h before they were
post-treated with ethanol aqueous solution (50 wt.%). At last, the
post-treated membranes were air-dried at room temperature
before they were used for crosslinking process.
2.4. Membrane modification
The PVDF hollow fiber membranes were crosslinked with PVA
solution. The solution was prepared by dissolving PVA in pure
water, magnetic stirring at 80 °C for 24 h to obtain the desired
PVA concentration. Concentrations of PVA ranging between 100
and 5000 ppm were investigated in this study. 30 mL of GA was
added to the PVA solution and magnetically stirred for a given per-
iod of time until the solution became homogenous. The process
was continued by immersing the membranes in the PVA–GA solu-
tion for a period of 30 min in room temperature before they were
taken out and washing thoroughly. At last, the surface-modified
membrane was dried in an oven at 60 °C to complete the crosslink-
ing process. The PVDF/PVA membranes were then labeled as
PVDF/100PVA, PVDF/500PVA, PVDF/1000PVA, PVDF/2000PVA and
PVDF/5000PVA, respectively, depending on the concentration of
PVA used during crosslinking process.
167
2.5. Membrane characterization
The membrane morphology was examined using tabletop scan-
ning electron microscope (SEM) (Model: TM 3000, Hitachi). Prior to
the analysis, a piece of hollow fiber was immersed in liquid nitro-
gen and fractured carefully in order to create a perfect cross sec-
tion. Contact angle of the hollow fiber membrane was studied
using contact angle goniometer (Model: OCA15plus,
Dataphysics). A total of 10 contact angles were gained from each
sample and the average contact angle was reported. Thermal prop-
erties of the membranes were examined using thermogravimetry
analyzer (TGA) (Model: TGA/SDTA851e, Mettler Toledo) in order
to characterize the decomposition and thermal stability of materi-
als under a variety of conditions and examine the kinetics of the
physical–chemical processes occurring in the sample.
Temperature that was used in TGA was up to 800 °C with
10 °C/min as the increase rate of heating. Functional groups of
the membranes were observed using Fourier transform infrared
(FTIR) spectroscope (Model: Nicolet5700, Thermo Electron
Corporation). The spectrum was analyzed to observe the difference
in the chemical structure of the membrane before and after
crosslinking process. Surface roughness of the membrane was
examined using atomic force microscope (Model: SPA-300HV,
Seiko). In order to examine the molecular weight cut-off (MWCO)
of the membrane, bovine serum albumin (BSA) (Mw: 60 kDa)
and polyvinylpyrrolidone (PVP) with different molecular weight
were added into the aqueous feed solution and their concentra-
tions before and after membrane filtration were examined using
UV–Vis spectrophotometer (Model: DR5000, Hach) and total
organic carbon analyzer (Model: TOC-LCPN, Shimadzu).
2.6. Lab-scale membrane filtration system
Deacidification of CPO was carried out using a lab-scale mem-
brane refining system as shown in Fig. 2. This system was designed
in dead-end filtration mode and the operating pressure for mem-
brane refining process was maintained at 2 bar using pure nitrogen
168 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173
Fig. 2. Pressure driven system of laboratory scale membrane crude palm oil refining system.
gas. In order to maintain temperature of the feed CPO at 65 °C, the
membrane permeation cell was immersed into a water bath in
which the temperature was controlled using multi-purpose
immersion coiled heater (Model: 830-S1, Protech Electronic). The
performance of the membranes was then evaluated in terms of
their flux and rejection.
To measure the oil flux, J achieved by each type of membranes,
the following equation was employed
Q branes were determined and the results are presented in Fig. 4.
J¼
At
where Q is quantity of permeate (kg), A is effective membrane area
(m2) and t is time to obtain the quantity of Q (h). The rejection of
FFA was calculated based on the following equation
 
Cp
Rð%Þ ¼ 1   100
Cf
where Cp and Cf are the content (%) of FFA in permeate and feed,
respectively.
2.7. Analytical methods
FFA, phosphorus and color content in the oil samples were
determined using American Oil Chemists’ Society (AOCS) method
– Cd 3d-63, Ca 12-55 and Cc 13e-92, respectively.
3. Results and discussion
3.1. Membrane morphology
The SEM cross-sectional and surface images of neat PVDF,
PVDF/100PVA and PVDF/5000PVA are shown in Fig. 3. The mem-
branes were collected from the same batch of spinning and there-
fore they were different only by the amount of PVA that
crosslinked on the membrane surfaces. As depicted in the SEM
images, all crosslinked membranes possessed very porous struc-
ture. This is expected to favourably improve the flux of sticky
and viscous CPO. In this study, since only low PVA concentration
was used for the membrane modification, no visible layer of PVA
was observed on the surface of the crosslinked membrane. The
outer surface of the membrane is observed to be very thin and
the shadow of the PVDF hollow fiber sponge-like structure can
be clearly seen.
3.2. Membrane hydrophilicity
The contact angles of the neat and crosslinked PVDF mem-
ð1Þ
As can be seen, the contact angle, which is the indication of the
hydrophobicity of hollow fiber membrane, decreased with the
increasing PVA concentration. Crosslinking of PVDF with the low-
est concentration of PVA resulted in only a small reduction in con-
tact angle while significant reduction could be seen when
5000 ppm of PVA was crosslinked onto the PVDF surface. The
ð2Þ
hydroxyl and ester groups are hydrophilic in nature and their
abundance increases with higher PVA concentration. As such, the
hydrophilicity of crosslinked PVDF surface increases as higher
PVA concentration is used. This result indicates that the hydrophi-
lic surface modification has been achieved and provided a clear
evidence for the successful crosslinking of PVA onto the PVDF
membrane surface.
3.3. Membrane thermal stability
Fig. 5 shows the TGA thermogram of the neat and crosslinked
membranes. As can be seen, the weight loss of membrane against
temperature remained almost constant for all of the membranes,
indicating excellent thermal stability of the crosslinked PVDF
membranes where they can be suitably applied for industrial
CPO refining which normally operates at temperature above
50 °C. Significant weight loss was recorded at approximately
420 °C and the polymer matrix continued to degrade which even-
tually turned the membrane into char yield at 900 °C. However, at
500 °C, it can be seen that neat PVDF (65% loss) exhibited a slight
higher weight loss if compared to the crosslinked PVDF (60% loss).
This slight improvement in thermal stability can be attributed to
the PVA crosslinking which has altered the structure of the outer
 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173 169

Fig. 3. SEM images (150, 400, and 5000 magnifications) of hollow fibers membrane (a) PVDF, (b) PVDF/100PVA and (c) PVDF/5000PVA.

PVA used, –OH characteristic peak was not clearly observed in

PVDF/5000PVA membrane. This may due to the formation of dense
layer which has led to the intramolecular crosslinking of PVA and
hindered the capability of intermolecular crosslinking between
PVA and PVDF. Existence of shoulder at around 1594 cm1 is due
to the dehydrofluorination which might be caused by the forma-
tion of (–CF = CH–) (Awanis Hashim et al., 2011). All membranes
possessed same absorption peaks in the fingerprint region that
occurred at the wavenumber between 750 and 1500 cm1. The
structure of PVDF is that of n-vinylidene fluoride units, –(–CH2–
CF2–)–n, added head-to-tail (Kuhn et al., 1987). FT-IR spectra

Fig. 4. Comparison of contact angle of neat and PVDF membranes crosslinked with
different concentration of PVA.

surface of the bulk polymer thus improved the mechanical stability

of the membranes (Du et al., 2009).

3.4. FT-IR analysis

From Fig. 6, FT-IR spectra of the membranes show existence of

two new peaks in the crosslinked samples. Existence of –OH broad
peaks in the region between 3200 and 3500 cm1 can be clearly
seen on the PVDF/100PVA membrane while a weak peak can be
seen in PVDF/5000PVA membrane. Based on the spectra, the pres-
ence of –OH groups can be attributed to the successful crosslinking Fig. 5. Thermal gravimetry analysis of neat and PVDF membranes crosslinked with
of PVA on the membrane surface. Despite the high concentration of different concentration of PVA.
170 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173
Fig. 6. FT-IR spectra of the neat and PVDF membranes crosslinked with different
concentration of PVA.
showed characteristic bands appeared at 876 cm1 (CF2),
1071 cm1 (CC) and 1181 cm1 (CC) were similar to the bands
observed for PVDF containing mainly a-phase while peaks at
840 cm1 (CH2), 1276 cm1 (CF2), and 1401 cm1 (CH2) could be
attributed to b-phase (Awanis Hashim et al., 2011; Roenig, 1971).
3.5. AFM analysis
Table 2 tabulates the mean roughness (Ra), the root mean
square of Z values (Rms), and maximum roughness (Rmax) of the
top surfaces of the PVDF membranes as evaluated over an area of
1  1 lm2. It is found that all roughness parameters increased with
the increasing PVA concentration. In fact, average roughness of
PVDF/5000PVA is twice as much as the neat membrane. As
depicted in Fig. 7, although peaks and valleys structures can be
clearly seen on the surface of all membranes, the crosslinking of
PVA on the PVDF surface has led to the formation of much higher
peaks thus increased the Rmax parameter. This phenomenon can
be attributed to the existence of PVA layer on the outer surface
of the membrane, causing the formation of an irregular surface
pattern that further increased the membrane surface roughness.
Similar observation has been found in the previous surface modifi-
cation study in which Xi et al. (2009) reported the thickening of
membrane surface layer upon the immersion of poly(3,4-dihydrox
yphenylalanine) (DOPA) solution. In this study, it is preferable not
to significantly change the properties of the bulk polymer in order
to retain the FFA removal properties rendered by the bulk PVDF
membranes.
3.6. MWCO and pure water flux
MWCO permeation test on the membrane samples are tabu-
lated in Table 3. The MWCOs of all the membranes were found
to be in between 60 and 360 kDa which are in the microfiltration
Table 2
Mean roughness of the PVDF membranes.
Membranes Outer surface roughness (nm)
Mean roughness (Ra)
PVDF 6.40
PVDF/100PVA 7.03
PVDF/500PVA 7.81
PVDF/1000PVA 8.51
PVDF/2000PVA 9.25
PVDF/5000PVA 12.38
(MF) range. With respect to water permeability, it is found that
all the membranes prepared demonstrated similar water flux
regardless of PVA content on the membrane outer surface.
However, PVDF/5000PVA exhibited flux that was slightly higher
compared to other membranes, probably due to the greater surface
hydrophilicity coupled with higher surface roughness.
3.7. Phosphorus and color removal
Fig. 8 shows the phosphorus removal performance using the
PVDF/PVA hollow fiber membranes. Neat PVDF membrane pos-
sessed the highest capability in removing phospholipids from
CPO while membranes crosslinked with much higher PVA concen-
tration showed poor performance in eliminating phospholipids
from the oil. This phenomenon can be attributed to the higher
hydrophobicity of the neat PVDF membranes which plays a role
in reducing the diffusion rate of phospholipids through membrane.
The surface modification of PVDF membrane with PVA tended to
make the membrane surface more hydrophilic, leading to the
increased phospholipids diffusion rate and reduced removal effi-
ciency. Removal as high as 90% has been achieved by neat PVDF
membrane in the first 30 min of operation but the efficiency
decline to 74.53% after 3 h of operation. On the other hand,
PVDF/5000PVA with contact angle of 57° exhibited the poorest
phospholipids removal, recording around 41%. It must be pointed
out that the separation mechanism of phospholipids from CPO by
membrane is not governed by sieving effect as the membrane
exhibited much greater pore dimension in comparison to the size
of the phospholipids. Thus, the removal of phospholipids could
be attributed to its relatively lower diffusion rate compared to
the triglycerides and/or the adsorption of phospholipids by the
polymeric membrane. The latter case is more reasonable by taking
into account the decreasing behavior of phospholipids removal as a
function of time. With respect to oil color results as tabulated in
Table 4, it is found that all the membranes studied did not appre-
ciably reduce the coloration of CPO. This is mainly due to the sig-
nificant smaller size of dye components present in CPO compared
to the pore size of the membrane used.
3.8. FFA removal
In terms of FFA rejection, neat PVDF membrane as well as cross-
linked membrane with PVA concentration higher than 1000 ppm
did not exhibit any capability of FFA removal from the CPO feed.
As depicted in Fig. 9, only 3 membranes, namely PVDF/100PVA,
PVDF/500PVA and PVDF/1000PVA, demonstrated FFA removal
capability. It is clearly observed that, only PVDF/100PVA exhibited
consistent performance to remove FFA throughout the 3-h opera-
tion time. The incapability of neat PVDF membrane in removing
FFA from the CPO feed is most likely due to the inertness of the
PVDF membrane surface toward FFA. As mentioned earlier, since
the amount of 5% FFA in the oil bulk was relatively low, the neat
PVDF was expectedly inefficient to separate the FFA from the
CPO bulk. By considering this constrain, the high affinity of the
membrane surface toward FFA constituent is of great importance
Root mean square of Z values (Rms) Maximum roughness (Rmax)
8.40 33.04
9.04 39.49
10.18 51.30
11.82 55.32
12.29 55.19
15.37 84.34
 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173 171

Fig. 7. Three-dimensional AFM images of the PVDF hollow fiber membranes: (a) PVDF; (b) PVDF/100PVA; (c) PVDF/500PVA; (d)PVDF/1000PVA; (e) PVDF/2000PVA; and (f)
PVDF/5000PVA.

to attract the FFA molecules toward the membrane selective layer case 100 ppm, the FFA can be promisingly removed through the
prior to the subsequent filtration process. When the surface of membrane filtration process in which rejection of 5.93% has been
PVDF was crosslinked with an appropriate amount of PVA, in our achieved. This phenomenon can be reasonably explained by the
172 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173

Table 3
MWCO and pure water flux of the PVDF membranes.
a
Membrane Solute rejection (%) Pure water flux (L m2 h1)
60 kDa 360 kDa
PVDF 2.33 96.14 2.63
PVDF/100PVA 0.94 94.91 2.65
PVDF/5000PVA 1.41 98.55 2.74
a
Pure waterflux was determined at operating pressure of 2 bar.

Fig. 9. FFA rejection of PVDF membranes crosslinked with different concentration

of PVA.

Fig. 8. Phosphorus rejection of PVDF membranes crosslinked with different

concentration of PVA.

interactions established between PVA layer and the FFA molecules.

The presence of –OH functional groups on the outer surface of the
PVDF membrane has attracted the FFA, reducing the molecules to
pass through the membrane as permeate. Although previous stud-
ies have reported that deacidification of CPO using membrane pro-
cess could go up to 30% removal, the addition of chemical was
unavoidable (Alicieo et al., 2002; Raman et al., 1996). This has
resulted in the formation of soap and severe oil loss. Hence, this
study has served as an attempt to exclude the chemical usage in Fig. 10. Comparison of oil fluxes of neat and PVDF membranes crosslinked with
the deacidification process. different concentration of PVA.
Higher concentration of PVA crosslinking on the surface of PVDF
has resulted in poor removal of FFA. It is because excessive attach-
ment of PVA could block the membrane surface, leading to adverse The permeate flux of all the membranes as a function of time is
effect on membrane separation. Based on the results obtained, it is shown in Fig. 10. All the membranes experienced a significant flux
deduced that, a thin layer of PVA coating with sufficient amount of decline as a function of operating time. The filtration process was
functional groups is critical to achieve desired FFA removal. kept constant for 3-h duration as this is the standard procedure

Table 4
Color reduction of CPO by using neat and crosslinked membrane.

Membrane Operation time (min) Lovibond color values

a
Feed Permeate PR
b b
Red Yellow 5R + Y Red Yellow 5R + Y (%)
PVDF 30 20 10 110 18 8 98 10.9
180 20 10 110 –
PVDF/100PVA 30 18 8 98 16 8 88 10.2
180 18 8 98 –
PVDF/500PVA 30 18 8 98 18 8 98 –
180 18 8 98 –
PVDF/1000PVA 30 18 8 98 16 8 88 10.2
180 18 8 98 –
PVDF/2000PVA 30 18 8 98 18 8 98 –
180 18 8 98 –
PVDF/5000PVA 30 18 8 98 16 8 88 10.2
180 18 8 98 –
a
PR = percentage reduction.
b
R = red and Y = yellow.
 R.A. Azmi et al. / Journal of Food Engineering 166 (2015) 165–173
applied in the physical refinery of CPO. Due to the hydrophilic nat-
ure of the PVA crosslinked membrane, all crosslinked membrane
exhibited lower flux compared to that of neat PVDF membrane.
Oil flux of neat PVDF membrane started with 2.22 kg m2 h1
and slowly reduced to 1.11 kg m2 h1 over 3-h operation while
all PVA crosslinked membranes started with lower flux of
around 2 kg m2 h1 and deteriorated to 0.56 kg m2 h1 at the
end of operation. As expected, relatively smooth surface of
PVDF/100PVA membrane has resulted in the lowest flux among
all the tested membranes. Meanwhile three membranes with high-
est surface roughness, i.e. PVDF/1000PVA, PVDF/2000PVA and
PVDF/5000 showed much higher oil flux. It is worth mentioning
that, membrane fouling has been recognized as a common issue
of membrane-based separation. In this context, suitable membrane
cleaning process is needed in order to remove the attached fou-
lants from the membrane surface. However, this topic is beyond
the scope of current study.
4. Conclusions
In this study, the feasibility of PVA crosslinked PVDF membrane
for FFA removal from CPO has been investigated. Contact angle
results showed that the hydrophobicity of PVDF decreased upon
PVA crosslinking. Average roughness of the membrane was
increased with increasing PVA concentration, indicating the pres-
ence of PVA layer on the membrane surface. Experimental results
showed that the PVDF membrane coated with 100 ppm PVA exhib-
ited the highest FFA rejection, which suggested that low concentra-
tion of PVA was sufficient enough to improve surface affinity
toward the FFA in CPO. The findings of this work conclude that
the membrane-based CPO refining has a potential to eliminate
not only FFA but also phospholipids without addition of any chem-
ical throughout the process. However, more efforts are needed to
put into further improve the efficiency of FFA removal using
membrane-based technology.
Acknowledgement
The authors are thankful to Sime Darby Research Sdn Bhd for
the research Grant (Vote number: A.J140000.6167.08601)
provided.
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