Journal of Bioresources and Bioproducts 7 (2022) 43–51

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Journal of Bioresources and Bioproducts

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Improving cold flow properties of palm fatty acid distillate

biodiesel through vacuum distillation
Siew Ping Yeong a, Yen San Chan b,∗, Ming Chiat Law a, Jordy Kim Ung Ling b
a
Department of Mechanical Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT 250, 98009 Miri, Sarawak, Malaysia
b
Department of Chemical and Energy Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT 250, 98009, Miri, Sarawak,
Malaysia

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

Keywords: Palm fatty acid distillate (PFAD), a by-product of refining process of crude palm oil can be used
Biodiesel as a potential feedstock for biodiesel production. However, the application of palm oil-based
Cold flow property biodiesel is often hinder by its poor cold flow properties (CFP). Biodiesel fuel with poor CFP may
Methyl palmitate
crystallize and result in clogging of fuel lines, filters and injectors that cause engine operability
Palm fatty acid distillate (PFAD)
problems. For that, a vacuum distillation method was designed and its feasibility and efficiency in
Vacuum distillation
improving the CFP was examined. A total of 13.60wt% of total saturated fatty acid methyl esters
were successfully removed from the PFAD biodiesel, resulting in the improvement of the cloud
point (CP), cold filter plugging point (CFPP) and pour point (PP) of PFAD biodiesel from 20 °C,
19 °C, and 15 °C to 13 °C, 11 °C, and 9 °C, respectively. It is remarkable that the improved CFPP
satisfied the requirements for grade C summer biodiesel for temperate climates in EN 14212
standard. Additionally, Sarin (UFAME ) empirical correlation was evaluated and it was found to
have a good prediction of CFP for PFAD biodiesel, with lower than 2 °C deviation.

1. Introduction

Today, many researchers have introduced and recommended the use of biodiesel as alternative to conventional diesel fuels man-
ufactured from petroleum sources as biodiesel reduces the greenhouse gas emissions, ensure sustainability and protect against higher
oil prices (Rashed et al., 2016; Adepoju, 2020; Murta et al., 2021; Pourhoseini et al., 2021). Biodiesel is defined as a combination of
saturated and unsaturated long chain fatty acid mono alkyl ester made from vegetable oils and animal fats, obtained by the process
of transesterification of an oil and fat with an alcohol (Ali et al., 2016; Soly Peter et al., 2021).
Palm oil is one of the most common biodiesel feedstocks and it was reported that palm oil-based biodiesel is cheaper and has
the highest oil yield as compared with other common biodiesel feed stocks. Ali et al. (2012) highlighted that the production of palm
oil-based biodiesel is about 12 times higher than that of soybean. During the physical crude palm oil refining, a non-edible by-product
known as palm fatty acid distillate (PFAD) is inevitably produced. The annual global production of PFAD is estimated at 2.5 × 106 t,
where Malaysia (29%) and Indonesia (58%) are the main contributors (Xu et al., 2020). On a stand point to fully-utilize the PFAD,
it has been widely used as raw material for soap and oleochemical products and also as feedstock for biofuel production (Akinfalabi
et al., 2017; Baharudin et al., 2020). However, the usage of palm oil-based biodiesel is often hinder by its poor cold flow properties
(CFP), which is generally determined by cloud point (CP), cloud filter plugging point (CFPP) and pour point (PP). The poor CFP of

∗
Corresponding author. Department of Chemical and Energy Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT
250, 98009, Miri, Sarawak, Malaysia
E-mail address: chanyensan@curtin.edu.my (Y.S. Chan).

https://doi.org/10.1016/j.jobab.2021.09.002
Received 20 April 2021; Received in revised form 29 June 2021; Accepted 5 July 2021
Available online 1 October 2021
2369-9698/© 2021 The Author(s). Published by Nanjing Forestry University. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
S.P. Yeong, Y.S. Chan, M.C. Law et al. Journal of Bioresources and Bioproducts 7 (2022) 43–51

palm oil-based biodiesel are mainly due to the presence of high amount of saturated palmitic acid methyl ester (C16꞉0) or methyl
palmitate (up to 48%). As a consequence, palm oil-based biodiesel is unsuitable to be used in geographical regions outside tropical
latitudes because the biodiesel is prone to solidification at low temperature and results in the clogging of fuel lines, filter and injectors
that can lead to engine start-up and operability problems (Abou-Arab and Abu-Salem, 2010; Yusup and Khan, 2010; Cukalovic et al.,
2013; Lv et al., 2013; Sia et al., 2020).
Clearly, the CFP of the palm oil-based biodiesel need to be improved to prevent it from being solidified easily at low temperature.
Several conventional techniques such as winterization, blending with petroleum diesel, transesterification with alcohol and the use
of chemical additives have been employed to enhance the CFP of biodiesel or fatty acid methyl esters (FAME). However, these
conventional techniques exhibit drawbacks that limit their application. For example, winterization could result in the loss of the
total yield of biodiesel. On the other hand, blending of biodiesel utilize large proportion of blending agent (diesel) which is not
sustainable and economically feasible (Edith et al., 2012; Sierra-Cantor and Guerrero-Fajardo, 2017; Sia et al., 2020). For that,
searching for alternative approach to improve the CFP of palm oil-based biodiesel is necessary. Particularly, distillation process can
be implemented to separate and obtain desired methyl esters (Dimian et al., 2007; Aqar et al., 2021). In that sense, distillation process
can be used to remove those saturated methyl esters with unfavourable high melting points and low boiling points from biodiesel,
which shall improve the CFP of biodiesel. Nonetheless, the conventional distillation process requires high cost and may induce thermal
decomposition (cracking) that could affect the characteristic of biodiesel (Iakovlieva et al., 2017). An analogous method, but easier to
implement, allows the esters to boiled at lower temperature and prevent cracking is to perform distillation under vacuum. Therefore,
in this study, a simple vacuum distillation method was designed to modify the compositions of esters in PFAD biodiesel, aiming to
improve its cold flow properties (CP, CFPP and PP). The composition of the PFAD biodiesel was analysed using gas chromatography
that equipped with a flame ionisation detector (GC-FID). In addition, empirical correlations including Sarin (PFAME ), Sarin (UFAME )
and Su’s methods were fitted to predict and validate the cold flow properties.

2. Materials and methods

2.1. Materials

The PFAD feedstocks were provided by Sarawak Oil Palm (SOP) Edible Oils Refinery Plant in Bintulu, Sarawak, Malaysia with free
fatty acid (FFA) content of more than 80%. The feedstocks were converted into PFAD biodiesel via microwave-assisted esterification
before the distillation experiment, as presented in our previous study (Yeong et al., 2019). The main fatty acid profile of the PFAD
sample was found to be 47.51% palmitic acid, 38.69% oleic acid, 9.04% linoleate acid, and 4.76% of stearic acid, which gave
an estimated molecular weight of 260.17 g/mol. The n-hexane (analytical grade), FAME-mix RM6 reference standard and methyl
heptadecanoate for GC-FID analysis were purchased from Merck, Malaysia.

2.2. Vacuum distillation experiment setup

The vacuum distillation experiment was set-up in a laboratory scale. In this work, methyl palmitate with higher melting point
was selected as the light key component (to be removed as distillate) while methyl oleate was selected as the heavy key component.
A schematic presentation of the vacuum distillation setup is depicted in Fig. 1. The reflux divider (LSG 09089 model) shown in Fig.
1 was purchased from Normag, Germany. It consists of a jacketed water-cooled coiled condenser, a ground joint fitting for insertion
of temperature measuring device, a distillate drains section (with two glass needle valves), a side-arm vacuum frame for venting or
connection to the vacuum supply (with two spindle valves), and a stopcock valve above the receiving end joint. Fibre optic probes
were inserted at two temperature measuring locations: 1) take-off section with ground joint fitting between the boiling flask and
reflux divider; and 2) in the boiling flask, to record the instantaneous vapour and reboiler temperature respectively. The boiling
flask (1 L) was half filled with the biodiesel sample to allow additional room for bubbling during boiling in experiment. This also
helps in preventing splashing of the sample into the reflux divider. During the experiment runs, the flask was heated in an oil bath
which is maintained at 210 °C under a vacuum pressure of 100 kPa. All the connecting joints of the glassware were lubricated with
Dow-Corning high vacuum silicone grease. The flask was connected to a reflux divider which was a combination of a coil condenser
and vacuum control valves that connect to a vacuum pump fitted with a cold trap. The collecting flask can be disconnected from the
reflux divider from time to time by shutting off the needle valve and spindle valve which were closest to the collecting flask. The
valves can be turned on to reintroduce vacuum into the collecting flask again. The distillates were collected in 10-min interval and
characterized using GC-FID analysis. The experiment ended when the collected distillate significantly reduced when the distillation
rate decreased below 0.3 g/min.

2.3. Determination of cold flow properties

2.3.1. Cloud point test

The biodiesel sample were poured into a test jar and pre-heated in a 40 °C water bath before test. Then, the sample is setup in a
test jar according to ASTM standard D2500 (ASTM, 2011. D2500-11: Standard Test Method for Cloud Point of Petroleum Products.
West Conshohocken, PA: ASTM International). A thermometer was inserted into the test jar. The temperature when a cloud of wax
form at the bottom was recorded as the cloud point. The test was carried out in triplicates.

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S.P. Yeong, Y.S. Chan, M.C. Law et al. Journal of Bioresources and Bioproducts 7 (2022) 43–51

Fig. 1. Schematic presentation of vacuum distillation experiment setup

2.3.2. CFPP test

The CFPP of biodiesel gives a proper estimate of the lowest temperature at which the fuel could flow trouble-free in the fuel systems.
The biodiesel sample was added into a CFPP apparatus as illustrated in ASTM standard D6371-05 (ASTM, 2010. D6371-05(2010):
Standard Test Method for Cold Filter Plugging Point of Diesel and Heating Fuels. West Conshohocken, PA: ASTM International). The
sample, which was cooled at 1 °C interval, was drawn into a pipette through a wire mesh filter under controlled vacuum. This process
was repeated until the amount of wax crystals formed was sufficient to stop or slow down the flow such that the time taken to fill
the pipette exceeded 60 s. The temperature indicated for the last successful filtration was recorded as the CFPP. The test was carried
out in triplicates.

2.3.3. Pour point test

The pour point test of the biodiesel sample was conducted according to ASTM standard D97 (ASTM, 2015. D97-15: Standard Test
Method for Pour Point of Petroleum Products. West Conshohocken, PA: ASTM International). Biodiesel sample was poured into a test
jar. Then, a thermometer was inserted into the jar such that the bulb was 1 inch from the bottom surface of the test jar. The test
jar was placed in the cloud and pour point bath (0 °C). The condition of the biodiesel sample was inspected every 3 °C drop in the
temperature. The temperature when the biodiesel sample did not flow at all after tilted horizontally for 5 s was recorded. The pour
point of the tested sample was identified by adding 3 °C to the recorded temperature. The test was repeated in triplicates.

2.4. FAME analysis

The GC-FID was employed for quantitative analysis of the FAMEs in the PFAD biodiesel samples. The analysis was carried out
using the Agilent 6890N Network GC system with an FID detector with operating conditions as reported by Yeong et al. (2019). The
GC system was installed with an Agilent HP-5 column (30 m × 320 μm × 0.25 μm) (Li et al., 2013). For quantitative FAME conversion,
a sample was prepared in a 2 mL vial by diluting 50 mg of biodiesel sample and 10 mg of methyl heptadecanoate in 1 mL n-hexane.
Methyl heptadecanoate with known concentration was used as an internal standard to determine the precise concentration percentage
for the peaks shown by the biodiesel compound in the chromatogram. The identification of the composition of the major fatty acids in
the biodiesel sample was carried out by comparing the components with FAME-mix RM6, which was used as the reference standard
(Ho et al., 2015). The FAME conversion was calculated by using Equation (1) as expressed in the EN 14103 standard (British Standards
Institution, 2011. BS EN 14103: 2011 Fat and oil derivatives-Fatty acid methyl esters (FAME)-determination of ester and linolenic
acid methyl ester contents):
∑
A − − AIS mIS
Est er cont ent = × × 100% (1)
AIS m
where ΣA is the sum of all FAME peak areas, AIS is the internal standard (methyl heptadecanoate) peak area, mIS is the mass of the
internal standard, and m is the mass of the sample.

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Table 1
Ester composition in palm fatty acid distillate (PFAD) biodiesel with their respective melting and boiling points

Ester Melting point (°C)a Boiling point (°C/1.33 kPa)a Composition (wt%)b Composition (wt%)c

Methyl myristate 18.1 161 Negligible 1.93

Methyl palmitate 28.5 184 47.51 45.68
Methyl stearate 37.7 205 4.76 4.25
Methyl oleate –20.2 201 38.69 40.19
Methyl linoleate –43.1 200 9.04 7.90
Total saturated FAMEs – – 52.27 51.86
Total unsaturated FAMEs – – 47.73 48.09

Notes: a, Cermak et al., 2012; b, in this work; c, Lokman et al., 2014.

2.5. Prediction of cold flow properties

The cold flow properties of biodiesel were estimated using several sets of empirical correlations as follows:

(1) Sarin method which is based on the content of methyl palmitate (PFAME , wt%) (Sarin et al., 2009; Sarin et al., 2010):
CP = 0.526PFAME − 4.992 (0 < PFAME ≤ 45), R2 = 0.963 (2)

PP = 0.571PFAME − 12.24 (0 < PFAME ≤ 45), R2 = 0.863 (3)

CFPP = 0.511PFAME − 7.823 (0 < PFAME ≤ 45), R2 = 0.863 (4)

(2) Sarin method which is based on the content of total unsaturated FAMEs (UFAME , wt%) (Sarin et al., 2009; Sarin et al., 2010):
CP = − 0.576UFAME + 48.255 (0 < UFAME ≤ 84), R2 = 0.973 (5)

PP = − 0.626UFAME + 45.594 (0 < UFAME ≤ 84), R2 = 0.874 (6)

CFPP = − 0.561UFAME + 43.967 (0 < UFAME ≤ 84), R2 = 0.872 (7)

(3) Su’s method which is based on the weighted average number of carbon atoms in FAME (Nc ) and the composition of total unsatu-
rated FAMEs (UFAME ) (Su et al., 2011):
CP = 18.134Nc − 0.790UFAME (8)

PP = 18.880Nc − 1.000UFAME (9)

CFPP = 18.019Nc − 0.804UFAME (10)

These correlations help to validate the cold flow tests of PFAD biodiesel before and after distillation.

3. Results and discussion

3.1. Vacuum distillation experiment

With the aim to improve CP, PP and CFPP of PFAD biodiesel, a simple vacuum distillation process described under Section 2.2 was
set-up to remove the selected FAME. The ester composition in the PFAD biodiesel with their respective melting and boiling points is
shown in Table 1 and compared with other studies (Cermak et al., 2012; Lokman et al., 2014). As shown in Table 1, methyl stearate
has the highest melting point (37.7 °C), followed by the methyl palmitate (28.5 °C). In spite of having higher melting points, methyl
stearate was not selected as the key component to be separated from the PFAD biodiesel because its amounts were relatively lower
as compared with methyl palmitate, which was only 4.76%. On the other hand, the composition of methyl palmitate was found to
be 47.51%, which was the highest among the four esters presented in the PFAD biodiesel. This is in agreement with the composition
reported by Lokman et al. (2014). For that, methyl palmitate was chosen as the key component to be separated.
The experiment was carried out under vacuum as Bonhorst et al. (1948) reported that the decomposition of saturated acid esters
would occur progressively at temperature above 205 °C under atmospheric pressure. As shown in Table 1, the boiling point of methyl
palmitate was 184 °C at an absolute pressure of 1.33 kPa. Thus, in order to avoid the thermal degradation of esters during the
distillation process, the experiment was carried out at the boiling temperature of methyl palmitate under 100 kPa vacuum pressure.
During the vacuum distillation experiment, the esters were successfully separated from the heated PFAD biodiesel sample, where
about 430 g of PFAD methyl esters were obtained in the boiling flask during the distillation run.

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S.P. Yeong, Y.S. Chan, M.C. Law et al. Journal of Bioresources and Bioproducts 7 (2022) 43–51

Fig. 2. Vapour and reboiler temperature profiles before and during vacuum distillation (t = 0, the distillation temperature)

Table 2
Ester components in PFAD biodiesel with their respective composition

Carbon Retention time Molar mass Normalized composition (%)

Ester chain (min) (g/mol) Pre-distillation Post-distillation Change

Methyl palmitate (C16꞉0) 9.19 270.5 47.36 31.91 –15.44

Methyl stearate (C18꞉0) 12.78 294.5 5.01 6.86 1.85
Methyl oleate (C18꞉1) 12.37 296.5 38.46 49.78 11.32
Methyl linoleate (C18꞉2) 12.21 298.5 9.17 11.45 2.28
Total saturated FAMEs – – – 52.37 38.77 –13.60
Total unsaturated FAMEs – – – 47.63 61.23 13.60

The temperature profiles of the liquid (in boiling flask) and vapour (before condensed into distillate) were recorded and presented
as Fig. 2. As shown in Fig. 2, the vapour temperatures were consistent, with 10 °C lower than the reboiler temperature throughout
the distillation experiment. It was observed that the PFAD biodiesel in liquid phase reached its boiling point about 35–40 min before
the distillation began. The highest biodiesel temperature recorded was 194.8 °C at the 35th minute before the first distillate sample
collection took place. At this stage, the molecules in the biodiesel sample possessed enough kinetic energy to escape from the liquid
phase to vapour phase. This was shown by the immediate increase in vapour temperature, where the vapour temperature rose from
the room temperature to over 180 °C, indicating that more vapour was actually produced to achieve stable total reflux condition in
the distillation system. Another interesting observation is that it was noticed that it is nearly impossible to distillate the esters with
lower boiling point than methyl palmitate (e.g., boiling point of methyl myristate: 161 °C) that present in small portion in the PFAD
biodiesel. In other words, only one distillate fraction was obtained as the vapour temperatures remained steady at the range of 183–
184 °C during the experiment. This was acceptable as taking subsequent fractions at higher temperature would inevitably remove a
higher amount of methyl oleate and methyl linoleate from the biodiesel which would beat the purpose of conducting distillation on
PFAD biodiesel.
The light key component, methyl palmitate, was removed from the system and collected in the form of distillate every 10 min
at a reflux ratio of 1꞉1. The amount of distillate collected at each interval during the distillation experiment is plotted in Fig. 3. It
was observed that the distillate removal rate increased during the first 60 min but decreased at a faster rate after that. By the 60th
minute, the amount of distillate obtained was 29.99wt% of the initial feed. After 100 min, the amount of distillate that was enriched
with methyl palmitate increased to 39.76 wt% whereas the bottom product left in the boiling flask was enriched in the higher boiling
component (methyl oleate). By the end of the experiment, the remained bottom product (distilled biodiesel) in the boiling flask was
collected.
In order to study the efficiency of the vacuum distillation, the composition of the biodiesel samples before and after distillation
were subjected to GC-FID analysis for fatty acid composition studies. The ester compositions in the PFAD biodiesel before and after
the distillation were identified from chromatograms (Fig. 4) and shown in Table 2. As shown in Table 2, the PFAD biodiesel before
distillation was composed of 47.36% methyl palmitate, 38.46% methyl oleate and 14.19% other esters. However, it was found that
the methyl palmitate content in the distilled PFAD biodiesel decreased by 15.44% after the distillation, from 47.36% to 31.91%.
Meanwhile, the amounts of other esters increased, where the methyl oleate, methyl linoleate and methyl stearate were increased by
11.32%, 2.28% and 1.85%, respectively. That said, the dominant ester in PFAD biodiesel after distillation have changed from the
saturated ester methyl palmitate to the unsaturated ester methyl oleate. The amount of total unsaturated FAMEs in the PFAD biodiesel
was increased by 13.60% after the distillation.

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Fig. 3. Distillate removal of palm fatty acid distillate (PFAD) biodiesel during vacuum distillation
a, at each interval; b, in a cumulative manner (mass fraction)

Fig. 4. Methyl esters composition fraction in distillate samples over time.

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Table 3
Cold flow properties prediction of PFAD biodiesel samples before and after distillation via empirical correlations

Cold flow property In this work (°C) Sarin (PFAME , °C)a ∆T (°C) Sarin (UFAME , °C)a ∆T (°C) Su’s method (°C)b ∆T (°C)

Pre-distillation PFAD biodiesel

CP 20 19.92 0.08 20.82 0.82 15.76 4.24
CFPP 19 16.38 2.62 17.24 1.76 13.02 5.98
PP 15 14.80 0.20 15.77 0.77 19.19 4.19
Post-distillation PFAD biodiesel
CP 13 11.79 1.21 12.99 0.01 10.72 2.28
CFPP 11 8.48 2.52 9.62 1.38 7.76 3.24
PP 9 5.98 3.02 7.26 1.74 11.53 2.53

Notes: a, Sarin et al., 2009; Sarin et al., 2010; b, Su et al., 2011.

The ester compositions of the ten distillate samples collected during the experiment at 10-minute interval were also identified
using GC-FID analysis (Fig. S1). By referring to Fig. 4, the changes in the FAME compositions of distillate over time was monitored. It
was observed that the ester compositions of the ten distillate samples were at the range of: about 60%–69% methyl palmitate, 19%–
29% of methyl oleate, 5%–7% of methyl linoleate, and 2%–3% of methyl stearate (Table S1). The first distillate sample contained the
highest fraction of methyl palmitate (68.60%) and the lowest fraction of methyl oleate (19.17%). Its content of methyl stearate and
linoleate were the lowest as well. However, in the subsequent samples, the fraction of methyl palmitate in distillate dropped gradually
while the composition of the other three esters in the distillate samples increased. Noticeably, the first four distillate samples had
relatively higher amounts of methyl palmitate, ranging from 66.21% to 68.60%. This dropped to 60.80% at the sixth sample when
the amount of distillate collected were the highest at (32.38±4.95) g (Fig. 3a). In this study, after the distillation, the total yield of
distillate obtained was 39.76% while the yield of bottom product (distilled biodiesel) was 59.62%. Align with this finding, the mass
balance of the vacuum distillation experiment is shown in Table S2.
Clearly, the yield of biodiesel after distillation is comparatively lower, but it is possible due to the small difference in boiling point.
At an absolute pressure of 1.33 kPa, which is close to the experimental operating pressure in this study, the difference between the
boiling points of methyl palmitate (light key) and oleate (heavy key) was 17 °C (Table 1) and this may greatly affect the distillation
performance. However, it is worth mentioning that a winterization process of removing 12.5wt% total saturated methyl esters from
soybean oil-based biodiesel took about one week time and only produced 25% total product yields, as reported by Dunn et al. (1996).
In contrast, in our study, 13.60wt% of total saturated methyl esters were removed in 170 min (including time taken to boil the
biodiesel) and the total product yield was found to be 59.62%, highlighting the potential of vacuum distillation in modifying the
compositions of esters, at the same time ensuring higher yield of biodiesel.

3.2. Cold flow properties

The CFP of biodiesel are generally accessed by the determination of CP, CFPP and PP (Sia et al., 2020). The CFP of the PFAD
biodiesel sample before and after the distillation were shown in Table 3. As shown in Table 3, prior to the distillation, the CP,
CFPP and PP of the PFAD biodiesel was 20 °C, 19 °C and 15 °C, respectively; whereas, after the distillation, the CP, CFPP and PP of
the PFAD biodiesel were found to reduce to 13 °C, 11 °C and 9 °C, respectively. The reduction was expected as a total of 15.44%
reduction of methyl palmitate (saturated ester) and a net increase of 11.32% of methyl oleate (unsaturated ester) was observed in
the distilled PFAD biodiesel sample (Table 2). With the removal of saturated ester and increment of degree of unsaturation in the
distilled PFAD biodiesel, the CFP would inevitably reduce, and this result is in good accordance to the results published by Elias et
al. (2016). Notably, the effectiveness of vacuum distillation designed in this study is found to be promising and comparable with
other techniques, considering the magnitude of CFP improvements are about the same. For example, it was reported that the CP and
CFPP of palm oil biodiesel was reduced from 18 °C and 16 °C to 11.33 °C and 8.67 °C, respectively after blending the palm oil methyl
ester-biodiesel with 30% of technical-grade of methyl oleate (Altaie et al., 2015). It can be noticed that the improvement of CP and
CFPP value of their study (∆CP = ∼7 °C, ∆CFPP = ∼8 °C) is about the same to our finding (∆CP = 7 °C, ∆CFPP = 8 °C), suggesting that
the vacuum distillation technique used in this study can be used as an alternative approach to improve CFP. On the other hand, Verma
et al. (2016) blend palm biodiesel with 20% of diesel and found that the CP and PP of palm biodiesel are improved from 21 °C and
19.7 °C to 8.9 °C and 6.2 °C, respectively. However, it is noteworthy that despite significant improvements, blending requires large
proportion of blending agent which is not environmentally friendly and economically feasible for the development of alternative fuel.
Another interesting finding is that the CFPP values improved the most among the three properties (∆CFPP = 8 °C). This could
be due to the increment of unsaturated esters, where it was reported that CFPP values are highly correlated to the contents of total
unsaturated esters (Park et al., 2008; Sarin et al., 2010). It is also remarkable that the improved CFPP satisfied the requirements
for grade C summer biodiesel for temperate climates in European Standard for Biodiesel (EN 14212 standard) (British Standards
Institution, 2014. BS EN 14214:2012+A1:2014 Liquid petroleum products—Fatty acid methyl esters (FAME) for use in diesel engines
and heating applications—Requirements and test methods: BSI Standards Limited 2014).
By using the designed vacuum distillation process reported in this study, improvement in cold flow properties of PFAD biodiesel
was observed, even though the difference in the boiling points of the light key and heavy key was less than 20 °C. With only 13.60%
removal of the total saturated FAMEs in the distilled PFAD biodiesel, the CFP of the PFAD biodiesel were improved by 6–8 °C after

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170 min of simple vacuum distillation (including boiling time for biodiesel). To further validate the obtained results, three empirical
correlation methods provided under Section 2.5, namely Sarin (PFAME ) method, Sarin (PFAME ) method and Su’s method were used
(Sarin et al., 2009; Sarin et al., 2010; Su et al., 2011).
In the case of pre-distillate PFAD biodiesel sample, it was found that Sarin (PFAME ) method was able to estimate the CP and PP
of the biodiesel sample with negligible temperature difference (∆T = 0.08–0.20 °C), but the CFPP value showed a ∆T of 2.62 °C. It is
important to point out that the amount of methyl palmitate of the sample was 47.36% (Table 2), which was slightly higher than the
upper boundary value (0 < PFAME ≤ 45wt%) given in Eqs. (2)–(4). Thus, the decision of implementing Sarin (PFAME ) method solely
based on the calculation on this sample remain doubtful. On the other hand, it was noticed that the Sarin (UFAME ) method was able to
predict CFP of the PFAD sample with less than 2 °C deviation. Whereas, the predicted values using Su’s method was found to exhibit
high temperature difference (∆T = 4.19–5.98 °C) which is the highest among the three methods.
For the post-distillation PFAD biodiesel sample, requirements for using both Sarin’s (PFAME ) (0 < PFAME ≤ 45wt%) and (UFAME )
(0 < UFAME ≤ 84wt%) correlation were satisfied. As shown in Table 3, it was found that the Sarin (UFAME ) method gave the lowest
temperature difference among the three methods. Noticeably, the CP value was estimated accurately with ∆T of 0.01 °C, but the
difference for CFPP and PP prediction was found to be slightly higher with ∆T of 1.38 °C and 1.74 °C, respectively. It is remarkable
that the predicted CFP of PFAD biodiesel sample were only deviated at less than 2 °C as compared to the experimental results. It
is important to point out that the temperature differences were comparatively lower than the errors predicted using Sarin (PFAME )
method. In short, it was found that the Sarin (UFAME ) correlation method allowed the best prediction of the CFP of PFAD biodiesel
samples in this work.

4. Conclusions

A simple vacuum distillation process was used to improve the cold flow properties of PFAD biodiesel. A total of 13.60wt% of
total saturated fatty acid methyl esters were separated from the biodiesel. As a result, the CP, CFPP and PP were reduced from 20
°C, 19 °C, and 15 °C to 13 °C, 11 °C, and 9 °C, respectively. Remarkably, the improved CFPP satisfied the requirements for grade C
summer biodiesel for temperate climates in EN 14212 standard. Among the three empirical correlations employed for the prediction
of biodiesel cold flow properties, Sarin (UFAME ) method was found to best predict the cold flow characteristics of PFAD biodiesel in
this work, with less than 2 °C deviation. Clear improvements were noticed by employing vacuum distillation as shown in this work
and can be considered as an alternative approach in industrial application. Nonetheless, simulation work shall be performed in the
future to validate the experimental results. Also, continuous mode of the vacuum distillation process should also be considered in
future studies as in general, the continuous flow mode of process could be more time-effective and productive. Additionally, due to
the complexity of sources to produce biodiesel, future studies are still needed to compare the effectiveness of vacuum distillation with
other conventional approaches like winterization and blending with diesel to improve the CFP of PFAD biodiesel and potentially the
combination of these technologies may offer novel prospect for the improvement of CFP in an efficient, economical and environment-
friendly manner.

Declaration of Competing Interest

The authors declare that there is no conflict of interest.

Acknowledgements

The study was supported by the Malaysian Ministry of Higher Education (No. FRGS/2/2014/TK06/CURTIN/02/1).

Supplementary materials

Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.jobab.2021.09.002.

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