Fuel 87 (2008) 3490–3496

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Fuel
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Biodiesel production from waste cooking oils

Anh N. Phan a,*, Tan M. Phan b
a
School of Chemical Engineering and Advanced Materials, Newcastle University, NE1 7RU, UK
b
Department of Science and Technology, HCMC, Viet Nam

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

Article history: Alkali-catalyzed transesterification of waste cooking oils, collected within Ho Chi Minh City, Vietnam,
Received 12 May 2008 with methanol was carried out in a laboratory scale reactor. The effects of methanol/waste cooking oils
Received in revised form 3 July 2008 ratio, potassium hydroxide concentration and temperature on the biodiesel conversion were investi-
Accepted 8 July 2008
gated. Biodiesel yield of 88–90% was obtained at the methanol/oil ratios of 7:1–8:1, temperatures of
Available online 15 August 2008
30–50 °C and 0.75 wt% KOH. Biodiesel and its blends with diesel were characterized for their physical
properties referring to a substitute for diesel fuel. The results showed that the biodiesel experienced a
Keywords:
higher but much narrower boiling range than conventional diesel. Carbon residue content was up to
Transesterification
Biodiesel
4 wt%. Blends with a percentage of the biodiesel below 30 vol% had their physical properties within
Waste cooking oil EN14214 standard, which indicated that these could be used in engines without a major modification.
Boiling range Crown Copyright Ó 2008 Published by Elsevier Ltd. All rights reserved.
Carbon residue

1. Introduction papers cited relating to biodiesel production from vegetable oils

Increasing concerns regarding environmental impacts, the soar-
ing price of petroleum products together with the depletion of fos-
sil fuels have prompted considerable research to identify
alternative fuel sources. Biofuel has recently attracted huge atten-
tion in different countries all over the world because of its renew-
ability, better gas emissions and its biodegradability. It is estimated
that biodiesel/bio-ethanol could replace approximately 10% of die-
sel fuel consumption within Europe and 5% of Southeast Asia’s to-
tal fuel demand.
Biodiesel is superior to conventional diesel in terms of its sul-
phur content, aromatic content and flash point. It is essentially sul-
phur free and non-aromatic while conventional diesel can contain
up to 500 ppm SO2 and 20–40 wt% aromatic compounds. These
advantages could be a key solution to reduce the problem of urban
pollution since transport sector is an important contributor of the
total gas emissions. Amongst vehicle fuels, diesel is dominant for
black smoke particulate together with SO2 emissions and contrib-
utes to a one third of the total transport generated greenhouse gas
emissions [31]. According to Utlu and Kocak [42], there was on
average of a decrease of 14% for CO2, 17.1% for CO and 22.5% for
smoke density when using biodiesel.
Biodiesel production from vegetable oils has been extensively
studied in recent literature reviews. There were more than 50
* Corresponding author. Tel.: +44 (0) 191 222 5747; fax: +44 (0) 191 222 5292.
E-mail address: a.n.phan@ncl.ac.uk (A.N. Phan).
in the Fukuda et al.’s work [17]. Many researchers have reported
the biodiesel production in several ways: (a) the effect of operating
parameters [3,15,16,29,36]; (b) the effect of the type of catalysts
such as enzyme catalysts [17,20,32,33,38], heterogeneous catalysts
[21,39] and acidic catalysts [4,28]. However, the raw material costs
and limited availability of vegetable oil feedstocks are always crit-
ical issues for the biodiesel production. The high cost of vegetable
oils, which could be up to 75% of the total manufacturing cost, has
led to the production costs of biodiesel becoming approximately
1.5 times higher than that for diesel [30,44].
Nevertheless, the price of waste cooking oils (WCO) is 2–3 times
cheaper than virgin vegetable oils. Consequently, the total manu-
facturing cost of biodiesel can be significantly reduced [44]. In addi-
tion, a similarity in the quality of biodiesel derived from WCO and
from vegetable oils could be achieved at an optimum operating
condition [6]. Increasing food consumption has increased the pro-
duction of a large amount of waste cooking oils/fats. It was,
for example, 4.5–11.3 million litres a year in USA or 4  105–6 
105 ton/year in Japan [34]. The conversion of this amount of WCO
into fuel also eliminates the environmental impacts caused by the
harmful disposal of these waste oils, such as into drains [41]. Bio-
diesel from WCO (or used frying oils) has been recently investigated
[6,11–13,18,24,27,37,41,45].
However, the optimum conditions for biodiesel production
(methanol/oils ratio and concentration of catalyst) are inconsis-
tent. They strongly depend on the properties of WCO. Dorado
et al. [10] found that the ester yield reached 90% at the
methanol/oil ratio of 3.48:1 and 1.26 wt% KOH; while Encinar et

0016-2361/$ - see front matter Crown Copyright Ó 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.07.008
 A.N. Phan, T.M. Phan / Fuel 87 (2008) 3490–3496 3491

al. [11] revealed that the best results obtained at the molar ratio of Table 2
6:1 and 1 wt% KOH. According Zhang et al. [44], only refined/crude Quantitative of fatty acids in WCO samples

oils have acid value less than 1 could be used in an alkali-catalyzed Component g/100 g total fatty acid methyl ester
process. A pre-treatment step was required for oils having acid va- Sample 1 Sample 2 Sample 3 Sample 4
lue higher than 2 [13]. Nevertheless, some authors had also carried
C6:0 0 0.88 1.31 1.02
out successfully the alkali-catalyzed transesterification of WCO C8:0 8.82 6.64 9.98 8.90
having an acid value up to 4.91 mg KOH/g [40]. C10:0 6.21 5.38 7.32 6.51
Numerous research projects on the utilization of biodiesel as C12:0 44.65 42.30 49.59 46.96
well as its blends in engines have been done [13,23,26]. However, C14:0 16.31 16.77 16.28 17.45
C15:0 0.00 0.00 0.00 0.00
most of these were focused on short-term tests on different types
C16:0 10.59 11.59 7.34 8.78
of direct injection engines in terms of gas emissions (CO, CO2, NOx, C16:1 0.00 0.24 0.00 0.00
un-burnt hydrocarbons etc.) and engine performances (power out- C17:0 0.00 0.00 0.00 0.00
put, specific fuel consumption). A suggested proportion of biodie- C18:0 3.29 4.16 2.01 2.54
C18:1 8.17 9.97 4.83 6.00
sel in a blend used in engines, therefore, varied and could be up
C18:2 1.96 1.82 1.34 1.69
to 50 vol% [2,26]. Most of the research has not taken into account C18:3 0.00 0.03 0.00 0.05
carbon deposit formation when fuelled with biodiesel. Carraretto C20:0 0.00 0.11 0.00 0.06
et al. [5] have recently suggested that the most viable option for C20:1 0.00 0.11 0.00 0.04
biodiesel is in boilers with a minor modification of nozzles and gas-
kets that give a comparable efficiency and less fouling.
Alkali catalysts used in transesterification can be potassium These WCO samples had 10–15 times higher viscosity than die-
hydroxide, sodium hydroxide or alkali methoxides. However, sel oil. They are composed mainly of saturated short length fatty
potassium hydroxide was considered as a best catalyst for transe- acid alkyl chains, which was 42–50 wt% of C12:0, 17 wt% C14:0,
sterification of used frying oils [11]. In this study, the transesterifi- 10 wt% C16:0 and less than 10 wt% of unsaturated compounds (Ta-
cation of WCO was carried out for a reaction temperature of up to ble 2). Methanol and KOH used were obtained from Aldrich Com-
70 °C. The molar ratio of methanol/WCO ranged from 5:1 to 12:1 in pany Ltd. Diesel was taken from commercial diesel (No. 2) with
the presence of KOH catalyst concentration varying from 0.5 wt% of their characteristics listed in Table 1. The WCO samples were
oil to 1.5 wt% of the WCO. The physical properties of biodiesel and mixed together prior to the transesterification.
its blends were characterized for distillation curve, carbon residue,
cloud and pour points, viscosity, density, calorific value and acid 2.2. Transesterification
value.
The transesterification was carried out in a 500 ml three-neck
2. Experiments glass flask connecting with a reflux condenser using tap water to
condense methanol vapour and a thermocouple probe. The mix-
2.1. Materials ture was agitated by using a stainless steel stirrer comprising of
a turbine. The reactor was placed in a heated water bath. KOH pel-
WCO samples were collected from restaurants and shops within lets were dissolved in methanol before being poured in the reactor
Ho Chi Minh City, Vietnam with 5–10 l each and filtered to remove containing about 200 g WCO heated up to a desired temperature,
inorganic residues. The WCO samples were obtained from different which was 30 °C, 50 °C or 70 °C.
ways: (a) collecting after being used several times for frying pur- The reaction was kept at a desired temperature for 20 min,
poses at small shops; (b) taking after being used once for big res- 40 min, 60 min, 90 min or 120 min. The molar ratio of methanol
taurants. The characteristics of the WCO samples are illustrated and WCO varied from 5:1 to 12:1 while the amount of KOH cata-
in Tables 1 and 2. lyst was ranging from 0.5 wt% to 1.5 wt% of the WCO.
Acid values of the samples varied from 0.67 to 3.64 mg KOH/g. After a certain time, the mixture was poured into a separating
The acid value was relatively low in the sample 4, where it was funnel. The ester layer was separated by gravity and located in
used once. The low level of free fatty acid content in the WCO sam- the upper layer. The glycerol, extra methanol and undesired prod-
ples could be an advantageous for an alkali catalyzed transesterifi- ucts were in the lower layer and were decanted. The ester layer
cation process. The samples had saponification values ranging from was washed several times with a small amount of hot water each
264 to 272 mg KOH/g oil. Considering the composition of the sam- until the washings were neutral. The ester layer was then dried
ples, the WCO molecular weights can be calculated between 670.1 over sodium sulphate and filtered. The conversation of biodiesel
and 694.3 g/mol. This value was much lower than WCO from other was determined as follows:
research, which had molecular weight ranging from 866 to 873.4 mester
Conversion ð%Þ ¼ moil  100;
g/mol [6,11]. 3  MW MWester
oil

Table 1
Physical properties of WCO samples and diesel

Quality Unit Sample 1 Sample 2 Sample 3 Sample 4 Diesel

Acid number mg KOH/g 2.36 1.80 3.64 0.67 0.11
Iodine number mg KOH/g 13.20 12.69 8.57 9.45 –
Saponification number mg KOH/g 268.22 264.10 272.00 270.60 –
Density g/cm3 0.92 0.92 0.92 0.92 0.83
Flash point °C 269 276 243 298 69
Cloud point °C 21.00 15.00 16.50 25.00 0
Pour point °C 18.00 13.00 14.00 18.50 <12
Viscosity @40 °C mm2/s 30.05 33.47 27.42 31.77 3.53
3492
where mester: weight of ester collected (g); moil: weight of the oil
sample (g); MWoil: averaged molecular weight of oil sample.
X for the last 60 min. The difference in the conversion was less than
MWoil ¼ 3  ðMWi  %mi Þ þ 38;
i
MWi: molecular weight of fatty acid i; %mi: percentage of fatty acid i
in the raw material. MWester: averaged molecular weight of fatty
acid ester.
X fere with the separation of ester product and by-products by
MWester ¼ ðMWi  %mi Þ þ 14:
i
2.3. Analysis
Fatty acid quantitative was determined by using a Hitachi
G-5000A GC (column length: 30 m; diameter: 0.25 mm, film thick-
ness: 0.25 lm). The physical properties of the raw samples, biodie-
sel and its blends with diesel were measured by using ASTM
standard methods, including density (D1298), kinetic viscosity
(D445), flash point (D93), cloud point (D2500), pour point (D97),
distillation curve (D86) and carbon residue (D189), calorific value
(D240) and acid value (D664).
3. Results and discussion
3.1. Transesterification of WCO with methanol
3.1.1. Effect of ratio of methanol to WCO
The methanol/oil ratio is one of the most important factors
affecting the yield of biodiesel. Although stoichiometric ratio re-
quires 3:1, the transesterification is commonly carried out with
an extra amount of alcohol in order to shift the equilibrium to
the proposed product, methyl ester. According to Centikaya and
Karaosmanoglu [6], for example, transesterification is insufficient
at the ratios of methanol/oils below 5:1. Furthermore, the metha-
nol/oil ratio is associated with operating parameters such as the
type of catalyst used and the quality of oils. The optimum ratio
of methanol/used frying oils was, for instance, 4.8 in the presence
of sodium hydroxide [13]; while it could be up to 250 in the pres-
ence of acidic catalysts [45].
Shown in Fig. 1 is the effect of the methanol/oil ratio on the con-
version of biodiesel at a temperature of 30 °C in the presence of
0.75 wt% KOH. The conversion reached a value of above 50% in just
20 min. Increasing the ratio from 5:1 to 8:1 increased the conver-
sion. It rose from 50% for the ratio of 5:1 to 64% for the ratio of 8:1.
100
90
Conversion (%wt)
80
70
60
50
40
0 20 40 60 80 100
Time (min)
Fig. 1. Effect methanol/WCO ratio on the conversion of biodiesel at a temperature
of 30 °C and 0.75 wt% KOH.
A.N. Phan, T.M. Phan / Fuel 87 (2008) 3490–3496
The difference in the conversion between the ratios of 5:1 and 8:1
was about 24% in the first 60 min and slightly decreased to 13–16%
2% when the methanol/WCO ratio increased from 8:1 to 9:1.
A further increase in the methanol/WCO ratio above 9:1 caused
a reduction in the conversion. It was 82% for the ratio of 12:1 com-
pared to 88% for the ratio of 8:1 after 80 min as illustrated in Fig. 1.
The reduction could be because the excess of methanol could inter-
increasing solubility of glycerol. Consequently, part of the diluted
glycerol remained in the ester phase, leading to foam formation
and therefore apparent lost ester product. In addition, the excess
of methanol could also drive the combination of ester product
and glycerol into mon-glycerides [11]. This indicated that the opti-
mum molar ratio of methanol/WCO was 7:1–8:1, giving a biodiesel
yield of approximately 88–90% after 80 min. The optimum ratio in
this study was in accordance with that obtained from other inves-
tigators [1].
Increasing the ratio also enhanced a settling process. The set-
tling time took hours for the molar ratios below 7:1 while it was
only approximately 30 min for the ratios of 7:1 and 8:1. The ester
layer isolated in the cases of 7:1 and 8:1 was yellowish and trans-
parent while it was translucent for the other cases. This indicated
that there was a certain amount of un-reacted glycerides diluted
in the ester phase at the ratios below 7:1.
3.1.2. Effect of concentration of catalyst
Felizardo et al. [13] revealed that the optimum concentration of
sodium hydroxide was 0.6 wt%. This value was much lower than
the finding of Georgogianni et al. [18]. Leung et al. [25] also studied
the effect of NaOH concentration on biodiesel derived from neat
Canola and used frying oil. The results showed that the optimum
value of NaOH concentration for neat Canola oil and used frying
oil was 1.0 wt% and 1.1 wt%, respectively. It could be concluded
that the concentration of alkali catalyst is strongly dependent on
the type of oils used.
Considering data from literature reviews, the concentration of
KOH was tested in a range of 0.5–1.5 wt% of WCO. Fig. 2 shows
the effect of concentration of KOH on the conversion at the meth-
anol/WCO ratio of 8:1. Increasing KOH concentration from 0.5 wt%
to 0.75 wt% increased the conversion. It was 82% and 90% at
0.5 wt% KOH and 0.75 wt% KOH, respectively during 120 min.
However, the conversion reduced to 75% in the case of
1.5 wt% KOH. This could be explained by the fact that the forma-
100
90 0.75%
1.00%
0.50%
Conversion (%wt)
80 1.25%
1.50%
70
5:1
6:1 60
7:1
8:1
9:1
12:1 50
40
120 140 0 20 40 60 80 100 120 140
Time (min)
Fig. 2. Effect of KOH concentration on the conversion of biodiesel at the methanol/
WCO ratio of 8:1 and a temperature of 30 °C.
 A.N. Phan, T.M. Phan / Fuel 87 (2008) 3490–3496 3493

tion of soap hindered the separation of the methyl ester phase dur-
ing the washing step. The soap particles formed emulsions with
a
500
water, which resulted in increased viscosity. This phenomenon
Biodiesel
did not occur at low KOH concentrations. As a consequence, the Diesel
yields of biodiesel were low for the cases of 1 wt% and 400
1.5 wt% KOH.

Temperature(˚C)
The optimum concentration of KOH in this study was proximate
close to the finding of Felizardo et al. [13]. However, it was slightly 300

lower than that from other research [11,36,40]. This was due to the
lower free fatty acid content in the WCO samples. The higher free
200
fatty acid requires an addition of KOH to compensate for this
acidity.
100
3.1.3. Effect of temperature
Transesterification can occur at different temperatures, depend-
ing on the properties of oils. It could be at ambient temperature 0
[40]; or at a temperature close to the boiling temperature of meth- IBP 5 10 20 30 40 50 60 70 80 90 95 FBP

anol [13,43]. However, high reaction temperatures speed up the % Volume Recovery
reaction and shortens the reaction time [8,30]. Freedman et al.
[16] found that biodiesel yield depended on temperature in the
b
400
first 30 min reaction. It was, for example, 94%, 87% and 64% at
the temperatures of 60 °C, 45 °C and 32 °C, respectively.
Fig. 3 shows the effect of temperature on the conversion at the
methanol/oil ratio of 8:1 in the presence of 0.75 wt% KOH. Increas- 300

ing the temperatures from 30 °C to 50 °C, the conversion increased Temperature(˚C)

10–13%. However, if the temperature increased up to 70 °C, there
was a slight reduction in the conversion. This is because high tem- 200 B5
perature enhances both transesterification and saponification B10
B15
reactions. B20
B25
100 B30
3.2. Characteristics of biodiesel and its blends with diesel B50
B75
3.2.1. Distillation curve
A distillation curve is used to characterize the volatility of fuel 0
and its tendency to form soot and smoke and considered as an IBP 5 10 20 30 40 50 60 70 80 90 95 FBP
important indicator for long-term analysis of fuel performance %Volume Recovery
relating to optimization and design engines. It is essential for bio-
Fig. 4. Distillation curves for (a) biodiesel and diesel and (b) biodiesel blends with
diesel and its blends since biodiesel is oxygenated fuel which is the
diesel.
distinct difference to conventional diesel.
Shown in Fig. 4a, the initial boiling point of the biodiesel (IBP)
was 213 °C compared to 162 °C for diesel. A much narrower boiling which was an average of 10–12 °C/10 vol% recovery. This narrow
range but higher value could be observed in the case of the biodie- range can be explained as the biodiesel consists mainly of alkyl es-
sel than in the case of diesel. The boiling temperatures kept almost ters that have a little difference in the boiling temperature. The dif-
constant at a value of 330 °C from 20 vol% fraction to 70 vol% frac- ference in boiling points among pure fatty acid methyl esters was
tion while it increased steadily in the case of conventional diesel, approximately 20–30 °C. The distillation curve behaviour was sim-
ilar for the biodiesel obtained from this study to those obtained
from soybean oil and rapeseed oil, which had a 8–10 °C different
100 boiling range from 10 vol% to 90 vol% [19].
Considering biodiesel obtained from other types of WCO [1], the
90
boiling points at 10 vol%, 50 vol% in this study was 20–30 °C lower
but was slightly higher at the boiling point at 90 vol%. This was be-
cause of the difference in the chemical properties of the raw mate-
Conversion (%wt)

80
30˚C rials. The WCO samples used in this study consisted mainly of
50˚C saturated short alkyl chain fatty acids (C12 and C14) compared
70˚C
70 to other raw used frying oil samples being composed mainly of
oleic (53%) and linoleic (33%).
60 The final boiling point (FBP), in contrast, was much lower in the
biodiesel than in diesel. They were 348 °C and 387 °C for the bio-
diesel and for diesel, respectively. The lower FBP for the biodiesel
50
was because the double bond of unsaturated of alkyl chains could
be polymerised at high temperatures. This, therefore, hindered the
40 volatilization of liquid at the end of the distillation process, which
0 20 40 60 80 100 120 140
could lead to the formation of gums, carbon residue in the nozzles
Time (min) or on the surface of pistons causing corrosions.
Fig. 3. Effect of temperature on the conversion of biodiesel at 0.75 wt% KOH and the Smoke formation occurs mainly in the local fuel-rich zones
methanol/WCO ratio of 8:1. where pyrolysis of the fuel is going on in accordance with a com-
3494
plicated multi-stage mechanism of fractioning and decomposing of
fuel molecules with air. The low volatility of the biodiesel (high
boiling point range) could cause a poor atomisation, leading to a
potential formation of soot particles and a proportion of un-burnt
and/or partially burned droplets. These droplets could potentially
survive due to a poor mixing with air and therefore could impinge
on cylinder walls and pistons or be released during the exhaust
process. Knothe et al. [22] found that there was a greater varnish
and deposits on the pistons and also a greater level of high molec-
ular weight organic compounds absorbing to particles when
fuelled with biodiesel than when fuelled with diesel. The high
10 vol% temperature of the biodiesel could also contribute to the
formation of billowing clouds of white smoke during premixed
combustion.
Blends of the biodiesel with diesel are designated as ‘‘B” fol-
lowed by a volumetric percentage of the biodiesel in the blend.
For example, B5 stands for the blend of 5 vol% biodiesel and
95 vol% diesel. Shown in Fig. 4b, the trend of distillation curves
of the blends was similar to that of diesel at a percentage of the
biodiesel below 50 vol%. The percentage of diesel had little influ-
ence on the IBP. The IBP was 170–172 °C for all the blends. How-
ever, the FBP decreased with increasing percentage of the
biodiesel. It was 368 °C for B5 while 354 °C for B75. As expected,
the mid-boiling point increased by increasing the proportion of
the biodiesel. They were, for instance, 304 °C, 328 °C and 334 °C
for B20, B50 and B75.
3.2.2. Carbon residue
Carbon residue is an important indicator to measure of the ten-
dency to form carbonaceous deposits in engines, which can cause
several operational problems such as blockage of nozzles, corro-
sion, cracking of components.
As shown in Fig. 5, the carbon residue content increased expo-
nentially with percentage of biodiesel. It was 0.15 wt%, 0.23 wt%,
0.27 wt% and 4.0 wt% for B10, B15, B20 and B100, respectively.
The relation between the carbon deposit (y) and percentage of
the biodiesel (x) in the blend could be described as follows by using
a 95% confidence limit:
y ¼ 0:1676  e0:0315x ;
with a correlation coefficient R = 0.9914.
The level of carbon residue content at a percentage of the bio-
diesel above 20 vol% was exceeding the current diesel specification
for carbon residue in the Petroleum Products Specifications Regu-
lations 2002 (PPSR), which is a maximum of 0.3 wt%. This is one
5 Although the amounts of free glyceride and total glyceride were
4 ity of the biodiesel, the calculated methyl ester content in this
Carbon residue (%wt)
3 again, this explained the formation of high carbon residue of the
2 much higher for the biodiesel than for conventional diesel. The
1
0
0 20 40 60
% Biodiesel
Fig. 5. Carbon residue (10% distillation residue).
A.N. Phan, T.M. Phan / Fuel 87 (2008) 3490–3496
of the disadvantages of biodiesel in considering it as a substitute
fuel for engines. For biodiesel, the carbon residue is an indicator
of not only the amount of the material left after vaporation and
pyrolysis but also the amount of glycerides (free glycerol, partially
reacted/un-reacted glycerides) and other residues remaining in the
biodiesel product (free fatty acids and catalyst residue). The free
glycerol and catalyst residue can be easily removed during the
washing step whereas the content of glycerides can be only con-
verted by using specific catalysts and reactions conditions or by
further distillation products. According to Fernando et al. [14],
increasing an amount of un-converted/partially converted glyce-
rides increased the amount of carbon residue. Therefore, the for-
mation of a high amount of residue could be due to the
polymerisation of unsaturated alkyl chains (approximately
10 wt%) and the degradation of glycerides and free fatty acid
remaining in the biodiesel at a high temperature. In addition, the
degradation of glycerides at high temperature can also act as a cat-
alyst for polymerisation of the unsaturated fatty acids [31].
Therefore, it is vital to have major modifications in engines
fuelled with 100% biodiesel in order to overcome operational prob-
lems as mentioned previously. Although not displayed in this
work, the 10 vol% distillation residues from B50, B75 and B100
were brownish and sticky compared to those from diesel and other
blends.
3.2.3. Other properties of biodiesel and its blends
As shown in Table 3, the properties of the biodiesel from WCO
in this study were in accordance with other investigators and with-
in EN 14214 standard. The biodiesel had a density of 0.88 g/ml and
was slightly higher than diesel, which is 0.83 g/ml.
Flash point strictly corresponds to the methanol content and
viscosity correlates with un-reacted triglycerides. According to
Felizardo et al. [13], the flash point could decrease 50 °C with
increasing only 0.5% of methanol content in the ester phase. The
flash point in this study was slightly lower than that from other re-
search [6,11] but much higher than biodiesel obtained from used
soybean oil and mixture frying oils [18]. The viscosity of the biodie-
sel in this study was 4.89 mm2/s, slightly lower than that from
other investigators [9,35]. Generally, the viscosity of the biodiesel
derived from WCO decreased 10 times compared to the original
WCO samples.
The properties of final product strongly depend on the yield of
methyl ester (purity of methyl ester phase). The presence of glyc-
eride types, in particular, in the fuel can cause serious problems
in commercial applications. According to EN 14214 biodiesel stan-
dard, there are strict limitations for both free and total glyceride
contents of biodiesel and the level of methyl ester content.
not measured, the purity of biodiesel can be determined by using
the viscosity measurement [7,13]. Regarding the measured viscos-
study was approximately 91–92%. This was slightly lower than
the minimum level of methyl ester content, which is 96.5%. Once
biodiesel mentioned in the previous section.
The flow properties, including cloud point and pour point, were
cloud and pour points were 3 °C and 0 °C for the biodiesel while
0 °C and <12 °C for conventional diesel. This indicates that the
biodiesel is less suitable in cold conditions. The cloud and pour
points of the biodiesel derived from WCO in this study are higher
than those from other research [10,18]. This is due to chemical
80 100 120 properties of the raw WCO samples, consisting of 90% saturated
fatty acid alkyl chains.
The acid value indicates the content of free fatty acid in biodie-
sel. The value found in this study was 0.43 mg KOH/g. Referring to
 A.N. Phan, T.M. Phan / Fuel 87 (2008) 3490–3496 3495

Table 3
Biodiesel characteristics

Quality EN 14214 Centinkaya et al. [6] Georgogianni et al. [16] Encinar et al. [10] This study
Density @15 °C, g/ml 0.86–0.90 0.8823–0.8874 0.857 0.826 0.890 (@25 °C) 0.88
Viscosity @40 °C, mm2/s 3.5–5.0 5.29–6.46 4.76 4.45 4.8 4.89
Cloud point, °C – 9 3 4 4.7 3
Pour point, °C – 3 4 5 3.9 0
Flash point, °C >101 176 67 83 177 120
Acid value, max, mg KOH/g 0.5 0.289 0.8 0.5 – 0.43
Water content, max, ppm 500 480.07 – – – Trace

Table 4
Physical properties of biodiesel blends with diesel

Quantity Unit Samples

B5 B10 B15 B20 B25 B30 B50 B75
Density g/ml 0.85 0.85 0.85 0.85 0.85 0.86 0.86 0.88
Viscosity @40 °C mm2/s 3.56 3.72 3.72 3.75 3.82 3.90 4.25 4.64
Cloud point °C 0 0 0 0 0 0 0 0
Pour point °C 12 11.5 9.5 9 8.5 8 6 4.5
Flash point °C 74 80.5 81 82 85 86 91 106.5
Calorific value kcal/kg 10,845 10,750 10,683 10,615 10,545 10,462 10,180 10,100
Water content wt% Trace Trace Trace Trace Trace Trace Trace Trace
Acid number mg KOH/g 0.11 0.12 0.13 0.16 0.20 0.23 0.32 0.35

EN14214 standard for bio-auto fuels, the biodiesel obtained from
this study was found to be within the limits in terms of density,
viscosity, flash point, acid value and water content.
As observed in Table 4, increasing the percentage of the biodie-
sel resulted in a reduction in calorific value but an increase in other
parameters such as acid number, viscosity and flash point. The
reduction in calorific value for the biodiesel and its blends com-
pared to diesel was due to the presence of oxygen in the biodiesel.
4. Conclusions
Although being collected from different sources, there was little
difference in properties among the WCO samples in terms of chem-
ical and physical properties. This could then assist the implementa-
tion of biodiesel production process from waste cooking oils. In this
study, biodiesel production from the WCO was carried out in the
laboratory scale reactor. The results showed that the highest yield
of biodiesel was obtained at the ratio of methanol/WCO of 7:1–
8:1 during 80–90 min at temperatures ranging 30–50 °C in the
presence of 0.75 wt% KOH. Although most of the physical properties
of the biodiesel were within standards for diesel fuel and for bio-
auto fuels (EN14214), the carbon residue was much higher in the
biodiesel than in diesel. The carbon residue was 4.0 wt% for the bio-
diesel but only 0.05 wt% for diesel. Furthermore, the volatility char-
acteristics of the biodiesel were much different to that of diesel as
clearly projected in the distillation curve. There was a very narrow
range of boiling temperature for biodiesel. The boiling temperature
remained approximately 330 °C from 20 vol% to 70 vol% fraction.
Mixing the biodiesel with diesel improved significantly the volatil-
ity and decreased the carbon deposits at a percentage of biodiesel in
the blends below 50 vol%. The results obtained showed that the
blend of 20 vol% the biodiesel and 80 vol% diesel (B20) could be ap-
plied in engines without major modification.
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