Waste Management 26 (2006) 487494

www.elsevier.com/locate/wasman

Production of biodiesel from waste frying oils

Pedro Felizardo a, M. Joana Neiva Correia a,*, Idalina Raposo b, Joao F. Mendes c,
Rui Berkemeier d, Joao Moura Bordado a
a

Department of Chemical Engineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
b
Escola Secundaria Alfredo dos Reis Silveira, Torre da Marinha, Av. 25 de Abril, 2840 Seixal, Portugal
c
SPACE Eco-Combustveis. Rua 8 de Dezembro No. 494, 4760-016 Vila Nova de Famalicao, Portugal
d
Quercus Associacao Nacional Conservacao da Natureza, Apartado 4333, 1503-003 Lisboa, Portugal
Accepted 9 February 2005
Available online 17 June 2005

Abstract
Waste frying oils transesterication was studied with the purpose of achieving the best conditions for biodiesel production.
Transesterication reactions were carried out for 1 h using waste frying oils (WFOs), methanol, and sodium hydroxide as catalyst.
In order to determine the best conditions for biodiesel production, a series of experiments were carried out, using methanol/WFO
molar ratios between 3.6 and 5.4 and catalyst/WFO weight ratios between 0.2% and 1.0%. For oils with an acid value of 0.42 mg
KOH/g, results show that a methanol/WFO ratio of 4.8 and a catalyst/WFO ratio of 0.6% gives the highest yield of methyl esters.
Furthermore, an increase in the amount of methanol or catalyst quantity seems to simplify the separation/purication of the methyl
esters phase, as showed by a viscosity reduction and an increasing purity to values higher than 98% for methyl esters phase.
2005 Elsevier Ltd. All rights reserved.

1. Introduction
The increasing production of waste frying oils
(WFOs) from household and industrial sources is a
growing problem in Portugal and all around the world.
This residue is regularly poured down the drain, resulting in problems for wastewater treatment plants and energy loss, or is integrated into the food chain through
animal feeding, thus becoming a potential cause of human health problems (Costa Neto et al., 2000). There
are several end-uses for this waste, such as the production of soaps or of energy by anaerobic digestion, thermal cracking (Zaher, 2003), and more recently the
production of biodiesel, a fuel that can be used as a mineral diesel substitute for engines. The core process of the
biodiesel production consists in the transesterication of
the raw materials, vegetable oils and fats, using a short
*

Corresponding author. Tel.: +351 21 8417344; fax: +351 21

8499242.
E-mail address: qjnc@mail.ist.utl.pt (M.J. Neiva Correia).
0956-053X/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2005.02.025

chain alcohol. Vegetable oils and fats are mainly constituted by triglycerides with minor amounts of mono and
diglycerides (Fig. 1).
The transesterication reaction (Reaction 1) takes
place between a lipid and an alcohol to produce an ester
and a by-product, glycerol, also known as glycerine.
This reaction occurs stepwise, with mono and diglycerides as intermediate products (Ullmanns, 1992). The
fuel thus obtained performs in a similar way to fossil
fuel, with the advantage of reducing greenhouse emissions because it is a renewable resource (Mittelbach
and Tritthart, 1988; Leung, 2001; Al-Widyan et al.,
2002; Dorado et al., 2003; Tashtoush et al., 2003; Ulusoy et al., 2004).
Meher et al. (2004) published an excellent review of
biodiesel production processes by transesterication.
The use of several low molecular weight alcohols and
homogeneous acid and basic catalysts for transesterication has been studied in recent years with success
(Peterson et al., 1983; Schudardt et al., 1998; Khan,
2002; Knothe et al., 1997; Nye et al., 1983). Basic

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P. Felizardo et al. / Waste Management 26 (2006) 487494

H2C O COR1

H2C O COR1

H2C O COR1

H2C O R1

HC O COR2

HC O COR2

HC O R2
H2C O R3

HC OH
H2C OH

H2C OH

H2C O COR3

Monoglyceride

Diglyceride

Triglyceride

R1

HC

R2

H 2C

R3

R1

3 ROH

catalyst

COOR

R2

COOR

R3

COOR

H2 C

OH

HC

OH

H2 C

OH

Reaction 1. Transesterication reaction.

homogeneous catalysts have surpassed the acid ones,

because the reaction is faster (only 30 min compared
to 18 h for the acid catalysis) and lead to the same
yield of transesterication (above 90% for both) (Schudardt et al., 1998). However, for oils with a high concentration of free fatty acids (acid value higher than 2
mg KOH/g), a pre-treatment step is recommended.
This step consists in an acid catalyzed reaction with
an alcohol in order to transform the free fatty acids
into their corresponding esters. Good results concerning the reduction of the acid value were achieved even
with high initial percentages of free fatty acids (Canakci and Gerpen, 2001, 2003; Pereda Marn et al.,
2003). After this pre-treatment, glycerides in the oil/ester phase are transesteried with basic catalysis. Sodium and potassium hydroxides and sodium and
potassium methylates have been preferred as catalysts
due to high yields in the transesterication reaction.
The methylate salts are more reactive than the corresponding hydroxides, but are expensive, cause formation of various by-products and require high quality
oils and water-free methanol (Schudardt et al., 1998;
Meher et al., 2004). On the other hand, sodium and
potassium hydroxides react with the alcohol to give
water. This reaction is undesirable, because water can
react with triglycerides, fatty acids, or esters in hydrolysis reactions (Reaction 2) and subsequent saponication (Reaction 3) (Schudardt et al., 1998). However, in
spite of their lower reactivity, sodium and potassium
hydroxides can also lead to high reaction yields just
by increasing the catalyst quantities.
The production of biodiesel has been actively investigated in the past 20 years. Several studies concerning the
production of methyl esters from fresh vegetable oils
and fats (Freedman et al., 1984; Peterson and Scarrah,
1984; Knothe et al., 1997; Conneman and Fischer,

RCOOR1

H2O

RCOOH

Reaction 2. Hydrolysis reaction.

R1

COONa

R2

COONa

R3

COONa

H2C OH

HC OH
H2C OH

Reaction 3. Saponication reaction.

Fig. 1. Structures of mono-, di- and triglycerides, where R1, R2 and R3

represent the fatty acids chains.

H 2C

NaOH

R1OH

1998; Schudardt et al., 1998; Zhang et al., 2003a), as well

as low-cost raw materials such as used frying oils, soap
stocks and animal fats (Nye et al., 1983; Mittelbach
et al., 1992; Haas et al., 2000; Canakci and Gerpen,
2001; Al-Widyan and Al-Shyoukh, 2002; Gonzalez
Gomez, 2002; Tomasevic and Siler-Marinkovic, 2003;
Tashtoush et al., 2004), have been conducted. Enzymatic catalysts like lipases are also able to catalyze the
transesterication of triglycerides. According to the literature, this reaction overcomes some of the drawbacks
of chemical transesterication, namely the diculty of
recovering glycerol, as well as the incomplete conversion
of the free fatty acids contained in WFO into alkyl esters. However, the production costs of the catalyst are
signicantly greater than those of an alkaline one (Meher et al., 2004).
The recent concerns with sustainability, environment,
and raw material costs have made the use of waste frying
oils attractive to the industry, especially if stimulated
with economic benets associated with the use of blends
of biodiesel and fossil diesel (Zhang et al., 2003b). Vegetable oils used in industrial or household frying undergo degradation by hydrolytic and oxidative reactions,
both processes being responsible for changes in the
chemical and physical properties, as compared to the
fresh oil (Costa Neto et al., 2000). During frying, the viscosity and acidity of the oil increases, and the oil becomes darker and develops an unpleasant odour.
This work describes the optimum conditions for biodiesel production using waste frying oils as raw material
in the transesterication process.

2. Materials and methods

WFO were collected in school cafeterias and local
restaurants, and from local domestic consumers. The
numerous fractions were blended in order to obtain
two dierent types of waste oils. Methanol chromatographic grade (99.5%), sodium hydroxide commercial
grade, and dry magnesium sulphate (>99%) were supplied by Jose M. Vaz Pereira (Lisbon, Portugal). The
reference standards for gas chromatography (GC) were
obtained from SigmaAldrich (Lisbon, Portugal).
2.1. Pre-treatment of the frying oil
Homogenous samples of the two WFO that were prepared were dried over magnesium sulphate and subsequently ltered under vacuum to remove any

P. Felizardo et al. / Waste Management 26 (2006) 487494

Table 1
Fatty acid composition (mass%) of WFO
Fatty acid

Oil sample 1

Oil sample 2

C16:0
C18:0
C18:1
C18:2
C18:3
C20:0

8.65
4.70
30.60
55.10
0.30
0.65

8.29
4.02
27.25
57.62
2.28
0.55

suspended matter and magnesium sulphate crystals. The

treated oil samples (here referred to as oil samples 1 and
2) presented, respectively, a water content of 0.07% and
0.13% by weight, an acid value of 0.42 and 2.07 mg of
KOH/g of oil, and an iodine value of 116.9 and 130.5
(determined by Hannus method Portuguese Standard
NP 941, 1985). The fatty acid composition of both samples was obtained by GC (Table 1).

489

dard NP 903, 1998) and the water content by the

KarlFischer method (ISO 12937, 2000). Sodium was
determined by ame photometry (EN 241, 2000). The
concentration of methanol was evaluated by heating at
75 C a known mass of methyl esters until constant
weight was achieved. The ash point was determined
by the Pensky-Martens method (ISO 2719, 2002). The
methyl ester composition was obtained by gas chromatography using a Varian Star 3400CX Gas Chromatograph, with a DB-WAX 52 column from Supelco. The
temperature program was as follows: 140 C for 5
min, heating until 240 C at a rate of 4 C/min and holding at 240 C for 10 min. The injector was set up for 250
C, as well as the FID detector. Helium was used as carrier gas, at a pressure of 10 bar. Methyl heptadecanoate
was used as an internal standard (Portuguese Standard
NP EN ISO 5508, 1997). Finally, the sulphated ashes
were quantied according to ISO 3987 (1994).

2.2. Transesterication procedure

3. Results and discussion
A sample of 200 g of WFO (equivalent to 228.6 mmol
considering a molar mass of 874.8 g/mol) was transferred to a two-neck Woulf ask equipped with a thermometer and a reux condenser. A magnetic bar was
used for stirring. The oil was heated until the desired
temperature was reached (65 C). At this point, a mixture of methanol and sodium hydroxide was added to
the oil and the transesterication reaction began. The
reactor was kept at around 65 C for 1 h (Freedman
et al., 1984; Meher et al., 2004). The study was carried
out using a molar ratio of methanol/WFO which varied
from 3.6 to 5.4 and a catalyst quantity equivalent to 0.2
1.0 mass% of oil.
2.3. Purication of methyl esters phase
At the end of the reaction period (1 h), the glycerol
rich-phase was separated from the methyl ester layer
in a decantation funnel. The latter phase was washed
with water, with a 0.5% HCl solution and again with
water to provide a puried biodiesel. The washed methyl
esters were then dried over magnesium sulphate and ltered under vacuum.
2.4. Analyses
The puried methyl esters were evaluated in a series
of tests to determine if the biodiesel produced met the
European Standard EN 14214 (2003). Measurements
of the density at 15 C by the hydrometer method and
of the kinematic viscosity at 40 C were carried out
according to ISO 3675 (1998) and ISO 3104 (1994),
respectively. The iodine value was calculated from the
methyl esters composition (EN 14214, 2003), while the
acid value was obtained by titration (Portuguese Stan-

3.1. Eect of WFO properties on the transesterication

reaction
Freedman et al. (1984) have studied the inuence of
the free fatty acids (FFA) and water content in the production process of biodiesel. They have found that the
oil acid value should be less than 1 mg KOH/g and that
all raw materials should be anhydrous (water content
<0.3%). If these requirements are not met it is still possible to produce biodiesel, but the yield of the reaction is
reduced due to the deactivation of the catalyst and the
formation of soaps. Although high acid values may be
corrected by the addition of sodium hydroxide, this procedure results in the saponication of the free fatty
acids, thus aecting the yield in methyl esters, as well
as the glycerol separation (Freedman et al., 1984).
To determine the inuence of the oil acid value on the
production of biodiesel, six experiments were conducted
using WFOs with acid values of 0.42 and 2.07. The
experimental conditions are presented in Table 2, together with the calculated mass of methyl esters (MEs)
produced per 100 g of WFO (mME/100 g WFO) and
the purity of methyl esters phases (% ME).
In the rst two experiments, although the yield in
methyl esters is similar for both oil samples, the purity
of the samples is quite dierent. In all experiments, the
biodiesel produced from the WFO with the lower acid
value had a purity higher than the one obtained from
the more acidic frying oil, by as much as 14%. It was
also observed that those ME layers could be more easily
separated from the glycerol-rich phases than the ones
produced using the more acidic WFO. For the latter, a
pre-treatment step would be advisable in order to obtain
higher purities.

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P. Felizardo et al. / Waste Management 26 (2006) 487494

Table 2
Inuence of acid value in methyl esters phase yield and purity
Experiment

Acid value (mg KOH/g)

mNaOH/mWFO (%)

MeOH/WFO (mol/mol)

mME/100 g WFO

Purity (% ME)

1
2
3
4
5
6

0.42
2.07
0.42
2.07
0.42
2.07

1.0
1.0
0.2
0.2
1.0
1.0

3.6
3.6
5.4
5.4
5.4
5.4

80.4
80.9
92.7
86.8
87.0
80.2

95.3
80.6
83.9
70.8
99.3
84.9

3.2. Eect of methanol/waste frying oil molar ratio

The methanol/WFO ratio is one of the most important variables in methyl esters production. Nye et al.
(1983) achieved a fuel containing 74% of methyl esters
by reacting WFO and methanol (molar ratio of 1:3.6)
at 50 C, for 24 h in the presence of 0.4% potassium
hydroxide. Freedman et al. (1984) obtained a maximum
conversion (9899% of methyl esters) by transesterifying
rened oil with methanol, for 1 h at 60 C, using a molar
ratio methanol/oil of 6:1 with 1% potassium hydroxide
or 0.5% sodium methoxide. De Filippis et al. (1995)
and, more recently, Tomasevic and Siler-Marinkovic
(2003) have also achieved high purity fuels using the
same molar ratio of 6:1 for methanol/frying oils. As recognized by Tomasevic and Siler-Marinkovic (2003), it is
dicult to nd sucient information about the methanolysis reaction of used frying oils in the literature. To
our knowledge, no information is available on the optimal value of the methanol/WFO molar ratio to be used
for various NaOH/WFO mass ratios and vice versa
measured in terms of the yield and purity of the methyl
ester phase.
Fig. 2 shows that for the oil sample with an acid value
of 0.42 mg KOH/g, at constant mass ratio of catalyst/
WFO, the yield of the reactions (expressed as the mass
of methyl esters produced per 100 g of WFO after 1 h

100
m M E/100 g of WFO

95
90
85
80
75
70
65
60
3

3.6

4.2
4.8
5.4
Methanol/WFO (mol/mol)

Fig. 2. Inuence of the methanol/WFO molar ratio on the yield of

biodiesel production. Experimental conditions: acid value of the oil:
0.42; reaction time: 1 h; catalyst/WFO mass ratio: r, 0.2%; }, 0.4%;
m, 0.6%; j, 0.8%; n, 1.0%.

of reaction) increases directly with the excess of methanol. It was also observed that the increase of the methanol excess facilitates the separation of the glycerol
from the MEs phase.
From Fig. 2, it may be concluded that the best catalyst/WFO ratio is 0.6% because it allows the maximum
yield of methyl esters to be achieved. Furthermore, the
use of methanol/WFO ratios higher than 4.2 is not
advantageous in terms of the methyl esters yield. However, as presented in Section 3.5, using a higher value
may be of importance since this ratio inuences the extent of the reaction and, consequently, the biodiesel purity and its apparent viscosity.
3.3. Eect of sodium hydroxide/frying oil mass ratio
The amount of catalyst used in the process is another
variable to take into account, not only because it determines the reaction rate, but also because it can cause
hydrolysis and saponication. Both reactions interfere
with the separation of the glycerol rich phase and with
the methyl esters purication. Freedman et al. (1984)
recommended the use of 1% NaOH or 0.5% NaOCH3
as the optimal concentrations of catalyst. In recent work
(Tomasevic and Siler-Marinkovic, 2003), concentrations
of 0.5%, 1.0%, and 1.5% of KOH were studied and the
optimum value found was 1% of potassium hydroxide.
Since no further data on the optimal sodium hydroxide
concentrations are available in the literature, the results
obtained for 0.2%, 0.4%, 0.6%, 0.8%, and 1.0% NaOH/
WFO mass ratios are presented below.
As shown in Fig. 3, the reaction yields after 1 h of
reaction are maximized when the ratio of catalyst/
WFO ranges from 0.4% to 0.8%. The inuence of the
catalyst/WFO ratio seems to be less important when
the methanol/frying oil ratio is higher than 4.8. Therefore, it is possible to reduce the consumption of sodium
hydroxide without aecting the yield of methyl esters.
3.4. Determination of the optimal conditions for biodiesel
production
As shown in Figs. 2 and 3, for a WFO with an acidity
of 0.42 mg KOH/g WFO and for a reaction time of 1 h,
the optimal conditions to produce biodiesel are a methanol/WFO molar ratio higher than 4.2 and, depending

95
90
85
80
75
70
65
60
55
50
0.0%

491

6.5
Vi scosity (mm2/s)

m M E/ 100 g of WFO

P. Felizardo et al. / Waste Management 26 (2006) 487494

6
5.5
5
4.5
4
3.5

0.2%

0.4%

0.6%

0.8%

1.0%

NaOH/WFO (m/m)
Fig. 3. Inuence of the catalyst/WFO mass ratio on the yield of
biodiesel production. Experimental conditions: acid value of the oil:
0.42; reaction time: 1 h; methanol/WFO molar ratio: r, 3.6; }, 4.2; m,
4.8; n, 5.4.

on the alcohol excess, a NaOH/WFO mass ratio

between 0.4% and 0.8%. However, a molar ratio of 4.2
may cause diculties because the reaction yield is too
sensitive to catalyst concentration changes (Fig. 3).
Therefore, it is advisable to use a methanol/WFO ratio
of 4.8 or higher. On an industrial scale, this is not a
problem since methanol can be recovered from the glycerol and methyl esters phase. However, increasing the
consumption of methanol will inevitably increase its
recovery costs. Concerning the catalyst mass ratio,
Fig. 2 clearly shows that 0.6% is the optimal value because it gives the higher yields. It is important to emphasize that these optimal values would correspond to
methanol and catalyst consumptions lower than the
ones cited in the literature (Freedman et al., 1984; Tomasevic and Siler-Marinkovic, 2003).
3.5. Characterization of biodiesel
To determine if the biodiesel produced under the different experimental conditions met the specications of
the standard EN 14214 (2003), several samples of biodiesel were submitted to a series of tests.
3.5.1. Density at 15 C
The standard for biodiesel states that the fuel should
have a density between 0.860 and 0.900 g/cm3. This
property is important mainly in airless combustion systems because it inuences the eciency of atomization
of the fuel (Ryan et al., 1984). The results obtained
showed that for all the conditions studied, the biodiesel
produced in this study had a density in the range of
0.8640.900 g/cm3.
3.5.2. Kinematic viscosity at 40 C
Even more than density, this is an important property
regarding fuel atomization, as well as fuel distribution.
For biodiesel to be used in diesel engines, the kinematic
viscosity must be between 3.5 and 5.0 mm2/s. The kine-

0.0%

0.2%

0.4%
0.6%
0.8%
NaOH/WFO (m/m)

1.0%

Fig. 4. Inuence of the biodiesel production conditions on the

apparent fuel viscosity. Experimental conditions: acid value of the
oil: 0.42; reaction time: 1 h; methanol/WFO molar ratio: r, 3.6; }, 4.2;
m, 4.8; n, 5.4. The broken line (5 mm2/s) indicates the maximum value
for viscosity (EN 14214, 2003).

matic viscosity of the biodiesel samples produced in this

work ranged from 4.1 to 6.3 mm2/s. It is worth noting
that the extent of the reaction, as well as the experimental conditions used in biodiesel production, greatly inuence the fuel properties and especially its apparent
viscosity (the same is to say, the viscosity of the methyl
esters phase after washing). Indeed, this quantity decreases when the methanol/WFO or the NaOH/WFO
ratios are increased, as shown in Fig. 4.
Dierent viscosities are due to the incomplete reaction
of the frying oils or to the inecient biodiesel purication, leaving conjugated or free glycerin in the methyl
esters phase. In fact, the presence of glycerides changes
the apparent viscosity of the methyl esters, revealing
the extent of the transesterication reaction and the
methyl esters phase purity (De Filippis et al., 1995).
As mentioned before, waste frying oils dier from
fresh oils mainly due to oxidation and polymerization
of triglycerides. Since a heat-up stage is carried out in the
pre-treatment step, further polymerization can occur,
raising the viscosity of the raw material even further.
To prevent polymerization and the consequent viscosity
increase, minor quantities of radical quenching agents or
antioxidants can be used. Addition of several inhibiting
polymerization reagents to the frying oil is currently
under research in order to determine their inuence.
3.5.3. Iodine value
The iodine value is an important measure that allows
determination of the unsaturation degree of the fuel.
This property greatly inuences fuel oxidation and the
type of aging products and deposits formed in diesel engines injectors. According to EN 14214 (2003), methyl
esters used as diesel fuel must have an iodine value below 120 g I2 per 100 g of sample.
Analyses of several samples of the produced biodiesel
revealed iodine values between 123 and 130. These high
values were expected since most of the frying oils used in

P. Felizardo et al. / Waste Management 26 (2006) 487494

Portugal are derived from sunower seeds and are characterized by iodine values between 120 and 140. Furthermore, the iodine value rises during the later stages
of oil degradation and especially if the oil is exposed
to temperatures higher than 180 C, due to elimination
reactions of the oxidized triglyceride molecules. Supple
et al. (2002) reported that during frying the formation
of C18:2 and C18:3 were enhanced.
Methods to lower the iodine value of biodiesel by
using reducing agents before transesterication are currently under research at Instituto Superior Tecnico.
Some preliminary results are encouraging as they show
the feasibility of producing biodiesel with an iodine value lower than 120, even when the raw material is derived from sunower oils.
3.5.4. Acid value
The acid value measures the content of free fatty
acids in biodiesel. Considering that the presence of free
fatty acids inuences fuel aging, the European Standard
species a maximum value of 0.5 mg of KOH/g of sample. The maximum acid value found for the biodiesel
produced in this work was 0.47, although for about
80% of the samples analyzed, this parameter ranged
0.150.25, which is well below the required value.
3.5.5. Water content
Fuel contaminated with water can cause engine corrosion or react with the glycerides to produce soaps
and glycerine. Therefore, EN 14214 (2003) imposes a
maximum content of 0.05% of water in fuels. In this
study, the produced biodiesels were routinely dried over
anhydrous magnesium sulphate. This technique,
although used in laboratory practice, is not very ecient
and the water content in several samples of the biodiesel
was consequently high, ranging from 0.08% to 0.21%.
On an industrial scale, dewatering is usually carried
out by distillation under vacuum (0.05 bar) at temperatures of 3040 C. Accordingly, two samples were also
distilled, in a bench-scale batch column, under similar
operating conditions. The water content in the biodiesel
samples was thus reduced from 0.12% and 0.21% to
0.02% and 0.04%, respectively.
3.5.6. Sodium content
Because the presence of high amounts of sodium in
biodiesel induces metal corrosion as well as saponication of the methyl esters phase, EN 14214 (2003) species a maximum value of 5 mg/kg. It is well known that
the content of sodium in biodiesel is mainly determined
by the eciency of the washing step. The sodium content of several biodiesel samples produced in this work
was in the range of 2.35.3 mg/kg of fuel and only two
productions were out of specication. These results indicate that the washing procedure used was ecient in sodium removal.

3.5.7. Purity of the methyl esters phase

According to EN 14214 (2003), the minimum
acceptable purity for biodiesel is 96.5% in methyl
esters. To evaluate the conformity of the biodiesel produced in this study to the European norm, all samples
were analyzed by GC. As shown in Fig. 5, the inuence
of the NaOH/WFO ratio on the biodiesel purity is signicant, especially up to 0.6%. The eect of the molar
ratio of methanol/WFO is also clearly illustrated in the
same gure.
It is therefore possible to conclude that the biodiesel
purity increases when the alcohol/WFO and catalyst/
WFO ratios are augmented up to 4.8% and 0.6%, respectively. The increase of the purity is the net result of an
ecient removal of glycerol and sucient reaction extent. It is worth noting that the acceptable EN 14214 purity could be achieved with consumptions of methanol
and catalyst lower than the ones cited in the literature
(Freedman et al., 1984; Tomasevic and Siler-Marinkovic,
2003).
3.5.8. Methanol content
Methanol is another possible contaminant of the
methyl esters phase responsible for metal corrosion, particularly of aluminium, and for the decreasing of the fuel
ash point. EN 14214 (2003) species a maximum content of 0.2% of methanol in biodiesel. The alcohol is easily removed from the esters phase during the washing
step, and in the laboratory biodiesel the methanol content varied from 0.02% to 0.11%. Even for the less pure
samples (<80% ME), the methanol content was within
the specications.
3.5.9. Flash point
EN 14214 (2003) species that biodiesel must have a
ash point higher than 120 C. In order to determine
how the methanol content inuences the fuel ash point,
this property was determined for some of the samples.

100
95

Purity (%)

492

90
85
80
75
70
0.0%

0.2%

0.4%

0.6%

0.8%

1.0%

NaOH/Frying Oil Ratio

Fig. 5. Inuence of the biodiesel production conditions in the methyl
esters purity. Experimental conditions: acid value of the oil: 0.42;
reaction time: 1 h; methanol/WFO molar ratio: r, 3.6; }, 4.2; m, 4.8;
n, 5.4; the broken line (96.5%) indicates the minimum methyl esters
purity (EN 14214, 2003).

P. Felizardo et al. / Waste Management 26 (2006) 487494

493

The results show that the samples of biodiesel containing less than 0.1% of methanol had a ash point from
160 to 170 C. However, for samples with a 0.5% methanol content, the measured ash points (98110 C)
were below the minimum acceptable value. It is, therefore, worth noting that an increase of only 0.5% in the
methanol content leads to a 50 C decrease of the biodiesel ash point.

Fig. 6 shows that, although the correlation coecient

of the simple linear equation tted to the experimental
data is lower than the one obtained by De Filippis et al.
(R2 = 0.998), it still allows a meaningful estimation of
the degree of transesterication. Taking into account
that the used frying oils had dierent properties, the proposed correlation can be considered of signicant value.

3.5.10. Sulphated ash

EN 14214 (2003) establishes a maximum value of
0.02% for sulphated ash. This property is important
since high values are generally associated with cocking
of injectors and fuel lters clogging. The values obtained
for the several productions were between 0.002% and
0.006%, meeting the fuel specications.

4. Conclusions

3.6. Correlation between viscosity of biodiesel and purity

of methyl esters phase
The content of methyl esters produced in the transesterication reaction is a variable of the utmost importance in the industrial production of biodiesel. De
Filippis et al. (1995) have established a fast analytical
method to determine the methyl esters phase purity, just
by making a single viscosity measurement at 40 C.
According to these authors, the mass fraction of methyl
esters in the biodiesel phase can be correlated with viscosity by
w a ln m b;

Puri ty (% ME)

where w represents the mass fraction of methyl esters, m

(mm2/s) is the measured viscosity and a and b are constants, which depend on the type of oil and temperature.
The method proposed by De Filippis et al. (1995) was
used in the present work and Fig. 6 presents the correlation established between the methyl ester layer purity
and its measured viscosity. The points presented in
Fig. 6 correspond to the results obtained in several biodiesel production experiments using the WFO with acid
values of 0.42 and 2.07.
100
95
90
85
80
75
70
65
60

y = -45.055x + 162.85
R 2 = 0.9268

1.3

1.5

1.7

1.9

Ln ( )
Fig. 6. Plot of methyl esters purity vs. ln m. Experimental data, r;
linear regression, ; slope, 45.055; interception, 162.85;
R2 = 0.9268.

The production of biodiesel from used frying oils is

feasible by basic catalyzed transesterication and the
biodiesel produced has the quality required to be a diesel
substitute. The results show that after 1 h of reaction, a
methanol/waste frying oil ratio of 4.8 and a catalyst/
waste frying oil weight ratio of 0.6% give the highest
yield of methyl esters and allow an ecient separation/
purication of the methyl esters phase, as shown by
the viscosity reduction and increased purity of this layer.
Further studies will be developed to produce biodiesel
on a pilot scale to meet the specications of EN 14214.
These studies are to be carried out in a full-automated
machine and concern the optimization of the production
of biodiesel on an industrial scale.

Acknowledgement
Thanks are due to Professor Maria de Fatima Farelo
(Instituto Superior Tecnico, Lisboa) for her help in
revising the manuscript.

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