Chemical Engineering Journal 160 (2010) 473–479

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

Study of esterification and transesterification in biodiesel production from used

frying oils in a closed system
M. Berrios, M.A. Martín ∗ , A.F.Chica, A. Martín
Departamento de Química Inorgánica e Ingeniería Química, Universidad de Córdoba, Campus Universitario de Rabanales, Edificio Marie Curie, 14071 Córdoba Spain

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

Article history: Used frying oils are a good alternative for biodiesel production but their treatment is more complex than
Received 19 October 2009 fresh vegetable oils. Used frying oils contain a large amount of free fatty acids, so an esterification step is
Received in revised form 18 March 2010 necessary before transesterification. This reaction is usually carried out in batch reactors with pressure
Accepted 19 March 2010
and temperature conditions (ambient pressure and 60 ◦ C) where the esterification reaction acts as the
limiting step of the production. The aim of this work was to investigate the acidity removal and the
Keywords:
subsequent transesterification at different temperatures and mole ratios in a batch reactor in order to
Used frying oils
improve the biodiesel production from used frying oils.
Esterification
Transesterification
The influence of temperature was studied in order to know the kinetics of esterification. The reaction
Closed system rate increased when the temperature was increased. The experimental results were found to fit a first-
Kinetics order kinetic law for the forward reaction and a second-order for the reverse reaction.
Polar FAME The influence of temperature was found to be insignificant on the transesterification reaction. Nev-
ertheless, methanol/oil mole ratio influenced up to 6.0:1. The influence of upper mole ratios was
insignificant on the FAME content evolution.
Based on the experimental results, biodiesel from used frying oil did not fulfil all the specifications from
EN 14214 Standard due to the chemical modifications in the oil during cooking (presence of polar com-
pounds). Therefore, biodiesel was proposed for use in combustion processes or in blends with biodiesel
from other vegetable oils or even animal fats, which had not undergone chemical modifications.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction industrial scale, alkaline catalyst is the most used due to its suitable
operational conditions: low cost, easy to install and, above all, its
Liquid biofuels are a growing and interesting alternative to high reaction rate which provides a decrease in the equipment size
petrol–based fuel because of the economic, environmental and sup- and in immobilized capital.
ply problems of fossil fuels. Biodiesel, an alternative diesel fuel, is The main disadvantage of using biodiesel is the high cost of the
made from renewable biological sources such as vegetable oils and raw material, which leads to a very expensive final product in com-
animal fats. It is biodegradable and non-toxic, has low emission pro- parison with petrol-diesel. In recent years many studies have been
files and so is environmentally beneficial [1]. It is an advantageous carried out on biodiesel production from used frying oils [2–5] as
option for the substitution or reduction of fossil fuel consumption. well as the research of new vegetable species [6–9], all of them with
Biodiesel is defined, according to The American Society for Testing a view to overcoming the economic barrier.
and Materials (ASTM), as monoalkyl esters of long chain fatty acids In this sense, used frying oils are a good raw material because
(FAME) derived from a renewable lipid feedstock, such as vegetable of their low cost and the environmental advantage of the residue
oil or animal fat [2]. valorisation. Spain is a large vegetable oil consumer, mainly olive
The most common way to produce biodiesel is by transester- and sunflower oils; in addition, used frying oils do not undergo
ification, which refers to a catalyzed chemical reaction involving significant alterations and can be easily adapted as biofuel because
vegetable oil and alcohol to yield fatty acid alkyl esters (i.e. they are unlikely to be reused.
biodiesel) and glycerol as a by-product [2]. Methanol is the most Cooking is a dehydration process; it means that water and sol-
commonly used alcohol because of its low cost and its physical- uble compounds are transferred from fried food to oil. At the same
chemical advantages (polar compound and short chain alcohol). At time, fried products absorb a part of the surrounding oil. Edible oils
are constantly exposed to chemical reaction during cooking, due to
their composition and external influences. The reactions are led by
∗ Corresponding author. Tel.: +34 957218586; fax: +34 957218625. oxygen, light and heat. Three main reactions take place: oxidation,
E-mail address: [email protected] (M.A. Martín). polymerization and hydrolysis.

1385-8947/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2010.03.050
474 M. Berrios et al. / Chemical Engineering Journal 160 (2010) 473–479

Table 1
Chemical analysis of used frying oil and fatty acid profile (free and linked acids).

Test Results (wt.%) Test Results (wt.%)

Polar compounds: 20.90 Triglycerides content 73.58

• FFA 2.14 Moisture 0.43
• Diglycerides content 1.97 Ash content 0.16
• Monoglycerides content n/d
• Other polar compounds a 16.79
Fatty acid profile % Fatty acid profile %
C14:0 Tetradecanoic (myristic) 0.19 C20:0 Eicosanoic (arachidic) 0.55
C16:0 Hexadecanoic (palmitic) 10.26 C20:1 Eicosenoic (gadoleic) 0.14
C18:0 Octadecanoic (estearic) 3.85 C22:0 Docosanoic (behenic) 0.65
C18:1 Octadecenoic (oleic) 47.83 C22:1 Docosenoic (erucic) 0.01
C18:2 Octadecadienoic (linoleic) 36.10 C24:0 Tetracosanoic (lignoceric) 0.04
C18:3 Octadecatrienoic (linolenic) 0.38
a
Polimeric triglycerides and oxidized monomeric triglycerides

(a) Oxidation produces oil ageing due to contact with atmospheric directly used for biodiesel fuel production applying the commonly
oxygen. Oxidation is accelerated because of temperature and used alkaline transesterification procedure; free fatty acids have
light. Triglycerides, which are present in oil, are oxidizable to be esterified before the transesterification of triglycerides can
organic compounds. In fact, when the number of double bonds take place [18]. Canakci and Van Gerpen [19] recommend this pre-
rises, oxidation takes place easily. As well as degraded products, treatment since, if the FFA level exceeds 0.5 wt.%, saponification
oxidation produces hydroperoxides, aldehydes and ketones. will hinder the separation of the ester from glycerine and reduce
(b) Polymerization is a chemical reaction where unsaturated fatty the yield and formation rate of FAME due to alkaline catalyst con-
acids - due to the influence of heat, heavy metals (Cu, Fe) or sumption. This is the case of used frying oils. So an esterification
light and by means of the breakage of the double bond - reacts step is necessary before transesterification. This reaction is usually
to form dimers (molecule composed of two identical subunits carried out in batch reactors with pressure and temperature condi-
or monomers linked together) and polymers of triglycerides. As tions (ambient pressure and 60 ◦ C) where the esterification reaction
a consequence of polymerization, the oil molecular weight rises acts as the limiting step of the production. The aim of this work was
and the oil becomes more viscous. to investigate the acidity removal and the subsequent transesteri-
(c) Hydrolysis is led by water acquisition in the fried product and fication at different temperatures and mole ratios in a batch reactor
is supported by certain products deep-fried in batter. Free fatty in order to improve the biodiesel production from used frying
acids (FFAs) are generated because triglycerides are broken oils.
down. Moreover, when the water evaporates through the oil,
monoglycerides, diglycerides and FFAs are created. 2. Materials and methods

Thus, the new products formed during frying are polymers, The raw material utilized in this work was used frying oil
dimers, oxidized triglycerides (hydroperoxides, aldehydes and (mainly olive and sunflower oil) from the refuse collection of the
ketones), as well as diglycerides and fatty acids [10]. So used fry- company BIDA, S.A. (Fuentes de Andalucía, Spain), with an acid
ing oils are heterogeneous as compared to crude or refined oils. All value of 4.26 mg KOH·g−1 oil (FFA level of 2.14 wt.%). Table 1 shows
these groups possess higher polarity that the initial triglycerides the most important characteristics of this used frying oil.
and can be easily quantified by means of adsorption chromatogra- All the properties of the samples were analyzed according to
phy [10–11] to find out the total degradation of frying oils. the Standard Methods. The polar compound content (in used fry-
Regarding the transesterification, it is found that crude oils (95% ing oil, esterified oil and biodiesel) was determined by a method
of triglycerides + partial glycerides) would give more than 98 wt.% in accordance with Standard Method 2507–IUPAC [11]. The non-
of FAME in a complete conversion. However, in the case of used polar FAME content was determined by a method in accordance
frying oils, non–altered FAME depend on the variable quality of with EN 14103 Standard [20]. The water content was determined
the used frying oil [10]. At present, the determination of polar by the Karl Fisher method (ISO 12937 Standard) [21] and the acid
compounds can be applied in used frying oils and FAME obtained value was determined by titration with KOH in accordance with EN
in order to know the real composition in biodiesel. In addition, 14104 Standard [22]. The monoglyceride (MG), diglyceride (DG),
Ruiz–Méndez et al. [10] proposed to study how polar compounds triglyceride (TG) and free glycerol contents were determined by a
might interfere in the standard gas chromatographic determina- method in accordance with EN 14105 Standard [23]. Kinematic vis-
tions for evaluating the quality of biodiesel (EN 14103; EN 14105). cosity and density were determined in accordance with ISO 3104
Due to the chemical reactions, the physical and chemical proper- Standard [24] and ISO 3675 Standard [25] respectively. The iodine
ties of the oil change during cooking [12]. A great deal of research value was determined by a method in accordance with EN 14111
has been conducted to characterize these physical and chemical Standard [26].
changes [13–16]. As previously mentioned, the percentage of FFAs Due to the chemical composition of used frying oil (Table 1),
has been found to increase due to triglyceride hydrolysis in the non–polar and polar FAME (oxidized monomeric FAME, dimeric
presence of food moisture. For instance, the level of FFAs in fresh FAME, and oligomeric FAME) were present in the biodiesel
soybean oil went from 0.04 wt.% to 1.51 wt.% after 70 h of frying obtained.
at 190 ◦ C [12,16]. It was also observed that the acid value, specific The experimental set-up (Fig. 1) used for both esterification and
gravity and saponification value of the used frying oil increased, transesterification was a batch stirring reactor close to the atmo-
but the iodine value decreased. The peroxide value increased to a sphere. The device is composed of a stainless steel tank reactor
maximum and then started to decrease [17]. (1 L capacity) with pressure and liquid phase temperature displays,
The effectiveness of the alkaline transesterification process where the heating system consisted of a jacketed reactor through
depends on the quality of the vegetable oil used for transesterifi- which thermostated glycerol at the required temperature was cir-
cation. Oil, containing a large quantity of free fatty acids, cannot be culated. Moreover, the system was made up of magnetic agitation,
 M. Berrios et al. / Chemical Engineering Journal 160 (2010) 473–479 475

Fig. 2. Relation between temperature and manometric pressure in esterification

experiments.

ification tests were carried out at 600 rpm (fixed speed in previous
Fig. 1. Batch reactor experimental set-up. paper; [30]), H2 SO4 as acid catalyst at concentration of 5 wt.% (rel-
ative to total acidity as oleic acid), using a methanol/oleic acid
which made it possible to control the agitation speed at the desired mole ratio of 60:1 and different temperatures (60, 70, 80, 90 and
interval. During the tests, samples of 5 mL of liquid phase were 100 ◦ C). Fig. 2 depicts the relation between the temperature and
withdrawn by using a line equipped with a stopping valve, similar the obtained manometric pressure.
to other used by Tesser et al. [27]. The system was charged with all The reaction development was checked by the acid value deter-
the reactants and when the temperature was reached, the reaction mination by means of the titration with KOH solution in accordance
time started. with the EN 14104 Standard [22]. Samples were taken from the
In all the tests, 20% (0,2L) of the total volume was maintained reactor at several times and were then washed with deionised
as headspace in order to find out the methanol number of moles in water in order to stop the reaction, centrifuged and dried under
the gas phase at each temperature. Given that the vapour pressure vacuum conditions to remove the washing water.
of methanol at 80 ◦ C is 1.82 atm [28] and if the perfect gas equa- The used frying esterified oil, which has been utilized in the
tion is applied, the calculated methanol mole number would be transesterification reaction, contains 9.6 wt.% FAME from a previ-
0.0126. This value was less than 0.5% approx. of the total amount of ous esterification (0.34 wt.% FFA content).
methanol in the liquid phase. Therefore, the methanol was in liquid The transesterification conditions were taken from the back-
phase only at selected conditions. ground literature [3,32,33] and modified in order to study the
With the aim of finding out the consumed power when the num- influence of the temperature and excess methanol over the
ber of revolutions of the stirrer is changed, the Reynolds number reaction. Transesterification tests were carried out at several tem-
was calculated. For stirred tanks, the Reynolds number is calculated peratures (60, 70 and 80 ◦ C), a methanol/oil mole ratio of 4.5:1, 6.0:1
by the next expression: and 7.5:1, 600 rpm and an alkaline catalyst concentration (KOH) of
1.0 wt.%.
Ni · Di2 ·  The transesterification development has been checked by the
Rei = (1)
 determination of methyl esters content in a VARIAN 3900 GC by
a method in agreement with the EN 14103 Standard [20]. Sam-
where Rei is the Reynolds number, Ni the number of revolutions
ples were taken from the reactor at several intervals and were then
of the stirrer, Di the stirrer diameter, ␳ the fluid density and ␮ the
kept cold. The glycerol-phase was removed and the methyl ester-
fluid dynamic viscosity.
phase was washed with deionised water to remove impurities, then
For the used system, with the diameter of the stirrer at 2.5 cm,
centrifuged and dried under vacuum conditions.
the agitation speed 600 rpm, the fluid density 0.915 g·cm−3 and the
fluid dynamic viscosity 0.295 g·cm−1 ·s−1 , the Rei was 194. There-
fore, the flow was turbulent (Rei > 10). Actually, during the initial 3. Results and discussion
stage, the Reynolds number controller is the oil dynamic viscos-
ity and it grows as the fluid dynamic viscosity decreases so the 3.1. Esterification
turbulent flow increases with the FAME formation.
For systems in turbulent mode, the consumed power was cal- The elimination of FFAs relies on the well-known esterification
culated by Doran [29]: reaction:

P = N  p ·  · Ni3 · Di5 (2) R 1 -COOH + R 2 -OH  R 1 -COO-R 2 + H2 O

where N is a constant value of the power number in turbulent which is catalysed by acids. In this work, R1 was a linear chain of
mode. Given that the power increases with the revolutions number 13–23 carbon atoms containing a variable number of unsaturations
cube, it is justified to work with the minimum value of Ni to avoid depending on the particular origin of the raw material, and R2 was
the reaction control by matter transfer. a methyl radical.
In previous studies [2,30,31] similar esterification conditions This reaction is heterogeneous (methanol is non-soluble in
were reported but only over ambient pressure conditions. Ester- sunflower oil), so it requires agitation in order to avoid mass trans-
476 M. Berrios et al. / Chemical Engineering Journal 160 (2010) 473–479

were maintained because the esterification conditions (65 ◦ C and

2 h) were not very extreme.

3.1.1. Kinetic model

The kinetic model used in this work is based on the following
assumptions:

(a) The esterification reaction was a reversible heterogeneous pro-

cess during which the chemical reaction controlled the rate of
the operating conditions.
(b) The rate of the non-catalyzed reaction was negligible in com-
parison to the catalyzed reaction.
(c) The chemical reaction occurred in the oil phase.
(d) The methanol/oleic acid mole ratio used was high enough for
the methanol concentration to remain constant throughout the
process.

These assumptions were proved in previous research [30].

Fig. 3. Variation of the conversion of FFA to FAME at different temperatures (60, 70,
Under these conditions, the reaction was assumed to be
80, 90 and 100 ◦ C). Methanol/oleic acid mole ratio of 60:1, H2 SO4 concentration of
5 wt.% and agitation speed of 600 rpm.
pseudo-homogeneous, first-order in the forward direction and
second-order in the reverse direction, and hence conforming to the
following kinetic law:
Table 2
Characterization of esterified used frying oil. −d [A]
= k1 · [A] − k2 · [C] · [D] (3)
Test Results (wt.%) dt
Polar compounds: 25.20 where [A] denotes the concentration of FFA in mg KOH·g−1 oil (i.e.
• FFA content 0.34 the acid value); [C] and [D] are the concentrations of FAME and
• Diglycerides content 5.62 water, respectively, formed during the reaction, both referred to
• Monoglycerides content 1.29
one gram of oil; so k1 and k2 are the kinetic constants for the
• Other polar compounds a 17.95
Non-polar FAME content 9.6 forward and reverse reaction, respectively.
Triglycerides content 68.60 Equation 3 can be transformed using the acid value conversion
Moisture 0.39 definition (XA ) in the following equation 4:
a
Polimeric triglycerides and oxidized monomeric triglycerides    
dXA 1 − XAeq
= k1 · (1 − XA ) − · XA2 (4)
dt X2
fer taking control of the process [1]. In this work, a speed of
where XAeq is the equilibrium conversion as the average of 70, 80,
600 rpm was used to examine the influence of the temperature
90 and 100 ◦ C tests due to the fact that equilibrium was reached
on the conversion of FFA to FAME, because this value was found
in all of the tests obtaining similar equilibrium conversion values.
to have no further effect on the reaction rate in previous research
So the mean value of XAeq = 0.859 has been utilized to transform
[30].
equation 4 into equation 5 which is the way to calculate k1 .
The conversion was defined as the percentage of FFA converted
to FAME. Fig. 3 shows the variation of the conversion of FFA to dXA  
= k1 · 1 − XA − 0.191 · XA2 (5)
FAME at different temperatures (60, 70, 80, 90 and 100 ◦ C) with dt
each curve starting at the conversion value reached at the initial The kinetic model, equation 5, was solved by the differential
time (isothermal conditions). It was found that the reaction rate method of Fourth Order Runge–Kutta with the Mathcad 14.0 ®
increased when the temperature rose. However, between 90 ◦ C and mathematical software. The value of k1 , which has been adopted
100 ◦ C the increase of the conversion did not justify the higher as the solution, was achieved when the sum of the squares of the
temperature and the associated costs. In all the tests, the equi- deviations between experimental and calculated values were at a
librium of the reaction was observed. The temperature increase minimum.
caused the decrease of oil viscosity, improving the contact between For example, the adjustment of the conversion at 80 ◦ C is shown
reactants. The reaction time to obtain oil, with an acid value below in Fig. 4. As can be seen, the modelled curve fits the calculated
1 mg KOH·g−1 oil (FFA level of 0.5 wt.%) was reduced considerably. conversion from experimental acid value concentration perfectly.
These improvements were possible thanks to the characteristics The influence of temperature on the esterification reaction was
of the experimental set-up. In order to optimize the operational evaluated through the Arrhenius equation by fitting k1 to temper-
conditions, the kinetics of the reaction was studied. ature:
Table 2 shows some chemical characteristics of esterified used  −E
frying oil, where it can be observed that the triglyceride content did k1 = A · exp (6)
R·T
not show any significant variation because the formation of FAME
from triglycerides in the esterification reaction is slower than in This is shown in Fig. 5, where the exponential relation was
the transesterification step. Thus, diglycerides and monoglycerides demonstrated. Both the frequency factor A and the energy of acti-
appeared from the breakage of triglycerides. However, the fatty vation E were obtained by nonlinear regression, using the Mathcad
acid content decreased up to the recommended value in the back- 14.0 ® software. The results are shown in Table 3.
ground literature. The increase of the polar compound percentage, An activation energy of about 28.7 kJ·mol−1 was found for the
between initial and esterified used frying oil, was as a result of the forward reaction, slightly lower than the values for similar reactive
appearance of new monoglycerides and diglycerides from the par- systems obtained by Tesser et al. [27] for free fatty acid (oleic acid)
tial breakage of triglycerides. Furthermore, other polar compounds esterification, by Berrios et al. [30] for olive fatty acids distillate in
 M. Berrios et al. / Chemical Engineering Journal 160 (2010) 473–479 477

Fig. 6. Influence of the temperature on the evolution of the transesterification of

Fig. 4. Adjustment of the kinetic model selected to the experimental data at 80 ◦ C. used frying oil.

Fig. 5. Influence of temperature on the reaction rate (Arrhenius equation) at a H2 SO4

concentration of 5 wt%, 600 rpm and 60:1 methanol/oleic acid mole ratio. Error bars Fig. 7. Influence of methanol/oil mole ratio (4.5:1, 6.0:1 and 7.5:1) on the evolution
indicate repeatability of the different measurements. of transesterification of used frying oil.

Table 3
Energy of activation and frequency factor for the esterification of used frying oil. hydroxide was used as a process catalyst as it is the most used at
industrial scale.
A (min-1 ) E (J mol-1 ) r
Fig. 6 shows the influence of temperature (60, 70 and 80 ◦ C) on
K1 363 28693 0.95 the evolution of the reaction when methanol/oil mole ratio was set
at 6.0:1. It can be observed that temperature did not have a sig-
nificant influence on the kinetics because the conversion to FAME
sunflower oil esterification and by Aranda et al. [34] for palm fatty
happened quickly. In this way, workings over 60 ◦ C did not improve
acid esterification. In contrast to these values, Sendzikiene et al.
the process.
[18] showed activation energy around 13 kJ·mol−1 and laid down
Something similar happened when the influence of
the assumption that diffusion restrictions were characteristic to
methanol/oil mole ratio was studied. Fig. 7 shows the influ-
the entire range of the concentrations and the reaction duration
ence of methanol/oil mole ratio (4.5:1, 6.0:1 and 7.5:1) on the
studied.
evolution of the reaction at 60 ◦ C. Although in the graph the
differences are not detected, when a methanol/oil mole ratio of
3.2. Transesterification 4.5:1 was selected, the FAME content was almost constant and
2 wt.% lower than the other runs. So a methanol/oil ratio of 6.0:1
Just like the esterification reaction, transesterification is a het- was selected as the most suitable amount of methanol.
erogeneous reaction: The obtained product in the test with the most suitable con-
Triglyceride + 3 Methanol  3 Methyl ester + Glycerol ditions (600 rpm, 1.0 wt.% KOH, 6.0:1 methanol/oil mole ratio and
60 ◦ C) was characterized by means of some of the EN 14214 Stan-
where the formation rate can be influenced by the agitation speed. dard specifications. Table 4 shows these results, which do not fulfil
As it is well known, the catalyst used in the reaction influences all specifications from the standard.
the yield and the kinetics. As a consequence, there is a great deal Polar FAME was a direct measurement of thermoxidative degra-
of research into transesterification with different kinds of cata- dation affecting unsaturated fatty acids [10]. The present polar
lyst: alkaline, acid or enzymatic [33,35–38]. In this work, potassium compounds in this fraction were polymeric FAME and oxidized
478 M. Berrios et al. / Chemical Engineering Journal 160 (2010) 473–479

Table 4
Characterization of obtained biodiesel from used frying oil in pressure system.

Run EN 14214

Minimum Maximum

Acid value (mg KOH·g-1 oil) 0.14 - 0.50

Density at 25 ◦ C (g·cm-3 ) 0.875 0.860 0.900
Kinematic viscosity at 40 ◦ C (mm2 ·s-1 ) 4.76 3.50 5.00
Iodine value (g I2 ·100 g-1 sample) 101.6 120
Non – polar FAME content (wt.%) 88.5 96.5
Linolenic acid methyl ester content (wt.%) 0.6 12.0
Polar FAME content (wt.%) 7.4
(Non – polar + polar FAME content) (wt.%) 95.9 96.5

monomeric FAME. As compared to the polar compounds in the ini- Acknowledgements

tial and esterified used frying oil, the polar compound percentage
was much lower as it only included the modified fatty acyl groups The authors are grateful to Ministry of Education and Science
in the triglyceride molecules (polar FAME). FFA, monoglycerides (MEC, Spain) for the PhD grant AP2005-3537 and the firm BIDA,
and diglycerides have been transformed to non-polar FAME during S.A. for funding this work. The authors would like to thank the lab
esterification and transesterification. According to Ruiz-Méndez et technician Inmaculada Bellido for her collaboration.
al. [10], there was a high correlation coefficient between polar com-
pounds and polar FAME by means of the expression:
References
Polar FAME(%) = 0.46 · Polar Compounds(%) − 1.4(R = 0.9768) (7)
[1] F. Ma, M.A. Hanna, Biodiesel production: a review, Bioresource Technol. 70
(1999) 1–15.
When the expression was applied to the polar compounds in [2] Y. Zhang, M.A. Dubé, D.D. McLean, M. Kates, Biodiesel production from waste
the used frying oils, the expected polar FAME was 8.2%, which was cooking oil: 1. Process design and technological assessment, Bioresource Tech-
nol. 89 (2003) 1–16.
0.8% higher than the obtained result (7.4%). It can be deduced that [3] A.V. Tomasevic, S.S. Siler-Marinkovic, Methanolysis of used frying oil, Fuel Pro-
the equation related the experimental data satisfactorily. cess. Technol. 81 (2003) 1–6.
It is necessary to emphasize that the reaction did not reach the [4] Y. Wang, S. Ou, P. Liu, Z. Zhang, Preparation of biodiesel from waste cook-
ing oil via two-step catalyzed process, Energ. Convers. Manage. 48 (2007)
desired non–polar FAME content. If the polar FAME content was 184–188.
taken into account, the EN 14214 specification would be almost [5] Y. Zhang, M.A. Dubé, D.D. McLean, M. Kates, Biodiesel production from waste
fulfilled: 95.9 wt.% (Table 4). The obtained biodiesel did not fulfil cooking oil: 2. Economic assessment and sensitivity analysis, Bioresource Tech-
nol. 90 (2003) 229–240.
the FAME specification set out in the EN 14214 Standard due to the [6] Y. Chisti, Biodiesel from microalgae, Biotechnol. Adv. 25 (2007) 294–306.
presence of polar compounds. Therefore, the polar FAME content [7] M.G. Kulkarni, A.K. Dalai, N.N. Bakhshi, Transesterification of canola oil in mixed
must be considered in order to fulfil the ester content specification methanol/ethanol system and use of esters as lubricity additive, Bioresource
Technol. 98 (2007) 2027–2033.
with used frying oils as raw material. So it is necessary before the [8] L.C. Meher, V. Dharmagadda, S.N. Naik, Optimization of alkali-catalyzed trans-
transesterification process to carry out a complete characterization esterification of Pongamia pinnata oil for production of biodiesel, Bioresource
of used frying oils. Otherwise, used frying oils cannot be used to Technol. 97 (2006) 1392–1397.
[9] A.K. Tiwari, A. Kumar, H. Raheman, Biodiesel production from jatropha oil
produce biodiesel with good quality parameters.
(Jatropha curcas) with high free fatty acids: An optimized process, Biomass
Bioenerg. 31 (2007) 569–575.
[10] M.V. Ruiz- Méndez, S. Marmesat, A. Liotta, M.C. Dobarganes, Analysis of
used frying fats for the production of biodiesel, Grasas y Aceites 59 (2008)
4. Conclusions 45–50.
[11] IUPAC 1992. Standard Methods for the Analysis of Oils, Fats and Derivates.
Standard Method 2507–International Union of Pure and Applied Chemistry.
To obtain biodiesel from used frying oils (mainly olive and sun-
1st supplement to 7th edition. Pergamon Press, Oxford.
flower oils), it was necessary to carry out 2 steps: esterification and [12] M. Canakci, The potential of restaurant waste lipids
transesterification. as biodiesel feedstocks, Bioresource Technol. 98
The acid value conversion was fitted satisfactorily to a kinetic (2007) 183–190.
[13] H.A. Al-Kahtani, Survey of quality of used frying oils from restaurants, J. Am.
model in accordance with a first order forward direction and second Oil Chem. Soc. 65 (1991) 936–938.
order in the reverse direction, plus the mean value of XAeq = 0.859. [14] Y. Chu, S. Luo, Effects of sugar, salt and water on soybean oil quality during
The influence of temperature over the kinetics of esterification deep-frying, J, Am. Oil Chem. Soc. 73 (1994) 1549–1555.
[15] L. Ovesen, T. Leth, K. Hansen, Fatty acid composition and contents of trans
reaction was studied. The reaction rate increased when temper- monounsaturated fatty acids in frying fats, and in margarines and shortenings
ature rose. Obtaining the acid value below 1 mg KOH·g−1 oil, an marketed in Denmark, J. Am. Oil Chem. Soc. 75 (1998) 1079–1083.
increase of temperature could be used in order to reduce reaction [16] V.K. Tyagi, A.K. Vasishtka, Changes in the characteristics and composition of
oils during deep-fat frying, J. Am. Oil Chem. Soc. 73 (1996) 499–506.
times. Increasing the temperature from 60 ◦ C to 80 ◦ C lead to the [17] M. Mittelbach, B. Pokits, A. Silberholz, Production and fuel properties of fatty
reaction rate being increased by 3. acid methyl esters from used frying oil. In: Liquid Fuels from Renewable
Temperature had no significant influence on the evolution of Resources. Proceedings of an Alternative Energy Conference. ASAE Publication,
Nashville, TN, USA, 74-78.
transesterification reaction. The kinetics was so fast in the range
[18] E. Sendzikiene, V. Makareviciene, P. Janulis, S. Kitrys, Kinetics of free fatty acids
selected than it is impossible to study with the available experi- esterification with methanol in the production of biodiesel fuel, Eur. J. Lipid Sci.
mental set-up. Variations in the methanol/oil mole ratio showed Technol. 106 (2004) 831–836.
[19] M. Canakci, J. Van Gerpen, Biodiesel production from oils and fats with high
a slight influence over the FAME content evolution. But to dis-
free fatty acids, Trans. ASAE 44 (2001) 1429–1436.
place the forward reaction, it was necessary to use at least 6.0:1 [20] EN 14103:2003. Fat and oil derivates. Fatty Acid Methyl Esters (FAME). Deter-
methanol/oil mole ratio. mination of ester and linolenic methyl ester contents.
The non-polar FAME content was 88.5 wt.% according to the EN [21] ISO 12937:2000. Petroleum products. Determination of water. Coulometric
Karl Fischer titration method.
14214 specification although it would be 95.9 wt.% including polar [22] EN 14104:2003. Fat and oil derivates. Fatty Acid Methyl Esters (FAME). Deter-
FAME content. mination of acid value.
 M. Berrios et al. / Chemical Engineering Journal 160 (2010) 473–479 479

[23] EN 14105:2003. Fat and oil derivates. Fatty Acid Methyl Esters (FAME). Deter- [32] D Darnoko, M. Cheryan, Kinetics of Palm Oil Transesterification in a Batch
mination of free and total glycerol and mono-, di-, triglyceride contents. Reactor, J. Am. Oil Chem. Soc. 77 (2000) 1263–1267.
[24] ISO 3104:1996. Petroleum products. Transparent and opaque liquids. Determi- [33] G. Vicente, M. Martínez, J. Aracil, Integrated biodiesel production: a comparison
nation of cinematic viscosity and calculation of dynamic viscosity. of different homogeneous catalysts systems, Bioresource Technol. 92 (2004)
[25] ISO 3675:1996. Crude petroleum and liquid petroleum products. Laboratory 297–305.
determination of density. Hydrometer method. [34] D. Aranda, R. Santos, N. Tapanes, A. Ramos, O. Antunes, Acid–catalyzed homo-
[26] EN 14111:2000. Fat and oil derivates. Fatty Acid Methyl Esters (FAME). Deter- geneous esterification reaction for biodiesel production from palm fatty acids,
mination of iodine value. Catal Lett 122 (2008) 20–25.
[27] R. Tesser, L. Casale, D. Verde, M. Di Serio, E. Santacesaria, Kinetics of free fatty [35] G. Arzamendi, I. Campo, E. Arguiñarena, M. Sánchez, M. Montes, L.M. Gandía,
acids esterification: Batch and loop reactor modelling, Chem. Eng. J. (2009), Synthesis of biodiesel with heterogeneous NaOH/alumina catalysts: Compari-
doi:10.1016/j.cej.2009.03.010. son with homogeneous NaOH, Chem. Eng. J. 134 (2007) 123–130.
[28] T. Boubík, V. Fried, E. Hála, The vapour pressure of pure substances, Elsevier [36] M. Di Serio, R. Tesser, M. Dimiccoli, F. Cammarota, M. Nastasi, E. Santacesaria,
Scientific Publishing Company, Amsterdam, 1973. Synthesis of biodiesel via homogeneous Lewis acid catalyst, J. Mol. Catal. A
[29] P.M. Doran, Bioprocess Engineering Principles, ed, Academic Press Ltd, London, Chem. 239 (2005) 111–115.
1995. [37] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Possible methods for biodiesel produc-
[30] M. Berrios, J. Siles, M.A. Martín, A. Martín, A kinetic study of the esterification tion, Renew. Sust. Energ. Rev. 11 (2007) 1300–1311.
of FFA in sunflower oil, Fuel 86 (2007) 2383–2388. [38] D. Royon, M. Daz, G. Ellenrieder, S. Locatelli, Enzymatic production of biodiesel
[31] J. Pereda Marín, F. Barriga Mateos, P. Alvarez Mateos, Aprovechamiento de las from cotton seed oil using t-butanol as a solvent, Bioresource Technol. 98 (2007)
oleínas residuales procedentes del proceso de refinado de los aceites vege- 6.
tales comestibles, para la fabricación de biodiesel, Grasas y Aceites 54 (2003)
130–137.