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Kinetics of the base-catalyzed sunflower oil ethanolysis

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DOI: 10.1016/j.fuel.2009.09.025

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Fuel 89 (2010) 665–671

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Kinetics of the base-catalyzed sunflower oil ethanolysis

Ana V. Marjanović, Olivera S. Stamenković, Zoran B. Todorović, Miodrag L. Lazić, Vlada B. Veljković *
Faculty of Technology, Bulevar Oslobodjenja 124, 16000 Leskovac, Serbia7

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

Article history: The kinetics of the sunflower oil ethanolysis process using NaOH as a catalyst was studied at different
Received 18 February 2009 reaction conditions. The reaction system was considered as a pseudo-homogeneous one with no mass
Received in revised form 19 September transfer limitations. It was also assumed that the chemical reaction rate controlled the overall process
2009
kinetics. A simple kinetic model consisting of the irreversible second-order reaction followed by the
Accepted 22 September 2009
Available online 7 October 2009
reversible second-order reaction close to the completion of the ethanolysis reaction was used for the sim-
ulation of the triglyceride conversion and the fatty acid ethyl ester formation. The proposed kinetics
model fitted the experimental data well.
Keywords:
Biodiesel
Ó 2009 Elsevier Ltd. All rights reserved.
Ethanolysis
Kinetics
Modeling
Sunflower oil

1. Introduction
Diesel fuels have an important part in the world industry but
their increased consumption and exhaust gases have a big impact
on the environment. This is the main reason why the alternative
fuels have become significantly important. Alternative fuels must
be technically feasible, economically competitive, environmentally
acceptable and readily available [1]. One of them is biodiesel,
which is a renewable, biodegradable and non-toxic fuel the use
of which, when compared to the use of fossil fuels, leads to many
environmental benefits: less pollution of air, water and soil and
less health risk [2].
The most often used process for the biodiesel production is
alcoholysis, a reaction between triglycerides (TG) found in oils
and fats (from a variety of plant and animal sources) and an alcohol
(most frequently methanol or ethanol) in the presence of a catalyst
(such as a base, an acid or an enzyme). Methanol is the most often
used alcohol in a biodiesel synthesis because of its suitable physi-
cal and chemical properties and low cost. Ethanol, which has been
rarely studied, is preferable to methanol because of its superior
dissolving power of vegetable oils and low toxicity [3]. The produc-
tion of ethyl esters, rather than methyl esters, is of considerable
interest because the ethyl ester based biodiesel is an entirely agri-
cultural fuel and the extra carbon brought by the ethanol molecule
increases both the heat content and the cetane number [4]. Ethyl
esters have lower cloud and pour points than methyl esters, which
* Corresponding author. Tel.: +381 16 247 203; fax: +381 16 242 859.
E-mail address: veljkovicvb@yahoo.com (V.B. Veljković).
improve the starts cold [3] and better storage properties [5]. Also,
ethyl esters have a less negative effect on the environment com-
pared to methyl ester due to low emissions of nitrogen oxides
(NOx), carbon monoxide (CO) and smoke density [6]. On the other
hand, ethanolysis is more energy consuming [7], traces of water in
the reaction mixture seem to have dramatic effects on esters yields
[8] and the separation of ethyl esters is more difficult [9]. Due to
more glycerol and ethanol moving from the glycerol to the ethyl
ester phase, it is necessary that the residual alcohol is removed
and recovered by distillation before the water wash step [10]. If
the mixture of methanol/ethanol is used for the alcoholysis reac-
tion then this would take advantages of better solvent properties
of ethanol and a desired conversion using methanol [11].
Base catalysts in homogeneous media are usually applied for
the industrial biodiesel production. Alkoxides are most efficient,
but NaOH and KOH are frequently used because they are cheaper
and easier to handle [12]. The variables that influence the alcohol-
ysis reaction are: the type and the amount of the catalyst, the mo-
lar ratio of methanol to vegetable oil, the reaction temperature, the
agitation intensity and the purity of the reactants. High yields of
methyl and ethyl esters are achieved when the fundamental reac-
tion conditions are optimized [13,14].
The kinetics of the base-catalyzed methanolysis has been most
frequently studied [15–22]. In the studies of the methanolysis
reaction kinetics, three regimes are well-recognized: an initial
mass transfer controlled regime (slow) followed by a chemically
controlled regime (fast), and a final regime close to equilibrium
(slow). In the modeling of the methanolysis kinetics only Stamenk-
ović et al. [20] included the mass transfer limitation in the initial
heterogeneous reaction regime. In the study of the kinetics of

0016-2361/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.09.025
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666 A.V. Marjanović et al. / Fuel 89 (2010) 665–671

Nomenclature

A preexponential factor, Eq. (9) (min1) R gas constant (kJ/(kmol K))

cA concentration of TG in the oil phase (mol/dm3) t time (min)
cAo initial concentration of TG (mol/dm3) t1 duration time of irreversible pseudo second-order reac-
cBA concentration of ethanol (mol/dm3) tion (min)
CBo initial concentration of ethanol (mol/dm3) T temperature (K)
cR concentration of FAEE (mol/dm3) TG content of TG in the FAEE/oil fraction of the reaction
cS concentration of glycerol (mol/dm3) mixture (%)
C1 integration constant (1) xAA TG conversion degree, 1
Ea activation energy of the reaction (kJ/kmol) xAe equilibrium TG conversion degree, 1
k2 reaction rate constant for the irreversible pseudo sec-
ond-order reaction (dm3(mol min)) Greek symbol
~
k2 reaction rate constant for the forward second-order D parameter in Eq. (6) (= 43M(1  K)  (1 + 3M)2 < 0), 1
reaction (dm3(mol min))
~
k2 reaction rate constant for the reverse reaction (dm3(mol Abbreviations
min)) TG triglycerides
K reciprocal value of the equilibrium constant for the DG diglycerides
overall ethanolysis reaction ð¼ ~k2 =~
k2 Þ, 1 MG monoglycerides
M initial molar ratio of TG to ethanol ð¼ cAo =cBo Þ 1 FAEE fatty acid ethyl esters
(rA) rate of TG disappearance (mol/(dm3 min))

base-catalyzed ethanolysis, mass transfer limitations have not
been observed, but the two latter regimes were well-recognized
[3]. The ethanolysis reaction is very fast in the initial reaction per-
iod and is then getting slower in the second period towards equi-
librium. The final concentration of ethyl esters was almost
reached in 10 min at the temperature reaction range of 25–75 °C
and the kinetic curves had an asymptotic tendency with time [3].
According to the best knowledge of the authors, the ethanolysis
kinetics has not been modeled yet.
In the present work, the ethanolysis of sunflower oil using
NaOH as a catalyst was studied at the temperatures between
25 °C and 75 °C. The main goal was to model the kinetics of the
ethanolysis reaction. A simple kinetic model, which did not require
a complex computation of the kinetic constants, was intended to
be used for the simulation of the TG conversion and the fatty acid
ethyl ester (FAEE) formation. The reaction system was considered
as a pseudo-homogeneous one with no mass transfer limitations.
2. Theoretical background
The overall vegetable oil ethanolysis reaction can be presented
by the following stoichiometric equation:
(f) The content of free fatty acid in the oil is negligible, so the
free fatty acid neutralization can be ignored.
(g) The saponification reaction is negligible and the catalyst
concentration remains almost constant. A low degree of
saponification (about 1%) was caused by using 0.5% of NaOH
as a catalyst in methanolysis of an ox fat, coconut oil and lin-
seed oil at 60 °C [23]. A large amount of soap and a reduction
in the methyl ester yield were observed when the NaOH
amount was above 1.5% (based on the oil weight) [24].
According to the assumption (c), the rate of the TG formation in
the first part of the reaction is as follows:
dcA
ðrA Þ ¼  ¼ k2 c2A ð1Þ
dt
where k2 is the reaction rate constant for the irreversible pseudo
second-order reaction and cA is TG concentrations in the oil phase.
Since the TG concentration is related to the conversion degree
of TG, xA :
cA ¼ cAo ð1  xA Þ ð2Þ
it follows from the Eq. (1):

Catalyst dxA
A þ 3B ¢ 3R þ S  ¼ k2 cAo ð1  xA Þ2 ð3Þ
dt
where A is TG, B is ethanol, R is FAEE and S is glycerol. where cAo is the initial TG concentration reaction.Upon the integra-
For the purpose of modeling the described process of ethanoly- tion of Eq. (3), the following equation is obtained:
sis, the following assumptions are introduced:
xA
¼ k2 cAo t ð4Þ
(a) The reaction mixture can be considered as a pseudo-homo- 1  xA
geneous system where there is no mass transfer limitation. The reaction rate constant k2 can be estimated from the slope of the
This can be expected due to high agitation intensity dependence of xA =ð1  xA Þ on t.
[18,21,22] and a high dissolving power of ethanol in oils [3]. According to the assumption (d), the ethanolysis reaction rate
(b) The overall process kinetics is chemically controlled. close to the equilibrium is:
(c) The ethanolysis of TG is the irreversible pseudo second-
dcA ~
order reaction in the early period of the reaction. Due to ðrA Þ ¼  ¼ k2 cA cB  ~
k2 C R C S ð5Þ
the excess of ethanol and a low product concentration, one dt
can expect the reverse reactions to be negligible. where ~k2 and ~
k2 are the reaction rate constants for forward and re-
(d) Near to the equilibrium, the forward and reverse reactions verse reactions, respectively, and cB , cR and cS are actual concentra-
follow the second-order overall kinetics. tions of ethanol, FAEE and glycerol, respectively.
(e) The reaction mixture is perfectly mixed, ensuring its uni- The following equation is obtained by the integration of Eq. (5)
form composition. [20]:
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A.V. Marjanović et al. / Fuel 89 (2010) 665–671 667

pffiffiffiffiffiffiffi
½6Mð1  KÞxA  ð1 þ 3MÞ  D
ln pffiffiffiffiffiffiffi ¼ f ðxA Þ
½6Mð1  KÞxA  ð1 þ 3MÞ þ D
pffiffiffiffiffiffiffi
¼~k2 cBo t D þ C 1 ð6Þ

where K ¼ ~ k2 =~
K 2 is the reciprocal value of the equilibrium constant
for the overall ethanolysis reaction, M ¼ cAo =cBo is the initial molar
ratio of TG to ethanol (= 1/6; 1/9 or 1/12), cBo is the initial concen-
tration of ethanol, D ¼ 4  3Mð1  KÞ  ð1 þ 3MÞ2 < 0 and C 1 is the
integration constant. The reaction rate constant ~ k2 can be estimated
from the slope of the Eq. (6).
The reciprocal value of the equilibrium constant can be calcu-
lated from the equilibrium degree of TG conversion, xAe , which
can be experimentally determined, since it is [20]:

3Mx2Ae  ð1 þ 3MÞxAe þ 1
K¼ ð7Þ
3Mx2Ae Fig. 2. The influence of the catalyst amount on the FAEE concentrations (reaction
conditions: 25 °C; ethanol to oil molar ratio 6:1; catalyst amount, %: 0.75 – (d); 1.00 –
(N); and 1.25 – (j); experimental data: symbols; kinetic model: straight lines).
3. Experimental

3.1. Materials

Refined and edible sunflower oil (Sunce, Sombor, Serbia) was

used. Absolute ethanol was purchased from Carlo Erba (Milano,
Italy). Sodium hydroxide pellets of min 98% purity were purchased
from Lach-Ner (Neretvice, Czech Republic). Hydrochloric acid,
conc., was obtained from Centrohem (Beograd, Serbia). Methanol,
2-propanol and n-hexane, all of HPLC grade, were obtained from
Lab-Scan (Dublin, Irland). The HPLC standards for ethyl esters of
palmitic, stearic, oleic and linoleic acids, triolein, diolein and
monoolein were purchased from Sigma Aldrich.

3.2. Equipment

The reaction was carried out in a 250 mL three-neck glass flask

equipped with a condenser and a two flat-blade paddle agitator.
Fig. 3. The influence of the ethanol–oil molar ratio on the FAEE production
The agitation speed, kept constant with a voltage regulator, was (reaction conditions: 50 °C; catalyst amount: 0.75%; ethanol to oil molar ratio:
measured with an optoelectronic counter (Laser, Leskovac, Serbia). 6:1 – (d); 9:1 – (N); and 12:1 – (j); experimental data: symbols; kinetic model:
The reactor was immersed in a glass chamber filled with water straight lines).
circulating from a thermostated bath (Dema, Ilirska bistrica, Slove-
nia) by means of a pump.

3.3. Reaction conditions

The ethanolysis of sunflower oil was carried out at 6:1, 9:1 and
12:1 molar ratios of ethanol to oil and the NaOH amount of 0.75%,

Fig. 4. The influence of the reaction temperature on the FAEE content (reaction
conditions: ethanol to oil molar ratio 6:1; catalyst amount: 0.75%; temperature, °C:
25 – (d); 50 – (N); and 75 – (j); experimental data: symbols; kinetic model:
straight lines).

Fig. 1. Variations of the reaction mixture composition with the progress of the
sunflower oil ethanolysis (FAEE – (s); MG – (D); DG – (h) and TG – (d)) (reaction
conditions: 25 °C, ethanol to oil molar ratio 12:1 and NaOH amount 1.00%).
1.00% and 1.25% (based on the oil weight). The reaction was carried
out at the atmospheric pressure and temperatures 25, 50 and
75 °C. The agitation speed of 600 rpm was applied in all
experiments.
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668 A.V. Marjanović et al. / Fuel 89 (2010) 665–671

to neutralize the NaOH and then centrifuged (3500 rpm for

15 min). The upper layer was withdrawn, dissolved in a 2-propa-
nol/n-hexane (5:4 v/v) in a ratio 1:200 and filtered through a
0.45 lm Millipore filter. The resulting filtrate was used for HPLC
analysis.

3.5. Composition of the reaction mixture

The composition of the samples of the reaction mixture was

determined by HPLC, as described elsewhere [19]. The conversion
degree of TG was calculated from the content of TG in the FAEE/
oil fraction of the reaction mixture, TG (in%), by the following
equation:

xA ¼ 1  TG=100 ð8Þ

Fig. 5. The irreversible pseudo second-order reaction model of TG ethanolysis

(open symbols; Eq. (4) – straight solid lines) and the reverse second-order reaction
model of TG ethanolysis (solid symbols; Eq. (6) – straight dash lines) at various
catalyst amount, %: 0.75 – (h), 1.00 – (D), 1.25 – (s) (reaction conditions: 25 °C; a
ethanol to oil molar ratio 6:1).

3.4. Experimental procedure

Ethanol and sodium hydroxide were agitated in the reactor at

the desired temperature for about 30 min. The sunflower oil
(45.96 g) was thermostated separately and added to the reactor.
As soon as the mechanical stirrer was turned on, the reaction
was timed. During the reaction, the samples (1 ml) were removed
from the reaction mixture, immediately quenched by adding a re-
quired amount of the aqueous hydrochloric acid solution (11% vol.)

Table 1 b
The rate constants for the irreversible pseudo second-order and the reverse second-
order reaction model at different reaction conditions.

Reaction Ethanol NaOH dm

K 2 mol
3
~ dm
k2 mol
3
~
k103 mol
dm
3
The relative
min min min
temper- to oil amount deviations
ature molar (%) of the
(°C) ratio calculated
and the
experimental
xA (%)
25 6:1 0.75 1.742 0.119 5.74 4.6
1.00 3.254 0.240 9.03 2.2
1.25 4.145 0.371 11.04 4.1
9:1 0.75 1.003 0.091 1.89 7.1
1.00 4.643 0.215 4.52 4.8
1.25 7.736 0.405 6.06 4.1
12:1 0.75 3.170 0.140 11.10 1.1
1.00 6.93 0.327 45.0 1.8 c
1.25 11.82 0.497 111.3 9.0
50 6:1 0.75 5.18 0.486 8.16 5.1
1.00 6.04 0.698 11.1 4.9
1.25 6.52 0.938 12.8 4.7
9:1 0.75 4.95 0.498 3.64 8.3
1.00 8.17 0.941 5.65 4.9
1.25 9.26 1.163 7.03 1.6
12:1 0.75 10.8 0.524 34.5 2.3
1.00 13.5 0.741 74.4 6.6
1.25 17.0 1.337 135.4 1.8
75 6:1 0.75 6.24 0.891 12.3 2.7
1.00 7.84 1.165 14.2 4.5
1.25 8.80 1.335 14.9 3.8
9:1 0.75 7.50 1.423 5.72 2.4
1.00 9.57 1.680 6.43 2.3
1.25 12.6 1.921 7.35 2.9
12:1 0.75 10.9 1.795 82.5 0.5 Fig. 6. Arrhenius plot of the reaction rate vs. temperature for the irreversible
1.00 16.1 2.310 135.3 1.5 second-order (a), the forward second-order (b) and the reverse second-order
1.25 20.8 2.956 201.4 2.1 reaction (c) (ethanol to oil molar ratio 6:1; catalyst amount, %: 0.75 – (j); 1.00 –
(N) and 1.25 – (d)).
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A.V. Marjanović et al. / Fuel 89 (2010) 665–671 669

Table 2
Activation energy of alkali-catalyzed alcoholysis at atmospheric pressure.

Oil Alcohol Catalyst/ Molar ratio T (°C) Reaction mechanism; kinetics model Activation References
quantity of alcohol energy
(% of oil) to oil (kJ/mol)
Palm Methanol KOH 1.0 6:1 55–65 Three consecutive reversible reactions; 26.8–61.5 [15]
second-order a
Soybean Butanol NaOBu 0.5 30:1 20–60 Three consecutive reversible reactions; 46.9–72.0 [16]
and 1.0 pseudo-first order forward and second-order
reverse reactions
Butanol NaOBu 1.0 6:1 20–60 Three consecutive reversible reactions; 34.2–71.5
second-order
Methanol NaOCH3 0.5 6:1 20–60 Combination of consecutive and shunt 56.8–83.8
reactions; second and forth order for
consecutive and shunt reactions, respectively
Soybean Methanol NaOH 0.2 6:1 30–70 Three consecutive reversible reactions; 21.7–83.1 [18]
second-order
Brassica carinata oil Methanol KOH 0.5–1.5 6:1 25–65 Three consecutive reversible reactions; 12.0–104.8 [22]
second-order
Sunflower Methanol KOH0.5–1.5 6:1 25–65 Three consecutive reversible reactions; 6.0–41.6 [21]
second-order
Sunflower Methanol KOH 1.0 6:1 10–30 Irreversible second-order overall reaction in 33.2–53.5 [20]
the middle period; the reversible second-order
overall reaction in the final period
Sunflower Ethanol NaOH 0.75, 6:1, 9:1 and 12:1 25–75 Irreversible second-order overall reaction in 3.4–43.9 This work
1.00 and 1.25 the initial period; the reversible second-order
overall reaction in the final period
a
Only the forward reactions were considered.

4. Results and discussion
4.1. Ethanolysis reaction analysis
The variations of the reaction mixture composition with the
progress of the sunflower oil ethanolysis at a set of reaction condi-
tions (25 °C, ethanol to oil molar ratio 12:1 and NaOH amount
1.00%, based on the oil weight) are presented in Fig. 1. The shape
of the curve representing the variations of FAEE fraction with time
indicated two periods of the reaction. In the initial stage of the pro-
cess the formation of FAEE was fast and then it became slower as
the reaction approached the completion. No mass transfer limita-
tion was observed in the initial reaction period. This type of the
ethanolysis reaction kinetics has already been observed [3,25]. A
decrease in the TG concentration followed the increase in FAEE
concentration. The concentrations of intermediate products,
monoglycerides (MG) and diglycerides (DG), increased at the
beginning of the reaction achieving their maximum, then de-
creased and finally stayed nearly constant. The concentrations of
MG and DG were smaller than 0.5% and 2%, respectively.
The reaction rate increased by increasing the catalyst amount in
the range of 0.75–1.25%, based on the oil weight, and consequently
the reaction approached the completion in a shorter time (Fig. 2).
These results agreed with those reported by Encinar et al. [3,25]
for NaOH and KOH catalyzed ethanolysis of Cynara cardunculus L.
oil and the used frying oil. They found that the optimal catalyst
concentration is 1% referred to the total mixture, which corre-
sponded to 1.25% based on the oil weight for the ethanol to oil
molar ratio of 6:1. There was less influence of the catalyst amount
on the reaction rate at higher ethanol–oil molar ratios. This can be
explained by a small difference in the total catalyst amount in the
reaction mixture when the ethanol quantity is increased.
The initial ethanol–oil molar ratio affected both the FAEE
production rate and the FAEE yield, as it can be seen in Fig. 3. The var-
iation of the FAEE moles (not the FAEE concentration) with time was
analyzed because the FAEE concentration was reduced with increas-
ing the ethanol to oil molar ratio at a constant oil mass, due to the
increase of the total reaction mixture volume. When the initial
ethanol to oil molar ratio was increased from 6:1 to 12:1 both the
reaction rate and the FAEE yield in moles generally increased.
The temperature dependence of the reaction rate is shown in
Fig. 4. As it can be seen, all the reactions were very rapid, achieving
very high ethyl esters concentrations. The reaction rate was
slightly lower at 25 °C, but the FAEE content was essentially the
same after approximately 20–30 min for all the temperatures.
Thus, an increase of the temperature is not indispensable if the
reaction time is longer. Our results were in conformity with other
reports [3,25–28]. In addition, some authors [29] found that at high
reaction temperatures the ester yield decreased due to accelerating
the saponification of the TG by the alkaline catalyst before the
completion of alcoholysis. We did not observe this effect.
4.2. Reaction kinetics model
According to the assumptions (c) and (d), the kinetic model in-
volved the irreversible pseudo second-order reaction mechanism
in the initial period and the reverse second-order model close to
equilibrium. Fig. 5 shows the dependences of the left side of Eqs.
xA
(4) and (6) on time. The linear variation of 1x with time in the ini-
A
tial part of the process confirms that the ethanolysis of TG is the
irreversible pseudo second-order reaction in the early period of
the reaction. The variation of f ðxA Þ, defined by Eq. (6), with time
in the final part of the process is also linear verifying that the eth-
anolysis follows the reverse second-order reaction kinetics. The
reaction rate constants were calculated from the slopes of the cor-
responding linear curves and are given in Table 1; the values of the
TG conversion degree, produced by the Boltzman function of the
experimental data, were used in these calculations. The values of
xA
the 1x constant corresponding to the reverse reaction were small,
A
especially at the lower temperature and the lower ethanol to oil
molar ratio. This could be caused by the immiscibility of ethyl es-
ters and glycerol which involved a mass transfer resistance in that
direction. All the rate constants increased with increasing both, the
reaction temperature and the catalyst amount. Generally, the rate
constants increased with increasing the ethanol to oil molar ratio.
The linear dependences of ln (k2), ln ð~ k2 Þ and ln ð~
k2 on 1=T
(Fig. 6) confirm that the Arrhenius equation could be applied for
determining the activation energies for the ethanolysis reactions:
k ¼ A  expðEa =RTÞ ð9Þ
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670 A.V. Marjanović et al. / Fuel 89 (2010) 665–671
a were in the range from ±0.5% to ±9.0% in all experiments (Table 1).
b be seen in Fig. 7, the kinetic model agreed well with the experimen-
c catalyzed methanolysis, which is a well-known mass transfer con-
Fig. 7. The comparison of TG and FAEE concentrations calculated by the kinetic
model (straight lines) with the experimental data (TG – (d) and FAME – (N)) at (a)
25 °C, (b) 50 °C and (c) 75 °C (reaction conditions: ethanol to oil molar ratio 9:1;
catalyst amount 1.25%).
where A is the preexponential factor, Ea is the activation energy, and
R is the gas constant. The activation energies were calculated to be
in the range 8.3–35.1, 22.3–43.9 and 3.4–34.6 kJ/mol for the irre-
versible second-order reaction, the forward second-order reaction
and the reverse second-order reaction, respectively. Generally, the
calculated activation energies are slightly lower than those for the
alcoholysis reaction obtained in other studies, as it can be seen in
Table 2.
4.3. Simulation of the ethanolysis process
The proposed kinetic model satisfactorily fitted the changes of
the FAEE concentration with the reaction time. The relative devia-
tions of the calculated and the experimental TG conversion degree
The TG conversion degree based on the proposed kinetic model
was calculated from the following equations:
– for 0 < t 6 t1 (the irreversible pseudo second-order reaction)
k2 cAo t
xA ¼ ð10Þ
1 þ k2 cAo t
– for t P t1 (the reversible pseudo second-order reaction)
pffiffiffiffiffiffiffi pffiffiffiffiffiffiffi
½ð1 þ 3MÞ  D  expð~ k2 cBo t D þ C 2 Þ
xA ¼ pffiffiffiffiffiffiffi ð11Þ
½6Mð1  KÞ½1  expð~k2 cBo t D þ C 2 Þ
The kinetic model and the experiment were also compared based on
the variations of the molar concentrations of TG and FAEE. As it can
tal data. The molar TG concentration was calculated by Eq. (4). The
molar FAEE concentration was calculated using the TG conversion
degree corrected for the MG and DG formation.
5. Conclusions
The NaOH catalyzed sunflower oil ethanolysis was studied un-
der various reaction conditions in order to analyze the effects of
the reaction conditions on both the FAEE yield and the reaction
rate and to model the ethanolysis reaction kinetics. A good agree-
ment between the simple model and the experimental data veri-
fied that the reaction mixture could be considered as a pseudo-
homogeneous system with no mass transfer limitations in the ini-
tial reaction period. This is an important difference from the base-
trolled in the initial region. The ethanolysis process kinetics was
only chemically controlled. As the methanolysis reaction after
the initial mass transfer controlled regime, the ethanolysis reaction
also followed the irreversible second-order reaction kinetics in the
early period of the reaction and the reversible second-order reac-
tion close to its completion.
Acknowledgment
This work has been funded by the Ministry of Science and Envi-
ronmental Protection of the Republic of Serbia (Project 19062TR).
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