Fuel Processing Technology 129 (2015) 147155

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Fuel Processing Technology

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

Kinetics of the NaOH-catalyzed transesterication of sunower oil with

ethanol to produce biodiesel
Ins Reyero, Gurutze Arzamendi, Silvia Zabala, Luis M. Ganda
Departamento de Qumica Aplicada, Edicio de los Acebos, Universidad Pblica de Navarra, Campus de Arrosada s/n, E-31006 Pamplona, Spain

a r t i c l e

i n f o

Article history:
Received 31 January 2014
Received in revised form 5 September 2014
Accepted 5 September 2014
Available online 21 September 2014
Keywords:
Biodiesel
Ethanolysis
Kinetics
Sunower oil
Transesterication

a b s t r a c t
A kinetic model for the NaOH-catalyzed ethanolysis of sunower oil has been formulated. In accordance with the
experimental observations the reaction mixture is considered as a homogeneous system. Main novelties of the
model are the incorporation of the hydroxide/ethoxide equilibrium and of saponication reactions. The model
described the evolution of the oil conversion and reaction products yields for a series of transesterication reactions performed to investigate the inuence of the ethanol-to-oil molar ratio, catalyst concentration and temperature. The ethanol-to-oil molar ratio and catalyst concentration have great inuence on the system performance
because if the values of these variables are not sufciently high, the reaction stops before reaching oil conversions
and products yields of practical interest. This is due to the gradual depletion of the catalyst by saponication reactions that consume hydroxide ions to form soaps. In this regard, a sufciently high excess of ethanol is essential
to preserve the catalytically active species (ethoxide ions). At 50 C and initial NaOH concentration of 0.3 wt.%, an
ethanol-to-oil molar ratio of 24:1 is necessary to obtain a sunower oil conversion above 99%. In these conditions,
80% of the NaOH is nally converted into soaps. The ethanolysis reaction is also characterized by relatively high
yields of diglycerides and, especially, monoglycerides, that reach values up to 10% even at almost complete oil
conversion, which is detrimental for the quality of the produced biodiesel. The activation energies of the
ethanolysis reactions range between 48.7 kJ/mol for the conversion of triglycerides into diglycerides and
53.9 kJ/mol for the formation of glycerol from monoglycerides. These values are slightly lower than the activation
energy of the saponication reactions (57.9 kJ/mol).
2014 Elsevier B.V. All rights reserved.

1. Introduction
At present, the homogeneous base-catalyzed transesterication
with methanol (methanolysis) of vegetable oils resulting in the corresponding fatty acid methyl esters (FAMEs) is the predominant technique used for the industrial production of biodiesel. The consumption
of biodiesel in 2012 amounted to 11.41 Mtoe in the European Union
(EU) that has established a number of sustainability criteria for biofuels
within the framework of the EU Directives 2009/28/EC and 2009/30/EC
[1]. Methanol is the alcohol most frequently used for the synthesis of
biodiesel. This is largely due to its wide availability and low cost. However, the transesterication of the triglycerides present in the vegetable
oils and animal fats can be also conducted with other short-chain alcohols, most notably ethanol (ethanolysis), which gives rise to the corresponding fatty acid ethyl esters (FAEEs) that are also considered as
biodiesel [2,3]. Compared with the FAMEs, FAEEs exhibit some improved fuel properties such as higher stability toward oxidation, better
lubricity, lower iodine value and cloud and pour points thus improving
the performance in cold weather. They have also slightly higher heat
Corresponding author. Tel.: +34 948 169605; fax: +34 948 169606.
E-mail address: lgandia@unavarra.es (L.M. Ganda).

http://dx.doi.org/10.1016/j.fuproc.2014.09.008
0378-3820/ 2014 Elsevier B.V. All rights reserved.

content and cetane number, but also higher viscosity and acid value
[2]. It is also of interest that ethanol can be obtained from renewable
sources thus contributing to improve the sustainability of biodiesel.
In the recent years, both the methanolysis [412] and ethanolysis
[1329] of vegetable oils with homogeneous basic catalysts have been
widely investigated. Much of the existing studies are devoted to the investigation and optimization of the main operating variables, namely
the initial alcohol-to-oil molar ratio, type and concentration of the catalyst and reaction temperature for a variety of vegetable oils, including
waste cooking oils. Whereas there is almost general agreement about
the inuence of the operating parameters on the methanolysis reaction,
this is not the case for the ethanolysis whose results show greater discrepancies among the published results [2]. In addition, the information
existing in the literature regarding the level of intermediate reaction
products (monoglycerides and diglycerides) formation during the
ethanolysis of vegetable oils is scarce. This is a very important issue because these products, along with unreacted oil, if present in signicant
amounts, generally above 1 wt.% in total, will cause that the biodiesel
does not meet the required quality standards.
Reaction kinetics is essential for reactor and process analysis, design,
simulation and control. As for the kinetics of the homogeneous basecatalyzed reactions, the information available is also much higher for

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I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

the methanolysis [3043] than for the ethanolysis [4450]. As concerns

the ethanolysis reaction, two main categories of kinetic models can be
distinguished. The rst one corresponds to some of the rst studies published [21,45,46]. These models are relatively simple; they are characterized by considering the reaction mixture as a homogeneous
medium and limiting the kinetic equations to one or two reaction rate
expressions. de Lima da Silva et al. [21] investigated the ethanolysis of
castor oil catalyzed by sodium ethoxide (NaOEt). The kinetic model
was formulated for a given set of values of the initial concentrations of
the reactants and the catalyst, and only the variation of the reaction
temperature was considered (3070 C). Triglycerides (TG), diglycerides (DG) and monoglycerides (MG) were lumped in a sole species
whose evolution was satisfactorily described by a kinetic equation corresponding to an irreversible reaction that was rst- and zeroth-order
with respect to the glycerides species and ethanol concentrations,
respectively. The activation energy was found to be 70.6 kJ/mol.
Marjanovi et al. [45] investigated the kinetics of the ethanolysis of sunower oil catalyzed by NaOH. These authors seem to be the rst ones in
performing considerations about the phase behavior of the reacting system on the basis on their previous works on the methanolysis reaction.
It is indicated that, in contrast with the methanolysis, the ethanolysis is
not affected by mass transfer limitations. Due to their simplicity and
good description of the system for a given initial composition, this
kind of models continue being considered in more recent studies, such
as in the case of Shahla et al. [47] who found an activation energy of
42.4 kJ/mol for the ethanolysis of palm oil catalyzed by NaOEt.
In the second type of ethanolysis models, the three stages of the
transesterication process are considered and modeled as elementary
reversible reactions; in addition, the rate equations explicitly include a
rst-order dependency on the catalyst concentration [4850]. Depending on the case, mass transfer limitations are taken into account. For example, Richard et al. [48] observed a biphasic annular ow system
during the ethanolysis of sunower oil in a microreactor constituted
by a tube with an internal diameter of 508 m. The reaction was assumed to take place in the alcoholic phase. Terms accounting for mass
transfer from the internal oily phase to the external alcoholic one
were included in the mass balances for TG, DG and MG. Likozar and
Levec [50] investigated the transesterication of a variety of vegetable
oils using the following alcohols: methanol, ethanol, isopropanol, nbutanol and tert-butanol. The reacting systems behaved as homogeneous media with the sole exception of the methanolysis reactions. In
this case, the kinetic model for the ethanolysis did not include equations
accounting for mass transfer rates.
Within this context, in this work, the effects of the main operating
variables on the NaOH-catalyzed ethanolysis of rened sunower oil
have been investigated. Special attention is paid to the effects on the formation of the intermediate reaction products. A kinetic model of the
ethanolysis reaction has been formulated for helping with the interpretation of the results. The model is inspired by a recent kinetic study by
Eze et al. [43] on rapeseed oil methanolysis catalyzed by KOH. Compared with previous ethanolysis models, the present one includes two
main novelties: the incorporation of the equilibrium between the
ethoxide and hydroxide ions, and saponication reactions which consume hydroxide ions and that can eventually lead at low NaOH concentrations to the depletion of the catalytically active species (ethoxide
ions).
2. Experimental procedures
The transesterication reactions were performed at atmospheric
pressure in a jacketed glass tank batch reactor of 1 L with mechanical
stirring (400 rpm). The reactor was tted with a reux condenser, a
thermocouple probe and a thermostatic circulating bath that was used
to control the reaction temperature within the 2360 C range. Rened
sunower oil (acidity 0.08 mg KOH/g oil) and HPLC grade ethanol were
used as reactants with initial alcohol/oil molar ratios of 6:1, 12:1 and

24:1. The oil and a fraction of the alcohol were charged into the reactor
and allowed to reach the reaction temperature. Then, the catalyst
(NaOH, Sigma-Aldrich pellets 99.998%) was added dissolved in the
rest of the ethanol according to the desired initial concentration between 0.06 and 0.30 wt.% referred to the oil mass.
Representative reaction samples (about 2 ml) were withdrawn by
means of a syringe during the experiments at various time intervals
and rapidly quenched by addition of about 0.1 g of a glacial acetic acid
solution (0.6 N) in HPLC grade tetrahydrofuran (THF) to neutralize the
catalyst and cooling and dilution with additional THF. Analyses were
carried out by means of size-exclusion chromatography (SEC) at room
temperature using THF as mobile phase according to the method described in a previous paper by our group [8]. This robust and accurate
method was originally developed for methanolysis reactions. It allows
obtaining a chromatographic peak for each category of substances: triglycerides (oil), diglycerides, monoglycerides, FAMEs (biodiesel), glycerol and methanol. It has been found that this SEC method is also valid
for monitoring ethanolysis reactions. As in the case of methanolysis, a
single peak is obtained during the ethanolysis reactions for the FAEEs
and ethanol. The experimental errors were 2% for the oil conversion
and FAEEs yield, 4% for the diglycerides yield, and 6% for the monoglycerides yield.
3. Kinetic model
3.1. Kinetic model formulation
In view of the information available in the literature as well as our
own experimental evidences, in this work, a kinetic model has been developed for the ethanolysis of triglycerides catalyzed by NaOH on the
basis of the following premises:
i. A perfectly mixed discontinuous stirred tank reactor of volume V is
considered.
ii. The reacting system is homogeneous so the concentrations of all the
chemical compounds are referred to the total volume of the reaction
mixture, V.
iii. The ethanolysis reaction is constituted by three consecutive stages
that are assumed reversible, elementary and whose rates are directly proportional to the catalyst concentration.
iv. The catalytically active species is sodium ethoxide (NaOEt) formed
by reaction of NaOH with ethanol (EtOH) which is a very fast reversible reaction.
v. NaOH is consumed to form soaps by the following irreversible reactions: neutralization of the free fatty acids (FFAs) of the sunower oil
and saponication of the glycerides and FAEEs.
To the best of our knowledge, the above two last points have not
been considered to date in the kinetic models of the ethanolysis reaction. Eze et al. [43] have very recently shown the importance of incorporating the equilibrium between the hydroxide (OH) and methoxide
anions into the mathematical model of the methanolysis process. The
reason is that the methoxide species is the catalytically active one,
whereas the hydroxide anion can participate in non-desired side reactions such as the saponication of glycerides and fatty acid alkyl esters.
In spite of the fact that it is routinely assumed that the alkali metals hydroxides are quantitatively converted into the respective alkoxides by
reaction with the alcohol used for the transesterication reaction [49],
in reality, an equilibrium is established between the alkoxide and OH
anions. Although the equilibrium greatly favors the alkoxide species,
the concentration of hydroxide is not negligible and increases in the
presence of even low amounts of water [51]. As concerns the saponication reactions, it is well-known that they are slower than the
transesterication ones [52]. However, as it will be shown afterwards,
we have found the formation of soaps during the course of the
ethanolysis reactions, which is in agreement with the observations of
other authors [18,5355].

I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

According to the model assumptions, the reaction scheme of the

sunower oil ethanolysis catalyzed by NaOH includes the three stages
of the transesterication reaction that lead to the formation of DG
(Eq. (1)), MG (Eq. (2)) and GL (Eq. (3)). In each step a molecule of biodiesel (BD) or fatty acid ethyl ester (FAEE) is formed:
k

TG EtOH DG BD

k1

149

dN MG

fk3  MG  EtOH k3  GL  BDg EtO   V

n
o
dt

ksap;3  MG ksap;2  DG  OH   V

12

dN BD
fk1  TG  EtOH k1  DG  BD k2  DG  EtOH
dt

k2  MG  BD k3  MG  EtOH k3  GL  BDg EtO 

Vksap;4  BD  OH   V

13

DG EtOH MG BD

k2

dNGL

fk3  MG  EtOH k3  GL  BDg  EtO 

dt

V ksap;3  MG  OH   V

14

MG EtOH GL BD

k3

In addition, the equilibrium between the hydroxide and ethoxide

species is included (Eq. (4)). As for the equilibrium constant (Keq), the
value of 0.73 calculated by Eze et al. has been adopted [43]. According
to Caldin and Long it is not expected that this value changes signicantly
as far as the temperature is below the boiling point of ethanol. [51].
kx

EtOH OH EtO H2 O;

Keq

ky

kx
ky

Finally, the reactions (Eqs. (5)(8)) leading to the formation of soaps

(R-COONa) by reaction between NaOH and TG, DG, MG and BD are considered:

ksap;1

ksap;2

TG Na OH RCOONa DG

DG Na OH RCOONa MG

ksap;3

MG Na OH RCOONa GL

ksap;4

BD Na OH RCOONa EtOH

dN DG

fk2  DG  EtOH k2  MG  BDg EtO   V

n
o
dt

ksap;2  DG ksap;1  TG  OH   V

16

dNEtO

kx  EtOHOH   Vky  EtO H2 O  V

dt

In order to improve the stability of the optimization algorithms the

dependency of the kinetic constants on the temperature (k(T)) has
been expressed in terms of a reparametrized Arrhenius equation taking
50 C (323 K) as reference temperature:

In this equation Ni gives the number of moles of species i, ij is the

stoichiometric coefcient of species i in reaction j, which is taken negative for the reactants and positive for the reaction products; Rij is the reaction rate for species i in reaction j. The volume (V) of the reacting
system has been calculated in each instant as the sum of the contribution of each component calculated from Ni and the density of the pure
substances. As a result, the individual balances written in terms of the
molar concentrations [i] are as follows:
dN TG

fk1  TG  EtOH k1  DG  BDg EtO   Vksap;1

dt

 TG  OH   V

n
o
dN OH
ksap;1  TG ksap;2  DG ksap;3  MG ksap;4  BD
dt

OH   Vkx  EtOHOH   V ky  EtO H2 O  V

Mass balances for the several chemical compounds (i) can be written from the following general expression:
dN i X

i j  Ri j  V:
dt
j

dNEtOH
fk1  TG  EtOH  k1  DG  BDk2  DG  EtOH
dt
k2  MG  BDk3  MG  EtOH

15
k3  GL  BDg  EtO   V

ksap;4  BD  OH   Vkx EtOH  OH   V

ky EtO   H2 O  V

10

11

kT k50  e

Ea 1
1
R  T 323

17

18

where k50 is the value of the kinetic constant at 50 C, T is the temperature in K, R is the universal gas constant and Ea is the activation energy.
To reduce the number of parameters, the kinetic constants of the reverse reactions were calculated as a function of the kinetic constants
of the forward reactions and the equilibrium constants (e.g. from
Eq. (4) ky = kx/Keq). The equilibrium constants were taken from the literature in the case of Keq [43] or estimated from groups contribution calculations in the case of Eqs. (1)(3) [56]. The dependency of the
equilibrium constants (KC(T)) on temperature was expressed according
to the integrated Van't Hoff equation taking 50 C (323 K) as one of the
integration limits:
H 1
 1
K C T K C;50  e R T 323

19

where KC,50 is the value of the equilibrium constant at 50 C (323 K), T is

the temperature in K, R is the universal gas constant and H is the reaction enthalpy which has been assumed constant within the range of
temperatures considered in this work (2350 C). With the aim of simplifying the model, it has been assumed that the kinetic constants of the
TG, DG and MG saponication reactions (Eqs. (5)(7)) are the same
(ksap,1 = ksap,2 = ksap,3 = ksap). This seems reasonable as a rst approximation given the great similarity between these reactions. Similarly,
the activation energy of the saponication of glycerides (Eqs. (5)(7))
and the saponication of FAEEs (Eq. (8)) have been assumed to be the
same.

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I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

3.2. Kinetic parameters

Integration of Eqs. (10)(17) was carried out using Compaq Visual
Fortran V6.6 that includes the IMSL subroutines library (IMSL Fortran
90 MP Library). The ordinary differential equations were solved using
the DIVPRK subroutine that applies the 5th and 6th orders adaptive
RungeKuttaVerner method. This allowed to obtain the number of
moles of each compound (Ni) with time and then, given the initial number of moles of oil (NTG0), calculating the oil conversion (XTG), and the
yields of biodiesel (YBD), diglycerides (YDG), monoglycerides (YMG) and
glycerol (YGL):
X TG

NTG0 NTG
NTG0

20

Y BD

NBD
3  NTG0

21

Yi

Ni
NTG0

i DG; MG; GL

iv. As expected, the formation of ethoxide from ethanol and NaOH is

very rapid. Regarding the saponication reactions, the kinetic constants indicate that they are slow processes, especially the saponication of FAEEs; therefore, it seems that the soaps are mainly formed
from the glycerides.
v. The activation energies of the ethanolysis reactions are very similar,
ranging from 48.7 kJ/mol for Eq. (1) to 53.9 kJ/mol for Eq. (3). These
values are in accordance with the ones reported in the literature:
3544 kJ/mol [45], 51 kJ/mol [46], and 42.4 kJ/mol [47].
vi. The activation energy of the saponication reactions (57.9 kJ/mol) is
higher than that of the ethanolysis reactions. This implies that, on increasing the temperature, the side reactions leading to soap formation are more favored than the ones producing biodiesel. The
result is that the reaction temperature, like other variables such as
the alcohol/oil molar ratio, should be established after an optimization process because it can introduce both positive and negative effects on the process. In the case of the KOH-catalyzed methanolysis
of soybean oil, Eze et al. [43] obtained slightly higher activation energies: 61.2 kJ/mol for the saponication of the FAMEs and 69.1 kJ/
mol for the saponication of the oil.

22
4. Results and discussion

Kinetic parameters estimation was carried out using a complex

method of direct search furnished by the DBCPOL optimization subroutine (IMSL Fortran 90 MP Library). An objective function given by the
sum of the differences between the experimental values the oil conversion and products yields and the values predicted by the kinetic model
was established. A rst set of values of the kinetic constants was obtained from the oil conversion and products yields data available at 50 C to
start the optimization process. Then, rst estimates of the activation energies were calculated using the data available at other temperatures.
Finally, the full set of experimental data was used to calculate the kinetic
parameters that provided the minimum of the objective function; their
values are compiled in Table 1. The most salient features of the estimated parameters are as follows:
i. The values of the equilibrium constants are relatively high which indicates that the transesterication reactions are thermodynamically
favored in accordance with the high values of the equilibrium values
of the conversions that characterize these reactions [57].
ii. Together, the transesterication reactions are slightly exothermic
but this does not mean that the heat of reaction is negligible. It
should be taken into account for the purpose of temperature control
in big size reactors and can be used to monitor the process by microcalorimetry [58].
iii. The kinetic constants of the transesterication reactions indicate
that the third step, the ethanolysis of MG into glycerol and biodiesel,
is the slowest one. The values obtained in this work are in accordance with the ones recently reported by Richard et al. [48]: 0.12,
0.15 and 0.05 L2 mol2 s1 for k1, k2 and k3, respectively.

4.1. Effects of the alcohol-to-oil molar ratio

The evolution of the sunower oil conversion with reaction time and
that of the FAEEs, DG and MG yields with the oil conversion are shown
in Fig. 1A and B, respectively. Transesterication reactions were carried
out at 50 C, catalyst concentration of 0.10 wt.% referred to the oil mass
and initial alcohol-to-oil molar ratios of 6:1, 12:1 and 24:1. The chisquare test has been used to examine the goodness of the model t.
Values of 2 for the sunower oil conversion and the yields of FAEEs, diglycerides and monoglycerides are as follows: .2.8, 4.3, 6.2 and 20.1, respectively. The full set of experimental data available was used to
calculate 2. These values are well below the critical points [59] at the
p-value of 0.99 and the available degrees of freedom (above 100), thus
conrming the goodness of the t.
For an ethanol-to-oil molar ratio of 6:1, the nal oil conversion is far
from the equilibrium value, which is very close to 100%. If the initial
ethanol-to-oil molar ratio increases to 12:1, and then to 24:1, the nal
oil conversion increases signicantly, being it possible to reach almost
100% conversion within 25 min of reaction. In contrast, at the early
stages of the ethanolysis reaction (conversion lower than about 55%)
the alcohol-to-oil ratio has very little inuence on the oil conversion.
This is also in contrast with the behavior of the methanolysis reactions.
In fact, Arzamendi et al. [8,9] have shown for the methanolysis of sunower oil catalyzed by NaOH that at short reaction times the oil conversion increased signicantly as the initial methanol-to-oil molar ratio
decreased. This could be explained by the different phase behavior of
these reactions. It is well-known that the methanolysis of triglycerides

Table 1
Parameters of the kinetic model developed for the NaOH-catalyzed ethanolysis of sunower oil.
Reaction

TG DG (Eq. (1))
DG MG (Eq. (2))
MG GL (Eq. (3))
OH EtO (Eq. (4))
TG soap (Eq. (5))
DG soap (Eq. (6))
MG soap (Eq. (7))
BD soap (Eq. (8))
a
b

Equilibrium constant (KC,50)

3.21
3.18
72.77
0.73

Reaction enthalpy (H)

Kinetic constant (k50) a

2

(kJ/mol)

(L mol

1.50
1.89
12.57

0.110
0.171
0,076
3.1 (L mol1 s1)
0.482 (L mol1 s1) b

48.7
49.3
53.9

57.9 b

0.062 (L mol1 s1)

57.9

Kinetic constants correspond to the forward reactions of the reversible processes.

Kinetic parameters have been assumed to be the same for Eqs. (5)(7) (see text).

Activation energy
(kJ/mol)

I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

Oil conversion

0.8

0.6

Ethanol-to-oil molar ratio

0.4

6:1
12:1

0.2

24:1
0

10

20

30

40

50

Time (min)
1

0.8
FAEEs

Yield

0.6

0.4

MG

0.2
DG

0.2

0.4

0.6

0.8

Oil conversion
Fig. 1. Evolution of the sunower oil conversion with reaction time (A) and that of the
FAEEs, DG and MG yields (B) with the oil conversion for ethanolysis reactions carried
out at 50 C, NaOH concentration of 0.10 wt.% and the initial ethanol-to-oil molar ratios indicated. Symbols: experimental data; lines: kinetic model t.

is a heterogeneous biphasic reaction constituted by an emulsion of

small drops of the alcoholic phase dispersed in the continuous oily
phase [42,60]. In the case of the ethanolysis, the reaction mixture is homogeneous after only a few seconds from the start of the reaction. Liu
et al. [61] found that the solubility of soybean oil in ethanol gradually increased as the FAEEs concentration increased. Moreover, the ternary
system oil/ethanol/FAEEs became a homogeneous solution at a FAEEs
content of 23.42 wt.% within the 3070 C temperature range. On the
other hand, whereas the ethanolysis reaction products (FAEEs and glycerol) are only partially miscible, they are soluble in ethanol [61,62]. So,
both ethanol and FAEEs act as co-solvents favoring the formation of a
homogeneous reacting system. The very different effect of the alcoholto-oil ratio at low oil conversions on the methanolysis and ethanolysis
of triglycerides could be due to the also different phase behavior of
these reaction mixtures. In the case of the methanolysis, as the volume
of alcohol increases, the concentration of the catalyst in the alcoholic
phase decreases for a given mass of oil loaded into the reactor. It is generally accepted that the reaction starts at the liquidliquid interphase

151

[63], so it is reasonable that as the catalyst concentration decreases

the oil conversion decreases too. As a matter of fact, Arzamendi et al.
[9] have shown that when both the methanol-to-oil ratio and the
NaOH loading are changed in order to maintain constant the catalyst
concentration referred to the alcohol, the initial methanolysis rate no
longer depends on the alcohol-to-oil ratio. In the case of the ethanolysis,
as the reaction volume is controlled by the oil loading, the volume increases only slightly with the excess of ethanol. This leads to a system
in which the catalyst concentration is much less sensitive to the
alcohol-to-oil molar ratio.
As concerns the nal oil conversion, the ethanolysis reaction seems
to stop at almost complete conversion (99.8%) at the highest alcoholto-oil molar ratio used (24:1), at about 98% oil conversion for a ratio
of 12:1 and 84% for the lowest initial alcohol-to-oil molar ratio of 6:1.
These large differences cannot be attributed to the possible inuence
of the alcohol in excess on the oil equilibrium conversion. In fact, at
40 C, atmospheric pressure and initial alcohol-to-oil molar ratio of
6:1, the equilibrium oil conversion is well-above 99% for both
methanolysis and ethanolysis [57]. Interestingly, Tsuji et al. [64] have
found that not the thermodynamic limitation on the oil conversion
but the catalyst depletion by side reactions is the main reason for the
positive effect of using alcohol-to-oil molar ratios above the stoichiometric value. According to these authors, the main side reaction is the
saponication of the triglycerides by reaction with the hydroxide ions
leading to the formation of soaps. Data on soaps formation in this
work are provided in the next section. In this way, the consumption of
hydroxide shifts the equilibrium (Eq. (4)) to the consumption of
ethoxide ions, thus lowering the rate of the ethanolysis reactions and,
eventually stopping them if the initial alkali metal hydroxide concentration is low. This allows explaining the strong positive effect on the nal
conversion of using high ethanol-to-oil ratios. The excess of alcohol favors the transesterication due to their direct inuence on the forward
transesterication steps (Eqs. (1)(3)) and also on the formation of the
catalytically active ethoxide species (Eq. (4)). Moreover, it negatively affects the concentration of hydroxide and therefore, the progress of the
saponication reactions, as also found by ernoch et al. [24]. But an excessively high value of the ethanol-to-oil molar ratio is not interesting
due to the difculties introduced in the recovery of the reaction products [27,65] as well as to the high cost associated to the ethanol purication for reuse in the reactors. It should be noted that due to the
homogeneous character of the reaction mixture it is necessary to remove the non-reacted ethanol at the end of the reaction for allowing
the separation of the produced biodiesel and glycerol by settling or centrifugation [20,66,67]. As a result of the opposite effects described, the
value of the initial ethanol-to-oil molar ratio should be established in
each case after an optimization process. In the literature, optimal values
of this variable between 5:1 and 20:1 can be found depending on the triglycerides source, the catalyst used, and the values of the remaining variables. Generally, the optimal initial ethanol-to-oil molar ratio increases
as the reaction temperature increases [2] and the catalyst concentration
decreases [3]. In our case, a low value of 0.10 wt.% NaOH was selected for
these experiments thus explaining the necessity of a high (24:1) initial
ethanol-to-oil ratio in order to achieve nal conversions close to the
equilibrium value. A low catalyst concentration was used in order to facilitate data acquisition at short reaction times as well as to the interest
in studying the ethanolysis system under conditions more favorable
from the point of view of the purity of the nal products [68].
As concerns the yields of the transesterication products, it can be
seen in Fig. 1B that the experimental data are concentrated at oil conversions above 50% which shows the difculties for monitoring the very
fast ethanolysis reaction even using low catalyst concentrations. The
biodiesel yield gradually increases as the reaction progresses and attains
a maximum value of about 95% at 99.8% oil conversion when the
ethanol-to-oil ratio is 24:1. For lower values of this variable, the maximum oil conversions decrease, and the biodiesel yields decrease as
well: 87% and 58.5% for ethanol-to-oil ratios of 12:1 and 6:1,

I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

4.2. Effects of the catalyst concentration

The evolution of the sunower oil ethanolysis conversion with reaction time at 50 C and several NaOH concentrations within the 0.06
0.30 wt.% range is shown in Fig. 2A and B for initial alcohol-to-oil
molar ratios of 6:1 and 12:1, respectively. As expected, for a given initial
concentration of the reactants, the oil conversion increases as the initial
NaOH concentration increases. As discussed in the previous section,
there is a great inuence of the excess of ethanol utilized. In fact, at
the relatively low ethanol-to-oil molar ratio of 6:1, Fig. 2A shows that
the nal oil conversions are between 69% and 98% for NaOH concentrations of 0.06 and 0.3 wt.%, respectively. If the ethanol-to-oil molar ratio
increases to 12:1, it is possible to reach almost complete oil conversion
within 15 min with an initial NaOH concentration of 0.3 wt.%. These results illustrate the importance of the excess of alcohol to preserve the
catalytically active ethoxide species during ethanolysis reactions catalyzed by NaOH. This positive effect is mainly based on the shift of the hydroxide/ethoxide equilibrium (Eq. (4)) towards the formation of the
alkoxide.
To support this interpretation, the evolution of the EtO/(NaOH)0
ratio according to the kinetic model predictions have been included in
Fig. 3A and B for ethanolysis reactions at 50 C and ethanol-to-oil
molar ratios of 6:1 and 12:1, respectively. This ratio is the quotient of
the instantaneous ethoxide ion concentration by the initial NaOH
concentration, and therefore, it gives the proportion of the catalyst
that remains active. It can be seen that the EtO/(NaOH)0 ratio attains

0.8

Oil conversion

respectively. These biodiesel yields are lower than the ones typically
obtained in the methanolysis of triglycerides under similar reaction
conditions [47]. The obvious reason is that there is an important
presence of intermediate ethanolysis products during the course of
the reaction. Maximum diglycerides yields reach values of about 25%
at oil conversion of 60%. In the case of the monoglycerides, maximum
yields are of the order of 35% at oil conversions of about 85%. It is important to note that at almost complete oil conversion the monoglycerides
yield is still about 10% which negatively affects the quality of the
biodiesel. Likozar and Levec [41] and Richard et al. [48] also reported
high concentrations of the intermediate products at high conversion
values (above 90%) of the ethanolysis of canola and sunower oil,
respectively. These results evidence differences between the kinetics
of the ethanolysis and methanolysis reactions. Actually the concentration of intermediate reaction products is signicantly lower during the
methanolysis; moreover, in this process, the concentration of diglycerides is higher than that of the monoglycerides [8,9,38], which is in contrast to the ethanolysis reaction. The facts that during the ethanolysis
reaction the maximum yield of monoglycerides is obtained at oil conversions as high as 85% and that the maximum monoglycerides yield
is higher than the maximum yield of diglycerides point to a slower conversion of monoglycerides into glycerol when ethanol is used as the
transesterication alcohol. As can be seen in Table 1, the kinetic constant of this step (k3) is the lowest of the three forward ethanolysis kinetic constants. However, in the case of the methanolysis, the lowest
kinetic constant is k1, corresponding to the rst transesterication step
the conversion of triglycerides in diglycerides [38].
It can be seen in Fig. 1B that, within the range of values of the
ethanol-to-oil molar ratio considered in this study (6:124:1), there is
a very slight effect of this variable on the products yields. The diglycerides and monoglycerides yields slightly decrease as the ethanol-to-oil
molar ratio increases. This seems reasonable because the increase of
the concentration of the only reactant (ethanol) that is common to the
three ethanolysis steps should favor the global conversion of the oil
into the nal products: FAEEs and glycerol. The model is capable of capturing this effect only for the monoglycerides. This lack of sensitivity
could be associated to the uncertainty of the experimental data which
is of the order of the differences provoked by the change of the
ethanol-to-oil ratio.

0.6

Ethanol-to-oil molar ratio

0.4

6:1
0.06 % NaOH

0.2

0.1 %
0.3 %

10

20

30

40

50

Time (min)
1

0.8

Oil conversion

152

0.6

Ethanol-to-oil molar ratio

0.4

12:1
0.06 % NaOH
0.1 %
0.2 %
0.3 %

0.2

10

20

30

40

50

Time (min)
Fig. 2. Evolution of the sunower oil conversion with reaction time for ethanolysis reactions carried out at 50 C, the ethanol-to-oil initial molar ratios of 6:1 (A) and 12:1
(B) and the NaOH concentrations (wt. %) indicated. Symbols: experimental data; lines: kinetic model t.

a maximum value between 93% and 96% just after starting the reaction
(about 6 s) that is slightly higher for the reactions conducted at ethanolto-oil ratio of 12:1. When the ethanol-to-oil ratio is 6:1 the proportion of
catalyst present as ethoxide anions decreases gradually until becoming
virtually zero before complete oil conversion has been reached. The rate
of catalyst depletion increases as the initial NaOH concentration
increases, likely due to the increase of the rate of the saponication
reactions. Even so, this does not compensate for the differences between
the initial catalyst concentrations, resulting that the ethanolysis reaction
stops at signicantly lower oil conversions as the initial NaOH concentration decreases. As the ethanol-to-oil ratio increases to 12:1 (Fig. 3B),
the proportion of catalyst present as active species remains at a level
that is sufcient to complete the reactions within short times of 7 and
15 min for initial NaOH concentrations of 0.3 and 0.2 wt.%, respectively.
For the lowest NaOH concentration of 0.06 wt.%, the active species become depleted and the reaction stops after reaching an oil conversion
of about 92%. In the case of an initial NaOH concentration of 0.1 wt.%

I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

0.8

A
0.8

0.1 %
0.06 %
(NaOH)

0.6

0.6

Ethanol-to-oil ratio 6:1

0.4

0.4

0.06
EtO-/(NaOH)0

Oil conversion

0.07

0.3 %

0.2

0.2

0
0

10

15

20

25

0
30

Free NaOH (wt.%)

0.1 %

(NaOH)0
Ethanol-to-oil ratio 12:1

0.8

0.6

0.4

0.4

0.3 %
0.2 %

0.2

10

20

30

40

0
50

Time (min)
Fig. 3. Evolution of the oil conversion and the ratio between the concentrations of ethoxide
ions and initial NaOH (EtO/(NaOH)0) according to kinetic model predictions for
ethanolysis reactions carried out at 50 C, ethanol-to-oil initial molar ratios of 6:1
(A) and 12:1 (B) and the initial NaOH concentrations (wt.%) indicated.

the nal proportion of active species is low (below 5%) and it seems that
complete conversion could be reached after a sufciently long reaction
time.
The model predictions have been checked experimentally. As concerns the presence of active catalyst, it has been estimated assuming
that it is concentrated in the glycerol phase at the end of the reactions.
Ethanolysis reactions were carried out at 50 C, ethanol-to-oil ratio of
12:1 and initial NaOH concentrations of 0.06, 0.1 and 0.3 wt.%. The glycerol phase obtained after 45 min of reaction and evaporation of the nonreacted ethanol was titrated with 0.01 M HCl using phenolphthalein as
indicator. The results are shown in Fig. 4A expressed as weight percentage referred to the amount of oil loaded into the reactor. The values of
active catalyst are in reasonable agreement with the model predictions
that can be seen in Fig. 3B. The initial NaOH concentrations of 0.06, 0.1
and 0.3 wt.% are reduced after 45 min of reaction to essentially zero,
0.007% and 0.06%, respectively. This clearly shows that there are processes such as the formation of soaps leading to the gradual consumption of the catalyst. The presence of soaps in the glycerol and biodiesel
(oily) phases obtained in the reactions carried out to obtain the results
shown in Fig. 4A has been analyzed according to the American Oil
Chemists' Society method Cc 1795 [69]. As can be seen in Fig. 4B, during the course of the ethanolysis reactions soaps are formed that mainly
concentrated in the glycerol phase. They should be formed by neutralization of the sunower oil acidity as well as by saponication of the
glycerides, presumably mainly the triglycerides because they are in
higher concentration. As expected, the soaps content increases with
the initial NaOH content. Mendow et al. [25,66] found that soaps formation is especially important for ethanolysis reactions, between 3 and 4
times higher compared with methanolysis reactions performed under
the same reaction conditions. The homogeneous character of the

0.06 %

0.10 %

0.30 %

Initial NaOH concentration (wt.%)

0.16

0.2

0.03

0.01

EtO-/(NaOH)0

Oil conversion

0.8

0.6

0.04

0.06 %

0.14

Soap content (g/gsample)

0.05

0.02

Time (min)
1

153

0.12

B
Oily phase
Glycerol phase

0.10
0.08
0.06
0.04
0.02
0.00

0.06 %

0.10 %

0.30 %

Initial NaOH concentration (wt.%)

Fig. 4. Free NaOH in the glycerol phase expressed as weight percentage referred to the oil
(A) and soap content of the oily and glycerol phases (B) for ethanolysis reactions carried
out at 50 C, ethanol-to-oil initial molar ratio of 12:1 and initial NaOH concentrations of
0.06, 0.1 and 0.3 wt.%.

ethanolysis seems to facilitate soaps formation. These authors used

NaOH, KOH, and the methoxides of Na and K as catalysts. Soaps were
formed in all cases, particularly when using the alkali metal hydroxides
that were completely consumed [25]. It has been recognized that the
problem of soaps formation cannot be avoided when using homogeneous catalysts based on alkali metals compounds [18,20]; as a matter
of fact, catalyst neutralization and washing are among the most important stages of conventional biodiesel purication [70].
4.3. Effects of the reaction temperature
The evolution of the sunower oil conversion with reaction time and
that of the DG and MG yields with the oil conversion are shown in
Fig. 5A and B, respectively, for a series of ethanolysis reactions carried
out with initial alcohol-to-oil molar ratio of 12:1, NaOH concentration
of 0.10 wt.% and temperatures of 23, 35 and 50 C. The nal oil conversion is the same for the three reaction temperatures considered,

154

I. Reyero et al. / Fuel Processing Technology 129 (2015) 147155

5. Conclusions

Oil conversion

0.8

0.6

0.4

0.2

20

40

60

80

100

Time (min)
0.5

B
MG

0.4

Yield

0.3

DG
0.2

The ethanolysis of triglycerides has potential for improving some

characteristics of biodiesel as fuel of compressionignition engines
and also increasing its sustainable character as far as bioethanol is
used as the alcohol source. Although there is an increasing interest
in this reaction, to date, it has been much less studied than the
methanolysis of triglycerides, particularly as concerns the reaction kinetics. In this work, a kinetic model has been developed for the NaOHcatalyzed ethanolysis of sunower oil. The model describes the effects
of the ethanol-to-oil molar ratio, catalyst concentration and reaction
temperature on the oil conversion and yields of the nal (biodiesel)
and intermediate (diglycerides and monoglycerides) transesterication
products. In order to capture the most important effects of these variables it is necessary that the model incorporates the equilibrium of interconversion between the hydroxide and ethoxide ions as well as
saponication reactions. In this way, it is possible to predict the depletion of the catalyst that can take place at low values of the catalyst concentration and ethanol-to-oil ratio. This is the result of the consumption
of hydroxide ions by saponication reactions mainly with the glycerides
to form soaps. As a result the equilibrium hydroxide/ethoxide is shifted
towards the hydroxide ions, in detriment of the catalytically active
ethoxide species. A sufciently high excess of ethanol, with ethanolto-oil molar ratios between 12:1 and 24:1 for low NaOH contents
(below 0.3 wt.%), is necessary to preserve the ethoxide ions by favoring
the ethanolysis and alkoxide formation reactions in detriment of the saponication processes. The depletion of the catalyst and the formation
of soaps have been veried experimentally in this work. As concerns
the reaction temperature, the ethanolysis is favored by the increase of
this variable but its effects are not as inuential as those of the catalyst
concentration and ethanol-to-oil ratio. The ethanolysis is characterized
by a high production of soaps and intermediate transesterication products which are detrimental for the quality of the produced biodiesel.
Acknowledgments

0.1

Financial support by the Spanish Ministry of Economy and Competitiveness (ENE2012-37431-C03 grant) is gratefully acknowledged.
I. Reyero gratefully acknowledges the fellowship granted by the
Innovation Department of the Navarre Government.

0.2

0.4

0.6

0.8

Oil conversion
Fig. 5. Evolution of the sunower oil conversion with reaction time (A) and that of the DG
(lled symbols) and MG (open symbols) yields (B) with the oil conversion for ethanolysis
reactions carried out with an initial ethanol-to-oil molar ratio of 12:1, NaOH concentration
of 0.10 wt.%, and temperatures of 23, 35 and 50 C. Symbols: experimental data; lines: kinetic model t.

however, it is achieved at shorter reaction times as the temperature

increases, as expected from the increase of the transesterication reactions rate. According to Table 1, the activation energy of the saponication reactions (57.9 kJ/mol) is slightly higher than the ones of the
ethanolysis reactions (48.753.9 kJ/mol). In principle, the saponication reactions should be somewhat more favored by an increase of the
temperature but is difcult to see any effect related to this fact on the
results. This may be due to the very small differences between the
values of the activation energies. Regarding the intermediate reaction
products (Fig. 5B), in general, the kinetic model captures the evolution
of the DG and MG yields with the oil conversion. The model predicts
that the maximum monoglycerides yield decreases as the reaction temperature increases. This could be due to the fact that the conversion of
MG into glycerol has the highest activation energy among the three
transesterication steps. However, this cannot be seen experimentally
due to lack of sensitivity of the data.

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