7978 Ind. Eng. Chem. Res.

2005, 44, 7978-7982

Kinetics of Oleic Acid Esterification with Methanol in the Presence

of Triglycerides
R. Tesser, M. Di Serio, M. Guida, M. Nastasi, and E. Santacesaria*,
Dipartimento di Chimica, Universita di Napoli Federico II, via Cintia 80126, Napoli, Italy, and ASER srl,
S.S. n.11 Padana Superiore 2/B, 20063 Cernusco sul Naviglio, Milano, Italy

In the present work, the kinetics of oleic acid esterification with methanol has been studied by
using an acid ion-exchange polymeric resin (Relite CFS) as the heterogeneous catalyst. The
kinetics of the reaction has been studied by performing batch runs at different temperatures
and in the presence of a certain amount of triglyceride for simulating an oil with a high content
of free fatty acids, which is of great potential interest as a raw material in the biodiesel production
process. The experimental data have been interpreted with a second-order, pseudo-homogeneous
kinetic model, and a good agreement between the experimental data and the model has been
obtained.

Introduction points through which the whole process can result in

One among the main topics in the framework of a
sustainable development is represented by the produc-
tion and usage of biofuels as a competitive renewable
energy source. Actually, the most attractive biofuel is
represented by biodiesel, which is constituted by a
mixture of fatty acids methylesters (FAME) or ethyl-
esters (FAEE), produced by a transesterification reac-
tion performed on high-quality vegetable oils with
methanol or ethanol. This transesterification process is
affected by several factors such as catalyst concentra-
tion, reactant molar ratio, and water and free fatty acids
content in the raw materials.1-3
The catalysts that are more widely used, and which
are the most effective in this step of the process, are
sodium and potassium hydroxide;1,2 acid catalysts, such
as sulfuric or hydrochloric acid, have also been proven
as effective in this reaction.1 Despite the fact that
alkaline catalysis is characterized by a higher reaction
rate with respect to an acid-catalyzed reaction, some
severe drawbacks must be accounted for in this case:
the presence of moisture and free acidity that strongly
influences the process performance and economics. In
fact, both water and free fatty acids (FFAs) rapidly react
with the catalyst, consuming it and giving way to long-
chain soaps for which the tenside properties do not allow
an efficient separation of the pure glycerol in the final
step of the process. In the case of an oil with a high
content of free fatty acids (FFAs), like usually happens
in waste materials, a pretreatment esterification step
must be considered as mandatory in order to eliminate
the free acidity that must be reduced below 1 wt %. On
the other hand, the opportunity to employ low-quality
or waste raw materials, as a starting point in the
biodiesel production cycle, is an essential aspect for
decreasing the production costs and making this alter-
native fuel competitive with traditional fossils fuels. On
the basis of these considerations, the improvement of
the esterification step could represent one of the key
* To whom correspondence should be addressed. E-mail:
santacesaria@chemistry.unina.it.
Universita di Napoli Federico II.
ASER srl.
10.1021/ie050588o CCC: $30.25 2005 American Chemical Society
Published on Web 09/17/2005
being economically convenient.
In the present work, the kinetics of the esterification
reaction of oleic acid with methanol, over a sulfonic ion-
exchange resin catalyst, has been investigated. The
experimental runs have been performed in the presence
of acidity-free soybean oil in mixture with oleic acid with
the aim to simulate the real mixture that must be
submitted to the preliminary esterification step in the
biodiesel production process.
While a lot of papers have been reported in the
literature concerning the esterification reaction of a
short-chain carboxylic acid with an alcohol,4-8 hetero-
geneously catalyzed by acid resin with sulfonic groups,
works devoted to the same reaction performed on long-
chain acids are rather scarce. Moreover, very few data
have been published regarding the esterification of high
free-acidity oils with methanol that, on the contrary, are
of great interest in biodiesel production. As an example,
very recently, Sendzikiene et al.9 have investigated the
effect of catalyst concentration and of the reactants
molar ratio on the esterification rate of an artificially
acidified rapeseed oil with methanol. The reaction has
been studied in homogeneous catalysis conditions, using
sulfuric acid as the catalyst, and the authors have found
that the esterification rate, in the temperature range
20-60 C, depends both on the amount of used catalyst
and on the initial oleic acid concentration.
A similar reaction system has also been investigated
by Steinigeweg and Gmehling:10 pure decanoic acid has
been converted to the corresponding methyl ester using
methanol and an ion-exchange resin as the catalyst in
a reactive distillation device. In this reactor configura-
tion, a simultaneous reactants conversion and products
separation were achieved, although a reactive column
section of about 10 m-long was required for obtaining
an almost complete carboxylic acid conversion.
A more sophisticated and innovative approach has
been proposed by Chemseddine and Audinos11 which
has adopted a membrane reactor in which the ion-
exchange is performed by the membrane itself. This
device allows an almost complete esterification of oleic
acid with methanol, at room temperature, by shifting
the equilibrium reaction toward ester formation caused
by water osmosis migration at one side of the mem-

Figure 1. Scheme of the reactor: 1, reactor; 2, circulation
thermostat; 3, stirrer; 4, sampling valve; 5, indicator for pressure
transducer; 6, indicator for liquid-phase thermocouple; 7, reactor
jacket.
brane. However, the described operation is rather
complex, and no information is given, in the correspond-
ing paper, about the possibility of utilizing the presence
of waste fried oils or fats of animal derivation as
representative feedstocks with high FFA content.
In all the mentioned papers, some kinetic data related
to the esterification of long-chain fatty acids have been
reported. In our work, we have deepened, in particular,
the kinetic approach by studying the esterification
performed in the presence of triglycerides with high FFA
content.
Experimental Section
The experimental runs have been performed in a
batchwise-operated stainless steel reactor (total volume
1 L) equipped with a magnetically driven stirrer and a
jacket. The thermal control is implemented by a circula-
tion thermostat that continuously feeds a thermal fluid
into the reactor jacket, allowing temperature control
within (0.5 C. Moreover, the reactor is equipped with
a pressure transducer fitted in the vapor space and with
a thermocouple in the liquid phase for the measurement
of the reaction temperature. Liquid-phase samples were
withdrawn at different times during a run, by means
of a sampling line equipped with a stopping valve. A
scheme of the reactor is reported in Figure 1.
The reactants employed are methanol (Carlo Erba,
purity 99.9% w/w), oleic acid (Carlo Erba, purity 99.9%
w/w), and a commercially available acidity-free soybean
oil (acidity <0.3% w/w). The withdrawn samples were
analyzed by a standard titration procedure for the
evaluation of free residual acidity. With the aim of
improving analysis repeatability, prior to submitting the
samples to titration, methanol in excess and water
formed are removed by heating the sample at 150 C
for 15 min in a ventilated oven. A weighed amount of
the sample was then dissolved in ethanol, some droplets
of timole blue as indicator were added, and the titration
is then performed by means of an alkaline 0.1 M NaOH
solution. The volume of alkaline solution consumed is
recorded, and the acidity of the sample can be calculated
by means of the following relation:
CtitrVtitrMOA
a) (% wt) (1)
1000Sw
The acidity evaluated by eq 1 refers to the oil phase
(triglyceride + oleic acid + ester) with an error that is
<1-2% according to the amount of free fatty acid.
Ind. Eng. Chem. Res., Vol. 44, No. 21, 2005 7979
Table 1. Properties of Catalyst
commercial name and producer Relite CFS by Resindion
matrix porous copolymer styrene-DVB
functional groups sulfonics
acidity 3.6 meq/g
particles mean diameter 0.7 mm
particles size range 0.3-1.18 mm
total exchange capacity 2.0 equiv/L
maximum operating temperature 140 C
bulk density 0.840 g/cm3
An acid sulfonic resin (Relite CFS furnished by
Resindion) has been used as the catalyst, and its main
properties are summarized in Table 1. The reactor was
heated after the acid oil and catalyst were charged, and
when the chosen reaction temperature was reached,
methanol was added in the desired amount. This instant
of time is assumed as the initial time for the reaction.
The total pressure of the system is the methanol vapor
pressure at the temperature of the experiment. In Table
2 are summarized the experimental conditions adopted
in each run and the used reactants and catalyst
amounts. At the temperatures of 50, 65, and 85 C, the
runs have been repeated by increasing the reaction time
by a factor of 5 and 10 in order to also investigate the
equilibrium behavior. This aspect is of crucial impor-
tance because, for a high efficiency in the successive
transesterification step of the process, the free acidity
must be lowered below the value of 1 wt %.
Results and Discussion
The esterification reaction between oleic acid and
methanol can be represented in the following schematic
form:
oleic acid + methanol a methyl oleate + water (2)
For the modeling of the experimental runs, a pseudo-
homogeneous second-order equilibrium model has been
used with an expression of the reaction rate, for eq 2,
that is as follows:
( )
1 x E xW
r ) kcxAxM 1 - C (3)
ke xAxM cat
xA, the molar fraction of the free oleic acid, has been
calculated by assuming an average molecular weight of
884 for the soybean oil, calculated on the basis of the
fatty acid composition of the used soybean oil that has
been determined by gas-chromatographic analysis. The
same approach has also been adopted for determining
the other molar fractions.
Different models have been reported in the litera-
ture5-8 that are able to describe, more or less accurately,
the kinetics of the esterification reactions. Other than
the pseudo-homogeneous model, represented by the
relation in eq 3, the Langmuir-Hinshelwood type
models have been used to describe heterogeneously
catalyzed esterifications.10 This class of models is char-
acterized by an increased number of parameters, one
for each component, that represent the adsorption
phenomenon. Furthermore, each of these additional
parameters is a function of temperature in the usual
two-parameter exponential form. In our investigation,
as a first approach, we have assumed that only metha-
nol and water are adsorbed by the polymeric resin,10
7980 Ind. Eng. Chem. Res., Vol. 44, No. 21, 2005

Table 2. List of Experimental Runs and Related Conditionsa

temp triglic. oleic acid methanol catalyst initial acidity molar ratio
run (C) (g) (g) (g) (g) (% by wt) methanol/oleic acid
1A 50 94.608 124.392 124.005 5.60 56.8 8.80
1B 65 90.634 119.166 120.010 5.42 56.8 8.89
1C1 85 85.068 118.932 116.010 5.40 58.3 8.61
1C2 85 86.400 113.600 117.160 10.00 56.8 9.10
1C3b 85 107.64 95.84 116.005 5.40 47.1 10.69
1D 100 85.536 112.464 106.000 5.25 56.8 8.32
2A 50 102.144 97.366 117.601 5.00 48.8 10.66
2B 65 89.677 108.723 116.980 5.00 54.8 9.50
2C 85 89.903 108.997 115.760 5.00 54.8 9.38
3A 50 108.738 140.862 147.580 5.00 56.4 9.25
3B 65 108.346 140.154 148.500 5.00 56.4 9.35
a Stirring speed ) 1500 rpm. b Powdered catalyst.

resulting in the following relation for the reaction, rate,

r)
kcxAxM
1 + KMxM + KWxW
1- (
1 xExW
C
ke xAxM cat ) (4)

in which two additional adsorption parameters, KM and

KW for methanol and water, respectively, are introduced.
The relation (eq 4) has been applied to the description
of experimental data (run 3B) without a significant
improvement in the fitting with respect to the pseudo-
homogeneous model (eq 3), and hence, this last has been
used for data correlation. Probably, a further increasing
of the number of adjustable parameters, corresponding
to the assumption that all the components are subjected
to adsorption onto the catalyst surface, could result in
a better fitting; however, for our purposes, the perfor-
mances of the model (eq 3) can be considered as
satisfactory. Figure 2. Arrhenius-type plot for the kinetic and equilibrium
The relation in eq 3 can be introduced into the constants.
material balance equations related to the batch reactor
from which the evolution with time of the mole number Table 3. Kinetic Parameters and Related Uncertainties
of each component can be evaluated. The material activation energy/
balance, for a generic component i, is therefore ex- parameter ln(preexponential factor) heat of reaction (kcal/mol)
pressed by an ordinary differential equation (ODE) of kc 12.93 ( 2.87 14.00 ( 0.99
the following form: ke 4.17 ( 0.04 2.68 ( 0.05

dni The determination of the kinetic parameters appear-

) irWcat
dt
The amounts of methanol and water that are present
in the vapor phase have been neglected in the molar
balance equation expressed by eq 5.
During the integration of the system of ODEs (eq 5),
(5) ing in eq 3, kinetic constant kc and equilibrium constant
ke, is performed by a nonlinear regression program that
iteratively adjusts these parameters until a predefined
criterion is satisfied. In our case, the criterion is the
minimization of an objective function of the following
type:

( )
sample withdrawing has been taken into account by
introducing a correction of the total volume of the liquid Nexp aexp - acalc 2

i i
phase corresponding to the sample volume (1-3 cm3). Fobj ) (7)
A further correction is introduced, knowing the sample i)1 aexp
i
composition, on the mole number of each component
that is decreased by the amount present in the sample. At each iteration in the parameter search, a complete
At the times corresponding to the sampling operations, integration in the time of the system (eq 5) has been
the variables are updated by using the following rela- performed with a fixed-step Runge-Kutta algorithm.
tions: The values of the parameters obtained at each temper-

{
ature have then been correlated by means of the usual
VL ) VL - VSj Arrhenius-type plot, allowing an evaluation of the
t ) tSj j ) 1, ..., NS i ) 1, ..., Nc
ni ) ni - nSj
i
activation energy and of the heat of the reaction. The
(6) obtained results are reported in Table 3, while in Figure
2, the Arrhenius-Vant Hoff plot is shown. The obtained
These corrections also allow the effect of catalyst value of the apparent activation energy, 14.0 kcal/mol,
concentration during the runs, although moderately is roughly in agreement with the value obtained by
occurring, to be taken into account, since catalyst is not Steinigeweg and Gmehling10 of 16.4 kcal/mol, related
withdrawn from the system. to the esterification of decanoic acid on a similar acid

Figure 3. Evolution of acidity with time for run 3A: comparison
between experimental data and model calculations.
Figure 4. Evolution of acidity with time for run 3B: comparison
between experimental data and model calculations.
resin, while the value obtained by Sendzikiene et al.9
in the presence of sulfuric acid as catalyst is much lower.
Our results related to the equilibrium constant show
that the reaction is characterized by a low endother-
micity (2.68 kcal/mol), because a slight increase of the
equilibrium constant with the temperature has been
observed. Also this result is in agreement with the
literature work of Steinigeweg and Gmehling,10 who
found an almost athermal reaction (0.92 kcal/mol) that
corresponds to a very slight increase of ke with the
temperature. A theoretical evaluation of the reaction
heat has furnished the low exothermic value of -0.67
kcal/mol that can be considered substantially in agree-
ment with the previous values by considering both the
relatively high uncertainty in the equilibrium constant
evaluation and the approximation of the literature data
used for the theoretical calculation.
Examples of the agreement between the model be-
havior and the collected experimental data on the
evolution with time of the mixture free acidity can be
appreciated in Figures 3-6. For the runs at tempera-
tures of 50, 65, and 85 C, for which equilibrium is
reached after several hours of reaction, long-term
behavior is reported. In these cases, no sample with-
drawals for the analysis were made during the night
(see Figure 4). On the contrary, at 100 C, a shorter
Ind. Eng. Chem. Res., Vol. 44, No. 21, 2005 7981
Figure 5. Evolution of acidity with time and effect of catalyst
concentration for runs 1C1 and 1C2: comparison between experi-
mental data and model calculations.
Figure 6. Evolution of acidity with time for run 1D: comparison
between experimental data and model calculations.
residence time is needed for reaching the equilibrium,
so only one run has been performed and is reported in
Figure 6.
Equation 3 is an expression of the intrinsic kinetics,
and the overall behavior of the reactive system can be
affected by mass transfer limitations for which a
contribution of both external and internal diffusion
resistances could be present.
The influence of the external diffusion resistance has
been evaluated by performing a set of preliminary runs
in which the stirring speed was varied from 200 to 1500
rpm. Above the threshold value of 1200 rpm, no
further increase of the reaction rate has been observed;
for the subsequent kinetic runs, a value of 1500 rpm
has been chosen.
The role of the internal diffusion coupled with chemi-
cal reaction has been investigated by performing an
additional run on finely powdered catalyst (run 1C3) at
the temperature of 85 C. The same amount of catalyst
used in run 1C1 (5 g) has been powdered (average size
< 0.05 mm) and introduced into the reactor in the same
concentration. In Figure 7 is reported the comparison
between the two runs in which only catalyst particle
size has been changed, and quite a low difference can
be observed. A quantitative evaluation of the effective-
ness factor has been made on the basis of the kinetic
7982 Ind. Eng. Chem. Res., Vol. 44, No. 21, 2005
Figure 7. Evolution of oleic acid conversion as a function of time
for runs 1C1 (catalyst in particles) and 1C3 (catalyst in powder).
constant for the two runs: 1.15 10-3 for run 1C1 and
1.20 10-3 for run 1C3, which corresponds to an
effectiveness factor of 0.96. This value has been
considered high enough to neglect the limitation related
to the internal diffusion. On the other hand, a change
in slope is not present in the Arrhenius plot between
85 and 100 C, and this confirms the absence of an
internal diffusion limitation.
Finally, in Figure 5, the capacity of the model to
describe the runs with different catalyst concentrations
is shown. In the mentioned figure, two runs at 85 C
with 5 and 10 g of catalyst, respectively, are reported
and described by the model with the same values of
kinetic and equilibrium constant. This information is
particularly useful if a scale-up or reactor-sizing calcu-
lation is performed.
Conclusions
The kinetics of oleic acid esterification with methanol
has been studied by using ion-exchange sulfonic resin
as the catalyst. Kinetic parameters of a pseudo-
homogeneous second-order model have been determined
by nonlinear regression on the experimental free-acidity
data collected in different runs performed in a batch,
well-stirred slurry reactor. A satisfactory agreement
between the model and the experiments has been
obtained, also considering that the model contains only
two adjustable parameters at a given temperature. The
kinetic parameters obtained are related to the intrinsic
kinetics, with the limitation of internal and external
mass transport separately investigated and excluded in
the operating condition applied.
As future developments and perspectives of the
present work, the extension of experimental activity in
different types of reactors will be considered. Moreover,
other factors affecting the reaction rate will be submit-
ted to investigation, such as the reactants molar ratio
and catalyst type.
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Received for review May 18, 2005
Revised manuscript received August 2, 2005
Accepted August 13, 2005
IE050588O