ARTICLE

pubs.acs.org/IECR

Reaction Kinetic Study of Biodiesel Production from Fatty Acids

Esterification with Ethanol
L. D. T. C^amara*,† and D. A. G. Aranda‡
†
Departamento de Engenharia Mec^anica e Energia (DEMEC), Instituto Politecnico da Universidade do Estado do Rio de Janeiro (IPRJ-
UERJ), Nova Friburgo-RJ, Brazil
‡
Departamento de Engenharia Química, Laboratorio de Tecnologias Verdes (GreenTec), Escola de Química da Universidade Federal do
Rio de Janeiro (EQ-UFRJ), Rio de Janeiro-RJ, Brazil

ABSTRACT: The kinetic of fatty acids esterification with ethanol utilizing niobium oxide catalyst (79.8% of NbO5 and 19.6% of
water) for the production of biodiesel was analyzed through a reversible kinetic modeling for the determination of the kinetic and
thermodynamic data of the reactions. The reactions were carried out with three kinds of fatty acids (stearic, palmitic, and lauric) with
anhydrous and hydrated ethanol. From the kinetic study it was possible to calculate the theoretical equilibrium data which were
compared to experimental data of each reaction. From the comparison between the experimental and calculated conversions it was
possible to analyze the accuracy of the estimations, providing a good way to apply statistical treatments in the improvement of the
kinetic and thermodynamic properties calculated.

1. INTRODUCTION reverse direction. They studied the esterification of free fatty

The production of biodiesel from raw materials that can be
used for food is not the best way to generate and develop
renewable energy.1 Therefore, the alternative sources, such as
the fatty acids (byproduct), are a good option as these materials
lead to low cost biodiesel production without interfering in food
production.2
In the literature there are many works related to research and
development of technologies for the conversion of fatty acids
into biodiesel.3-20 There are researches where the main objective
is the conversion of pure fatty acids,3-11 and others in which
the fatty acids are part of the oil phase medium.12-20 In the latter
case sometimes it is necessary to convert the fatty acids to reduce
the problems of saponification which reduce the yield of the
reaction of transesterification by alkali.
In the reactions of esterification for the production of biodiesel
a great variety of catalyst are found, such as sulfuric acid,4,5,12,13
acid resins,3,7,9-11 acid polymers17,18 and others (tungstophos-
phoric acid,14,16 tungstosilicic acid,16 niobium oxide (Nb2O5),19
zinc hydroxide nitrate (Zn5(OH)8(NO3)2 3 2H2O)8 and Fe2-
(SO4)3/C).6 The most common is sulfuric acid and acid resins
used in the catalysis of such reactions. The use of niobium oxide is
a promising possibility observed in a previous work.19 In the
work of Aranda et al.19 different catalysts were tested and com-
pared in the esterification of a mixture of fatty acids residue. They
observed a better performance of the polynaphthalene sulfonic
acid and the niobium oxide (Nb2O5) if compared to that of a
zeolite catalyst. The authors also observed higher conversion
when utilizing the methanol if compared to using the ethanol.
From the literature can be seen works related to the kinetic
modeling studies of the esterification reactions of fatty acids for
the production of biodiesel.4,6,10,11,19,20 In the work of Berrios
et al.4 the authors applied a reversible reaction kinetic model that
is first order in the forward direction and second order in the
acids in sunflower oil with methanol and sulfuric acid. They
determined the activation energies by the Arrhenius equation,
observing a decrease in the activation energy with an increase in
the catalyst concentration. Tesser et al.10 applied a detailed kinet-
ic/equilibrium model that takes into account different aspects of
the esterification of oleic acid with soybean oil with methanol and
acid exchange resins. The developed kinetic model was able to
correctly represent the experimental data both as a function of
temperature and of catalyst concentration. In the work of Aranda
et al.19 the authors applied two different kinetic models to study
the esterification of fatty acids with polynaphthalene sulfonic
acid, niobium oxide, and zeolite catalyst utilizing ethanol and
methanol. They studied an empiric heterogeneous model and a
homogeneous model. The parameters for both models were
obtained utilizing the Statistical software and applying nonlinear
regression. The authors observed that the homogeneous model is
more adequate to represent the esterification with methanol,
whereas the heterogeneous model better represents the ester-
ification with ethanol.
This work presents the study of the kinetics of fatty acid
esterification with ethanol and niobium oxide catalyst (NbO5) for
the production of biodiesel. A reversible kinetic model was
assumed in the determination of the kinetic parameters of three
different kinds of pure fatty acids (stearic, palmitic, and lauric)
with anhydrous and hydrated ethanol. From the experimental
equilibrium data, it was possible to analyze the accuracy of the
Special Issue: IMCCRE 2010
Received: March 10, 2010
Accepted: June 24, 2010
Revised: June 23, 2010
Published: July 12, 2010

r 2010 American Chemical Society 2544 dx.doi.org/10.1021/ie1005806 | Ind. Eng. Chem. Res. 2011, 50, 2544–2547
Industrial & Engineering Chemistry Research ARTICLE

Table 1. Experimental and Calculated Data for Esterification of Stearic Acid

temp (oC) k1 (L/(mols 3 min)) k2 (L/(mols 3 min)) keq = k1/k2 expt convn (%) calcd convn (%) ΔH (kJ/mol), ΔS (J/(mol 3 K))

stearic HE 150 0.0021 0.0999 0.021 22 21 193.2, 428.6

200 0.0116 0.0016 7.25 77 94

stearic AE 150 0.0063 0.2958 0.021 21 22 145.5, 311.3

200 0.0171 0.0108 1.58 78 81

Table 2. Experimental and Calculated Data for Esterification of Palmític Acid

temp (oC) k1 (L/(mols 3 min)) k2 (L/(mols 3 min)) keq = k1/k2 expt convn (%) calcd convn (%) ΔH (kJ/mol), ΔS (J/(mol 3 K))

palmitic HE 150 0.0106 1.1673 0.01 17 15 151.3, 319.3

200 0.0104 0.0111 0.94 73 74

palmitic AE 150 0.0108 0.0587 0.18 52 49 111.7, 249.8

200 0.0174 0.0034 5.11 84 92

Table 3. Experimental and Calculated Data for Esterification of Lauric Acid

temp (oC) k1 (L/(mols 3 min)) k2 (L/(mols 3 min)) keq = k1/k2 expt convn (%) calcd convn (%) ΔH (kJ/mol), ΔS (J/(mol 3 K))

lauric HE 150 0.0081 0.0485 0.17 50 47 55.9, 117.2

200 0.0100 0.0110 0.91 75 74

lauric AE 150 0.0029 0.0708 0.04 31 28 189.2, 420.4

200 0.0155 0.0013 11.9 84 96

estimations and determine the thermodynamic properties of the

reactions studied.

2. EXPERIMENTAL SECTION
Three types of fatty acids (acid stearic, palmitic, and lauric)
were studied in terms of esterification with ethanol (anhydrous
ethanol AE and hydrated ethanol HE) for the production of
biodiesel.21 The HE utilized comprised 4% w/w water. The
reactions were carried out in autoclave batch reactor with
temperature control (Parr Instruments 4560). The solid catalyst
utilized was the niobium oxide (79.8% NbO5 and 19.6% water;
superficial area of 180 m2/g) at 20% w/w in relation to the
quantity of fatty acid. The excess molar ratio of alcohol was set to
3 to provide a more favorable reaction kinetic for the formation of
products. The reaction products were analyzed through gas
Figure 1. Correlation between the kinetic model and the experimental
chromatography with samples taken periodically from the re- data for the palmitic acid esterification at 200 °C (HE, hydrated ethanol;
actor. The analytical method was based on the EN 14103 method AE, anhydrous ethanol).
using a capillary column (Carbowax 20M) 30 m
0.32 mm

0.25 μm and methyl heptadecanoate and heptadecanoic acid as The R2W is a simple method of search by random estimations in
internal standards. the domain of the parameters. In this inverse routine initially
there is a random estimation of the parameters, and after the
determination of the best solution there is a new restricted search
3. KINETIC AND THERMODYNAMICAL MODELING near the best solution encountered in the previous step. The best
The reaction of esterification was modeled through a rever- solution is obtained by the square residue function (Q) which is
sible kinetic model (eq 1) with the kinetic constants k1 and k2 obtained through the comparison between the experimental
related, respectively, to the direct and inverse reaction. The (Cexpt) and calculated (Ccalcd) concentrations (eq 2).
correlation with the experimental data, to calculate the kinetic X
n
constants k1 and k2, was done utilizing the stochastic routine Q ¼ ðCexpti - Ccalcdi Þ2 ð2Þ
R2W (Random Restricted Window).22 i¼1

dCbio From the calculations of the equilibrium constant utilizing the

¼ k1 Cf at acid Cethanol - k2 Cbiodiesel Cwater ð1Þ
dt kinetic constants k1 and k2 (eqs 2) it was possible to determine
2545 dx.doi.org/10.1021/ie1005806 |Ind. Eng. Chem. Res. 2011, 50, 2544–2547
Industrial & Engineering Chemistry Research
Table 4. Statistical Treatment for the Esterification of Stearic Acid at 200 °C
case k1 (L/(mols 3 min)) k2 (L/(mols 3 min))
stearic HE 1 0.0116 0.0016
2 0.0133 0.0034
Figure 2. Statistical analysis in the correlation between the kinetic
model and the experimental data for the stearic acid esterification at
200 °C.
the free Gibbs energy and the enthalpy and entropy variation
(eqs 4 and 5).
k1
keq ¼ =k 2
ΔG ¼ - RT lnðkeq Þ
ΔG ¼ ΔH - TΔS
From the equilibrium constant calculated before, the theoretical
conversion of the reaction utilizing the following expression
(eq 6) can be determined. In eq 6 the equilibrium constant is
related to the concentration of the species considering the
stoichiometry of the reaction. The concentration of the com-
pounds in eq 6 can be converted in a conversion that is
determined with the value of the equilibrium constant
(calculated conversion can be found in Tables 1, 2, and 3). In
the case of alcohol excess, eq 6 must take into account such an
effect in the calculation of the equilibrium constant.
Cbiodiesel Cwater
keq ¼
Cf at acid Cethanol
4. RESULTS AND DISCUSSION
The first step in this work was the calculation of the kinetic
constants (eq 1) utilizing the experimental data of fatty acid
esterification with ethanol. Figure 1 shows the good fit between
the kinetic model and the experiments of palmitic fatty acid
utilizing hydrated ethanol (HE) and anhydrous ethanol (AE).
Figure 1 shows the more favorable reaction (in general) for the
use of anhydrous ethanol (AE). In general it can be observed that
there is a higher conversion when utilizing the anhydrous ethanol
(HE), but higher results of conversion also can be obtained with
hydrated ethanol. Experimentally it was observed that depending
ARTICLE
keq = k1/k2 expt convn (%) calcd convn (%) residue Q (mol/L)
7.25 77 94 101.7
3.97 77 90 7.0
on the reaction condition any fatty acid can achieve a higher
conversion with hydrated ethanol. Probably the molecular size
has a significant effect as the higher molecular fatty acid led to a
higher number of conversions with hydrated ethanol (stearic
fatty acid).
The Table 1 presents the kinetic constants (k1 and k2), the
equilibrium constant, the experimental conversion at the equi-
librium (considered 60 min of reaction), the calculated conver-
sion at the equilibrium (from eq 5) and the enthalpy and entropy
(from eq 4), respectively, for the esterification reaction of stearic
acid with HE and AE. In a comparison of the experimental and
theoretical values of conversion, it can be observed that the
results are very close to each other, which validates the kinetic
model applied to the reaction of esterification and the values of
kinetic constants estimated for each condition of temperature.
Some discrepancies can be attributed to the error associated to
the experimental measurement; therefore, a statistical analysis
can be used to improve the correlation leading to an estimation of
the parameters with higher accuracy.
The same properties were obtained for the esterification of
palmitic acid (Table 2) and lauric acid (Table 3) also showing the
results of experimental and theoretical conversion being very
close to each other. The results of enthalpy and entropy variation
ð3Þ
for the esterification of the three types of fatty acids showed
reactions with endothermic behavior and positive increase in the
ð4Þ entropy. Marchetti et al.7 also observed endothermic behavior
studying the esterification of fatty acids with acid resins and
anhydrous ethanol. For the stearic and palmitic acid the enthalpy
ð5Þ and entropy variation was lower for the esterification with anhy-
drous ethanol (AE) if compared to the hydrated ethanol (HE). The
inverse behavior was observed for the esterification of lauric acid.
The influence of hydrated ethanol in the thermodynamic
properties can be probably attributed to different dissociation
constants of the carboxylic acids associated with stabilization of
the carboxylic anion by water. The dissociation constants of
carboxylic acids (pka) increase with the decrease in the molecular
chain size (pka of stearic acid > palmitic > myristic > lauric).23
The presence of water in the reaction medium stabilizes the
conjugate base (A:(-)) of the fatty acid which shifts the
equilibrium to the right. The fatty acid with the lower dissocia-
tion constant is the stearic acid, so the aqueous medium can
ð6Þ probably influence the reaction more significantly. In this case
the water probably has a more significant effect in the dissociation
of the stearic acid, which manifests into a higher number of
conversions with HE.
Table 4 presents a statistical treatment for the condition of
high deviation between the experimental and calculated conver-
sion for the esterification of stearic acid (T = 200 °C and HE).
The residue Q represents the deviation between the experimental
data and the simulation results. A higher residue Q represents a
higher deviation. The original correlation, with all experimental
points (black and white points), can be seen in Figure 2 in which
the black line corresponds to simulations from the kinetic model.
The statistical treatment of the experimental data was performed
omitting the experimental points with more deviation from the
2546 dx.doi.org/10.1021/ie1005806 |Ind. Eng. Chem. Res. 2011, 50, 2544–2547
Industrial & Engineering Chemistry Research
curve (points 2 and 4). This procedure leads to simulation results
with better agreement between the experimental data and the
kinetic model (gray line in Figure 2). From Table 4 it can be seen
that the optimized condition (case 2) leads to a closer conversion
calculated (90%) with a lower residue Q, indicating a lower
deviation between the experiments and the simulations.
5. CONCLUSIONS
From the reaction kinetic model it was possible to represent
the experimental data of fatty acids esterification for the produc-
tion of biodiesel. The inverse routine applied (R2W) led to a
good fit between the experimental data and the simulation results
which validates the utilization of such a kinetic model in such
reactions. The veracity of the kinetic constants is verified through
the comparison between the experimental and calculated con-
version values at the equilibrium obtained from the equilibrium
constants. The equilibrium constants also were used in the
determination of the thermodynamic properties, enthalpy and
entropy. In all cases the increase in the temperature increased
both the enthalpy and entropy. The increase in the enthalpy is
related to endothermic behavior. The influence of hydrated etha-
nol in the thermodynamic properties can probably be attributed
to different dissociation constants of the carboxylic acids asso-
ciated with stabilization of the carboxylic anion by water. Statisti-
cal treatment of the experimental data can be used to improve the
accuracy in the estimation of the kinetic constants and conse-
quently the calculation of the enthalpy and entropy.
’ NOMENCLATURE
HE = hydrated ethanol
AE = anhydrous ethanol
C = concentrations
k1 and k2 = kinetic constants, L/(mols 3 min)
keq = equilibrium constant
ΔG = variation in free Gibbs energy
ΔH = variation in the enthalpy, kJ/mol
ΔS = variation in the entropy, J/(mol 3 K)
T and R = temperature and universal constant (8.314
j/mol 3 K), respectively
Q = square residue
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: dcamara@iprj.uerj.br.
’ ACKNOWLEDGMENT
The authors acknowledge the financial support provided by
CNPq, FAPERJ, CAPES, UFRJ, UERJ (Instituto Politecnico-
IPRJ) and CBMM.
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dx.doi.org/10.1021/ie1005806 |Ind. Eng. Chem. Res. 2011, 50, 2544–2547