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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.
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
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
curve (points 2 and 4). This procedure leads to simulation results (3) Ni, J.; Meunier, F. C. Esterification of free fatty acids in sunflower
with better agreement between the experimental data and the oil over solid acid catalysts using batch and fixed bed-reactors. Appl.
kinetic model (gray line in Figure 2). From Table 4 it can be seen Catal., A 2007, 333, 122.
that the optimized condition (case 2) leads to a closer conversion (4) Berrios, M.; Siles, J.; Martín, M. A.; Martín, A. A Kinetic study of
calculated (90%) with a lower residue Q, indicating a lower the esterification of free fat acids (FFA) in sunflower oil. Fuel 2007, 86,
2383.
deviation between the experiments and the simulations. (5) Marchetti, J. M.; Errazu, A. F. Esterification of free fatty acids
using sulfuric acid as catalyst in the presence of triglycerides. Biomass
Bioenergy 2008, 32, 892.
5. CONCLUSIONS
(6) Mengyu, G.; Deng, P.; Li, M.; En, Y.; Jianbing, H. The kinetics of
From the reaction kinetic model it was possible to represent the esterification of free fatty acids in waste cooking oil using Fe2-
the experimental data of fatty acids esterification for the produc- (SO4)3/C catalyst. Chin. J. Chem. Eng. 2009, 17, 83.
tion of biodiesel. The inverse routine applied (R2W) led to a (7) Marchetti, J. M.; Miguel, V. U.; Errazu, A. F. Heterogenous
good fit between the experimental data and the simulation results esterification of oil with high amount of free fatty acids. Fuel 2007, 86,
which validates the utilization of such a kinetic model in such 906.
reactions. The veracity of the kinetic constants is verified through (8) Cordeiro, C. S.; Arizaga, G. G. C.; Ramos, L. P.; Wypych, F. A
new zinc hydroxide nitrate heterogeneous catalyst for the esterification
the comparison between the experimental and calculated con- of free fatty acids and the transesterification of vegetables oils. Catal.
version values at the equilibrium obtained from the equilibrium Commun. 2008, 9, 2140.
constants. The equilibrium constants also were used in the (9) Ozbay, N.; Oktar, N.; Tapan, N. A. Esterification of free fatty
determination of the thermodynamic properties, enthalpy and acids in the waste cooking oils (WCO): Role of ion-exchange resins. Fuel
entropy. In all cases the increase in the temperature increased 2008, 87, 1789.
both the enthalpy and entropy. The increase in the enthalpy is (10) Tesser, R.; Casale, L.; Verde, D.; Di Serio, M.; Santacesaria, E.
related to endothermic behavior. The influence of hydrated etha- Kinetics and modeling of fatty acids esterification on acid exchange
nol in the thermodynamic properties can probably be attributed resins. Chem. Eng. J. 2010, 157, 539.
to different dissociation constants of the carboxylic acids asso- (11) Tesser, R.; Casale, L.; Verde, D.; Di Serio, M.; Santacesaria, E.
Kinetics of fatty acids esterification: Batch and loop reactor modeling.
ciated with stabilization of the carboxylic anion by water. Statisti-
Chem. Eng. J. 2009, 154, 25.
cal treatment of the experimental data can be used to improve the (12) Chongkhong, S.; Tongurai, C.; Chetpattananondh, P. Conti-
accuracy in the estimation of the kinetic constants and conse- nous esterification for biodiesel production from palm fatty acid distillate
quently the calculation of the enthalpy and entropy. using economical process. Renewable Energy 2009, 34, 1059.
(13) Chongkhong, S.; Tongurai, C.; Chetpattananondh, P.; Bunyakan,
’ NOMENCLATURE C. Biodiesel production by esterification of palm fatty acid distillate.
Biomass Bioenergy 2007, 31, 563.
HE = hydrated ethanol (14) Srilatha, K.; Lingaiah, N.; Devi, B. L. A. P.; Prasad, R. B. N.;
AE = anhydrous ethanol Venkateswar, S.; Prasad, P. S. S. Esterification of free fatty acids for
C = concentrations biodiesel production over heteropoly tungstate supported on niobia
k1 and k2 = kinetic constants, L/(mols 3 min) catalyst. Appl. Catal. A 2009, 365, 28.
keq = equilibrium constant (15) Yujaroen, D.; Goto, M.; Sasaki, M.; Shotipruk, A. Esterification
ΔG = variation in free Gibbs energy of palm fatty acid distillate (PFAD) in supercritical methanol: Effect of
ΔH = variation in the enthalpy, kJ/mol hydrolysis on reaction reactivity. Fuel 2009, 88, 2011.
ΔS = variation in the entropy, J/(mol 3 K) (16) Caetano, C. S.; Fonseca, I. M.; Ramos, A. M.; Vital, J.;
T and R = temperature and universal constant (8.314 Castanheiro, J. E. Esterification of free fatty acids with methanol using
heteropolyacids. Catal. Commun. 2008, 9, 1996.
j/mol 3 K), respectively
(17) Caetano, C. S.; Guerreiro, L.; Fonseca, I. M.; Ramos, A. M.;
Q = square residue Vital, J.; Castanheiro, J. E. Esterification of fatty acids to biodiesel over
polymers with sulfonic acid groups. Appl. Catal., A 2008, 9, 1996.
’ AUTHOR INFORMATION (18) Grossi, C. V.; Jardim, E. O.; Araujo, M. H.; Lago, R. M.
Sulfonated polystyrene: A catalyst with acid and superabsorbent proper-
Corresponding Author ties for the esterification of fatty acids. Fuel 2010, 89, 257.
*E-mail: dcamara@iprj.uerj.br. (19) Aranda, D. A. G.; Gonc-alves, J. A.; Taft, C. A. The use of acids,
niobium oxide and zeolite catalyst for esterification reactions. J. Phys.
Org. Chem. 2009, 22, 709.
’ ACKNOWLEDGMENT (20) Alenezi, R.; Leeke, G. A.; Winterbottom, J. M.; Santos, R. C. D.;
The authors acknowledge the financial support provided by Khan, A. R. Esterification kinetics of free fatty acids with supercritical
CNPq, FAPERJ, CAPES, UFRJ, UERJ (Instituto Politecnico- methanol for biodiesel production. Energy Convers. Manage. 2010, 51,
IPRJ) and CBMM. 1055.
(21) Le~ao, L. S.; Empirical and kinetic study of esterification of fatty
acids on niobium acid. Master Thesis, Federal University of Rio de
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