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1598
Research Article
Kinetic analysis for the esterication of high free fatty acid
feedstocks with a structural identiability approach
Efrn AguilarGarnica1, Yadira E. SilvaRomero1, Rosaura HernndezMontelongo2,
Juan Paulo GarcaSandoval2 and CsarArturo AcevesLara3, 4, 5
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Esterication is the rst step in the biodiesel production process from low cost feedstock, which is typically
characterized by its high content (>5%) of free fatty acids (FFAs). Although multiple attempts have been
made to describe the kinetics of the esterication process for this feedstock, there is no consensus regarding
which model is the most suitable. In this paper, two models were evaluated as candidates to describe the
esterication of grease trap wastes, a synthetic mixture of tallow fat and canola oil, and oleic acid, which all
have a high degree of acidity. The rst model considers a pseudorst order reaction, whereas the second
model considers the reversibility of the reaction. All parameters involved in these models are structurally
identiable and are estimated with the LevenbergMarquardt method. A statistical analysis based on
Akaikes weights show that the reversible model provides the best t for all experimental runs compared to
the rst order model. This result was obtained from variations in catalyst loading and moisture content.
Practical applications: The design and implementation of monitoring algorithms or robust control
laws for a process carried out in a continuous stirred tank reactor (CSTR) require the knowledge of its
dynamical mathematical model that contains a kinetic term. In the particular case of the esterication
reactions for feedstock with high content of FFAs developed in the presence of homogeneous acid
catalyst, there exists a discrepancy on the mathematical structure of such kinetic term. In this study we
perform some batch experiments, considering industrial reagent grade alcohols, to deduce which model
(among the two simplest kinetic models) better describes the esterication of oleic acid, grease trap wastes
and a mixture of tallow fat and canola oil. Then, the results obtained from this basic research could be
applied if monitoringregulation tasks are required for the esterication of the feedstock considered herein
when such esterication be carried out in a CSTR under industrial conditions.
Keywords: Biodiesel / Esterification / Grease trap wastes / Kinetics / Structural identifiability
Received: January 31, 2014 / Revised: May 12, 2014 / Accepted: June 5, 2014
DOI: 10.1002/ejlt.201400059
Additional Supporting Information may be found in the online version of this article http://dx.doi.org/
10.1002/ejlt.201400059
1 Introduction
Organic esters are of great interest in diverse industrial areas,
such as perfumery and agrochemistry [1], and special
Correspondence: Dr. Efrn AguilarGarnica, Av. Patria 1201, Guadalajara, Jalisco 44100, Mexico
Email: efren.aguilar@edu.uag.mx, eyi_20@hotmail.com
Fax: 52 33 36 48 88 24x32220
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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E. AguilarGarnica et al.
3.2 Experimental
3.2.1 Moisture and FFAs content in feedstock
The analysis of the water present in the grease trap wastes
and in both brands of industrial reagent grade methanol
(Pochteca and Diquisa) was carried out with a KarlFischer
Titrator (Mettler DL18), which automatically provides
the moisture content of the sample using the titration
volume of the Hydranalcomposite 2 reagent and the exact
weight of the sample (150 mg). The FFAs content for the
feedstocks (i.e., oleic acid, tallow fatcanola oil mixture and
grease trap wastes) was computed using the American Oil
Chemists Society Ofcial Method Cd 3d63 (AOCS,
1998). In this technique, the sample is dissolved in a
mixture of solvents (50% isopropyl alcohol/50% toluene)
and then titrated with a 0.1 N KOH solution using
phenolphthalein as the indicator. The percentage of FFAs
is expressed as
%FFAs
5:61V
2m
3.1 Materials
The wastes from grease traps were supplied by a local
company (Solucin Ambiental de Mxico, Guadalajara,
Jalisco, Mxico) and had suspended solids, triglycerides,
moisture, and FFAs with the following fatty acid distribution:
44.72% oleic acid, 20.31% palmitic acid, 13.50% linoleic
acid, and 11.83% stearic acid according to GC (Agilent 6980)
analysis. Remarkably, the presence of esters was not
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2%FFAsmFFAo
AV mFFAo
100056:1V r
100056:1V r
5a
This version of the RKM has been derived from Eq. (5)
considering the stoichiometry for CE and CW, the absence of
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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F
S yy
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E. AguilarGarnica et al.
2pi pi 1
N pi 1
Figure 1. Effect of the brand of alcohol and the catalyst content in the
esterication of oleic acid. For methanol Pochteca: C M 0 16:87M
and C W 0 0:091M. For methanol Diquisa: C M 0 14:89M and
C W 0 3:608M ((a) Pochteca, 5 wt% cat., (b) Pochteca, 2.5 wt%
cat., (c) Diquisa, 5 wt% cat., (d) Diquisa, 2.5 wt% cat.).
Table 1. Initial concentration for oleic acid, the tallow fatcanola oil
mixture and the grease trap wastes
Feedstock
Oleic acid
Tallow fatcanola oil mixture
Grease trap wastes
%FFAs
CA (0) (M)
99.00
58.85
78.47
0.844
0.705
0.798
1603
Figure 2. Effect of the brand of alcohol and the catalyst content in the
tallow fatcanola oil mixture. For methanol Pochteca: C M 0 14:10M
and C W 0 0:076M. For methanol Diquisa: C M 0 12:25M and
C W 0 2:968M ((a) Pochteca, 5 wt% cat., (b) Pochteca, 2.5 wt% cat.,
(c) Diquisa, 5 wt% cat., (d) Diquisa, 2.5 wt% cat.)
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Kinetic model
FOKM
RKM
FOKM
RKM
FOKM
RKM
FOKM
RKM
Estimation results
k1
k1
k2
k1
k1
k2
k1
k1
k2
k1
k1
k2
0:075
0:089
0:067
0:057
0:065
0:077
0:0021
0:0034
0:0045
0:0010
0:0015
0:0038
Confidence interval
0:042 < k1
0:065 < k1
0:033 < k2
0:027 < k1
0:037 < k1
0:008 < k2
0:0015 < k1
0:0023 < k1
0:0009 < k2
0:0008 < k1
0:0012 < k1
0:0021 < k2
< 0:109
< 0:112
< 0:100
< 0:088
< 0:094
< 0:146
< 0:0028
< 0:0045
< 0:0081
< 0:0011
< 0:0017
< 0:0055
R2
wi
0.988
0.999
0.001
0.999
0.965
0.990
0.036
0.964
0.881
0.965
0.048
0.952
0.951
0.993
0.003
0.997
R2
wi
0.994
0.999
0.001
0.999
0.993
0.997
0.161
0.839
0.724
0.907
0.078
0.922
0.771
0.939
0.032
0.968
Table 3. Parameter estimation results for the tallow fatcanola oil mixture esterication
Reaction conditions
Kinetic model
FOKM
RKM
FOKM
RKM
FOKM
RKM
FOKM
RKM
Estimation results
k1
k1
k2
k1
k1
k2
k1
k1
k2
k1
k1
k2
0:026
0:027
0:016
0:014
0:014
0:0094
0:0019
0:0038
0:0099
0:0012
0:0026
0:010
Confidence interval
0:022 < k1
0:025 < k1
0:011 < k2
0:012 < k1
0:013 < k1
0:0007 < k2
0:0011 < k1
0:0019 < k1
0:0009 < k2
0:0009 < k1
0:0015 < k1
0:002 < k2
< 0:030
< 0:029
< 0:022
< 0:016
< 0:017
< 0:018
< 0:0025
< 0:0059
< 0:019
< 0:0016
< 0:0038
< 0:018
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Table 4. Parameter estimation results for the grease trap wastes esterication
Reaction conditions
Kinetic model
FOKM
RKM
FOKM
RKM
FOKM
RKM
FOKM
RKM
Figure 4. Inuence of catalyst amount and initial water concentration over the kinetic parameter k1 involved in the RKM for diverse
feedstock.
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Estimation results
k1
k1
k2
k1
k1
k2
k1
k1
k2
k1
k1
k2
0:074
0:091
0:080
0:029
0:040
0:056
0:0036
0:025
0:056
0:0019
0:0076
0:023
Confidence interval
0:042 < k1
0:070 < k1
0:047 < k2
0:016 < k1
0:026 < k1
0:023 < k2
0:0010 < k1
0:008 < k1
0:010 < k2
0:0008 < k1
0:0023 < k1
0:002 < k2
< 0:105
< 0:112
< 0:115
< 0:042
< 0:054
< 0:090
< 0:0062
< 0:044
< 0:101
< 0:0029
< 0:013
< 0:044
R2
wi
0.984
0.999
0.001
0.999
0.965
0.996
0.001
0.999
0.113
0.930
0.001
0.999
0.327
0.925
0.004
0.996
5b
FFAO
where f 100056:1V
and AV0 is the initial value of the
r
sample. Let us rst consider the results obtained by Marchetti
et al., for the esterication of oleic acid with ETHANOL at
45C, 200rpm and a 6.124:1 molar ratio of ethanol to FFAs
content considering 5 wt% catalyst loading. In this contribution, the experimental results are described graphically as the
conversion of FFAs (XFFA) and they can be easily transformed into acid value according with the expression
AV AV01 X FFA . These experimental data are shown
as dots in Fig. 5 with AV0 21:368 (i.e., 10.684 %FFAs).
In this study, the esterication of oleic acid at 60C, 500 rpm,
a 20:1 molar ratio of methanol to FFAs content with 5 wt%
catalyst loading is the experiment whose operation conditions
remain closer than the conditions reported by Marchetti et al.
For this case the estimated kinetic parameters were: k1
0:089 and k2 0:067. Besides, for this experiment:
mFFAO 119:2 g, V r 0:5 L and C M 0 16:87M. Thus,
mFFAO
0:004. The
k k1 C M 0 1:493 and f 100056:1V
r
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