Eur. J. Lipid Sci. Technol.

2014, 116, 15981607

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
1
2
3
4
5

Departamento de Qumica, Universidad Autnoma de Guadalajara, Guadalajara, Mxico

Departamento de Ingeniera Qumica, Universidad de Guadalajara, Guadalajara, Mxico
Universit de Toulouse, INSA, UPS, INP, Toulouse, France
INRA, UMR792, Ingnierie des Systmes Biologiques et des Proceds, Toulouse, France
CNRS, UMR5504, Toulouse, France

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

attention has recently been paid to their use as biodiesel.

This biofuel provides a number of environmental benets,
such as nonsulfur emissions, nonparticulate matter and
lower CO emissions, in comparison to the diesel derived from
petroleum [2]. Biodiesel is conventionally produced by a
reaction known as transesterication, where the rened
feedstock reacts with a shortchain alcohol in the presence of
a homogeneous inorganic basic catalyst [3]. This rened
feedstock mainly contains saponiable lipids such as
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Eur. J. Lipid Sci. Technol. 2014, 116, 15981607

triglycerides and free fatty acids (FFAs) with a triglycerides

content much higher than the FFAs content. However, if the
transesterication is performed for cheaper feedstock (which
is usually characterized by its high FFAs content (>5%)),
then soap will form, which appreciably reduces the process
yield. Therefore, it is strongly recommended that the
biodiesel production process should be conducted in two
stages [4]. In the rst stage (known as esterication), the free
fatty acids (FFAs) in the feedstock are converted into organic
esters in the presence of a homogeneous acid catalyst. Then,
the esteried product passes through the conventional
alkaline homogeneous transesterication technology. For
scale up, for regulation purposes or if behavioral prediction is
desired for this process, it is necessary to know the kinetics at
both stages. The transesterication kinetics using homogeneous alkaline catalysts has been extensively studied with a
generalized consensus on the use of a secondorder kinetic
model for all the reactions involved in the mechanisms (see
e.g., [57]). The esterication kinetics of feedstock with high
FFAs content in the presence of homogeneous acid catalysts
has also been largely analyzed but, in this case, there is a
discrepancy concerning the reaction order. For instance, a
rstorder kinetic model has been proposed for describing the
esterication of diverse feedstock such as palmitic acid [8],
oleic acid [9], palm fatty acids [10], and waste fryer oil [11].
On the contrary, there are some researchers that have been
proposed to consider the reversibility of the esterication
reaction in the kinetic study. In one case, a pseudo
homogeneous reaction: rst order in the forward direction
and second order in the reverse direction has been considered
to describe the esterication kinetics of FFAs in sunower oil
with alcohol excess [12]. In other approaches, a second order
kinetic model (in both reaction directions) has been proposed
to describe the esterication kinetics of FFAs in jatropha
oil [13] and the esterication kinetics of oleic acid [14].
In spite of all these esterication kinetic studies for diverse
feedstock with high content of FFAs, there still remain to
study the esterication kinetics of diverse feedstock such as
grease trap wastes, which contains a complex blend of FFAs.
These wastes are routinely collected from the grease traps of
large food processing and service facilities before entering the
sewage system. Then, they are abundantly available and this
causes a municipal solidwaste disposal problem [15, 16].
The transformation of these wastes into biodiesel might
address this problem and this is why these wastes were
analyzed herein.
Specically, in this paper, a kinetic study for grease trap
wastes esterication with industrial grade alcohols and
homogeneous acid catalyst is developed considering the
existing discrepancy on the esterication kinetic model
approach. That is, the aim of this study is to dene which
model, among the rstorder model and a model considering
esterication reversibility, is the one that best ts the
experimental data. The esterication of another feedstock,
such as oleic acid and a mixture of tallow fat with canola oil,
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Kinetic analysis for the esterification of high free fatty

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has also been studied in order to compliment the present

study. Specically, the mixture was selected because it has
similar fatty acid content to the grease trap wastes, but it has
the benet that it can be easily treated, as it is odorless with
no moisture content. The oleic acid was also evaluated as
a feedstock in this research because it is the common
component in both the grease trap wastes and the synthetic
mixture. Finally, it is important to remark that kinetic study
that has been developed in this contribution includes a
structural identiability analysis for the parameters of the
kinetic models which is necessary, but often ignored, in most
of the kinetic analysis that have been published.

2 Mechanism and kinetics

Fischer and Speier [17] have proposed a mechanism for
the homogeneous acidcatalyzed esterication of carboxylic
acids (FFAs) whose overall reaction of the aforementioned
mechanism can be schematized by the equation
AM $E W

where A represents the carboxylic acid, M is the alcohol, E

denotes the organic ester, and W is water. The kinetic model
that governs an esterication reaction carried out in batch
process can be readily derived from a mole balance of Eq. (1)
to obtain:
dC A
k1 C A C M k2 C E C W
dt

where k1 and k2 are the kinetic parameters, C A ; C M ; C E ;

and C W represent the concentration of each chemical
involved in the reaction and t is the time. If an excess of
methanol over the FFAs content is used, the previous
equation can be rewritten as
dC A
kC A
dt

or according to Berrios et al. [12], Eq. (2) can also be

rewritten as
dC A
kC A k2 C E C W
dt

Equation (3) will be labeled here as the (pseudo) First

Order Kinetic Model (FOKM). Notably, the term containing
the concentration of the products disappears in this model.
An excess of alcohol will enhance the production of esters
and water (according to the wellknown LeChteliers
principle); therefore, the kinetic model will solely depend
on the concentration of the reagents. The concentration of the
FFAs is explicitly considered in the model, whereas the
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Eur. J. Lipid Sci. Technol. 2014, 116, 15981607

constant concentration of the alcohol is embedded within

the pseudoconstant k. That is, k k1 C M with CM being
approximated as C M C M 0 where C M 0 is the initial
concentration of methanol. This fact is also considered in
Eq. (4) that denes the esterication reaction as pseudo
homogeneous: rst order for products formation and second
order in the reverse direction. Eq. (4) can be rewritten as
dC A
kC A k2 C E 0 C A 0  C A
dt
 C W 0 C A 0  C A

when the concentrations of the ester and water are

represented in terms of the FFAs concentration using
stoichiometry of Eq. (1) as follows:
C E C E 0 C A 0  C A ; C W C W 0 C A 0  C A
Equation (5) differs from Eq. (3) primarily because it
preserves the term containing the concentration of products. This implies that Eq. (5) retains the hypothesis of
reversibility in the esterication process and therefore
such equation can be known as Reversible Kinetic Model
(RKM).
Many other kinetic models have been deduced for
esterication processes carried out with homogeneous acid
catalyst. For instance, Arajo et al. [18] have been described
the esterication of vegetable cotton seed oil with a model
containing three kinetic parameters model or Marchetti
et al. [19] have been proposed a ve kinetic parameters
model to describe the esterication of rened sunower oil.
According to the principle of parsimony [20], a mathematical
model should contain the smallest possible number of
parameters for adequate representation of the data. For this
reason, the FOKM (that includes only one parameter (k)) and
the RKM (that involves two parameters (k, k2)) have been
considered in this work rather than the aforementioned
models. The parameters of these models are structurally
identiable (see supplementary information). This means
that it is possible to reach a unique value to each parameter
when they are being estimated independently of their initial
estimated values [21].

3 Materials and methods

detected by this analysis (i.e., C E 0 0). The wastes were

immersed in a water bath and heated to 50C. Then, they
were ltered through a 100 mesh stainless steel screen to
remove the suspended solids. The wastes were reheated to
105C for 2 h to remove the moisture content.
Tallow fat was provided by QUIMIKAO (Guadalajara,
Jalisco, Mxico) with the following fatty acid prole: 39.69%
oleic acid, 23.21% palmitic acid, 19.87% stearic acid, and
2.42% linoleic acid according to the same GC analysis
performed for the grease trap wastes. A mixture was prepared
by adding tallow fat to commercial canola oil as the source of
triglycerides. Because the fatty acid prole for the tallow fat is
very similar to the one obtained for the grease trap wastes, this
mixture can be considered a simulated mixture of the wastes.
The remaining reactants were: oleic acid (Almacn de Drogas
La Paz, purity >99%), sulfuric acid (Fermont, purity>99%),
industrial reagent grade methanol (Pochteca, Mxico),
industrial reagent grade methanol (Diquisa, Mxico),
KOH (Golden Bell, ACS), phenolphthalein (Golden Bell,
USA), toluene (Fermont, purity>99.9%), isopropyl alcohol
(Fermont, purity>99.7%). Hydranalcomposite 2 was supplied by Fluka Analytical (USA) and the standard substances
for GC analysis were all purchased from SigmaAldrich.

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

where V is the volume of KOH required to neutralize the

sample and m is the exact weight of the sample (0.5 g).

3.2.2 Reaction conditions

The esterication reactions were carried out at atmospheric
pressure in a 1 L threenecked batch reactor with mechanical
agitation, a thermometer and a sampling port. The reactor
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Kinetic analysis for the esterification of high free fatty

was immersed in a temperatureregulated water bath. All

reactions were carried out twice for 1 h in a controlled
temperature of 60C, adjusting the stirring speed to
500 rpm and utilizing a 20:1 molar ratio of methanol to
FFAs content in the feedstock [4]. The experimental runs
were designed to decide which model (the FOKM or the
RKM) better explains the esterication reactions under
variations in feedstock (oleic acid, tallow fatcanola oil
mixture, grease trap wastes), alcohol (Pochteca, Diquisa)
and catalytic sulfuric acid content (2.5 and 5 wt% of the %
FFAs in the sample).

3.2.3 Sampling and analysis

At various time points, a sample was quickly withdrawn
manually from the batch reactor and then cooled by
immersion into cold water (7C) for several minutes. The
immersion terminated the reaction [22]. The oil phase was
removed from the sample and then placed into a vial located
inside a drying oven at 80C for 1 h, which evaporated the
methanol in the oil phase. The percentage of FFAs (g of
FFAs/g sample) in the free alcohol phase was computed as
described in Section 3.2.1 (see Eq. (6)) and its corresponding
concentration (in mol FFAs/L) was computed with the
following relationship:
CA

2%FFAsmFFAo
AV mFFAo

100056:1V r
100056:1V r

where the product 2%FFAs represents the acid value of the

sample (AV), which is the mass of KOH (in mg), that is,
required to neutralize one gram of the sample medium.
Moreover, mFFAO (g) is the weight of the feedstock to be
esteries in a reaction medium with volume Vr (L). The
remainder of the factors employed in Eq. (7) are included
from a dimensional analysis that considers the chemical
reaction between 1 mol of FFAs and 1 mol of KOH.

3.3 Nonlinear regression

The nonlinear regression method proposed by Levenberg
Marquardt [23], that is, contained in MATLAB (nlint
command) was used for the estimation of the kinetic
parameters involved in the FOKM and the RKM. Here it
is important to remark that the estimation procedure for
the parameters of the RKM has been conducted with the
modied version of the model, which is shown below
dC A
C A 0  C A 2
kC A k2 C W 0 C A 0  C A
dt
C W 0

5a
This version of the RKM has been derived from Eq. (5)
considering the stoichiometry for CE and CW, the absence of
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esters in the feedstock and the factorization of the term

k2 C W 0. In fact, the product k2 C W 0 was settled as the
parameter to be estimated because is structurally identiable
(see supplementary information). Then, for each estimation
result, the kinetic parameter k2 was readily computed. A
similar procedure has been conducted for the estimation of
the kinetic parameter k1. In this case, the pseudoconstant k is
also structurally identiable and as a consequence, it was
settled as the parameter to be estimated. Then, since k
k1 C M 0 and C M 0 is known for each experiment, k1 was
readily obtained. The condence intervals for the parameters
were also deduced with MATLAB using the nlparci command
(MATLAB, 2010).

3.4 Calculation of measures for goodnessoft

One of the measures for goodnessoft is the coefcient
of determination (R2), which can be computed with the
following equation:
R2 1 

F
S yy

where F is known as residual sum of squares and is computed

as F x  xT x  x. Here, x is the vector of the
experimental observations corresponding to the dependent
variable, whereas x is the vector of the calculated values
obtained from the integration of the proposed kinetic
model. Additionally, Syy is a measure of the deviations of
each observation
(xi  ) from their mean (x ); therefore,
X 

xi  x . For linear regressions, this measure
S yy
i1
is widely used because it provides a very satisfactory
interpretation of how much the variance generated by
experimental data is explained by the t. Nevertheless, for
nonlinear regression analysis (such as the one conducted
in this paper) the coefcient of determination is poorly
dened. For this reason, many authors have decided to label
the measure computed by Eq. (8) as pseudoR2 [24, 25].
This measure is calculated here only to enhance the
incorrect conclusions that can be deduced when it is
being used to test the validity of nonlinear ts. Moreover,
the recommended measure in the validation of nonlinear
regressions is the use of the Bayesian Information Criterion
(BIC) or 2loglikelihood. Another approach to test the
validity of nonlinear ts is the Akaikes weights for a certain
model i (wi), and they are computed as follows. First, the
Akaikes Information Criterion for a certain model (AICi)
is derived as
AICi 2pi N ln 2p 1  ln N ln Fi
where pi and Fi denote the number of parameters and the
residual sum of squares, respectively, for the ith model,
whereas N is the number of data points (observations).
From this measurement, it is possible to compute the bias
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corrected Akaikes Information Criterion (AICCi) for small

sample sizes (N/pi<40; [26])
AICCi AICi

2pi pi 1
N  pi  1

Then, it is necessary to compute the difference in the

AICCi values for every considered model as follows:
DAICCi AICCi  minAICC , where minAICC is the lowest
AICCi. Finally, the Akaikes weights for the ith model is
derived by:


Ci
exp  DAIC
 2

wi Xj1
DAICCj
exp

2
M

where M is the number of models being analyzed or tted.

These weights and the pseudoR2 are computed for the
FOKM and for the RKM in each esterication experiment.

4 Results and discussion

The moisture content was below 0.01% for the grease
trap wastes, 0.30% for Pochteca methanol and 12% for
Diquisa methanol. This implies that the moisture content
in the reaction medium is predominantly provided by the
brand of methanol and not by the grease trap wastes,
conrming the moisture content removal from these wastes
was successful. In the available literature, most of the studies on
the reaction kinetics of the esterication process use a reagent grade
alcohol where the moisture contribution is virtually zero. In this
case, we used industrial grade alcohols (Pochteca, Diquisa), which
might be more economically attractive for industrial use; however,
the moisture content can shift the balance of the reaction and
therefore it is of great importance to consider reaction reversibility
in the kinetic study.
The percentages of FFAs for the feedstocks considered in
this work, including their corresponding concentrations (i.e.,
initial conditions for FFAs), are depicted in Table 1.
According to these results, all feedstocks used have a high
content of FFAs. The experimental results for the esterication reactions of oleic acid, the tallow fatcanola oil mixture
and the grease trap wastes are reported graphically as dots in
Figs. 13, respectively. These results are expressed in terms of

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

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

the concentration of FFAs and they are obtained with the

initial conditions for FFAs shown in Table 1 and with the
initial conditions for methanol and water described below
each gure. These results were derived from the average of
duplicate esterication experiments for each feedstock with
variations in the brand of methanol (i.e., moisture content)
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Kinetic analysis for the esterification of high free fatty

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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.)

Figure 3. Effect of the brand of alcohol and the catalyst content in

grease trap wastes. For methanol Pochteca: C M 0 15:78M and
C W 0 0:084M. For methanol Diquisa: C M 0 14:03M and
C W 0 3:400M ((a) Pochteca, 5 wt% cat., (b) Pochteca, 2.5 wt%
cat., (c) Diquisa, 5 wt% cat., (d) Diquisa, 2.5 wt% cat.)

and catalyst content. Furthermore, such results were used to

compute the pseudokinetic parameters k k1 C M 0 for the
FOKM and k k1 C M 0; k2 C W 0 for the RKM via the
LevenbergMarquardt method. The simulation results for
the FOKM and for the RKM with the estimated parameters
are also shown in Figs. 13 as a dashdotted and continuous
lines, respectively.

The structural identiability of the parameters in the

FOKM and in the RKM can be analytically proved (see
supplementary information). Now, let us explain how this fact
can be proved numerically considering the experimental
results for the esterication of oleic acid with methanol
Pochteca (5 wt% catalyst). For instance, if the initial
conditions of the parameters to be estimated in the RKM

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are settled as zero (i.e., k0 0, k2 C W 0 0), then the

estimated values will be k 1:493 and k2 C W 0 0:006. If
we modify the initial value of the parameter to be estimated
(i.e., k0 0:02, k2 C W 0 0:005) then the estimated
values will be again k 1:493 and k2 C W 0 0:006. That
is, in spite of the diversity of initial conditions for k and k2 C W ,
the regression algorithm always converge to the same values
which is a numerical proof for their unicity. In this case, from
the estimated values k 1:493 and k2 C W 0 0:006 is
possible to compute the kinetic parameters k1 0:089 and
k2 0:067, respectively since C M 0 and C W 0 are known.
This numerical proof for the unicity or structural identiability can also be done for the parameter involved in the
FOKM obtaining similar results. The numerical values of
the kinetic parameter k1 for the FOKM and k1 and k2 for the
RKM provided by the nlint command and considering the
calculation process described above, are shown in Tables 24.
The units of these parameters are equal to L mol1 s1 .
Besides, in these tables the condence intervals for these
parameters, the pseudo coefcient of determination and

Akaikes weights are also depicted. The results in Table 2

regarding the esterication of a pure substance, such as oleic
acid, will be discussed rst. In this case, the pseudo coefcient
of determination (R2) either for the FOKM or the RKM is
relatively high and it also remains very similar for both models
in the four experiments. Thus, one might conclude that both
models can be used to describe the esterication of oleic acid.
However, the Akaikes weights computed from Eq. (9) for
the RKM are higher than those for the FOKM. Therefore, the
RKM was considered to be the best explanation for the
esterication. In fact, for the rst experiment from Table 2
(Pochteca, 5 wt% catalyst) the relationship among the weights
is 0.999/0.001 999. This implies that the RKM is 999 times
more likely to be the best t. Similar conclusions on this
subject are derived from the analysis of Table 3 and Table 4.
From the results of these tables, it is possible to analyze
how the catalyst loading and the brand of methanol (i.e.,
initial water concentration) affect the behavior of the kinetics
parameters involved in the RKM. It has been decided to
conduct such analysis for the RKM since is the model that

Table 2. Parameter estimation results for the oleic acid esterication

Reaction conditions

Kinetic model

Methanol Pochteca, C W 0 0:091M5 wt% catalyst

FOKM
RKM

Methanol Pochteca, C W 0 0:091M 2.5 wt% catalyst

FOKM
RKM

Methanol Diquisa, C W 0 3:608M 5 wt% catalyst

FOKM
RKM

Methanol Diquisa, C W 0 3:608M 2.5 wt% catalyst

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

Methanol Pochteca, C W 0 0:076M 5 wt% catalyst

FOKM
RKM

Methanol Pochteca, C W 0 0:076M 2.5 wt% catalyst

FOKM
RKM

Methanol Diquisa, C W 0 2:968M5 wt% catalyst

FOKM
RKM

Methanol Diquisa, C W 0 2:968M 2.5 wt% catalyst

FOKM
RKM

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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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Eur. J. Lipid Sci. Technol. 2014, 116, 15981607

Kinetic analysis for the esterification of high free fatty

1605

Table 4. Parameter estimation results for the grease trap wastes esterication
Reaction conditions

Kinetic model

Methanol Pochteca, C W 0 0:084M 5 wt% catalyst

FOKM
RKM

Methanol Pochteca, C W 0 0:084M 2.5 wt% catalyst

FOKM
RKM

Methanol Diquisa, C W 0 3:400M 5 wt% catalyst

FOKM
RKM

Methanol Diquisa, C W 0 3:400M 2.5 wt% catalyst

FOKM
RKM

best ts the experimental data. First, let us describe the

behavior of k1 as a function of the catalyst content and the
initial moisture concentration, which is shown in Fig. 4. For
all the esterication procedures, the kinetic parameter k1
shows a maximum value at the highest level of catalyst loading
and the lowest level of initial water concentration. This led us
to infer that k1 can be directly proportional to the catalyst
concentration as it was pointed out in previous works (see
e.g., Marchetti et al. [19]). On the other hand, the kinetic
parameter k2 shows a similar behavior than the one exhibited
by k1 with an exception on the oleic acid esterication where
k2 for 2.5 wt% catalyst loading is higher than k2 for 5 wt%
catalyst loading at the lowest initial water concentration (see
Table 2). Now, let us make a comparison between k1 and k2
that are obtained under the same operation conditions for
all the available feedstock. Specically, let us consider the
esterications carried out with methanol Diquisa and 2.5 wt%
catalyst loading. For all these reactions: k2 > k1 . That is, the
high humidity content in methanol Diquisa and the low
catalyst content favor the reverse reaction over the direct
reaction affecting the esterication yield as it was also
observed by Liu et al. [27]

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

Now, the RKM and the parameters estimated with the

experimental data obtained from this study can be used to
t experimental data described in a couple of independent
contributions. The rst contribution is related with the
esterication of oleic acid and it has been developed by
Marchetti et al. [28], and the second one describes the
esterication of a synthetic mixture formed by soybean oil
and palmitic acid. This contribution has been developed by
Canakci and Van Gerpen [4]. In both cases, the experimental
results have been obtained with anhydrous alcohols and they are
expressed in terms of acid value of the sample instead of the
concentration of FFAs. Thus, it is necessary to express Eq. (5a)
in terms of the acid value. This is done by considering the
relationship among CA and AV dened by Eq. (8) and that
C W 0 0 because the absence of moisture in the alcohols.
In this case, Eq. (5a) is reduced to:
dAV
kAV k2 f AV0  AV2
dt

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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1606

E. AguilarGarnica et al.

Figure 5. Experimental results provided by Marchetti et al. [28] for

the esterication of oleic acid with ethanol (dots) and simulation
results with the RKM and kinetic parameters estimated for the
esterication of oleic acid with methanol (continuous line).

Eur. J. Lipid Sci. Technol. 2014, 116, 15981607

mFFAO
0:006. The integration of (5b)
0:380 and f 100056:1V
r
with these parameters is described in Fig. 6 as a continuous
line. This line predicts almost exactly the behavior of the acid
value. This is probably because the methanol was used in both
esterications and the operating conditions in these reaction
processes remains very similar.
At this point it is important to remark that the
experimental results depicted by Marchetti et al., and by
Canakci and Van Gerpen, show an extremely fast descent on
the FFAs, when 5 wt% catalyst is used under a very low
content of moisture. Even when this phenomenon has been
previously reported, it has not been numerically characterized
as in the present kinetic study.

5 Conclusions and perspectives

integration of (5b) with these parameters is described in Fig. 5
as a continuous line. This line is able to describe the behavior
of the experimental data provided by Marchetti et al., but
not in an exact or close way and this is probably because the
operation conditions and the type of alcohol used during the
esterications differs.
Finally, the data obtained by Canakci and Van Gerpen
for the esterication of mixture formed by soybean oil and
palmitic acid with METHANOL at 60C, a 9:1 molar ratio
of methanol to FFAs content considering 5 wt% catalyst
loading. In this contribution, the experimental results are
depicted in a table as acid value and they are shown as dots in
Fig. 6 with AV 0 41:33 (i.e., 82.66%FFAs). In this study,
the esterication of a synthetic mixture of canola oiltallow fat
oil 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 Canakci and Van Gerpen. In this case the
estimated kinetic parameters were: k1 0:027 and
k2 0:016. Besides, for this experiment: mFFAO 173:6g,
V r 0:5L and C M 0 14:1M. Thus, k k1 C M 0

Figure 6. Experimental results provided by Canakci & Van

Gerpen [4] for the esterication of synthetic mixture: soybean oil
palmitic acid with methanol (dots) and simulation results with the
RKM and kinetic parameters estimated for the esterication of a
synthetic mixture tallowfat/canola oil with methanol.
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

In this paper, two kinetic models, whose parameters are

structurally identiable, were compared to describe the
esterication of feedstocks with a high content of FFAs tested
using variations in catalyst and initial moisture contents.
According to a statistical analysis based on the concept of
Akaikes weight, the kinetic model that considers the
reversibility of the esterication reaction offers a better t
for the experimental data than does the model that assumes
a rst order reaction. This result was expected for the
experiments in which the initial moisture content was
relatively high (due to the presence of water in the reagents
and the consequent product), but the reversible kinetic model
also offers satisfactory results with low initial moisture
content. The kinetic parameter k1 in this reversible model
shows a very clear behavior for all the esterication runs with a
maximum value at the highest level of catalyst loading and at
the lowest level of initial moisture content. In addition,
the reversible kinetic model and the estimation parameter
results obtained for the esterication of oleic acid and for the
esterication of the synthetic mixture formed by tallow fat and
canola oil, were considered to t a couple of independent
experiments obtaining satisfactory results in spite of variations
in the operation conditions. The estimation parameter results
obtained in the esterication of grease trap wastes represent a
step forward in the eld of lipids science and this is why
they were not compared with previous studies. Regarding
these results, it is important to remark that they cannot be
considered as global results (i.e., for all the grease trap wastes)
due to the heterogeneous nature of this feedstock. Nevertheless, the methodology proposed here (which is developed on
the basis of lowcost measurements such as titrations and
the use of industrial grade alcohols) can be considered as a
guideline for future kinetic studies regarding this specic
feedstock.
The authors gratefully acknowledge nancial support from the
Consejo Nacional de Ciencia y Tecnologa (CONACYT) through
the Project CB200901133554 to carry out this study. The
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Eur. J. Lipid Sci. Technol. 2014, 116, 15981607

authors also express their thanks to QUIMIKAO and Solucin

Ambiental de Mxico for providing the tallow fat samples and the
grease trap wastes.
The authors have declared no conict of interest.

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