Energy Conversion and Management 105 (2015) 1149–1156

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Optimization of sunflower oil ethanolysis catalyzed by calcium oxide:

RSM versus ANN-GA
Jelena M. Avramović a, Ana V. Veličković a, Olivera S. Stamenković a, Katarina M. Rajković b, Petar S. Milić c,
Vlada B. Veljković a,⇑
a
University of Niš, Faculty of Technology, Bulevar oslobodjenja 124, 16000 Leskovac, Serbia
b
High Chemical and Technological School for Professional Studies, Kruševac, Serbia
c
High Medical School of Professional Studies, Ćuprija, Serbia

a r t i c l e i n f o a b s t r a c t

Article history: The ethanolysis of sunflower oil catalyzed by calcium oxide was modeled and optimized in terms of the
Received 25 June 2015 following operating conditions: reaction temperature (65–75 °C), ethanol:oil molar ratio (6:1–18:1), cat-
Accepted 21 August 2015 alyst loading (10–20% based on oil weight) and reaction time (360–480 min). Response surface method-
Available online 14 September 2015
ology (RSM) and artificial neural network (ANN) approaches were used for modeling the content of fatty
acid ethyl esters (FAEE) and optimizing the four process variables. Both models were determined to be
Keywords: reliable in terms of predicting the FAEE content, but the ANN model was found to be more accurate than
Artificial neural network
the RSM model. The highest FAEE content of 99.2% was determined using the ANN model combined with
Ethanolysis
Fatty acid ethyl esters
a genetic algorithm optimization method, which agreed well with the experimental value (97.8%). A good
Full factorial design agreement between the predicted and actual maximum FAEE contents was observed for both models. The
Genetic algorithm generalization of the ANN model developed for heterogeneously catalyzed alcoholysis was also tested on
Response surface methodology several oily feedstocks.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Consistently growing negative effects caused by fossil fuel
usage on the climate, as well as severe consequences toward soci-
ety, the environment and the world economy, have focused efforts
to develop technologies based on renewable energy sources. New
sources could partially replace fossil fuels, reduce the emission of
pollutants and minimize any possible impacts on the environment.
One possibility is to use biodiesel, a non-toxic, renewable,
safe-to-handle and biodegradable fuel that would produce less
air, water and soil pollution, as well as cause minimal impact on
human health and help reduce greenhouse gas emissions. Biodiesel
production generally involves the alcoholysis reaction between
triacylglycerols (TAGs) from vegetable oils, animal fats or algal oils
and alcohol in the presence of a catalyst.
The most commonly used alcohols for the production of biodie-
sel are methanol and ethanol, each with their own advantages and
disadvantages. The most important positive characteristics of
methanol include its suitable physicochemical properties, low cost,
mild reaction conditions, fast reaction time and easy phase separa-
tion. However, because of its low boiling point, the explosion risk
⇑ Corresponding author. Tel.: +381 16 247 203; fax: +381 16 242 859.
E-mail address: veljkovicvb@yahoo.com (V.B. Veljković).
associated with methanol vapors and the extreme toxicity of both
methanol and methoxide [1], new trends in the area of biodiesel
production are oriented toward the use of ethanol. Compared to
methanol, ethanol is characterized by its superior vegetable oil dis-
solving power, lower toxicity and biodegradability [2]. The draw-
backs of ethanol’s use in biodiesel production are related to the
difficult separation of ethyl esters caused by the stable emulsion
formed during the ethanolysis reaction, significant dependence of
fatty acid ethyl ester (FAEE) yield on the presence of water in the
reaction mixture and a greater hindrance effect of ethoxide ions
located on the active surface sites in the case of a heterogeneously
catalyzed reaction [3,4].
There are several benefits of using FAEEs instead of fatty acid
methyl esters (FAMEs). Due to the extra carbon atom (from the
ethanol molecule), FAEEs have slightly higher values for heat con-
tent, a higher cetane number and improved storage properties
[2,5]. Another advantage of FAEEs are lower cloud and pour points,
which improve engine start at low temperatures [2,6,7]. In
addition, FAEEs are more environmentally friendly compared to
FAMEs because of lower nitrogen oxide and carbon monoxide
emissions, as well as lower smoke density [1,8]. Moreover,
FAEE-based biodiesel is a completely biorenewable fuel because
both reactants (vegetable oil and ethanol) can be produced from
biorenewable resources.

http://dx.doi.org/10.1016/j.enconman.2015.08.072
0196-8904/Ó 2015 Elsevier Ltd. All rights reserved.
1150 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156

To date, homogeneously catalyzed ethanolysis of different oily
feedstocks has been more frequently studied than heterogeneously
catalyzed ethanolysis [4]. However, the use of heterogeneous cata-
lysts improves the ethanolysis reaction, as separation from the
reaction mixture is easy and catalysts can be reused; this makes
the process environmentally and economically more favorable
[9]. The primary deficiency of heterogeneous catalysts is the for-
mation of three phases leading to diffusion limitations and the
reduction of the reaction rate [10]. The reuse possibility of the cat-
alyst is a benefit, but until now only a few catalysts are recycled
without loss of activity [11,12].
A literature survey on the application of ethanolysis in biodiesel
production is shown in Table 1. A limited number of edible (sun-
flower and soybean oils) and waste frying oils have been used as
oily feedstocks in the presence of various solid catalysts. Although
calcium-based catalysts have been most frequently employed to
date, pure calcium oxide has not been applied yet. Only CaO loaded
with Ca(OH)2 has been used to catalyze the conversion of soybean
oil to FAEEs [16].
To increase biodiesel production processes’ efficiency and to
reduce costs, these processes should be conducted under optimal
reaction conditions, which are usually determined with the help
of statistical and mathematical methods, such as response surface
methodology (RSM) and artificial neural network (ANN). However,
these methods have not previously been employed for modeling
and optimization of heterogeneously catalyzed ethanolysis reac-
tion conditions. RSM has more frequently been employed [21–
26] than ANN [27,28], and both methods have been proven to be
powerful tools for modeling and optimizing the methanolysis of
various vegetable oils. ANN is generally demonstrated to have bet-
ter generalization capability than RSM, which is attributed to its
universal ability to simulate non-linear variations. Until recently,
there were several investigations comparing the efficiencies of
the two methods for transesterification [29–35] and esterification
[36] of various feedstocks by applying different catalysts. These
methods have also been employed in the modeling and optimiza-
tion of two-step processes, where esterification is followed by
transesterification [37]. Both methods are not mechanistic, so they
do not contribute to any deeper insight into the chemical reaction
under the study. However, their application will expand knowl-
edge about the effects of the process factors and their interactions
with FAEE content, as well as help identify (1) the optimum prop-
erties that ensure maximum FAEE content and (2) the capabilities
of RMS and ANN as mathematical tools for modeling and optimiza-
tion of the ethanolysis reaction. In this way, they bring valuable
results that help us better understand and reliably improve biodie-
sel production processes with less cost, effort and time. To make a
general conclusion on their modeling and optimization capabili-
ties, these methods should be tested and validated for each combi-
nation of feedstock, alcohol, catalyst, process and operating
condition [30].
It is worth mentioning that both RMS and ANN have not previ-
ously been employed for the modeling and optimization of hetero-
geneously catalyzed ethanolysis reaction conditions. Moreover, the
present study is the first attempt to apply RSM and ANN combined
with a genetic algorithm (GA) for modeling the FAEE content and
optimization of CaO-catalyzed sunflower oil ethanolysis reaction
conditions in a batch reactor. Additionally, to the best of the
authors’ knowledge, the ethanolysis of vegetable oils in the pres-
ence of a solid catalyst has not been modeled and optimized to
date using RSM and ANN methods. Thus, the novelty of the present
study is in both the reaction used for biodiesel production and the
comparison of the efficiencies of the RSM and ANN methods as
modeling and optimization tools for this reaction. Furthermore,
the evaluation of generalization ability of the developed ANN
model for other oils, alcohols and catalysts is also a valuable
approach that has rarely been employed in the modeling of alco-
holysis reactions. Both models give energy efficient process condi-
tions leading to the maximum FAEE content. Main goals of the
study were to evaluate the effect of the reaction conditions on
the FAEE content through analysis of variance (ANOVA); correlate
the FAEE content with the process variables; and optimize the pro-
cess variables to achieve the maximum FAEE content using RSM
and ANN combined with GA (ANN-GA). Additionally, developed
RSM and ANN models were compared against each other with
respect to the accuracy of the FAEE content prediction to better
select a mathematical tool for modeling and optimization of the
CaO-catalyzed sunflower oil ethanolysis. Finally, physicochemical
properties of the sunflower oil ethyl esters obtained under the
optimum reaction conditions were determined.
2. Experimental
2.1. Materials
Refined, edible sunflower oil (Sunce, Sombor, Serbia) was used,
and its physicochemical properties can be found elsewhere [21].
Ethanol (99%) and calcium oxide (min. 96% purity) were obtained
from Fisher Chemical (Leicestershire, UK) and Lachema (Nera-
tovice, Czech Republic), respectively. Hydrochloric acid (36%) was
from Centrohem (Belgrade, Serbia), while HPLC grade 2-propanol
and n-hexane were purchased from Lab-Scan (Dublin, Ireland).
The HPLC standards for esters of palmitic, stearic, oleic and linoleic

Table 1
Review of heterogeneously catalyzed ethanolysis with different feedstocks.

Oily feedstock Reaction temperature (°C) Ethanol/oil molar ratio (mol/mol) Catalyst/loading (%) Yield (%)/time (h) Reference
Sunflower oil 65–75 6:1–15 CaO/10-20 98.1/8 Present work
Sunflower oil 200 12:1 ZrX-MCM/14.6 91.5/– [13]
Sunflower oil 78 20:1 Calcium zincate/3 95/3 [14]
Sunflower oil 70–90a 6:1–15:1a Ca(OCH2CH3)2/0.5–4a 31.4–80.5a/2.5 [2]
80b 4:1–8:1b Ca(OCH2CH3)2/0.25–1b 96.5
Soybean oil 70 20:1 La50SBA-15/1 80/6 [15]
Soybean oil 70 9:1 Ca(OH)2/CaO/3.7% 96.3/10 [16]
Soybean oil 120 20:1 SO4/ZrO2/5 92/1 [17]
Waste frying oil 60–200 40:1 ZnAl2O4/1–10 95/2 [18]
Waste frying oil 100–200c 40:1c ZnAl2O4/1–10c >96.5/2c [19]
Triolein 50 3:1–10:1 Ion-exchange resin/20–40d 100/1.5 [20]
a
First stage.
b
Second stage.
c
Supercritical CO2.
d
Weight percent on the total reaction mixture.
 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156
acids, triolein, diolein and monoolein were obtained from Sigma
Aldrich (St. Louis, USA).
2.2. Reaction conditions and FAEE characterization
2.2.1. Ascertainment of external and internal diffusion limitations
First, the influence of both external liquid–solid mass transfer
and intraparticle diffusion limitations was ascertained. Using the
correlation of Dossin et al. [38], the minimum agitation speed that
ensured perfect mixing, complete suspension of the catalyst parti-
cles and no external mass transfer limitation was calculated to be
in the range between 692 and 868 rpm for the reaction conditions
applied; hence, the reaction was carried out at 900 rpm for all
experiments. Existence of internal mass transfer resistance was
checked by calculation of the Thiele modulus, which indicated if
the pore diffusion offered a resistance [39]. Considering all reaction
conditions applied and limited values for catalyst particle porosity
[40] and tortuosity [41], the highest Thiele modulus was calculated
to be 0.009 or 0.003 for the diffusion of TAG through TAG and etha-
nol, respectively. Being significantly smaller than the limit one
(
0.4), these values of Thiele modulus confirmed the ignorable
internal diffusion resistance in the investigated system.
2.2.2. Equipment and reaction conditions
Experimental work was performed in accordance with a 34 fac-
torial design with five center points (with a total of 86 experimen-
tal runs). Ranges of the process variables in this set of experiments
are given in Table 2. This set of data was used for modeling and
optimization of the FAEE content by the RSM. In addition, the FAEE
content was monitored at 30 min intervals up to the third hour of
the reaction, then hourly up to the end of the reaction (with a total
of 330 data points). This set of data was used in the ANN-GA mod-
eling and optimization of the FAEE content.
The reaction was carried out in a 250 mL glass three-neck,
round-bottom flask equipped with a condenser and a two-
bladed, flat paddle agitator. The reactor was immersed in a glass
chamber filled with water circulating from a thermostated bath
(Dema, Ilirska bistrica, Slovenia) by means of a pump. Agitation
intensity, measured with an optoelectronic counter, was controlled
with a voltage regulator.
Samples of the reaction mixture (0.5 mL) were taken during the
progress of the ethanolysis reaction to determine the FAEE content.
After being withdrawn, samples were instantly neutralized by add-
ing the required amount of hydrochloric acid (5 mol/L) in aqueous
solution and centrifuged at 3500 rpm for 10 min. The FAEE-oil
layer was separated, dissolved in a solution of 2-propanol and n-
hexane (5/4 ml/ml), filtered through a Millipore filter (0.45 lm)
and analyzed by the HPLC method described elsewhere [22].
2.2.3. Physicochemical characterization of FAEEs
The FAEEs obtained under the optimal reaction conditions
determined by the RSM were characterized according to the pre-
scribed standards. The FAEE fraction (the upper layer), obtained
after the centrifugal separation, was neutralized with the
Table 2
Process factors and their levels for the RSM modeling and optimization.
Notation for Process factor Unit Lower Middle
factor level level
(1) (0)
A Ethanol:oil mol/mol 6:1 12:1
molar ratio
B Catalyst loadinga % 10 15
C Reaction temperature °C 65 70
D Reaction time min 360 420
a
Based on the oil weight.
1151
hydrochloric acid (5 mol/L) and washed with distilled water (14%
based on the FAEE weight) to remove the remaining impurities
(catalyst salts, ethanol and glycerol). Water and FAEE phases were
separated by centrifugation, and the latter phase was dried at
120 °C for 4 h. The physical and chemical properties of the purified
biodiesel were determined according to the appropriate standard
methods. The physical and chemical properties of the obtained bio-
diesel were determined according to the appropriate standard
methods: density (EN ISO 3675:1988), kinematic viscosity (EN
ISO 3104:2003), flash point (EN ISO 2719:2002), iodine value (EN
14111:2003), acid value (EN 14104:2003), water content (EN ISO
12937:2000), FAME content (EN 14103:2003), as well as the con-
tent of mono-, di- and tri-acylglycerols (EN 14105:2003).
2.3. Modeling and optimization
2.3.1. RSM modeling and optimization
The quadratic equation was applied in modeling the FAEE con-
tent as a function of process variables and for optimizing the pro-
cess conditions:
X XX X
Y ¼ a0 þ ai X i þ aij X i X j þ aii X 2i ð1Þ
i i j>i i
where Y is the FAEE content (response), X is the process (indepen-
dent) variable (ethanol:oil molar ratio, catalyst loading, reaction
temperature and reaction time, i.e., A, B, C and D, respectively), a0 ,
ai , aij and aii are regression coefficients (i = 1, 2, 3, 4 and j > i). The
set of data used in the RSM modeling and optimization can be found
in the Supplementary material (Table S1). Statistical significance of
the process variables was estimated using analysis of variance
(ANOVA). For optimizing the factors, maximum FAEE content was
selected as the goal of optimization. The Design-Expert 7.0.0 Trial
software (Stat-Ease Inc., Minneapolis, MN) program was used for
the purpose of modeling and optimization.
2.3.2. ANN modeling and ANN-GA optimization
ANN and ANN-GA combination were applied in non-parametric
modeling and the optimization of the FAEE content, respectively
using the MATLAB’s Neural Network and Genetic Algorithm Tool-
boxes (MATLAB 8.1.0.604). A feedforward, back-propagation multi-
layer ANN was performed using the Levenberg–Marquardt (LM)
algorithm because of its power in function modeling and fast train-
ing. Hyperbolic tangent transfer function (tan h) was chosen for
both input and output hidden layers. The selected ANN had an
input layer with four neurons (ethanol:oil molar ratio, catalyst
loading, reaction temperature and reaction time), a hidden layer
and an output layer with one neuron (FAEE content). The number
of hidden neurons was defined by testing different numbers of
neurons until the mean relative percentage deviation (MRPD) value
of the output data was minimized. Optimal number of hidden neu-
rons was found to be 10 (see Fig. S1 in Supplementary material)
because further increasing the number of these neurons made
the model less accurate. It might be worth mentioning that this
increase would simply increase the complexity of the model and
should not decrease the accuracy unless the optimization/fitting
is incomplete or stuck in a local minimum. Moreover, with addi-
Upper
level tional optimization efforts, it should be possible to improve the
(1) fit of the model with more neurons. However, for practical reasons,
18:1 selection of 10 hidden neurons was correct, as the additional com-
putation effort required might be notably large. The main charac-
20 teristics of the ANN model are presented in Supplementary
75 material (Table S2). The set of input–output data points (330 in
480
total) mutually interrelated with the FAEE content and process
variables and was divided into three subsets: training (70% of the
1152 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156

total data points), testing (15% of the total data points) and validat- content. These observances are valid only for the ranges of operat-
ing (15% of the total data points). ing conditions applied in the present study.
Input interval of the developed ANN model was optimized to Because no study on statistical optimization of heterogeneously
search for optimal operating conditions and lead to the highest catalyzed ethanolysis has been reported so far, the effects of the
FAEE content using GA. The main characteristics of GA are pre- process variables on heterogeneously catalyzed methanolysis of
sented in the Supplementary material (Table S2). The objective various vegetable oils have briefly been discussed. The FAME yield
function used to maximize the FAEE content in the ranges of the in the methanolysis of jatropha oil using calcium oxide [43], a
process variables was applied. GA parameters, such as population mixed oxide (CaO–MgO) catalyst [23], KSF clay, Amberlyst 15
size, number of generations, crossover rate and mutation probabil- [24] and aluminum oxide modified Mg–Zn catalyst [44] was
ity, were first optimized using sensitivity analysis [42], and their influenced by all process variables. The same was observed
values were as follows: 20, 50, 0.8 and 0.01, respectively. Then, in the methanolysis of waste cooking palm oil over Sr/ZrO2 [25]
the optimum set of the process variables was determined by apply- and the methanolysis of soybean oil over CaO from low-cost
ing GA over the ANN model. The evolution profile of optimal search mussel shells [45].
by the ANN-GA model is shown in the Supplementary material The multiple regression method was applied to the experimen-
(Fig. S2), which depicts the values of the FAEE content in terms tal data of the FAEE content to fit the quadratic equation, Eq. (1),
of the best and mean values at each generation. Fifty generations using coded levels of the process variables:
are enough for GA to reach the accurate optimization.
Y ¼ 92:0 þ 2:46A þ 7:09B þ 11:03C þ 8:28D þ 1:02AB
2.3.3. Evaluation of the mathematical models  0:82AC  1:67AD  7:00BC  3:83BD  5:12CD
The performances of RSM and ANN models were statistically
 0:46A2  2:48B2  6:41C 2  2:11D2 ð2Þ
measured by F-and p-values of the model and the lack of fit, as well
as the coefficient of determination (R2) and the MRPD. Individual process variables, the interaction of the ethanol:oil
molar ratio and catalyst loading have positive effects on the FAEE
3. Results and discussion content, while other interactions and squares influenced the FAEE
content negatively.
3.1. RSM modeling The Fmodel-value (13.05), which was higher than the critical
value (F0.05,14,71 = 1.86) and the very low pmodel-value (<0.0001),
Results of ANOVA are summed up in Table 3 in terms of the sum indicated that the model was significant at the 95% confidence
and means of squares of residuals, corresponding degrees of free- level. Value of the correlation coefficient (R = 0.850) showed strong
dom and F- and p-values. Statistical significance of the model, indi- correlation between FAEE content and the process variables.
vidual factors, their squares and interactions was estimated from According to the value of the coefficient of determination
their F- and p-values. As the p-value is less than 0.050, catalyst (R2 = 0.720), mathematical prediction of the FAEE content was
loading (B), reaction temperature (C), reaction time (D), two-way not the best because only 72.0% of variation in the FAEE content
interactions of catalyst loading with reaction temperature and could be explained by the fitted model. In addition, the lack of fit
reaction time (BC and BD), reaction temperature and reaction time was insignificantly relevant to the pure error because its p-value
(CD), and the square of the reaction temperature (C2) have statisti- (0.133) was higher than 0.050, meaning that the model was ade-
cally significant effects on the FAEE content at the 95% confidence quate for the prediction of the FAEE content. The MRPD between
level, as can be observed in Table 3. Among the individual process the predicted and actual values of the FAEE content of  10.1%
variables, the most important was reaction temperature, followed (based on 86 data points) indicated their good agreement. Devia-
by reaction time and catalyst loading. However, the ethanol:oil tions between the predicted and actual values higher than ±30%
molar ratio, as well as their square and interactions with other pro- were observed if the FAEE content was lower than approximately
cess factors did not have statistically significant effects on the FAEE 50% (only 6 data points), and if these ‘‘bad” data points were not
considered, the MRPD was reduced to ±6.9%. There was no problem
with the normality in the distribution of experimental data, so the
ANOVA results were valid. In addition, the Cook’s distances values
Table 3
The results of ANOVA.
were lower than 0.15 (far from the limit value of 0.8), suggesting
that there were no outliers in analyzed data set.
Source of Sum of Degree of Mean square F value p-value
By removing the insignificant model terms that have
variation squares freedom
a p-value higher than 0.05 (Table 3), Eq. (2) can be simplified as
Modela 17926.05 14 1280.43 13.05 <0.0001 follows:
A 327.92 1 327.92 3.34 0.072
B 2713.63 1 2713.63 27.66 <0.0001
Y ¼ 92:0 þ 7:09B þ 11:03C þ 8:28D  7:00BC  3:83BD
C 6571.23 1 6571.23 66.97 <0.0001
D 3706.46 1 3706.46 37.77 <0.0001  5:12CD  6:41C 2 ð3Þ
AB 37.31 1 37.31 0.38 0.539
AC 24.35 1 24.35 0.25 0.620 with the following values of the most important statistical criteria:
AD 100.84 1 100.84 1.03 0.314
BC 1762.60 1 1762.60 17.96 <0.0001
the insignificant lack of fit (p = 0.113 > 0.050) relative to the pure
BD 527.39 1 527.39 5.37 0.023 error, R2 = 0.691 and MRPD = ±10.5%.
CD 943.82 1 943.82 9.62 0.003 Response surfaces and contour plots show the influence of the
A2 4.08 1 4.08 0.042 0.839 ethanol:oil molar ratio on the FAEE content as less significant
B2 120.34 1 120.34 1.23 0.272
and dependent on the reaction time (Fig. 1a). The FAEE content
C2 804.54 1 804.54 8.20 0.006
D2 87.12 1 87.12 0.89 0.349 increases slightly with increasing ethanol:oil molar ratio at shorter
Lack of fit 6791.53 66 102.90 2.94 0.113 reaction times, which could be attributed to the positive effect of
Pure error 175.09 5 35.02 ethanol amount on the conversion rate. As the reaction progresses,
Corrected total 24892.67 85 the effect of the ethanol:oil molar ratio on the FAEE content is not
a
A – ethanol:oil molar ratio; B – catalyst loading; C – reaction temperature significant. This was explained by the presence of FAEEs and inter-
and D – reaction time. mediate products, which contributed to the increase of liquid–liq-
 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156 1153

Fig. 1. Response surface and contour plots for FAEE content (experimental data points: d) as a function of (a) ethanol:oil molar ratio and reaction time (catalyst loading: 15%
and reaction temperature: 70 °C) and (b) catalyst loading and reaction temperature (ethanol:oil molar ratio: 12:1 and reaction time: 420 min).

uid interfacial area, thus reducing the importance of ethanol solu-
bility in the oil. The same effect was observed in the sunflower oil
methanolysis [46]. Additionally, formation of FAEEs in the
CaOZnO-catalyzed sunflower oil ethanolysis was negligible at
molar ratios less than 20:1, while it decreased in the range from
20:1 to 50:1 [14]. Similarly, the soybean oil conversion varied
slightly as the ethanol:oil molar ratio increased from 9:1 to 15:1,
but decreased once reaching the ratio of 18:1 [16].
The effect of catalyst loading and reaction temperature on the
FAEE content is shown in Fig. 1b. The high slope of the contours
indicated great influence of both process factors on the FAEE con-
tent, although the effect of reaction temperature was higher. The
effect of reaction temperature was more pronounced at lower cat-
alyst loadings, but became less important at higher catalyst load-
ings (approximately >18%). Catalyst loading significantly
improved the FAEE content at low reaction temperatures, but its
effect was less significant at high reaction temperatures. Addition-
ally, the shape of contours confirmed significance of the interaction
between the catalyst loading and the reaction temperature.
Obtained results were in agreement with the results of Alves and
coworkers [18,19].
3.2. ANN modeling
Correlation between the FAEE content and process variables
was determined using ANN with 4-10-1 topology. Good agree-
ment between the predicted and experimental values of FAEE
content was indicated by the MRPD value, which was only
±6.9% (330 data points). R-value of the ANN model was 0.973,
indicating its better capability of FAEE content prediction com-
pared to the RSM model. Surface and contour plots obtained by
the ANN model that present the predicted FAEE content as a func-
tion of reaction temperature and reaction time at an ethanol:oil
molar ratio of 12:1 and catalyst loading of 15% are shown in
Fig. 2. It can be noted that the FAEE content increases with the
progress of reaction, reaches a plateau and remains almost
constant at longer reaction times. The effect of the reaction tem-
perature is more significant in the initial reaction period and
1154 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156

Fig. 2. Response surface and contour plots for the predicted FAEE content (experimental data points: d) as a function of reaction temperature and time (ethanol:oil molar
ratio: 12:1 and catalyst loading: 15%).

Table 5
becomes insignificant at reaction times above 420 min, which can
Comparison of optimal process conditions and maximum FAAE contents determined
be explained by achieving the reaction equilibrium; therefore, fur- by RSM and ANN-GA optimization.
ther increase of the temperature has no significant effect on the
Process variable RSM optimization ANN-GA optimization
FAEE content. Contour plot shows that reaction time has more
significant influence on the FAEE content than reaction tempera- Ethanol:oil molar ratio 14:1 12:1
Catalyst loading (%) 17 15
ture. Plateau is reached at reaction times and temperatures higher
Reaction temperature (°C) 72 75
than 420 min and 70 °C, respectively. Reaction time (min) 440 415
Generalization ability of the developed ANN model was judged FAEE content, model (%) 98.8 99.2
with unseen data of heterogeneous methanolysis reaction systems FAEE content, actual (%) 98.2 97.8
taken from the literature [31,47]. The type of vegetable oil, solid
catalyst and alcohol, ranges of the process variables as well as
MRPD values are presented in Table 4. MRPD values for three differ-
ent reaction systems demonstrate significant generalization ability 3.4. Physicochemical properties of FAEEs
of the developed ANN for predicting the ester yield achieved by
both ethanolysis and methanolysis of various oily feedstocks, Investigated physicochemical properties of the FAEEs obtained
which is imputed to its universal capability to simulate non- under the optimum reaction conditions, along with the data
linearity of studied reaction systems. reported in previous studies and limits of the quality properties
prescribed by the EN14214 and USA ASTM D6751 biodiesel quality
standards, are shown in Table 6. Except for the iodine value regard-
3.3. Optimization of process variables by RSM and ANN-GA
ing the EN14214 standard, all properties of sunflower FAEEs are
within the limits of both standards. According to the EN14214
Maximum predicted values of FAEE content found through opti-
standard, maximum allowed iodine value is 120, while the USA
mization using both the RSM and ANN-GA model are compared in
ASTM D6751 standard does not specify its value. Additionally,
Table 5. As it can be observed, the RSM model predicts the highest
some researchers argue that further limitation of iodine value by
FAEE content at a higher ethanol:oil molar ratio, as well as larger
the EN14214 standard is not necessary [50]. Moreover, required
catalyst loading, longer reaction time and somewhat lower reac-
oxidation stability can be achieved by adding antioxidants to the
tion temperature than ANN-GA model. Both models predict almost
biodiesel product. Hence, an iodine value that is somewhat higher
the same best FAEE contents and agree with experimental values
than the standard specification will not limit the use of these
determined under optimum reaction conditions.

Table 4
Generalization ability of the developed ANN model.

Oil Catalyst Alcohol Design of Alcohol-to-oil Catalyst Reaction Reaction Number MRPD Ref.
experimentsa molar ratio loading (%) temperature time (h) of data (%)
(mol/mol) (°C) points
Sunflower Calcium oxide Ethanol FFD 6–18 10–20b 65–75 Up to 16 330 ±6.9 Present study
Waste cooking oil H3PW12O.406H2O Methanol CCD 30–90 5–12.5 55–75 6–22 30 ±8.8 [47]
Yellow oleander Calcinated plantain peels Methanol BBFD 0.09–0.30 1–5c 60 0.5–1.5 17 ±2.1 [31]
a
BBFD – Box–Behnken factorial design; CCD – central composite design; FFD – full factorial design.
b
Based on the oil weight.
c
w/v.
 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156 1155

Table 6
Fuel characteristics of FAEEs.

Fuel characteristic Unit Type of oil Standard

Sunflower Mustard Sunflower Rapeseed Olive Used frying EN14214 ASTM D6751
Density at 15 °C kg/m3 874.7 899.5 882.7 881.2 881.5 888.5 860–900 –
Kinematic viscosity at 40 °C mm2/s 3.7 8.33 4.63 4.84 4 5.81 3.5–5.0 1.9–6.0
Flash point °C 175 120 178 181 182 188 min 101 93 min
Iodine value g I2/100 g oil 131.9 105 – – – – max 120 –
Acid value mg KOH/g 0.38 0.33 0.15 0.35 0.19 0.46 max 0.5 max 0.5
Water content mg/kg 227 – 154 189 208 376 max 500 max 500
Cetane number 51 – – – – – min 51 min 47
FAEE % 96.8 91.0 96.7 97.2 97.8 93.2 min 96.5 –
MAG % 0.3 – 0.478 0.512 0.644 1.367 max 0.8 –
DAG % 2.5 – 0.152 0.095 0.130 2.228 max 0.2 –
TAG % 0.4 – 0.087 0.275 0.116 3.132 max 0.2 –
Calcium and magnesium 2.1 – – – – – max 5
Reference Present work [48] [49]

FAEES as biodiesel. Obtained FAEEs have similar fuel properties as
the biodiesels produced from other vegetable and used frying oils
that make use of homogeneous catalysts (KOH [48] and NaOH
[49]).
4. Conclusions
RSM and ANN models were developed for modeling and opti-
mization of the FAEE content in the ethanolysis of sunflower oil
using CaO as a catalyst to increase the process efficiency and to
define the energy efficient process conditions, leading to maxi-
mum FAEE content. Both models provide good quality prediction
of the FAEE content in terms of reaction temperature, ethanol:
oil molar ratio, catalyst loading and reaction time. However, based
on the R and MRPD values (RSM: 0.850 and ±10.1%; and ANN:
0.973 and ±6.9%), the ANN model was found to be more accurate
in predicting FAEE content than the RSM model. This was attrib-
uted to better predictive ability of ANN as a modeling technique
for representing nonlinearities rather than the quadratic equation
used in RSM. It should be emphasized that the excellent fitting of
experimental data was achieved with a rather simple back propa-
gation ANN performed using the LM algorithm. RSM and ANN (in
combination with GA) models are also proved to be acceptable
tools for optimizing the ethanolysis reaction conditions to achieve
the highest FAEE content. RSM model predicts the FAEE content of
98.8% in 440 min under the following conditions: reaction tem-
perature of 72 °C, ethanol:oil molar ratio of 14:1 and catalyst
loading of 17%. According to the ANN-GA model, the FAEE content
of 99.2% corresponds to an ethanol:oil molar ratio of 12:1, catalyst
loading of 15%, reaction temperature of 75 °C and reaction time of
415 min. With both models, a good agreement between the
predicted and actual maximum FAEE contents was observed.
Generalization ability of the developed ANN model was well doc-
umented for a couple of heterogeneously catalyzed alcoholysis
reactions.
Although ANN is superior over RSM in terms of accuracy, these
models complement each other in interpreting the experimental
FAEE content. While ANN is more reliable in capturing the nonlin-
ear relationship between the FAEE content and process variables,
RSM notes the statistical importance of the individual process vari-
ables and their interactions via ANOVA.
Acknowledgment
This work has been funded by the Ministry of Education,
Science and Technological Development of the Republic of Serbia
– Serbia (Project III 45001).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.enconman.2015.
08.072.
References
[1] Leung DYC, Wu X, Leung MKH. A review on biodiesel production using
catalyzed transesterification. Appl Energy 2010;87:1083–95.
[2] Anastopoulos G, Dodos GS, Kalligeros S, Zannikos F. Biodiesel production by
ethanolysis of various vegetable oils using calcium ethoxide as a solid base
catalyst. Int J Green Energy 2013;10:468–81.
[3] Kim M, Di Maggio C, Yan S, Salley SO, Ng KYS. The synergistic effect of alcohol
mixtures on transesterification of soybean oil using homogeneous and
heterogeneous catalysts. Appl Catal A Gen 2010;378:134–43.
[4] Stamenković OS, Veličković AV, Veljković VB. The production of biodiesel from
vegetable oils by ethanolysis: current state and perspectives. Fuel
2011;90:3141–55.
[5] Clark S, Wagner JL, Schrack MD, Piennar PG. Methyl and ethyl soybean esters
as renewable fuels for diesel engines. J Am Oil Chem Soc 1998;61:1632–8.
[6] Encinar JM, Gonzalez JF, Rodriguez-Reinares A. Ethanolysis of used frying oil.
Biodiesel preparation and characterization. Fuel Process Technol
2007;88:513–22.
[7] Joshi H, Moser BR, Toler J, Walker T. Preparation and fuel properties of
mixtures of soybean oil methyl and ethyl esters. Biomass Bioenergy
2010;34:14–20.
[8] Makareviciene V, Janulis P. Environmental effect of rapeseed oil ethyl ester.
Renew Energy 2003;28:2395–403.
[9] Dossin TF, Reyniers MF, Berger RJ, Marin GB. Simulation of heterogeneously
MgO-catalyzed transesterification for fine-chemical and biodiesel industrial
production. Appl Catal B Environ 2006;67:136–48.
[10] Mbaraka IK, Shanks BH. Conversion of oils and fats using advanced
mesoporous heterogeneous catalysts. J Am Oil Chem Soc 2006;83:79–91.
[11] Li E, Xu ZP, Rudolph V. MgCoAl–LDH derived heterogeneous catalysts for the
ethanol transesterification of canola oil to biodiesel. Appl Catal B Environ
2009;88:42–9.
[12] Sreeprasanth PS, Srivastava R, Srinivas D, Ratnasamy P. Hydrophobic, solid acid
catalysts for production of biofuels and lubricants. Appl Catal A Gen
2006;314:148–59.
[13] Jiménez-Morales I, Santamaría-González J, Maireles-Torres P, Jiménez-López
A. Calcined zirconium sulfate supported on MCM-41 silica as acid catalyst for
ethanolysis of sunflower oil. Appl Catal B Environ 2011;103:91–8.
[14] Rubio-Caballero JM, Santamaria-Gonzalez Merida-Roble JJ, Moreno-Tost R,
Alonso-Castillo ML, Vereda-Alonso E, Jimenez-Lopez A, et al. Calcium zincate
derived heterogeneous catalyst for biodiesel production by ethanolysis. Fuel
2013;105:518–22.
[15] Quintella SA, Saboya RMA, Salmin DC, Novaes DS, Araújo AS, Albuquerque
MCG, et al. Transesterification of soybean oil using ethanol and mesoporous
silica catalyst. Renew Energy 2012;38:136–40.
[16] Watcharathamrongkul K, Jongsomjit B, Phisalaphong M. Calcium oxide based
catalysts for ethanolysis of soybean oil. Songklanakarin J Sci Technol
2010;32:627–34.
[17] Garcia CM, Teixeira S, Marciniuk LL, Schuchardt U. Transesterification of
soybean oil catalyzed by sulfated zirconia. Bioresour Technol 2008;99:
6608–13.
[18] Alves CT, de Oliveira AS, Carneiro SAV, Santos RCD, Vieira de Melo SAB,
Andrade HMC, et al. Transesterification of waste frying oils using ZnAl2O4 as
heterogeneous catalyst. Proc Eng 2012;42:1928–45.
1156 J.M. Avramović et al. / Energy Conversion and Management 105 (2015) 1149–1156
[19] Alves CT, Andrade HMC, Santos RCD, Vieira de Melo SAB, Torres EA.
Transesterification reaction using zinc aluminate as heterogeneous catalyst
and supercritical carbon dioxide. Chem Eng Trans 2013;32:883–8.
[20] Shibasaki-Kitakawa N, Honda H, Kuribayashi H, Toda T, Fukumura T,
Yonemoto T. Biodiesel production using ion-exchange resin as
heterogeneous catalyst. Bioresour Technol 2007;98:416–21.
[21] Avramović JM, Stamenković OS, Todorović ZB, Lazić ML, Veljković VB. The
optimization of the ultrasound-assisted base-catalyzed sunflower oil
methanolysis by a full factorial design. Fuel Process Technol 2010;91:1551–7.
[22] Veličković AV, Stamenković OS, Todorović ZB, Veljković VB. Application of the
full factorial design to optimization of base-catalyzed sunflower oil
ethanolysis. Fuel 2013;104:433–42.
[23] Lee HV, Yunus R, Juan JC, Taufiq-Yap YH. Process optimization design for
jatropha-based biodiesel production using response surface methodology. Fuel
Process Technol 2011;92:2420–8.
[24] Zanette AF, Barella RA, Pergher SBC, Treichel H, Oliveira D, Mazutti MA, et al.
Screening, optimization and kinetics of Jatropha curcas oil transesterification
with heterogeneous catalysts. Renew. Energy 2011;36:726–31.
[25] Wan Omar WNN, Amin NAS. Optimization of heterogeneous biodiesel
production from waste cooking palm oil via response surface methodology.
Biomass Bioenergy 2011;35:1329–38.
[26] Liu M, Niu S, Lu C, Cheng S. An optimization study on transesterification
catalyzed by the activated carbide slag through the response surface
methodology. Energy Convers Manage 2015;92:498–506.
[27] Moradi GR, Dehghani S, Khosravian F, Arjmandzadeh A. The optimized
operational conditions for biodiesel production from soybean oil and
application of artificial neural networks for estimation of the biodiesel yield.
Renew Energy 2013;50:915–20.
[28] Badday AS, Abdullah AZ, Lee K-T. Artificial neural network approach for
modeling of ultrasound-assisted transesterification process of crude Jatropha
oil catalyzed by heteropolyacid based catalyst. Chem Eng Process
2014;75:31–7.
[29] Stamenković OS, Rajković KM, Veličković AV, Milić PS, Veljković VB.
Optimization of base-catalyzed ethanolysis of sunflower oil by regression
and artificial neural network models. Fuel Process Technol 2013;114:101–8.
[30] Rajković KM, Avramović JM, Milić PS, Stamenković OS, Veljković VB.
Optimization of ultrasound-assisted base-catalyzed methanolysis of
sunflower oil using response surface and artificial neural network
methodologies. Chem Eng J 2013;215–216:82–9.
[31] Betiku E, Ajala SO. Modeling and optimization of Thevetia peruviana (yellow
oleander) oil biodiesel synthesis via Musa paradisiacal (plantain) peels as
heterogeneous base catalyst: a case of artificial neural network vs. response
surface methodology. Ind Crops Prod 2014;53:314–22.
[32] Betiku E, Omilakin OR, Ajala SO, Okeleye AA, Taiwo AE, Solomon BO.
Mathematical modeling and process parameters optimization studies by
artificial neural network and response surface methodology: a case of non-
edible neem (Azadirachta indica) seed oil biodiesel synthesis. Energy
2014;72:266–73.
[33] Sarve A, Sonawane SS, Varma MN. Ultrasound assisted biodiesel production
from sesame (Sesamum indicum L.) oil using barium hydroxide as a
heterogeneous catalyst: comparative assessment of prediction abilities
between response surface methodology (RSM) and artificial neural network
(ANN). Ultrason Sonochem 2015;26:218–28.
[34] Betiku E, Okunsolawo SS, Ajala SO, Odedele OS. Performance evaluation of
artificial neural network coupled with generic algorithm and response surface
methodology in modeling and optimization of biodiesel production process
parameters from shea tree (Vitellaria paradoxa) nut butter. Renew Energy
2015;76:408–17.
[35] Stamenković OS, Veličković AV, Kostić MD, Joković NM, Rajković KM, Milić PS,
et al. Optimization of KOH-catalyzed methanolysis of hempseed oil. Energy
Convers Manage 2015;103:235–43.
[36] Fauzi AHM, Amin NAS. Optimization of oleic acid esterification catalyzed by
ionic liquid for green biodiesel synthesis. Energy Convers Manage
2013;76:818–27.
[37] Maran JP, Priya B. Comparison of response surface methodology and artificial
neural network approach towards efficient ultrasound-assisted biodiesel
production from muskmelon oil. Ultrason Sonochem 2015;23:192–200.
[38] Dossin TF, Reyniers MF, Marin GB. Kinetics of heterogeneously MgO catalyzed
transesterification. Appl Catal B 2006;61:35–45.
[39] Levenspiel O. Chemical reaction engineering. 3rd ed. New York: John Wiley
and Sons; 1999.
[40] Aris R. Introduction to the analysis of chemical reactors. New York: Prentice-
Hall; 1965.
[41] Carberry J. Chemical and catalytic reaction engineering. New York: McGraw-
Hill; 1976.
[42] Rajendra M, Jena PC, Raheman H. Prediction of optimized pretreatment
process parameters for biodiesel production using ANN and GA. Fuel
2009;88:868–75.
[43] Zhu H, Wu Z, Chen Y, Zhang P, Duan S, Liu X, et al. Preparation of biodiesel
catalyzed by solid super base of calcium oxide and its refining process. Chin J
Catal 2006;27:391–6.
[44] Olutoye MA, Hameed BH. Synthesis of fatty acid methyl ester from crude
jatropha (Jatropha curcas Linnaeus) oil using aluminum oxide modified Mg–Zn
heterogeneous catalyst. Bioresour Technol 2011;102:6392–8.
[45] Rezaei R, Mohadesi M, Moradi GR. Optimization of biodiesel production using
waste mussel shell catalyst. Fuel 2013;109:534–41.
[46] Stamenković OS, Lazić ML, Todorović ZB, Veljković VB, Skala DU. The effect of
agitation intensity on alkali-catalyzed methanolysis of sunflower oil. Bioresour
Technol 2007;98:2688–99.
[47] Talebian-Kiakalaieh A, Amin NAS, Zarei A, Noshadi I. Transesterification of
waste cooking oil by heteropoly acid (HPA) catalyst: optimization and kinetic
model. Appl Energy 2013;102:283–92.
[48] Fadhil AB, Abdulahad WS. Transesterification of mustard (Brassica nigra) seed
oil with ethanol: purification of the crude ethyl ester with activated carbon
produced from de-oiled cake. Energy Convers Manage 2014;77:495–503.
[49] Anastopoulos G, Zannikou Y, Stournas S, Kalligeros S. Transesterification of
vegetable oils with ethanol and characterization of the key fuel properties of
ethyl esters. Energy 2009;2:362–76.
[50] Costenoble O, Mittelbach M, Schober S, Fischer J, Haupt J. Improvements
needed for the biodiesel standard EN 14214. EC project TREN/D2/44-LOT 1/
S07.54676, NEN, University of Graz and AGQM; 2008. <http://ec.europa.eu/
energy/renewables/biofuels/doc/standard/lot1.pdf> [March, 2014].