Ultrasonics Sonochemistry 23 (2015) 192–200

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Comparison of response surface methodology and artificial neural

network approach towards efficient ultrasound-assisted biodiesel
production from muskmelon oil
J. Prakash Maran a,⇑, B. Priya b
a
Department of Food Technology, Kongu Engineering College, Perundurai, Erode 638052, Tamil Nadu, India
b
Department of Food Process Engineering, SRM University, SRM Nagar, Kattankulathur, Chennai 603203, Tamil Nadu, India

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

Article history: The present study is to evaluate and compare the prediction and simulating efficiencies of response
Received 3 June 2014 surface methodology (RSM) and artificial neural network (ANN) based models on fatty acid methyl esters
Received in revised form 16 October 2014 (FAME) yield achieved from muskmelon oil (MMO) under ultrasonication by two step in situ process. In
Accepted 17 October 2014
first in situ process, free fatty acid content of MMO was reduced from 6.43% to 0.91% using H2SO4 as acid
Available online 23 October 2014
catalyst and organic phase in the first step was subjected to second reaction by adding KOH in methanol
as basic catalyst. The influence of process variables (methanol to oil molar ratio, catalyst concentration,
Keywords:
reaction temperature and reaction time) on conversion of FAME (second step) was investigated by central
Two-step in situ process
Ultrasound
composite rotatable design (CCRD) of RSM and Multi-Layer Perceptron (MLP) neural network with the
Muskmelon oil topology of 4-7-1. Both (RSM and ANN) were statistically compared by the coefficient of determination,
Biodiesel root mean square error and absolute average deviation, based on the validation data set. The coefficient of
RSM determination (R2) calculated from the validation data for RSM and ANN models were 0.869 and 0.991
ANN respectively. While both models showed good predictions in this study. But, the ANN model was more
precise compared to the RSM model and it showed that, ANN is to be a powerful tool for modeling
and optimizing FAME production.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction transesterification [1]. The transesterification process is the most

Rising prices of crude petroleum oil in the past few years,
depletion of fossil oil reserves and also increasing environmental
concerns have prompted much research into the production of
alternative energy substitutes for petroleum based fuels. Currently,
extensive work is being carried out towards the exploration of
alternative renewable fuel sources. The researchers have found
several types of biomass derived liquid fuels such as bio-ethanol,
bio-methanol, methyl esters from vegetable oils and animal fats
as an alternative to fossil fuel. Among the different possible
resources for the production of alternative fuels, biodiesel appears
to be the most promising alternative to petroleum based diesel fuel
because it is renewable in nature and can be produced locally, as
well as being environmentally friendly. ‘‘Biodiesel’’ is defined as
mono-alkyl esters of long-chain fatty acids derived from vegetable
oils/animal fats.
There are many ways and procedures to biodiesel fuel from
vegetable oil such as pyrolysis, dilution, microemulsion and
⇑ Corresponding author. Tel.: +91 4294 226606; fax: +91 4294 220087.
E-mail address: prakashmaran@gmail.com (J.P. Maran).
viable and economical process. Biodiesel produced via transesteri-
fication process has proven to be a viable alternative fuel with
similar characteristics to diesel fuel. Two-step esterification and
transesterification process was used to produce biodiesel from oil
[2]. As a result, the important properties of the biodiesel were
within the ASTM biodiesel specification. In the past few years,
various non-edible vegetable oils (Moringa oleifera [3], Hevea
brasiliensis [4], Pongamia pinnata [5], Jatropha curcas [6], Hibiscus
esculentus [7], Camelina sativa [8] and Coriandrum sativum [9]) were
used as sources for biodiesel synthesis.
Intensification of biodiesel synthesis process had focused on
development of process technologies involving microwave radia-
tion, static mixers, micro-channel, oscillatory flow and cavitational
methods [10]. These technologies can render high product yield
through enhancement of mass and heat transfer in the reactor.
Biodiesel production by transesterification of refined sunflower
oil through ultrasonic irradiation was found energy efficient [11].
Ultrasonic irradiation causes cavitation bubbles to form near the
phase boundary between the alcohol and oil phases. The collapse
of the cavitation bubbles disrupts the phase boundary and causes
emulsification by ultrasonic jets that impinge from one liquid upon

http://dx.doi.org/10.1016/j.ultsonch.2014.10.019
1350-4177/Ó 2014 Elsevier B.V. All rights reserved.
 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200
the other. Cavitation may also lead to a localized increase in tem-
perature at the phase boundary enhancing the transesterification
reaction. In addition, research literature has been reported on the
advantages of the ultrasonic irradiation assisted transesterification
process that indicates advantages such as excellent biodiesel yield,
a much shorter reaction time, a low amount of catalyst required
and less energy consumption than the conventional mechanical
stirring method [12].
Response surface methodology (RSM) is one of the multivariate
techniques that can deal with experimental design and statistical
modeling. It is used to examine the relationship between one or
more response variables and a set of quantitative experimental
variables or factors. ANN modeling, which was inspired from the
functioning of biological nervous systems, has proved to be a pow-
erful technique for complex and nonlinear problems with strong
ability to learn and predict. The application of both techniques in
a research work will make the researchers to compare the results
of both approaches and understand the process in a better manner.
Although there is already a considerable amount of research
applied to different areas; such as modeling of extrusion process
[13], fermentation media optimization [14], modeling and optimi-
zation of heterogeneous photo-fenton process [15], modeling of a
microwave-assisted extraction method [16], by using both RSM
and ANN techniques in the literature. But, there are few studies
on the biodiesel synthesis [17–19].
However, a method for biodiesel synthesis from muskmelon oil
(MMO) under ultrasonication using RSM and ANN techniques does
not take place in the literature. Hence, the objectives of the present
study has been made to prepare biodiesel from MMO under ultra-
sonication using two-step in situ reaction (acid-catalyzed esterifi-
cation followed by base-catalyzed transesterification) process. A
four factors five levels central composite rotatable design (CCRD)
and a Multi-Layer Perceptron (MLP) neural network with three lay-
ers (input (4 neurons), hidden (7 neurons) and output (1 neuron)
based models were developed to predict the experimental vari-
ables (methanol to oil molar ratio, catalyst concentration, reaction
temperature and reaction time) on conversion of MMO to fatty acid
methyl esters (FAME) for base catalyzed in situ transesterification
process. Subsequently, the results predicted by the ANN and RSM
techniques were compared for their predictive and generalization
capabilities on the FAME conversion process. Furthermore, the
efficiency of both the models was statistically compared by the
coefficient of determination (R2), root mean square error (RMSE)
and absolute average deviation (AAD) based on the validation
experimental data set. To the best of our knowledge, this is the first
research report exhibit the biodiesel production from MMO by
in situ two-step process under ultrasonication using RSM and ANN.
2. Materials and methods
2.1. Materials
Muskmelon oil (MMO) was procured from local suppliers near
Chennai, Tamil Nadu, India. The acid value of the raw oil was mea-
sured to be 12.8 mg KOH g1 oil, which corresponds to 6.43 wt% of
free fatty acids (FFA). The chemicals used in the experiment, which
include sulfuric acid (H2SO4), potassium hydroxide (KOH), and
methanol, were purchased from the Merck Chemical Company
(Mumbai) and all the chemicals used in this study was analytical
grade.
2.2. Experimental set up
An ultrasonic processor (VCX 400, Sonics and Materials, USA)
operated at 20 kHz with a power of 400 W was used as the source
193
of ultrasound for the enhanced production of biodiesel. The ultra-
sonic times for the reactions were adjustable from 1 to 90 min. All
the experimental reactions were carried out in an ultrasonic batch
reactor (1000 ml) made of stainless steel equipped with a thermo-
couple probe and a sampling port. The ultrasonic batch reactor was
immersed in a water bath placed on the hot plate. The tip of a horn
with a diameter of 10 mm and a length of 120 mm was used to
transmit the ultrasound into the solution and was submerged up
to 55 mm deep into the solution contained in the ultrasonic batch
reactor (in the methanol phase). The temperature of the reaction
mixture was controlled by a water bath.
2.3. Two step in situ process by ultrasound
The MMO used in this study was found to contain 6.43 wt% of
FFA, which is much higher than the safe limit for a direct transeste-
rification reaction [20] using an alkaline catalyst. Hence, biodiesel
production from high FFA oil needs a two-step transesterification
process; namely, in situ esterification (acid catalyzed esterifica-
tion) followed by in situ transesterification (alkaline catalyzed
transesterification) to get a high yield of biodiesel. Two-step
in situ method included in situ esterification by sulfuric acid as
acid catalyst followed by in situ transesterification by KOH as base
catalyst respectively.
2.3.1. In situ esterification
The in situ esterification process conditions were considered
which reduced the FFA of the feedstock, shortened the reaction
time and reduced the amount of reagent required. A methanol to
oil molar ratio of 6:1 was used for the pre-treatment process using
3 wt% of sulfuric acid (H2SO4) as catalyst. The reaction was carried
out with an ultrasonic irradiation time of 30 min at room temper-
ature (30 °C). After the acid catalyzed esterification reaction, the
product was allowed to settle for 8 h or overnight before gum,
unreacted methanol and water fraction in the bottom layer were
removed. The acid value of the product from the acid catalyzed
esterification was determined by a standard titration method. In
this process, the FFA of the raw oil was reduced from 6.43 wt% to
below 0.91 wt%. The product was then used for the in situ transe-
sterification process.
2.3.2. In situ transesterification
A known amount of MMO (300 g) was added to the reactor,
which was preheated to the desired temperature on a heating plate
before the reaction was started. The catalyst (KOH) was dissolved
in methanol to the desired amount before the solution was charged
into the reactor. The mixing intensity of the ultrasonic irradiation
was fixed at 20 kHz frequency and supported by a power of
400 W. Different molar ratio of methanol to oil, catalyst concentra-
tion, reaction temperature and reaction time were carried out
according to the Table 1. After the reaction was completed, the
reaction product was allowed to separate overnight by gravity
before removing the glycerol layer from the bottom in a separation
funnel. This upper phase consisted of methyl ester or biodiesel, the
lower phase being glycerol. The biodiesel was washed several
times with a small amount of fresh hot water until the washing
water was found to be neutral. Finally, the alcohol and water
content was evaporated by means of heating.
2.4. Determination of FAME content
The composition of fatty acid methyl esters (FAME) or biodiesel
in the upper layer of the two-step reactive extraction products was
analyzed using a gas chromatograph equipped with flamed ionized
detector (FID). Helium was used as the carrier gas with flow rate
3 ml/min while n-hexane was used as the solvent. The oven
194 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200

Table 1
Experimental design matrix with observed and predicted values.

Independent variables Unit Symbols Level of factors

a (2) 1 0 1 a (2)
Methanol to oil molar ratio X1 3.0 4.5 6.0 7.5 9.0
Catalyst concentration wt% X2 0.50 0.75 1.00 1.25 1.50
Reaction temperature °C X3 30 35 40 45 50
Reaction time min X4 10 20 30 40 50

Std. order Point type X1 X2 X3 X4 Conversion to biodiesel (%)

Observed RSM ANN
1 Factorial 1 1 1 1 90.28 90.25 90.18
2 Factorial 1 1 1 1 92.83 92.29 92.78
3 Factorial 1 1 1 1 96.15 96.04 96.18
4 Factorial 1 1 1 1 97.76 97.34 97.65
5 Factorial 1 1 1 1 90.21 90.42 90.09
6 Factorial 1 1 1 1 92.17 92.56 92.19
7 Factorial 1 1 1 1 95.49 95.06 95.42
8 Factorial 1 1 1 1 96.75 96.47 96.73
9 Factorial 1 1 1 1 91.82 91.88 91.77
10 Factorial 1 1 1 1 92.79 93.52 92.82
11 Factorial 1 1 1 1 95.24 95.15 95.29
12 Factorial 1 1 1 1 96.49 96.06 96.44
13 Factorial 1 1 1 1 93.08 93.80 93.11
14 Factorial 1 1 1 1 95.66 95.55 95.71
15 Factorial 1 1 1 1 95.61 95.93 95.59
16 Factorial 1 1 1 1 96.62 96.95 96.67
17 Axial 2 0 0 0 91.75 91.47 91.81
18 Axial 2 0 0 0 94.34 94.54 94.29
19 Axial 0 2 0 0 89.58 88.90 89.62
20 Axial 0 2 0 0 95.49 96.09 95.48
21 Axial 0 0 2 0 94.79 95.24 94.75
22 Axial 0 0 2 0 96.82 96.29 96.84
23 Axial 0 0 0 2 94.36 95.00 94.39
24 Axial 0 0 0 2 97.83 97.11 97.78
25 Center 0 0 0 0 96.27 97.15 96.45
26 Center 0 0 0 0 97.57 97.15 97.52
27 Center 0 0 0 0 97.18 97.15 97.13
28 Center 0 0 0 0 97.51 97.15 97.46
29 Center 0 0 0 0 96.85 97.15 96.81
30 Center 0 0 0 0 97.53 97.15 97.48

temperature was set at 110 °C and then increased to 220 °C at a
rate of 10 °C/min. The temperature of the detector and injector
were set at 220 and 250 °C, respectively. Comparing the retention
time of each component in the samples with the peaks of pure
methyl ester standard compound identified the peaks of different
methyl esters. Triglycerides conversion to FAME was calculated
by using the following equation [6]:
2.5. Experimental design
2.5.1. Response surface methodology
Response surface methodology (RSM) is an empirical statistical
modeling technique used for multiple regression analysis by
quantitative data obtained from experiments. In this study,
5-level-4-factors central composite rotatable design (CCRD) was

P P
ð Mono; di; tri glyceride in oilÞ  ð Mono; di; tri glyceridein FAMEÞ
Conversion ð%Þ ¼ P  100 ð1Þ
ð Mono; di; tri glyceridein oilÞ

For the determination of FAME composition at optimal
conditions, HPLC (Perkin Elmer; model 1022) fitted with a pump
(Perkin Elmer series 200 LC pump) and RI detector (Perkin Elmer
series 200 RI) was used by maintaining a methanol (mobile phase)
flow rate of 1 ml min1, injection volume of 20 ll, and at a
controlled temperature of 45 °C [21]. Based on the calibration
curves of standard, the concentrations of FAME in the produced
biodiesel were calculated.
used to evaluate the effect of process variables (methanol to oil
molar ratio, catalyst concentration, reaction temperature and
reaction time) on conversion of oil to FAME for base catalyzed
in situ transesterification process. The CCRD is a suitable design
for sequential experiments to obtain appropriate information for
testing lack of fit without a large number of design points [22]. A
total number of 30 experiments (Table 1) were determined from
CCRD, which includes 16 factorial points, 8 axial points and 6
 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200
center point replications. The number of the axial points on the
axis of each design factor at a distance of ±a (a = 2k/4 = 2; k is num-
ber of independent variables). The response (FAME conversion)
was expressed as the function of independent variables, according
to the following equation:
X
k X
k XX
k
Y ¼ b0 þ bj xj þ bjj x2j þ bij xi xj þ ei
j¼1 j¼1 i <j¼2
where Y is the response; xi and xj are variables (i and j range from 1
to k); b0 is the model intercept coefficient; bj, bjj and bij are interac-
tion coefficients of linear, quadratic and the second-order terms,
respectively; k is the number of independent parameters (k = 4 in
this study); ei is the error [23].
The statistical software package (Design Expert 8.0.7.1, Statease,
USA) was used in this study to generate design of experiment
(DOE), perform the statistical analysis, optimize and create a
model.
2.5.2. Artificial neural network
Artificial neural network (ANN) can be used as an alternative to
the polynomial regression based modeling tool, which provides the
modeling of complex nonlinear relationships. The ANN model is
potentially more accurate by including all the experimental data
[24]. Developing an ANN is not simple, but involves many critical
steps; viz., (1) select a data generator, (2) data generation, (3) data
processing, (4) neural network structure selection, (5) training
algorithm selection, (6) neural network training, (7) testing of
the trained artificial neural networks, and (8) using the trained
ANN for simulation and validation [25]. The reporting ability of
feed forward architecture of ANN, also known as multilayered
perceptron (MLP) neural network with logistic sigmoid transfer
function at hidden layers and a purelin transfer function at output
layers were selected and trained in this study. The MLP network
uses a back-propagation learning algorithm. Different back-
propagation (BP) algorithms (Scaled Conjugate Gradient (SCG),
Levenberg–Marquardt (LM), Gradient Descent with variable learn-
ing rate back propagation (GDX) and Resilient back Propagation
(RP)) were used for network training in order to select the best
suited BP algorithm. In order to develop ANN model, logistic
sigmoid transfer function at hidden neurons and purelin transfer
functions at output neurons were used in this study and it is
expressed as:
1 high (29.94) with very low probability value (p < 0.0001), which
f ðxÞ ¼
1 þ expðxÞ
f ðxÞ ¼ x
In order to achieve the reduction of network error and higher
homogeneous results, inputs and output are normalized in the
range of 0–1 as follows:
X  X min
X norm ¼
X max  X min
where Xnorm, X, Xmin, and Xmax are normalized value, actual value,
minimum value, and maximum value, respectively.
Train, test and validate the neural network model for FAME con-
version from MMO is done by the experimental data obtained from
CCRD matrix. For this purpose the experimental data were ran-
domly divided into three sets. One set was considered as training
data, another set was used as testing data and another set was uti-
lized as validation data for the neural network model. The residual
between expected and actual data is computed with sum squared
error according to the following equation:
X
n
2
SSE ¼ ðY 1  Y 1 Þ
i¼1
195
where, Yi and Y i are actual and predicted data. MATLAB 6.5 (The
Mathworks Inc.) with neural network toolbox was used in this
study for the development of neuromorphic model.
3. Results and discussion
ð2Þ
3.1. Modeling and optimization of FAME conversion using RSM
Experiments were carried out in triplicate according to the
CCRD matrix and the average experimental data was taken for
the data analysis as well as modeling of FAME conversion process.
The experimental design and results were presented in Table 1. To
decide about the adequacy of models among various models
(linear, interactive, quadratic and cubic) to represent FAME conver-
sion from MMO, two different tests namely the sequential model
sum of squares and model summary statistics were carried out
on the experimental data in this present study and the results
are given in Table 2. From the results, it was found that, quadratic
model was found to have maximum determination coefficient (R2),
adjusted determination of coefficient (R2a ), predicted determination
of coefficient (R2p ) values and also exhibited low p-values than
other models. Moreover, the model was demonstrated to cover
the experimental range of studies adequately.
Analysis of variance (ANOVA) for quadratic model for the FAME
conversion was used to justify the adequacy of the models. ANOVA
is a statistical technique that subdivides the total variation in a set
of data into component parts associated with specific sources of
variation for the purpose of testing hypotheses on the parameters
of the model [26]. The ANOVA results (Table.2) showed the linear,
interactive and quadratic relationship between the effects of
independent variables on dependent variable. The significance of
each term was assessed according to their corresponding p-values.
The p-value is used as a tool to check the significance of each of the
coefficients. The p-value less than 0.0001 indicating that the model
is significant, while values greater than 0.05 indicate that the
model is insignificant [27]. The analysis of variance concluded that,
the developed model was highly significant at probability level of
p < 0.0001. From the p-values of each model terms, it could be
concluded that three linear (X1, X2 and X4), all quadratic
(X 21 ; X 22 ; X 23 and X 24 ) and five interactive (X1X2, X1X3, X2X3, X2X4 and
X3X4) coefficients were significant.
The Fisher’s F-test (F values) were calculated and found to be
ð3Þ
exhibits a high degree of adequacy of quadratic model and also
showed that the process variable combinations were highly signif-
ð4Þ
icant [28]. From Table 2, it is evident that, linear terms (catalyst
concentration (X2), methanol to oil molar ratio (X1) and reaction
time (X4)), interactive terms (catalyst concentration and reaction
time (X2X4) and quadratic terms (catalyst concentration (X2) and
methanol to oil molar ratio (X1)) have large effects on conversion
ð5Þ due to its higher F values as well as low p-values.
Determination co-efficient (R2), correlation coefficient (R) and
adjusted determination co-efficient (R2a ) and co-efficient of
variance (CV) was also determined to evaluate the goodness of
the model. The determination coefficient (R2 = 0.965) value of the
quadratic regression model, indicating that only 0.035% of the total
variations was not explained by the model [29]. The value of the
adjusted determination coefficient (R2a ¼ 0:933) is very high and
confirmed that the model was highly significant. If there are many
terms in the models and the sample size is not enough large, the R2a
may be noticeably smaller than R2. In this study, the R2a value
(0.916) was found to be very close to the R2. Moreover, a very high
value of the correlation coefficient (R = 0.982) exhibited an excel-
ð6Þ lent correlation between the experimental and predicted response
values [30]. The low CV (0.67) not only indicated a high degree of
196 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200

Table 2
RSM model adequacy and ANOVA analysis.

Source Std. Dev. R2 Adjusted R2 Predicted R2 p-Value PRESS Remarks

Adequacy of the model tested
Linear 1.74 0.567 0.498 0.413 0.0002 103.08
2FI 1.84 0.632 0.439 0.337 0.7572 116.51
Quadratic 0.64 0.965 0.933 0.916 <0.0001 29.28 Suggested
Cubic 0.88 0.941 0.912 0.849 0.1298 44.03 Aliased

Source Coefficient estimate Sum of squares Degree of freedom Standard error Mean square F value p-Value
ANOVA
Model 97.15 169.65 14 0.26 12.12 29.94 <0.0001
X1 0.77 14.06 1 0.13 14.06 34.74 <0.0001
X2 1.80 77.36 1 0.13 77.36 191.17 <0.0001
X3 0.26 1.65 1 0.13 1.65 4.07 0.0618
X4 0.53 6.63 1 0.13 6.63 16.37 0.0011
X12 0.18 0.54 1 0.16 0.54 1.33 0.0012
X13 0.03 0.01 1 0.16 0.01 0.03 0.0036
X14 0.10 0.15 1 0.16 0.15 0.38 0.5465
X23 0.29 1.31 1 0.16 1.31 3.23 0.0327
X24 0.63 6.31 1 0.16 6.31 15.60 0.0013
X34 0.44 3.09 1 0.16 3.09 7.63 0.0145
X21 1.04 29.48 1 0.12 29.48 72.85 <0.0001
X22 1.16 37.18 1 0.12 37.18 91.87 <0.0001
X23 0.35 3.30 1 0.12 3.30 8.15 0.0120
X24 0.27 2.06 1 0.12 2.06 5.10 0.0393
Residual 6.07 15 0.40
Std. Dev. 0.64
Mean 94.89
C.V.% 0.67
Ade. Pre 18.76

precision but also had a good deal of reliability in conducted exper-

iments [31]. The adequate precision is the measure of signal to
noise ratio and the ratio is greater than 4 is desirable in support
of the fitness of the model [32]. For the present study, the signal
to noise ratio was found to be 18.74, which indicates best fitness
of the quadratic model.
The regression analysis was employed to generate the full
quadratic model to predict the conversion of FAME from MMO in
terms of coded factors is given below:

Conversion ð%Þ ¼ 97:15 þ 0:77X 1 þ 1:8X 2 þ 0:26X 3 þ 0:53X 4

 0:18X 1 X 2 þ 0:027X 1 X 3  0:098X 1 X 4
 0:29X 2 X 3  0:63X 2 X 4 þ 0:44X 3 X 4
 1:04X 21  1:16X 22  0:35X 23  0:27X 24 ð7Þ

where, X1 is methanol to oil molar ratio, X2 is catalyst concentration,

X3 is reaction temperature and X4 is reaction time.
Process variables (linear, interaction and quadratic) effects in
FAME conversion from MMO with respect to sum of squares (SS)
of each variable obtained from ANOVA were also investigated in
this study and the results are shown in Fig. 1. From the figure, it
is seen that, linear effect of process variables have predominant
effect (54.32%) on conversion process, followed by quadratic effect
of process variables (39.24%). The effects of interactive terms
(6.22%) on conversion percentage were found to be minor
compared to other terms. The residual error measures amount of
variation in the response left unexplained by the model and its
effect was very low (0.22%) in FAME conversion process.
3.2. Effect of process variables
In order to visualize and study the interactive relationship
between the response and process variables, three dimensional
(3D) surface and contour plots were generated from the fitted
polynomial equation. It can be seen from the figure that an
increase in the catalyst concentration from 0.75% to 1.2% results
Fig. 1. Linear, interactive and quadratic effect of process variables on FAME
conversion.
in an increase in the biodiesel yield, however, a further increase
in the catalyst concentration% does not show a significant increase
in the biodiesel yield. An initial increase in the catalyst loading rep-
resents increase in the catalyst activity and hence biodiesel yield
increases. However, further increase in catalyst loading beyond
the 1.2% has no effect on biodiesel yield irrespective of excess cat-
alyst activity and hence any excess use of the catalyst must be
avoided so as to minimize the separation requirements. From the
results, it was observed that, the biodiesel yield was increased with
increasing methanol to oil molar ratio from 3:1 to 7:1. However a
further increase in the methanol to oil molar ratio had no signifi-
cant influence on the biodiesel yield and the observed biodiesel
yield at molar ratio of 9:1 was slightly less as compared to the
7:1 molar ratio. The obtained result can be attributed to the fact
that the use of significantly higher molar ratio results in diluted
 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200 197

products of biodiesel and glycerol which might initiate the reverse

reaction to reduce the effective yield. The results indicate that, an
increase in temperature from 30 to 40 °C increased the biodiesel
yield whereas a further increase in the reaction temperature from
40 to 50 °C results only in a marginal increase in the biodiesel
yield. The obtained results can be attributed to the enhanced solu-
bility of methanol in oil phase with an increase in the reaction tem-
perature resulting into better contact of the reactants leading to
higher yield of biodiesel from WCO. Any further increase in the
temperature has no significant effect on the final conversion to
ester which can be also attributed to lower extent of cavitational
effects at higher operating temperatures contributing in a negative
manner [33].

3.3. Modeling with ANN

In the last two decades, ANN has proved to be a more powerful

tool in modeling and simulation in various engineering fields, to
predict the behavior of a non-linear multivariate system. ANN
would require many more experiments than the RSM, to construct
a suitable model. But in actual fact, ANN can also work well even
with reasonably small data, if the data in the input and output
domains were statistically significant, which is the case with the
DOE. Therefore, the experimental data obtained through RSM,
could be adequate to build effective ANN models [14].
One of the most important tasks in constructing the ANN is the
choice of the number of hidden layers and numbers of neurons
[34]. Selection of the correct network size is very important in
the ANN modeling. If network size is very small (few neurons in
the hidden layer), the performance of the network will not be sat-
Fig. 2. Determination of optimum number of neurons for selected algorithms: (a)
isfactory. Conversely, if too many neurons exist in the hidden layer,
networks training (b) networks testing.
the training will be so long and may be compromised by local min-
ima or over-fitting [35]. between the experimental results and ANN predicted data. From
There are several ANN models and architectures that have been the above figure, it is evident that the trained neural network has
used in engineering applications to model or approximate proper- efficient approximated experimental values. The distribution of
ties. The most widely used ANN models among feed forward mod- the experimental values and its residual error is shown in the
els, are the Multi-Layer Perceptron (MLP) and the Radial Basis Fig. 5 and it is observed that the deviations of the predicted and
Function (RBF) models [36]. According to Swingler [37], MLP net- its residual values are relatively vary small for ANN model com-
work with one hidden layer will never require neurons more than pared with RSM model.
twice as many as inputs; therefore in this study MLP network was
tested involving 4–8 neurons on the one hidden layer. In this study, 3.4. Comparison of RSM and ANN
different training algorithms (SCG, LM, GDX and RP) were tested by
varying the number of neurons (4–8) by training the MLP network, At this stage, comparison criteria are needed to quantify the dif-
in order to select the optimal architecture based on the minimiza- ference between values produced by both models and the actual
tion of the performance function based on sum squared error (SSE). values. In order to validate and test the extrapolative capability
The original experimental data sets were categorized into three of both the ANN and RSM models, a completely new set of 10
subsets comprising of training (60% of the original experimental experiments was conducted on the experimental range, which
data sets), testing (20% of the original experimental data sets) does not belong to the training data sets. The experimental and
and validation (20% of the original experimental data sets). The predicted values of the response for both the ANN and RSM models
purpose of splitting the experimental data was to measure the per- are given in Table 3. The performance of newly constructed ANN
formance of the neural network for the prediction of unseen data, and RSM models were statistically measured, in terms of the root
that were not used for training and to assess the generalization mean square error (RMSE), co-efficient of determination (R2) and
capability of the ANN. absolute average deviation (AAD) as follows [38–39]:
As evident in Fig. 2 with regard to training and testing errors, !1=2
the optimum number of hidden layer neurons is determined to 1X n
RMSE ¼ ðY i  Y di Þ2 ð8Þ
be nine and also the LM training algorithm was found to have a n i¼1
superior performance and the training stops with SSE of
6.59  1030 at 97 epochs, which are close to the acceptance limit Pn !
2
for the SSE set to zero. The current work used the MLP network 2 i¼1 ðY i  Y di Þ
R ¼1 Pn 2
ð9Þ
with three layers input (4 neurons), hidden (7 neurons) and output i¼1 ðY di  Y m Þ
(1 neuron) to estimate the FAME conversion from MMO and the
n  !
typical architecture was shown in Fig. 3. 1X Y i  Y di
The scatter diagrams that compare the experimental data ver- AAD ¼  100 ð10Þ
n i¼1 Y di
sus the computed neural network data in both training, testing
and validation networks are shown in Fig. 4. Almost all data scatter where, n is the number of points, Yi is the predicted value, Ydi is the
around the 45° line that is the indication of excellent compatibility actual value, and Ym is the average of the actual values.
198 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200

Fig. 3. Typical architecture of ANN.

Fig. 4. Neural network model with training, validation, test and all prediction set.
 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200 199

Fig. 5. Comparison of experimental and predicted value obtained by the ANN and RSM models: (a) for each experimental run (b) distribution of residual values.

found as 0.869 and 0.991 respectively. The AAD for RSM and
Table 3
Validation and comparison of experimental data set. ANN was found to be 2.287 and 0.212. From the results, it was
observed that, both models were fitted well to experimental data.
Run order X1 X2 X3 X4 Conversion to biodiesel (%)
However, predictive power of ANN was found to be more powerful
Actual RSM ANN than RSM. RSM has the advantage of giving a regression equation
1 3 0.75 35 15 83.26 85.32 82.05 for prediction, showing and identifying the insignificant main fac-
2 4.5 1 45 25 92.51 94.64 92.28 tors and interaction factors or insignificant quadratic terms in the
3 6 1.25 30 20 95.52 97.15 95.24
model and thereby can reduce the complexity of the problem in
4 9 1.5 50 50 86.39 89.64 86.13
5 5 1 40 30 94.27 96.18 94.31
comparison with ANN. However, the main limitation of RSM
6 7 1 50 10 90.08 92.60 90.15 assumes only quadratic non-linear correlation and this technique
7 5 0.5 30 40 82.53 85.36 82.23 requires good definition of ranges for each factor to ensure that
8 5.5 0.8 40 45 94.18 95.52 94.31 the response(s) under consideration changes in a regular manner
9 3.5 1 45 35 91.47 93.36 91.54
within this range. But ANN can inherently capture almost any form
10 4 1.3 30 25 93.49 94.32 93.68
RMSE 2.303 0.033 of non-linearity, it can easily overcome the limitation of RSM [14]
R2 0.869 0.991 and this methodology does not require a standard experimental
AAD 2.287 0.212 design to build the model. In addition, ANN model is flexible and
permits to add new experimental data to build a trustable ANN
The RMSE for RSM and ANN was found as 2.303 and 0.033. model [39]. In this study, the performance of the neural network
These results indicate that the RSM prediction has a greater devia- for predicting the FAME conversion from MMO is found to be very
tion than the ANN prediction. R2 values for RSM and ANN were impressive and give deeper knowledge of the non-linear system.
200 J.P. Maran, B. Priya / Ultrasonics Sonochemistry 23 (2015) 192–200
3.5. Optimization of FAME conversion and determination of FAME
composition
Numerical optimization technique [40] was employed to opti-
mize the process variables on the maximum FAME conversion
from MMO using Design expert software. The optimized condition
was to be: methanol to oil molar ratio of 6.6:1, catalyst concentra-
tion of 1.15%, reaction temperature of 41.89 °C and reaction time of
3.56 min respectively. Under this condition, the maximum FAME
conversion yield was 97.90%. The optimal condition determined
by the RSM optimization approach was used to validate the exper-
imentally (triplicate experiments). The average FAME conversion
yield from the triplicate experiments was 97.56 ± 0.63%, which
was very close to predicted value. The FAME composition at opti-
mal condition was determined using HPLC. The produced biodiesel
at optimal condition contain four FAMEs namely methyl linoleate,
methyl plamitate, methyl oleate and methyl stereate respectively.
The concentration of the four FAMEs were calculated based on the
calibration curve and the results indicated that, methyl oleate
(40.87%) was present in bigger amount than other methyl esters
(methyl palmitate (27.11%), methyl stearate (20.39%) and methyl
linoleate (7.81%)).
4. Conclusion
In this study, RSM-CCRD with four independent variables at five
levels and ANN-MLP network (LM training algorithm) with nine
neurons in hidden layer were used to develop model for FAME con-
version from MMO using ultrasound technology. The performance
and generalization capabilities of RSM and ANN models were com-
pared and statistically determined (RMSE, R2 and AAD) with actual
values, which confirms that, the ANN model has finest prediction
capability of target values in comparison to RSM model. To con-
clude, the model developed by ANN has superior ability than the
RSM model.
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