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Fuel 143 (2015) 262–267

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Modeling of ultrasound assisted intensification of biodiesel production


from neem (Azadirachta indica) oil using response surface methodology
and artificial neural network
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

h i g h l i g h t s

 First report on ultrasound assisted biodiesel production from neem oil.


 Response surface and artificial neural network approach is used for modeling.
 Comparison of prediction and generalization abilities of RSM and ANN model.
 ANN was superior to RSM for predicting FAME conversion from neem oil.

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

Article history: In the present work, modeling of ultrasound-assisted intensification of biodiesel production from neem
Received 25 July 2014 (Azadirachta indica) oil was investigated using four factors three level central composite rotatable design
Received in revised form 11 November 2014 (CCRD) of response surface methodology (RSM). The experimental data obtained through CCRD was used
Accepted 17 November 2014
to train the artificial neural network (ANN) model. RSM and ANN models were developed and compared
Available online 27 November 2014
for their predictive and generalization abilities. To evaluate the accuracy of results, additional experi-
ments were conducted which does not belong to experimental design. The results showed that, both
Keywords:
models having the ability to predict the experimental data, but ANN was found to be more reliable
Biodiesel
Neem oil
and superior than RSM.
Ultrasound Ó 2014 Elsevier Ltd. All rights reserved.
RSM
ANN

1. Introduction virgin oils makes biodiesel more expensive than diesel fuel and it
causes to increase in vegetable oil prices. Therefore, selecting the
The energy needs of the world are currently derived from best feedstock is vital for ensuring low production costs and should
petroleum, mineral coal and natural gas. The world is presently be used in biodiesel production. Thus, there is an urgent need to
confronted with the two main crises of fossil fuel depletion and find an alternative, cheaper feedstock, non-edible, readily available
environmental degradation. Therefore, there is an increasing and in large quantities.
worldwide concern for environmental protection and for the Biodiesel is among the promising alternatives for fossil fuels
conservation of non-renewable natural resources [1]. Among the and is mainly produced from animal fats and vegetable oils. There
different possible resources for the production of alternative fuels, are many ways and procedures to biodiesel fuel from vegetable oil
biodiesel appears to be the most promising alternative to petro- such as pyrolysis, dilution, microemulsion and transesterification
leum based diesel fuel because it is renewable in nature and can [2]. Biodiesel produced via transesterification process has proven
be produced locally, as well as being environmentally friendly. Bio- to be a viable, economic and alternative fuel with similar charac-
diesel has received significant attention in all countries since it is teristics to diesel fuel [3]. Different intensification methods such
nontoxic, biodegradable and renewable diesel fuel. Biodiesel is as ultrasonic, microwave irradiation, hydrodynamic cavitation,
generally produced from cooking vegetable oils. Using high-quality addition of co-solvents or mass transfer catalysts and application
of supercritical synthesis conditions have been tried out to elimi-
⇑ Corresponding author. Tel.: +91 4294 226606; fax: +91 4294 220087. nate or minimize the mass transfer limitation in order to improve
E-mail address: prakashmaran@gmail.com (J. Prakash Maran). the biodiesel production process over the traditional methods.

http://dx.doi.org/10.1016/j.fuel.2014.11.058
0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
J. Prakash Maran, B. Priya / Fuel 143 (2015) 262–267 263

Cavitational reactors can offer a useful energy-efficient intensifica- NO. The stainless steel ultrasonic batch reactor (1000 ml) equipped
tion approach for biodiesel production as compared to other with a thermocouple probe and a sampling port was immersed in a
approaches for intensification such as microwave irradiation, oscil- temperature water bath. The ultrasonic transducer (horn with a
latory flow reactor, microchannel reactor, addition of co-solvent diameter of 10 mm and a length of 120 mm) was submerged and
and supercritical uncatalyzed transesterification [4]. Ultrasonic used to transmit the ultrasound into ultrasonic batch reactor
irradiation causes cavitation bubbles to form near the phase contained the solution (in the methanol phase). The higher FFA
boundary between the alcohol and oil phases. The collapse of the content of NO is much higher than the safe limit for direct transe-
cavitation bubbles disrupts the phase boundary and causes emul- sterification reaction [1] using an alkaline catalyst. Hence, two-step
sification by ultrasonic jets that impinge from one liquid upon transesterification process (in situ esterification-acid catalyzed
the other. Cavitation may also lead to a localized increase in tem- esterification followed by in situ transesterification-alkaline cata-
perature at the phase boundary enhancing the transesterification lyzed transesterification) was adopted in this study to obtain high
reaction [5]. Ultrasound assisted transesterification gives the amount of biodiesel.
advantages of shorter reaction period and hence less energy con-
sumption along with using an effective molar ratio of methanol
to oil as compared to conventional mechanical stirring [6]. Ultra- 2.2.1. In situ esterification and transesterification process
sound has been successfully employed to produce biodiesel from The esterification reaction was carried out with a methanol to
vegetable edible and non-edible oils are mostly used although oil molar ratio of 6:1, catalyst (sulfuric acid (3 wt%)) and ultra-
oil-bearing materials such as seeds [7–9], rice bran [10], waste sonic irradiation time of 30 min at room temperature (30 °C).
cooking oils [11–14], fish oils [15,16], animal fats [17] and side- After the acid catalyzed esterification reaction, the product was
streaming products from edible oil production [18]. allowed to settle down for 8 h, the unreacted methanol and
Neem oil (Azadirachta indica) is non-edible oil available in huge water fraction in the bottom layer were removed. From the
surplus quantities in South Asia. Annual production of neem oil in results of acid value of the product, the FFA content of the oil
India is estimated to be 30,000 tons. It has been used as insecticide, was found to be 0.86 wt% and it was used for transesterification
lubricant and in medicine to various kinds of diseases. Traditionally; process. The alkali (KOH) catalyzed transesterification process
it has been used as fuel in lamps for lighting purpose in rural areas was performed using ultrasonic irradiation at 20 kHz frequency
and is used on an industrial scale for manufacturing of soaps, cos- and supported by a power of 400 W. The experiments were car-
metics, pharmaceuticals and other non-edible products. Muthu ried out with different molar ratio of methanol to oil, catalyst
et al. [19], Aransiola et al. [20] and Dhar et al. [3] synthesized biodie- concentration, reaction temperature and reaction time (Table 1).
sel from NO using a two-step transesterification process. However, At selected time, the product was taken from the reactor and
application of ultrasound for biodiesel production from NO was allowed to separate overnight by gravity in a separating funnel.
not reported in the literature. Therefore, the present work is aimed The upper phase in the separation funnel consisted of methyl
to produce biodiesel from NO using ultrasonication by two-step ester or biodiesel and the lower phase being glycerol. The lower
in situ (acid-catalyzed esterification followed by base-catalyzed phase was removed from the funnel. The upper phase was
transesterification) process. The alkali catalyzed transesterification washed several times with a small amount of fresh hot water
process was evaluated and compared through experimental design until the washing water was found to be neutral. Finally, the
and artificial neural network methodology approach. Four factors methanol and water content was evaporated by means of
(methanol to oil molar ratio, catalyst concentration, reaction tem- heating.
perature and reaction time) five level central composite rotatable
design (CCRD) and multi-layer perceptron (MLP) neural network
with three layers (input (4 neurons), hidden (9 neurons) and output 2.3. Determination of FAME content
(1 neuron) based models were developed to predict the experimen-
tal data on conversion of NO to fatty acid methyl esters (FAME) for Gas chromatograph equipped with flame ionized detector
alkali catalyzed in situ transesterification process. (FID) was used to find out the composition of fatty acid methyl
esters (FAME) or biodiesel and helium was used as the carrier
2. Materials and methods gas with the flow rate of 3 ml/min, while n-hexane was used
as the solvent. The oven temperature was set at 110 °C and then
2.1. Materials 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, respec-
Neem oil (NO) was purchased from local suppliers near Chen- tively. Comparing the retention time of each component in the
nai, Tamil Nadu, India. The free fatty acid (FFA) content of the oil samples with the peaks of pure methyl ester standard
was found to be 5.87 wt%. Analytical grade of Sulfuric acid compound, the composition of the FAME was determined.
(H2SO4), potassium hydroxide (KOH), and methanol were obtained Triglycerides to FAME conversion was calculated by using the
from the Merck Chemicals, Mumbai. following equation [21]

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

2.2. Experimental set up and procedure 2.4. Response surface methodology (RSM) modeling

An ultrasonic processor (VCX 400, Sonics and Materials, USA, In this study, four factors five level central composite rotatable
20 kHz, 400 W) was utilized for the production of biodiesel from design (CCRD) was employed for alkali catalyzed in situ
264 J. Prakash Maran, B. Priya / Fuel 143 (2015) 262–267

Table 1
CCRD with experimental 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

Run order X1 X2 X3 X4 Conversion to biodiesel (%)


Observed RSM ANN
1 0 2 0 0 87.45 86.69 87.39
2 0 0 0 0 95.38 95.02 95.37
3 0 0 0 0 94.14 95.02 94.11
4 1 1 1 1 93.36 92.95 93.35
5 1 1 1 1 94.36 93.87 94.32
6 0 0 0 2 95.70 95.12 95.68
7 0 0 0 0 95.40 95.02 95.43
8 1 1 1 1 88.15 87.89 88.16
9 2 0 0 0 89.62 89.45 89.63
10 2 0 0 0 92.21 92.39 92.22
11 1 1 1 1 89.69 89.95 89.67
12 0 0 2 0 92.66 93.16 92.69
13 0 0 0 2 92.23 92.83 92.21
14 1 1 1 1 94.03 93.72 94.08
15 1 1 1 1 93.58 93.73 93.56
16 1 1 1 1 95.06 94.51 95.05
17 0 0 0 0 94.72 95.02 94.73
18 0 0 0 0 95.44 95.02 95.45
19 1 1 1 1 93.92 93.55 93.93
20 1 1 1 1 94.23 94.75 94.19
21 1 1 1 1 95.63 95.18 95.61
22 1 1 1 1 90.25 89.82 90.28
23 0 0 0 0 95.05 95.02 95.03
24 0 0 2 0 94.69 94.20 94.68
25 1 1 1 1 94.28 94.31 94.26
26 1 1 1 1 90.04 90.67 90.06
27 1 1 1 1 90.95 91.65 90.92
28 0 2 0 0 93.36 94.13 93.34
29 1 1 1 1 90.66 91.33 90.63
30 1 1 1 1 87.85 88.05 87.92

transesterification process in order to study the effect of process (MLP) neural network with logistic sigmoid transfer function at
variables (methanol to oil molar ratio, catalyst concentration, reac- hidden layers and a purelin transfer function at output layers were
tion temperature and reaction time) on the conversion of oil to selected and trained. Different back-propagation (BP) algorithms
FAME. A total number of 30 experiments (Table 1) includes 16 fac- (Scaled Conjugate Gradient (SCG), Levenberg–Marquardt (LM),
torial points, 8 axial points and 6 center point replications was car- Gradient Descent with variable learning rate back propagation
ried out in this study. The number of the axial points on the axis of (GDX) and Resilient back Propagation (RP)) were used to train
each design factor at a distance of ±a (a = 2k/4 = 2; k is number of the MLP network in order to select a suitable BP algorithm. To
independent variables) [22]. The relationship between indepen- achieve high homogenous results with reduced network error,
dent variables and response (FAME conversion) was exhibited by the inputs and outputs were normalized in the range 0–1. The
a second order polynomial equation and its generalized form was experimental data obtained from CCRD matrix was used to train,
given below test and validate the neural network model in order to predict
the FAME conversion from NO. The sum of squared error between
X
k X
k XX
k
Y ¼ b0 þ bj xj þ bjj x2j þ bij xi xj þ ei ð2Þ predicted and actual data was computed according to the following
j¼1 j¼1 i <j¼2 equation

where Y is the response; xi and xj are variables (i and j range from 1 to X


n
 2
k); b0 is the model intercept coefficient; bj, bjj and bij are interaction SSE ¼ Yi  Yi ð3Þ
i¼1
coefficients of linear, quadratic and the second-order terms, respec-
tively; k is the number of independent parameters (k = 4 in this where Yi and Y i are actual and predicted data. The ANN modeling
study); ei is the error [23]. The construction of experimental design was done with the help of MATLAB 6.5 (The Mathworks Inc.)
and analysis of experimental data was carried out with the help of software with neural network toolbox.
statistical package software (Design Expert 8.0.7.1, Statease, USA).
3. Results and discussion
2.5. Artificial neural network modeling
3.1. RSM modeling
Artificial neural network (ANN) is one of the tools used to model
the complex nonlinear relationship between experimental data Experiments were carried out according to the CCRD matrix and
and responses [24]. In this study, a multilayered perceptron the results were shown in Table 1. The experimental data was
J. Prakash Maran, B. Priya / Fuel 143 (2015) 262–267 265

Table 2
Adequacy of model tested and ANOVA analysis of RSM model.

Adequacy of the model tested


Source Std. Dev. R2 Adjusted R2 Predicted R2 p-Value PRESS Remarks
Linear 1.77 0.573 0.505 0.415 0.0037 107.62
2FI 1.84 0.652 0.469 0.366 0.0028 116.62
Quadratic 0.68 0.963 0.928 0.816 0.2116 33.92 Suggested
Cubic 0.48 0.991 0.964 0.757 0.6011 44.67 Aliased

ANOVA
Source Coefficient estimate Sum of squares Degree of freedom Standard error Mean square F value p-Value
Model 95.02 177.18 14 0.28 12.66 27.61 <0.0001
X1 0.74 12.99 1 0.14 12.99 28.35 <0.0001
X2 1.86 82.99 1 0.14 82.99 181.06 <0.0001
X3 0.26 1.62 1 0.14 1.62 3.53 0.0800
X4 0.57 7.87 1 0.14 7.87 17.16 0.0009
X12 0.26 1.11 1 0.17 1.11 2.41 0.1410
X13 0.17 0.48 1 0.17 0.48 1.04 0.3229
X14 0.14 0.30 1 0.17 0.30 0.66 0.4293
X23 0.38 2.31 1 0.17 2.31 5.04 0.0403
X24 0.70 7.94 1 0.17 7.94 17.33 0.0008
X34 0.39 2.38 1 0.17 2.38 5.19 0.0378
X21 1.02 28.77 1 0.13 28.77 62.78 <0.0001
X22 1.15 36.38 1 0.13 36.38 79.39 <0.0001
X23 0.33 3.06 1 0.13 3.06 6.69 0.0207
X24 0.26 1.88 1 0.13 1.88 4.10 0.0611
Residual 6.87 15 0.46
Std. Dev. 0.68
Mean 92.80
C.V.% 0.73
Ade. Pre 17.73

fitted to various models (linear, interactive, quadratic and cubic) precision measures the signal-to-noise ratio and the ratio greater
[25] and the results showed that quadratic model incorporating than 4 is desirable [33]. In this study, the adequate precision was
linear, interactive and quadratic terms exhibited higher R2, found to be 17.13, which indicates the best fitness of the developed
adjusted R2, predicted R2 and also low p-values, when compared model.
to other models (Table 2). The relationship between independent The sum of square (SS) value of each process variables acquired
variables and response was exhibited by an empirical quadratic from the ANOVA table (Table 2) was used to investigate the effect
model developed through multiple regression analysis [26] of of process variables (linear, interaction and quadratic) [34] on
experimental data and the final model acquired in terms of FAME conversion from NO and the results are shown in Fig. 1. From
uncoded factors is given below the figure, it was found that, significant effect was exhibited by the
linear effect of process variables (54.93%) on the conversion pro-
FAME conversion ð%Þ ¼ 10:595 þ 6:007X 1 þ 69:116X 2 þ 1:055X 3 cess, followed by quadratic effect of process variables (36.518%).
þ 0:243X 4  0:701X 1 X 2 þ 0:023X 1 The interactive effects of process variables (7.56%) showed negligi-
ble effect on the conversion process compared to other terms. The
very low effect (0.97%) was exhibited by the residual error (mea-
X 3  9:166E  003X 1 X 4  0:304X 2 X 3  0:281X 2 X 4 þ 7:71E sure of amount of variation unexplained by the model).
 003X 3 X 4  0:455
3.2. ANN modeling
X 21  18:428X 22  0:133X 23  2:617E  003X 24 ð4Þ
In ANN modeling, appropriate selection of network size, the
The developed quadratic model was evaluated through Pareto choice of number of hidden layers and neurons is one of the impor-
analysis of variance (ANOVA) and the results were shown in tant tasks for constructing suitable ANN model to predict the
Table 2. ANOVA of the regression model (Eq. (4)) showed that experimental data [35,36]. In this study MLP network was tested
the developed quadratic model was highly significant, as was evi- with 4–10 neurons on the one hidden layer. Different training algo-
dent from the Fisher’s F-test (F model = 27.61) with a very low rithms (SCG, LM, GDX and RP) were used and tested by varying the
probability value (<0.0001) [27]. The goodness of fit of the model number of neurons (4–10) in order to train MLP network and select
was evaluated by the determination co-efficient (R2), adjusted the optimal architecture based on the minimization of the perfor-
determination co-efficient (R2a ) and co-efficient of variance (CV) mance function. The experimental data obtained from the experi-
and signal to noise ratio (S/N). In this study, the value of determi- ments were divided into three categories (training (60%), testing
nation coefficient (R2 = 0.962) indicated that only 0.38% of the total (20%) and validation (20%)) in order to measure the performance
variations were not explained by the developed regression model of the neural network for the prediction of unseen data and to
[28,29]. In addition, the value of adjusted determination coefficient assess the generalization capability of ANN. From the results of
(R2a ¼ 0:927) was also very high, indicating a high significance of training and testing errors, LM training algorithm with nine
the model developed through experimental data [30,31]. Further- neurons in the hidden layer was found to have higher performance.
more, a very high degree of precision and a good deal of the Hence, in this study, MLP network with three layers (input (4
reliability of the conducted experiments were indicated by a low neurons), hidden (9 neurons) and output (1 neuron) was used to
value of the coefficient of variation (CV = 0.73%) [32]. Adequate estimate the FAME conversion from NO and the results were
266 J. Prakash Maran, B. Priya / Fuel 143 (2015) 262–267

Fig. 1. Effect of process variables (a) individual (b) combined.

shown in Table 1. The residual error was calculated from the exper-
imental and predicted data by RSM and ANN. From the results, it
was found that, the residual error between experimental and pre-
dicted data by ANN was very lower when compared to RSM model
(Fig. 2).

3.3. Comparison of RSM and ANN

To test and compare the predictive ability of RSM and ANN


models, a new set of ten experiments were performed in the exper-
imental process variables range, which does not belongs to the
training, testing and validation data and the results were shown
in Table 3. Three statistical measures such as root mean square
error (RMSE), co-efficient of determination (R2) and absolute aver-
age deviation (AAD) [37–39] were used to determine the perfor-
mance and predictive capacity of developed ANN and RSM
models. From the results (Table 3), it was found that, both models
have the ability to predict the experimental data. However, the
predictive capability of ANN model was higher than the RSM

Fig. 2. Residual errors between experimental and predicted data by RSM and ANN.

Table 3
Validation of RSM and ANN model for additional experimental data.

Run order X1 X2 X3 X4 Conversion to biodiesel (%)


Actual RSM ANN
1 3.5 0.5 40 15 74.29 77.84 74.23
2 5 3 35 20 41.36 44.30 41.42
3 4 1.25 50 25 86.25 90.76 86.23
4 8 1.3 45 50 89.31 92.84 89.36
5 6.5 0.8 40 35 89.94 93.48 89.86
6 7 1.2 50 30 92.72 94.47 92.64
7 4 0.5 45 20 82.26 80.83 82.31
8 6.5 1.3 50 30 91.51 94.00 91.53
9 5.5 0.5 35 45 84.68 86.74 84.67
10 3 0.8 50 30 87.27 85.90 87.19
RMSE 4.196 0.001
R2 0.919 0.999
AAD 2.872 0.009 Fig. 3. Comparison of prediction capacity of RSM and AAN for unseen experimental
data.
J. Prakash Maran, B. Priya / Fuel 143 (2015) 262–267 267

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