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abstract
Article history:
reaction was developed to produce biodiesel from mixture of Mahua (M) and Simarouba (S)
oils with high free fatty acids (FFA). The acid pretreatment reduced the high FFAs of the
25 February 2010
mixture of oils to around 1% which were then transesterified with methanol and KOH as
neural network (ANN-GA) model to obtain the best pretreatment process parameters for
bringing down the FFA level of individual vegetable oils to around 1% was modified to
Keywords:
include the wide range of oils and validated for mixtures of M and S oils. The quality of
Mixture of oils
biodiesel produced was analyzed by gas chromatography (GC), which indicated above 90%
Madhuca indica
ester conversion. The fuel properties of biodiesel were found to be comparable to diesel
Simarouba glauca
ANN-GA
Biodiesel
Production
Fuel properties
1.
Introduction
1109
2.
Improvement of ANN model for the
prediction of AV of vegetable oil after
pretreatment
The number of experiments required to get optimized values
of pretreatment process parameters for the vegetable oils are
quite large. Hence, a generalized technique to determine the
optimum pretreatment process parameters to reduce the AV
to less than 2 (FFA as 1%) needs to be explored. For this, ANN
model to predict the final acid value (FAV) and GA to obtain the
optimum pretreatment process parameters based on IAV of
various vegetable oils was used.
A feed forward back propagation ANN model of 4-7-13-1
configuration was developed to predict the FAV of vegetable
oil from four independent pretreatment process parameters,
viz., IAV, methanol-to-oil ratio, catalyst concentration and
reaction time. The input layer received 4 independent
pretreatment process parameters. The output layer generated
the FAV corresponding to 4 input parameters. Two hidden
layers with 7 neurons in first hidden layer and 13 neurons in
the second hidden layer were used to assist in performing
a non-linear feature extraction on the data provided by the
input layers. In the neurons of hidden layers and output layer,
sigmoid function given by f(x) [1 exp(x)]1 was used as
the activation function. However, the ANN model had the
ability to predict the FAV of oil for the oils with IAV in the
range of 1434. In order to improve its prediction ability to
a wide range of oils, additional dataset consisting of IAV in the
range of 813 along with their pretreatment process parameters and FAV were added to the training dataset. A new input
output dataset unknown to the trained ANN model were
developed by conducting experiments and analysis through
Response Surface Methodology (RSM) based on Central
Composite Rotatable Design (CCRD) using jatropha and
mahua oils for the validation of the improved ANN model
1110
(Table 2). The network was trained by on-line (pattern-bypattern) learning mode of supervised learning without
changing the configuration of the network. The input data
used in the network training and validation process were
normalized between 1 and 1 using the following expression (Eq. (1)):
2X Xmin
1
Xmax Xmin
Xnorm
(1)
X Xmin
Xmax Xmin
(2)
(3)
(4)
DTHi t L$vE=vUk t
(5)
where, L indicates the learning rate and t indicates the iteration number. vE/vWjk and vE/vUk can be determined using the
chain rule of differentiation as given below (Eqs. (6) and (7)):
vE=vWjk vE=vYk $vYk =vUk $ vUk =vWjk
(6)
(7)
3.
3.1.
Materials
Mahua (M) and simarouba (S) oils were purchased from Jhargram Oil Industry, West Bengal India and the chemicals used
in the experiments such as methanol (99.5%) and sulfuric acid
(99% pure) were of analytical reagent (AR) grade. The KOH in
pellet form was used as a base catalyst for transesterification
reaction. Mixture of oils at different proportions by volume
(75:25, 50:50 and 25:75 designated as 75M25S, 50M50S and
25M75S, respectively) was prepared for using as feedstock for
biodiesel production.
3.1.1.
The acid value of mixture of oils, and biodiesel was determined by a standard titrimetry method as per European
standard EN14104. About 510 g of oil was taken in a 250 cc
conical flask. A 50 cc solvent mixture (1:1 dehydrated ethyl
alcohol and diethyl ether) was added to it. The flask was
slightly heated to completely dissolve the oil sample in the
solvent mixture. Five drops of 1% phenolphthalein indicator
were added to it. Titration was done with 0.1 M KOH (56.1 g
KOH in 1 l dehydrated alcohol) using vigorous stirring until
a definite pink colour persisted for 10 s. The AV was expressed
as mg KOH per g of oil (Eq. (8)) taking average of three
replications.
1111
AV 56.1NV/M
(8)
3.1.2.
3.1.3.
Fuel properties
The fuel properties namely density (kg m3), acid value (mg
KOH per g-oil), viscosity (mm2 s1), calorific value (MJ kg1),
flash point ( C), pour point ( C) and ash content (%) of the M
and S oil mixtures as well as their biodiesels were determined
following the American and European standards D 4052,
EN14104, D 446, D 240, D 93, D 97 and D 482, respectively and
are compared with the Indian (IS15607), American (D6751) and
European (EN12414) biodiesel standards.
Mahua, wt%
Simarouba, wt%
17.8
14.0
46.3
17.9
10.90
25.60
59.10
3.30
3.2.2.
F 1/(1 FAV)
(9)
3.2.
3.2.1.
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Table 2 Optimization points obtained for pretreatment of mahua and jatropha oil from Design Expert package.
Variables
Methanol-to-oil ratio ME (v/v)
Sulfuric acid C (% v/v)
Reaction time T (min)
Mahua oil
0.36
1.49
89.05
0.35
1.41
84.95
0.35
1.45
84.20
0.35
1.41
86.74
Variables
Methanol-to-oil ratio ME (v/v)
Sulfuric acid C (% v/v)
Reaction time T (min)
N
1X
Fi Fm 2
N i1
0.27
1.54
72.69
0.28
1.43
89.52
0.40
1.4
58.77
0.31
1.42
66.63
(10)
3.2.3.
0.35
1.48
88.21
0.35
1.43
84.04
0.34
1.40
85.57
0.35
1.40
85.00
0.35
1.43
84.10
0.33
1.52
59.72
0.40
1.4
47.38
0.28
1.43
88.88
0.33
1.43
48.63
Jatropha oil
MFSE
0.35
1.40
86.26
0.39
1.4
39.76
0.37
1.52
75.97
4.
4.1.
Identification of optimum pretreatment process
parameters using GA
The IAV of the mixtures of oils 75M25S, 50M50S and 25M75S
was entered in the GA program to obtain the set of solutions
for reducing the AV of oil to less than 2. The 10 best obtained
values of pretreatment process parameters (ME, C and T ) for
achieving the FAV of these mixture of oils to below 2 through
the search of solutions using GA has been presented in Table
3. The user can select any one of these combinations for
carrying out the pretreatment successfully. Since, cost of
processing mainly depends on the cost of methanol, it is
advisable to select the solution that results in low requirement
of methanol. Considering this, the combination of pretreatment process parameters highlighted in Table 3 was selected
for each mixture of oils for the pretreatment process.
Experiments were conducted using the best obtained
pretreatment process parameters for each oil to validate the
FAV prediction by ANN model. The actual FAVs obtained from
the experiments were very close to that predicted by ANN
model (Fig. 3). The maximum absolute percent relative error
between the actual and predicted values was found to be 4.82,
14.77 and 13.98% for 75M25S, 50M50S and 25M75S oils,
respectively. The absolute percent relative error was more
than 10% for only 3 data points. This indicates that the
modified ANN model can be used for the prediction of process
parameters to reduce IAV of both individual and mixture of
oils to around 2. The actual FAVs for the selected combination
of pretreatment process parameters from among the sets
given in Table 3 were found to be 1.91, 1.87 and 1.94 as
compared to the predicted value of 2.
4.2.
Transesterification
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Table 3 Best obtained values of pretreatment process parameters for the mixture of oils through optimization process
using GA.
Variables
75M25S
0.306
1.276
61.200
2.005
0.0023
0.281
1.182
65.613
2.005
0.0025
0.259
1.321
50.748
2.006
0.0026
0.294
1.218
64.219
2.006
0.0028
0.246
1.370
65.845
2.002
0.0029
Variables
0.277
1.257
54.232
2.006
0.0030
0.305
1.114
60.503
2.005
0.0030
0.302
1.070
71.187
2.005
0.0031
0.297
1.295
47.497
2.007
0.0031
0.228
1.268
67.239
2.006
0.0026
0.230
1.276
77.458
2.007
0.0026
0.234
1.342
64.684
2.005
0.0028
0.228
1.295
43.780
2.004
0.0029
0.217
0.958
69.794
2.004
0.0023
0.233
0.997
66.077
2.005
0.0023
0.235
1.206
81.639
2.003
0.0023
0.234
1.068
70.490
2.006
0.0024
50M50S
0.234
1.261
51.910
2.005
0.0023
0.239
0.924
69.329
2.004
0.0023
0.233
1.075
61.897
2.003
0.0024
0.236
1.400
60.503
2.004
0.0024
0.225
1.338
62.361
2.003
0.0024
Variables
0.232
1.229
77.690
2.003
0.0026
25M75S
0.234
1.625
50.516
2.008
0.0018
0.236
1.497
79.31
2.005
0.0018
0.231
1.675
64.916
2.008
0.0016
0.237
1.130
76.065
2.009
0.0020
4.3.
0.308
1.052
73.045
2.006
0.0029
2.08
Predicted by ANN
Acid v al u e, mg KOH/g -o il
2.36
2.04
2
1.96
1.92
1.88
1.84
1.8
2.28
2.2
2.12
2.04
1.96
1.88
1.8
4
5
6
7
Experiment number
10
Experiment number
75M25S
50M50S
Predicted by ANN
2.34
Aci d v al u e, mg KOH/ g -o il
Aci d v al u e, mg KOH/ g -o il
0.219
1.433
67.239
2.008
0.0022
0.235
0.814
51.910
2.003
0.0021
2.26
2.18
2.1
2.02
1.94
1.86
1.78
1.7
1
4
5
6
7
Experiment number
10
25M75S
Fig. 3 Validation of ANN model for the prediction of FAV of mixture of oils.
10
1114
Fig. 4 Chromatogram for different biodiesel obtained from mixtures of mahua and simarouba oils.
4.4.
Fuel properties of mixture of M and S oils and their
biodiesels
The fuel properties of biodiesels obtained from these mixtures
of oils are summarized in Table 4.
4.4.1.
Density
1115
Table 4 Fuel properties of diesel, M and S oil mixtures and their biodiesel.
Fuel properties
Density at 15 C, kg m3
Viscosity at 40 C, mm2 s1
Acid value, mg KOH g1
Calorific value, MJ kg1
Flash point, C
Pour point, C
Ash content, %
HSD
812
2.85
42.50
52
20
0.01
75M25S
50M50S
25M75S
Biodiesel standards
Oil
BD
Oil
BD
Oil
BD
BIS
IS15607
ASTM
D6751
DIN
EN14214
913
42.20
19.37
36.27
238
13.00
1.12
860
4.38
0.479
37.00
138
3.20
0.012
912
43.94
14.38
36.04
242
14.20
1.00
856
4.77
0.445
37.02
134
3.60
0.011
912
42.54
8.50
36.31
235
14.00
1.05
857
4.56
0.332
37.01
164
3.50
0.011
860900
2.56.0
0.5
120
1.96.0
<0.80
>130
<0.02
860900
3.55.0
<0.5
>120
<0.02
4.4.2.
4.4.7.
Viscosity
4.4.3.
Calorific value
4.4.4.
4.4.5.
Flash point
4.4.6.
Ash content
The mixture of oils had a very high level of ash content, which
is one of the main reasons for its unsuitability as a fuel in the
long run. However, biodiesel obtained from mixture of oils
was found to have ash content varying from 0.012 to 0.011
similar to that of HSD and is within the limits prescribed for
biodiesel standards.
Pour point
5.
Conclusions
Acknowledgement
The authors are grateful to Petroleum Conservation Research
Association (PCRA), Ministry of Petroleum Oil and Natural gas,
Govt. of India for providing financial support to carry out this
work.
1116
references