biomass and bioenergy 34 (2010) 11081116

Available at www.sciencedirect.com

http://www.elsevier.com/locate/biombioe

Biodiesel production from mixture of mahua and simarouba

oils with high free fatty acids
Prakash C. Jena, Hifjur Raheman*, G.V. Prasanna Kumar, Rajendra Machavaram
Agricultural and Food Engineering Department, Indian Institute of Technology, Kharagpur 721302, India

article info

abstract

Article history:

A suitable process comprising acid pretreatment followed by main base transesterification

Received 20 October 2009

reaction was developed to produce biodiesel from mixture of Mahua (M) and Simarouba (S)

Received in revised form

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

Accepted 26 February 2010

catalyst at a reaction temperature of 60  C. A genetic algorithm coupled with artificial

Available online 25 March 2010

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

and were conforming to the latest biodiesel standards.

2010 Elsevier Ltd. All rights reserved.

ANN-GA
Biodiesel
Production
Fuel properties

1.

Introduction

Economic, environmental and energy security concerns

resulting from excessive reliance on fossil fuels like petroleum
are forcing countries the world over to search for alternatives
like biofuels. Since biofuels can be produced from diverse
crops, each country is adopting a strategy that exploits the
comparative advantages it holds with respect to such crops.
Biodiesel fuel derived from vegetable oils and animal fats is
one such biofuels, gaining worldwide popularity as a substitute for diesel fuel. Government of India has recently formulated a biofuel policy in which it is expected to use 10% of
biodiesel by the end of 20162017 [1]. This will require a total of
8.35 Mt of biodiesel in 20162017. To achieve this target more
and more feedstocks are to be explored with technology for
handling these feedstocks for biodiesel production. Since

India is not self sufficient in edible oil production, unlike

Europe and America, more efforts are required to search for
non-edible oils to be used as feedstock for biodiesel production. A few non-edible oils, karanja and jatropha, have been
successfully proven as potential tree born oils for biodiesel
production in India [27]. A few more oils are to be explored to
meet the huge demand for biodiesel. One such oil could be
Simarouba glauca, which is obtained from the seeds of Simarouba tree, commonly known as paradise tree. It is a multipurpose tree capable of growing on the degraded soils and can be
adapted to a wide range of temperatures (1045  C) and altitudes up to 1000 m above sea level. Its seeds contain 5065%
oil that can be extracted by conventional methods. Each wellgrown tree yields 1530 kg nutlets per year equivalent to
2.55 kg oil. This amounts to 12 t oil per ha per year and about
the same quantity of oilcake [8]. The other oil could be Madhuca

* Corresponding author. Tel.: 91 03222 83160; fax: 91 03222 282244/255303.

E-mail address: hifjur@agfe.iitkgp.ernet.in (H. Raheman).
0961-9534/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2010.02.019

biomass and bioenergy 34 (2010) 11081116

indica, which is obtained from the seeds of M. indica tree,

commonly found in deciduous forests. Its seed contains about
3540% oil. Each tree yields about 2040 kg of seed per year and
the total oil yield per ha is 2.7 t per year. This tree has an
estimated annual production potential of 181 kt in India [9].
Availability of these oils is region specific and it is not possible
to have sufficient amount of oil at one place to produce biodiesel to cope with the increasing demand for energy in terms
of diesel consumption.
It is therefore, needed to try different mixtures of oil for
biodiesel production for fulfilling the requirement of the
country without depending on the availability of a specific oil. A
few studies have been carried out on the production of biodiesel from mixture of castor oil, soybean oil, cottonseed oil,
waste frying oil and pork lard. It was reported that biodiesel
could be produced by mixing castor oil having viscosity of
225.8 mm2 s1 at 40  C with either soybean (30.6 mm2 s1) or
cottonseed oil (34.6 mm2 s1) using base catalyzed transesterification [10]. In an another study, biodiesel was obtained
by transesterification from mixtures of soybean oil, waste
frying oil and pork lard with a yield varying from 81.7 to 88.8%
(wt %) [11]. It was found that the use of at least 12% lard in
soybean oil and lard mixture would be effective in reducing the
iodine value of biodiesel to acceptable values in order to get
good quality of biodiesel. Likewise, methyl and ethyl esters
from mixture of canola oil and used cooking oil at different
ratios (80:20, 60:40, 40:60 and 20:80 by wt) were produced using
base catalyzed transesterification [12]. A high quality ethyl ester
was obtained with at least 60% of canola oil in the oil mixture.
In all of the above cases, the acid value (AV) of oil was within
2 mg KOH per g of oil (FFA content was 1%), hence, transesterification with base catalyst was successfully carried out.
When FFA content of feedstock is more than 1%, transesterificastion with base catalyst will lead to soap formation.
Hence, a suitable production process is to be developed for
handling higher FFA oils. A few researchers tried a two stage
process, i.e. esterification (pretreatment) with acid catalyst
followed by transesterification with base catalyst in producing
biodiesel from individual oils with high FFA [4,6,1316].
However, biodiesel production from mixture of oils such as
jatropha, simarouba, karanja and mahua having higher FFA
has not been reported. Since, India is focusing on these oils for
biodiesel production, there is a genuine need to develop a suitable production process for handling these mixtures of oils.
In general, the pretreatment processes were different for
different vegetable oils. In order to overcome this difficulty,
a Genetic Algorithm (GA) technique based on Artificial Neural
Network (ANN) model was developed to identify the optimum
combination of methanol-to-oil ratio, catalyst concentration
and reaction time for oils with acid value (AV) in the range
between 14 and 34 mg KOH per g-oil [17]. The initial acid value
was measured following the standard procedure EN14104
(henceforth only the number will be reported for AV instead of
both number and unit throughout the paper). They reported
that the search of optimum process parameters using GA
based on ANN model is a very effective tool for the identification of pretreatment process parameters of any vegetable
oil in the range of AV considered for the study. However, it was
found that the model needs improvement for predicting the
pretreatment process parameters of oils with AV ranging from

1109

8 to 13. Keeping these factors in view, the present work was

undertaken with the following objectives:
(i) To improve the ANN model developed to include the
pretreatment process parameters of oils with AV from 8
to 13.
(ii) To use the GA coupled with improved ANN model to
obtain the best pretreatment process parameters for
carrying out acid pretreatment of mixtures of mahua
and simarouba oils (for bringing down the FFA level to
around 1%).
(iii) To test the quality of biodiesel produced and determine
its fuel properties.
The rest of the text is organized as follows: Section 2
explains the details of ANN model developed and the
improvements made to include the pretreatment process
parameters of oils with AV from 8 to 13. Section 3 describes the
details of materials used for the production and testing of
biodiesel and methodology followed for the biodiesel
production process, testing and determination of its fuel
properties. Results are discussed in Section 4. Some
concluding remarks are made in Section 5.

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

biomass and bioenergy 34 (2010) 11081116

(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)

Similarly, the output data were normalized between 0 and 1

using the following expression (Eq. (2)):
Xnorm

X  Xmin
Xmax  Xmin

(2)

where, Xnorm is the normalized value of a variable, X indicates

the value before normalization, Xmin and Xmax are the
minimum and maximum values of the variable, respectively.
The error considered during training of the network was
computed using Eq. (3).
1
E Ti  Oi 2
2

comparison of the FAV obtained through the experiments

(training dataset) and predicted by the ANN model is shown in
Fig. 1. A high R2 (0.99) and low MSE (0.0037) between actual and
predicted values indicated a good agreement between these
two. The prediction ability of the developed ANN was tested
using the validation dataset generated using jatropha and
mahua oils by analysis through RSM based on CCRD. Fig. 2
shows a good agreement between observed and predicted
FAVs (overall mean absolute percentage relative error 2.73%),
which confirmed a very good generalization of the developed
ANN for pretreatment process of any new oil.

(3)

where, Ti and Oi represent the target and predicted values of

the response, respectively. Back propagation algorithm, which
works based on a steepest descent method, was used to
update the weights (W ) of the synaptic joints and threshold
value (TH) of the neurons (hidden layers and output layer
neurons) of the network (Eqs. (4) and (5)), as given below:




DWjk t L$ vE=vWjk t

(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)

vE=vUk vE=vYk $vYk =vUk

(7)

where, Yk and Uk represent the output and input, respectively

of the kth neuron lying on the output layer. This process was
repeated for the entire set of training data several times
(epochs or iterations), till the error considered during the
training of the network as given in Eq. (3) became a very small
value and no improvement in the value was observed for the
last 10 iterations. During training of the network, learning rate
was varied from 0.3 to 0.9. A constant learning rate of 0.7 was
found to be most suitable as it resulted in the faster development of the network model with least error. As initial weights
of synaptic joints and bias values of neurons were randomly
selected, the entire procedure was repeated 10 times, each time
taking new values for synaptic joints and threshold values. The
network, which provided lowest value of percent error
between the predicted and observed output data, was stored.
This is the required neural network, which can be used to
predict the FAV of vegetable oils within the range of input
parameters considered for the experiment, i.e., IAV from 8 to
34, methanol-to-oil ratio from 0.2 to 0.4, catalyst concentration
from 0.5 to 1.75, and reaction time between 30 to 90 min. The

3.

Materials and methods

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.

Acid value determination

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.

Fig. 1 Comparison of FAV predicted using ANN model

with actual FAV obtained using experiments (Training
dataset).

1111

biomass and bioenergy 34 (2010) 11081116

Table 1 Major fatty acid composition of mahua and

simarouba oil.
Fatty acids
Palmitic acid (C16:0)
Stearic acid (C18:0)
Oleic acid (C18:1)
Linoleic acid (C18:2)

Fig. 2 Observed and predicted FAVs for the validation

data.

AV 56.1NV/M

(8)

where, AV is acid value in mg KOH per g of oil, N is 0.1

(normality of KOH solution), V is titre volume in ml and M is
weight of sample oil in g.
The FFA levels of M and S oils were 13 and 1.43  0.5%,
respectively. The mixture was prepared to reduce the FFA
level of M oil as it has high FFA content compared to S oil.

3.1.2.

Quality checking of fatty acid methyl esters (FAME)

Analysis of biodiesel for methyl ester content was carried out

using a Perkin Elmer (Clarus 500) Gas chromatography (GC)
system equipped with Elite-1 dimethylpolysiloxane capillary
column (30 m  0.25 mm  0.25 mm) and flame ionization
detector. The parameters like temperature and split flow were
adjusted using the Window 2000 platform-based Total
Chrom Workstation software. The programmed oven
temperature was started initially with 100  C with a hold for
1 min and then it was ramped to 160  C at a rate of 10  C per
min. The final ramp was 280  C at a rate of 30  C per min and
was held for 15 min. FID temperature was set at 300  C. For
this analysis, methyl pentadecanoate was used as internal
standard and N2 gas was used as carrier gas. Chromatogram
analysis, standard curve and quantification were done using
the same software.

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

mixtures 75M25S, 50M50S and 25M75S was found to be 19.37,

14.38 and 8.5  0.5, respectively. These AVs are far above the
limit 2 for satisfactory transesterification reaction using base
catalyst. Therefore, a two stage process was followed [6,1316].
FFAs were first converted to esters in a pretreatment process
with methanol using an acid catalyst (H2SO4). The optimum
values of methanol-to-oil ratio, catalyst concentration and
reaction time for the pretreatment process were determined
using GA. After the reaction, the mixture was allowed to settle
for 6 h and the methanolwater suspension that separated at
the top was removed in a separating funnel. The acid value of
the product separated at the bottom was determined. The
product having acid value less than 2  0.25 mg KOH per g-oil
was used for the transesterification reaction.

3.2.2.

Selection of pretreatment process parameters

The developed GA technique was used to obtain the optimum

values of process variables influencing pretreatment process.
The GA operates on a coded form of the problems parameters.
This results in the search of the global minimum being independent from the continuity of the function or the existence
of its derivative. The sampling procedure starts from a set of
points (initial population), therefore the possibility of entrapment in a local minimum is reduced. The sampling procedure
is carried out using the genetic operators which are stochastic
and not deterministic in nature. As GA tries to maximize the
fitness function and the objective of the pretreatment process
is to bring down the FAV to less than 2 the fitness function (F )
formulated in reference [17] was the minimization of FAV of
oil, as given below (Eq. (9)):

F 1/(1 FAV)

(9)

The GA methodology consisted of the following steps:

(i) A random initial population with 200 population strings
was formed using an indirect encoding scheme, where
combination of methanol-to-oil ratio (ME), catalyst
concentration (C ) and reaction time (T ) for the given IAV
was encoded in each chromosome or population string. A
typical population string had string length of 15 bits with
4, 6 and 5 bits to represent ME, C and T, respectively as
shown below:
10101
0010 101001
ME |{z}
T

3.2.

Biodiesel production process

3.2.1.

Pretreatment first step in biodiesel production

The fatty acid profile of M and S oil is given in Table 1 [2,14].

Following the standard titrimetry method, the IAV of oil

(ii) The initial population was decoded to its phenotypic form

and fitness value was determined for each population
string by computing the FAV of oil using the developed
ANN.

1112

biomass and bioenergy 34 (2010) 11081116

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)

where, MFSE is the mean fitness square error and N is the

number of population strings. Fi and Fm are individual and
mean fitness values of N population strings, respectively. As
the initial population strings were randomly generated, the
entire GA operation was repeated 10 times, each time taking
new population strings. The combination of 10 datasets which
provided lowest value of MFSE was stored as the best obtained
pretreatment process parameters for the given oil or mixture
of oils. The IAV of 75M25S, 50M50S and 25M75S was entered in
the GA program to obtain the best combination of pretreatment process parameters to obtain the FAV less than 2. The
combinations of parameters obtained through GA were verified by comparing the AV of pretreated oil obtained by actually
conducting the experiments.

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

(iii) The evolutionary process began by the selection of strings

with fitness value more than or equal to 3.33 (FAV less
than or equal to 2) for tournament selection. Only ten
different elite population strings were selected after the
tournament selection. It was followed by standard single
point crossover and bit-wise mutation. The crossover rate
and mutation probability were set to 0.9 and 0.1 respectively. The population string obtained after one generation (selection, crossover and mutation) was called
offspring.
(iv) Steps (ii) and (iii) were executed again for the offspring
that are produced.
(v) The offspring were reinserted into the population
replacing the least fit parents. The fitness function of the
elite strings was compared with that of the offspring and
the better one was stored.
(vi) Steps (iii)(v) were executed until the average of the
square of difference between the mean and individual
fitness value of the strings, as given in Eq. (10), became
a very low value and no substantial improvement in the
value was observed for the last 10 iterations (stopping
criteria):

MFSE

0.35
1.40
86.26

Transesterification second step in biodiesel production

The transesterification reaction was carried out with 5:1 molar

ratio of ME and KOH (3.5 g FAV) per litre of pretreated oil.
This was arrived based on the amount needed to neutralize
the unreacted acids in the second stage product plus 0.35% for
virgin oil. The reaction was carried out at 60  C for half an hour

0.39
1.4
39.76

0.37
1.52
75.97

and the products were allowed to settle for overnight before

removing the glycerol layer from the bottom in a separating
funnel to get the ester layer on the top, separated as biodiesel.
All the experiments were conducted using 250 ml conical
flasks in a water bath incubator shaker maintained at 60  C
and shaked at a constant speed of 230 rpm.

4.

Results and discussion

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

Transesterification of acid pretreated oil was carried out by

taking 5:1 molar ratio of ME and KOH. The yield of biodiesel

1113

biomass and bioenergy 34 (2010) 11081116

Table 3 Best obtained values of pretreatment process parameters for the mixture of oils through optimization process
using GA.
Variables

75M25S

Methanol-to-oil ratio ME (v/v)

Sulfuric acid, C (% v/v)
Reaction time, T (min)
FAV, mg KOH/g-oil
MFSE

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

Methanol-to-oil ratio ME(v/v)

Sulfuric acid, C (% v/v)
Reaction time, T (min)
FAV, mg KOH/g-oil
MFSE

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

Methanol-to-oil ratio ME (v/v)

Sulfuric acid, C (% v/v)
Reaction time, T (min)
FAV, mg KOH/g-oil
MFSE

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

obtained from all these mixtures of oils was found to be

around 98%.

4.3.

0.308
1.052
73.045
2.006
0.0029

The chromatograms for FAME obtained from mixture of M

and S oils are shown in Fig. 4. From this figure, it was
found that the amount of oleic methyl ester was varying
between 49 and 54.5% in biodiesel followed by methyl
Predicted by ANN

Obtained from experiment

2.08

Predicted by ANN

Obtained from experiment

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

Obtained from experiment

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

stearate and palmitate. The retention time for methyl

palmitate, methyl oleate, methyl stearate and methyl
linoleate was observed to be 10.84, 11.68, 11.78 and
12.60 min, respectively. The high peak shown in Fig. 4 at
retention time 2.15 min is n-hexane and should not be
confused with other methyl ester peaks. The overall
conversion of oil to methyl esters was calculated on the
basis of their relative area percentage and was found to be
above 90%.

Quality of FAME produced

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

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biomass and bioenergy 34 (2010) 11081116

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

The density of biodiesel obtained from 75M25S, 50M50S and

25M75S oils was found to be 860, 857 and 856 kg m3 respectively, as compared to 913, 912 and 912 kg m3 for the original
mixture of oils. It decreased on an average by 5.9% and this

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biomass and bioenergy 34 (2010) 11081116

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

decrease was more with decrease in percentage of M oil in the

mixture of oils. However, the density of biodiesel obtained
from mixture of oils are very much satisfying the different
biodiesel standards.

was higher with increase in percentage of M oil in the oil

mixture. This is due to the fact that there was a decrease in the
percentage of saturated fatty acid ester and increase in
unsaturated fatty acid ester in biodiesel.

4.4.2.

4.4.7.

Viscosity

The viscosity of biodiesel obtained from mixture of vegetable

oils was varying between 4.38 and 4.77 cSt as compared to 2.85
for high speed diesel (HSD) and 42.2043.94 cSt for individual
oils. It decreased with increase in the percentage of M oil in the
oil mixture.

4.4.3.

Calorific value

Calorific value is the net heat content of fuel and it affects

brake thermal efficiency and specific fuel consumption of
diesel engine. From Table 4, it can be seen that the calorific
value (higher heating value) of biodiesel obtained from
different mixture of oils is very close to each other and is
around 37 MJ kg1 as compared to 42.5 MJ kg1 for HSD. The
effect of blend ratio has no much effect on the calorific
values of the esters present in biodiesel as they are almost
same.

4.4.4.

Acid value (AV)

The AV of oil mixtures was found to be varying from 14.38 to

19.37 and it is increasing with increase in the percentage of M oil
in the mixture. But the AVs for biodiesels were found to be lying
between 0.332 and 0.479 and were within the limits prescribed
by both American and European biodiesel standards. Hence, the
procedure followed for biodiesel production was quite
successful in handling different feedstocks of high AV.

4.4.5.

Flash point

One of the most important advantages of biodiesel is its flash

point being greater than that of HSD. The mixture of oils and
their biodiesel had higher flash points, i.e. varying from 134 to
164  C as compared to 52  C for HSD. This property did not
show linearity with the increase in percentage of either S or M
oil in the mixture of oils.

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

The total saturated fatty acids content and unsaturated fatty

acids content in M oil was observed to be 12.87% less and
2.80% more, respectively than those of S oil. From Table 4, it
can be seen that the pour point of mixture of oils decreased
from 14.2 to 3.5  C when converted to biodiesel. This decrease

5.

Conclusions

Biodiesel could be obtained from mixtures of M and S oils

with high FFA following a two stage process: first stage for
reducing FFA value to around 1% using methanol and H2SO4
as acid catalyst (pretreatment process) and second stage for
carrying out transesterification using methanol and KOH as
base catalyst. The best pretreatment process parameters for
the mixture of oil were obtained through the search process
using GA based on ANN model. The modified ANN had a good
generalization ability to predict the FAV of both individual as
well as mixture of oils. The search of best combination of
pretreatment process using GA reduces all the time and cost
of conducting experiments using RSM based on CCRD or
other similar experimental techniques. The biodiesel was
prepared from the mixture of oil using the best combination
of process parameters from among the set of pretreatment
process parameters generated by GA. An average yield of
biodiesel and ester conversion to around 98% and 90%,
respectively was possible following the two stage biodiesel
production process. The fuel properties of biodiesel so
obtained were found to be satisfying the prescribed standards for biodiesel.

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.

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biomass and bioenergy 34 (2010) 11081116

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