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1. Beena Mishra et al Int. Journal of Engineering Research and Applications
ISSN : 2248-9622, Vol. 3, Issue 6, Nov-Dec 2013, pp.2082-2089
RESEARCH ARTICLE
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OPEN ACCESS
Production of Bio-Diesel from Non-Edible Thumba (Citrullus
Colocyntis) Seed Oil Using Mechanical Stirring Methodology and
Analysis of Fuel Properties
R B Sharma1, Beena Mishra2, Amit Pal3
1
HOD, Mechanical Engineering Department, RJIT, BSF Academy, Tekanpur, Gwalior, MP
Research Scholar, RJIT, BSF Academy, Tekanpur, Gwalior, MP
3
Associate Professor, Mechanical Engineering Department, DTU, Delhi
2
Abstract
The depletion of fossils fuels are going on very rapidly. After few decades fossils fuels will be exhausted. So to
fulfil the demand of the fossils fuel there is a big need to find out the alternative fuel of the fossils fuel. The
fuels which are based on petroleum play a very significant role in the development and growth of the industries,
transportation, agriculture field and many other human requirements sector. Though these petroleum base fuels
are limited and lessening day by day as the demand and consumption is increasing very rapidly. In addition,
petroleum fuels are also polluting the environment and creating problem to human being as well as society also.
Therefore, there is a need of research for alternative fuels and Biodiesel is a very good alternative fuel. In India,
there is a various type of trees, shrubs, seeds and herbs are copiously available, which can be subjugated for the
production of biodiesel.
Citrullus colocyntis (Thumba) is a type of non edible fruit which is widely found in western Rajasthan region
and Gujarat state. It can be well used for production of biodiesel. In the present work, biodiesel has been
obtained from Thumba seed oil (Citrullus colocyntis) using transesterification process with methanol &
potassium hydroxide as catalyst by Mechanical stirring production technique. The properties of this Bio-diesel
have been evaluated and it is found that the properties of Thumba Bio-diesel are comparable to conventional
diesel fuel and can be acceptably used as alternative fuel with better performance compared with diesel and it
may play a very vital role for the overall economic development.
Keywords: Thumba Seed Oil (Citrullus colocyntis), Transesterification, Bio- Diesel, Mechanical stirring
production technique.
I.
Introduction
The scarcity of conventional fossils fuels and
the emissions produced by these fuels are serious
concern in front of us. The world wide use of fossils
fuels are continuously increasing as well as price of
crude oil is also rising day by day. The economical
growth of any developing country is based on
agriculture and industrial sector. The basic power
source of industrial sector as well as agriculture sector
is diesel fuel. The expansion of economics is always
come with increase in the transport [1]. India will be
the third largest consumer of transportation fuel by
2020 after USA and China. In year 2009-10 India
imported 159.26 million tons of crude oil [2]. About
90% of the total imported oil is consumed in
transportation, many of the alternates of fossils fuels
are available but the most efficient alternate is the
biodiesel [3]. It is proposed by biodiesel mission
Government of India, that by 2017, 20% of energy
needs of India should be met by biodiesel. To meet
this expectation it would require 12 to 13 million
hectare of land for biodiesel feed stock plantation [4].
Bio-diesel is safe, renewable, non-toxic, and
biodegradable in water (98% biodegrades in just a few
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weeks), contains less sulfur compounds and has a high
flash point (>130 oC). Biodiesel can be produced from
edible or non edible vegetables oils, paper wastes,
cooking wastes animals fats etc. Biodiesel is
considered renewable because its primary feed stocks
are vegetable oil and animal fat[5]. Diesel engines
operated on biodiesel have lower emissions of carbon
monoxide, unburned hydrocarbons, particulate matter,
and air toxics than when operated on petroleum-based
diesel fuel. At present biodiesel mostly produced by
the transesterification process of vegetables seeds
(edible or non-edible) using methanol and consistent
catalyst [6]. The most common method is
transesterification and its leads to mono alkyl esters of
vegetable oils and fats, now called Bio-diesel when
used for fuel purposes. The methyl ester produced by
transesterification of vegetable oil has a high cetane
number, low viscosity and improved heating value
compared to those of pure vegetable oil which results
in shorter ignition delay and longer combustion
duration and hence low particulate emissions [7]. Biodiesel can be used in pure form (B100) or may be
blended with petroleum diesel at any concentration in
most injection pump diesel engines.
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2. Beena Mishra et al Int. Journal of Engineering Research and Applications
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II.
Potential Feedstock in India
India is the sixth largest consumer of crude
oil in the world with about 70% of its local
requirement met through imports. It produced 70,000
barrel/day of crude oil in 2007, while the consumption
of petroleum products was at 2.5 million barrel/day.
The oil import bill surged to US$77 billion in 2007-08
from US$6 billion in 1990-91. Consequently, the
share of crude oil imports in the total import bill
increased to 32.7% in 2007 from 25% in 1990 [9]. In
India 70% of the population live in 638,596 villages
and to a large extent thrive on farming [10]. With
growing population, farming community is under
pressure to grow more food.
Jatropha, Pongamia pinnata or Karanj,
Calophyllum inophyllum or Nagchampa, Hevea
brasiliensis or Rubber seeds, Calotropis gigantia or
Ark, Euphorbia tirucalli or Sher, Boswellia
ovalifololata, Citrullus colocynthis or Thumba,
Sunflower, Soybean, Corn, Rapeseed, Palm, Coconut,
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Peanut, Mahua seed, Waste vegetables oil, Canola,
Olive, Mustered. Non-edible oil feedstock`s are:
Daturastramonium, Opium poppy oil, Cottonseed,
Sunflower, Castor, Karanja seed.
In this work, biodiesel has been prepared
from Thumba oil by homogeneous catalyst e.g. KOH.
Citrullus colocynthis (Thumba) seeds are rich in oil
and protein and can be utilized on an industrial scale.
Considering Citrullus colocynthis’s potential as an
oilseed feedstock for biodiesel Centre for Jatropha
Promotion & Biodiesel (CJP) has honour to establish
this untapped resource as alternative source for Biodiesel industry of future. The Citrullus colocynthis
Plant must be regarded as a sure source of 2 nd
Generation Biodiesel and the foundation around which
a profitable business plan can be built with
combination of other non food biodiesel crops for its
ability to provide large amount of oil and its pure
hardiness and stress handling ability. Fig 1 shows the
Thumba plant
Stage I
Stage II
Stage III
Figure Error! No text of specified style in document.: Thumba Creeper Plant and Seeds
It is found wild in the warm, dry and sandy
parts throughout India. It is most abundant in northwestern plains of India, especially in the Barmer,
Bikaner, Jaisalmer and Jodhpur districts of Rajasthan,
and in Gujarat [8].
III.
Transesterification of vegetable oil:
Vegetable oil and animal fats were
investigated well before the energy crisis of the
1970s. The early 1980s sparked renewed interest in
alternative fuels. It is also known that Rudolf Diesel
(1858-1913), the inventor of the diesel engine that
bears his name, had used peanut oil as fuel in his
invention. High fuel viscosity in compression ignition
is the major problem associated with the use of
vegetable oils; viscosities of vegetable oil are ranging
10 to 20 times higher than diesel fuel.
Bio-diesel is the product of the process of
vegetable oil’s transesterification [13]. Bio-diesel is
biodegradable, non-toxic and essentially free from
sulphur; it is renewable and can be produced from
agriculture and plant resources. Bio-diesel is an
alternative fuel, which has a correlation with
sustainable development, energy conservation,
management,
efficiency
and
environmental
preservation. Transesterification is the reaction of a
fat or oil with an alcohol to form esters and glycerol.
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Alcohol combines with the triglycerides to form
glycerol and esters. Among the alcohols that can be
used in the transesterification process are methanol,
ethanol, propanol, butanol and amyl alcohol. A
catalyst is usually used to improve their action rate
and yield. The process of transesterification brings
about extreme change in viscosity of vegetable oil [14].
Transesterification is the process of separating the
fatty acids from their glycerol backbone to form fatty
acid esters (FAE) and free glycerol. Fatty acid esters
commonly known as Bio-diesel can be produced in
batches or continuously by transesterifying
triglycerides such as animal fat or vegetable oil with
lower molecular weight alcohols in the presence of a
base or an acid catalyst. This reaction occurs
stepwise, with monoglycerides and diglycerides as
intermediate products. The "R" groups are the fatty
acids, which are usually 12 to 22 carbons in length.
The large vegetable oil molecule is reduced to about
1/3 its original size, lowering the viscosity making it
similar to diesel fuel. The resulting fuel operates
similar to diesel fuel in an engine. The reaction
produces three molecules of an ester fuel from one
molecule of vegetable oil. In such reaction known as
transesterification, a triglyceride is allowed to react
with a threefold excess of an alcohol such as ethanol
or methanol, and this alcohol takes the place of the
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ISSN : 2248-9622, Vol. 3, Issue 6, Nov-Dec 2013, pp.2082-2089
ester linkage to glycerol, yielding three fatty acid
esters of the new alcohol and glycerol. Above the
process using methanol is shown in figure 2.
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Here three molecules of one alcohol are replacing
glycerol, another alcohol, in the triglyceride. Where,
term R’ represents different alkyl groups.
Figure 2: Transesterification Chemical Reaction
The Bio-diesel thus produced by this process
is totally miscible with mineral diesel in any
proportion. Bio-diesel viscosity comes very close to
that of mineral diesel hence no problems in the
existing fuel handling system. Flash point of the Biodiesel gets lowered after etherification and the cetane
number gets improved. Even lower concentrations of
Bio-diesel act as cetane number improver for Biodiesel blend. Calorific value of Bio-diesel is also
found to be very close to mineral diesel. The overall
process is normally a sequence of three consecutive
steps, which are reversible reactions. In the 1st step
from triglycerides, Diglycerides are obtained, in 2nd
step from Diglycerides, monoglyceride is produced
and in last step from mono glycerides, glycerin is
obtained. In all these reactions esters are produced.
The stoichiometric relation between alcohol and the
oil is 3:1. However, an excess of alcohol is usually
more appropriate to improve the reaction towards the
desired product.
IV.
Experimental work of Bio-diesel
Production by Mechanical Stirrer
Technique
In the present work Bio- diesel has been
produced from Thumba oil using Mechanical Stirrer
Technique which is purchased at local market of New
Delhi.
Determination of FFA (Fee Fatty Acid)
[Titration]:
For the determining the percent of FFA (free
fatty acid) in the oil, a process called titration is used.
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Three samples have been taken for find out of FFA%
and data as follows:
Table 1: FFA content in Thumba seed oil
Sample No.
Ml titration
% FFA
1
3
2.14
2
3.3
2.32
3
2.9
2.08
In the present work, the %FFA is determined
of Thumba oil which is about 2.18 (average of three
samples as mentioned in table 1) so only
transesterification process is performed for production
of biodiesel with alkali catalyst.
V.
Mechanical Stirrer Technique
Principle
Conventional mechanical stirring machine
consist of temperature controller to control temp
within the range of 0-100°C and speed controller is
for controlling speed of stirrer in terms of revolution
per minute (rpm). In this machine hot plate functions
as a heating source to maintain the temperature of the
solution. The beaker is placed on the hot plate then
vegetable oil as per the requirement was poured into it
at the beginning. The reaction started when a
quantitative amount of methanol liquor dissolved in
catalyst was poured into the beaker and then
immediately drops the magnetic stirrer so that through
its stirring action at a particular rpm, dilution of
mixture can take place by switching the button on.
Experimental Set-up
The transesterification reactions were carried
by conventional mechanical stirring method, which is
shown in Figure 3.
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Figure 3: Mechanical Stirrer Equipment
Conventional mechanical stirring equipment
consist of temperature controller to control
temperature within the range of 0-100°C and speed
controller is for controlling speed of stirrer. In this
machine hot plate functions as a heating source to
maintain the temperature of the solution. The beaker
(500 ml) is placed on the hot plate and Thumba oil
(400 g) was poured into it at the beginning. The
reaction started when a quantitative amount of
methanol as per molar ratio is dissolved with KOH
was poured into the beaker. The magnetic stirrer due
to its stirring action enhances the transesterification
reaction.
VI.
Reagents and Material used
1. Thumba oil, 400g/sample for preparing
experimental biodiesel sample.
2. Methyl alcohol (CH3OH) (99% pure) as per molar
ratio.
3. Base catalyst (KOH) (85% pure) for accelerating
the reaction mixture.
Experimental Procedure
This experiment has been performed to evaluate
performance of mechanical stirring method of
biodiesel production in terms of yield (%) and time.
Experiment has been performed with the following
steps:
1. Thumba oil (400g) is taken in a beaker and filtered
it to remove impurities. The raw oil is heated up to
1100C in order to remove water content of oil to avoid
soap formation. This oil is allowed to cool up to 550C
temperature for the reaction to take place.
2. Now methyl alcohol (CH3OH) is taken with a
molar ratio of (1:4.5 & 1:6) and Catalyst (KOH) is
taken as (0.5%, 0.75% and 1% by weight of oil).The
mixer of methyl alcohol and KOH stirred until KOH
dissolve in methyl alcohol.
3. This mixture is mixed with Thumba oil. The
methanol is immiscible with the oil.
4. A magnetic capsule is dipped in the mixture of oil,
methanol and catalyst and rotated with the help of
magnetic stirrer.
5. During the reaction the temperature of mixture is
kept between 55-60degC.
6. When reaction is completed the beaker is kept for
the separation. Fatty acid has higher specific weight
therefore it will settle at bottom. Separation of methyl
ester and glycerol will take 2 to 3 hr duration.
Figure 4: Washing process of biodiesel.
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7. After complete separation bio-diesel (methyl Ester)
is visible in the upper layer and glycerol at the
bottom.
8. Bio-diesel is separated from beaker for purification
process. The catalyst present in the methyl ester is
impurity.
9. Excess methanol present in biodiesel has been
removed by vaporization process.
10. To remove the catalyst, water at around 600C is
mixed with the methyl ester and left for settling
down. Water due to its higher specific gravity
collected at bottom, this is shown in Figure
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11. Excess water is removed by heating the biodiesel.
Experimental Data
The experiments are performed with alcohol
to oil for the molar ratio as 6:1 and 4.5:1. The amount
of oil, alcohol and catalyst taken is shown in Table 2.
The main aim of this experiment is to calculate the
maximum yield% (methyl ester for Thumba oil) of
biodiesel production with time, catalyst percentage
and molar ratio (alcohol/oil). The results
(Experimental Data) obtained from Mechanical
Stirrer Technique are shown in table 3.
Table 2: Oil, alcohol and catalyst during the experimentation
Quantity of Quantity
of
Catalyst(KOH)
non-edible
methanol(g)
0.5%
0.75%
(alcohol/oil)
oil (g)
Molar ratio
1.0%
6:1
400g
88g
2.0g
3.0g
4.0g
4.5:1
400g
66.24g
2.0g
3.0g
4.0g
Table 3: Time and yield (%) of Thumba oil for different molar ratio and catalyst percentage
Percentage of
Molar ratio 6:1
Molar ratio 4.5:1
catalyst (KOH)
Time (min)
Yield (%)
Time (min)
Yield (%)
20
85.65
20
82.26
84.81
89.28
91.11
91.70
89.38
40
50
60
20
87.06
88.06
87.61
86.27
30
93.48
30
90.32
94.67
40
93.50
95.74
50
94.83
60
96.93
60
94.39
20
90.76
20
88.62
30
93.56
30
92.94
40
94.61
40
94.53
50
95.36
50
95.98
60
VII.
30
50
1
86.95
40
0.75
30
40
50
60
20
0.5
97.82
60
95.76
Results & Discussion
Figure 5.1 and 5.2 shows the graphical
representation of Biodiesel yield with respect to time
for 6:1 and 4.5:1 molar ratio respectively at different
percentage of catalyst (KOH). It has been observed
that there is higher yield in case of 6:1 molar ratio as
compared to 4.5:1 molar ratio. It may be because of
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alcohol using for 6:1 molar ratio is more than that of
4.5:1 molar ratio. The yield for 0.5% KOH is less as
compare to 0.75% and 1% KOH in both the cases. It
may be because of 0.5% KOH is not sufficient to
enhance the reaction. The maximum yield obtained
is 97.82 at 1% KOH for 6:1 molar ratio.
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100
95
Y
I
E
L
D
%
90
85
0.5% KOH
0.75% KOH
1% KOH
80
75
15
25
35
45
55
65
Time in min
Figure 5.1: Time Vs Yield graph at 4.5:1 molar ratio for different KOH percentage
100
Y
I
E
L
D
95
%
80
90
85
0.5% KOH
0.75% KOH
1% KOH
75
15
25
35
45
55
65
TIME IN MIN.
Figure.5.2: Time Vs Yield graph at 6:1 molar ratio for different percentage of KOH
VIII.
Experimental data for physical and
chemical properties
The experimental values of properties of
fuels are specified below:
Table 4: Experimental data of physical and chemical properties
S. No.
Properties of fuel with data
Diesel Fuel
Bio-diesel
1
Viscosity@40oCcSt
1.25to 1.40
4.32
2
Density@15o C Kg/L
0.821
0.870
3
Cloud point(oC)
-23to12.5
4.5
4
Pour point(oC)
6to7
7.2
5
Flash point(oC)
47to70
91
6
Fire point (oC)
75
110
7
Calorific Value KJ/Kg
42000
37000
8
Boiling point (oC)
180-340
321
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7. Beena Mishra et al Int. Journal of Engineering Research and Applications
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IX.
Conclusion
Thumba (Citrullus colocyntis) has huge
capability for biodiesel production. The most
important feature of this Thumba is that it grows in
the form of climbing plant in sandy soil with in a six
month crop cycle. As we know that availability of the
raw material controls the economics of the product.
So, there should be a proper management for the
plantation of neglecting trees and their usage to
investigate the benefits from this Thumba Oil Plant.
Bio-diesel is found better substitute for petroleum
diesel and also most advantageous over petro-diesel
for its environmental friendliness. The quality of
biodiesel fuel was found to be considerable for its
doing well use on compression ignition engines and
ensuing replacement of non-renewable fossil fuels.
Biodiesel produce from Thumba seed oil also yield
comparable results with petroleum diesel. The
important conclusions are as follows:
It is found that in mechanical stirring the yield
obtained at 1% KOH is higher.
Maximum yield up to 97.82% is obtained from
Thumba oil by mechanical stirrer technique.
From results of experimental investigation of
Thumba Biodiesel, it is found that it is having the
properties similar to diesel. So blends are having
the potential to reduce the over burden of the
imports of diesel fuel.
Finally, it is concluded that Thumba
Biodiesel can be made successfully by mechanical
stirring method and can be suitably used in vehicles
as Alternative of diesel fuel.
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