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Department of Mechanical Engineering, B.S. Abdur Rahman University, Vandalur, Chennai 600 048, India
Institute for Energy Studies, Anna University, Chennai 600 025, India
h i g h l i g h t s
Development of a new biodiesel from fruit seeds which is not yet reported in literatures.
Optimization of four major inuencing parameters of transesterication of the new oil using Taguchi method.
Report on production of the new biodiesel with optimized process parameters and its physiochemical properties.
Physicochemical properties of the new biodiesel meeting the requirements of EN 14214 standards for biodiesel.
A new renewable source of energy for use in unmodied diesel engine applications.
a r t i c l e
i n f o
Article history:
Received 17 April 2014
Received in revised form 25 September
2014
Accepted 25 September 2014
Available online 5 October 2014
Keywords:
Manilkara zapota
Optimization
Taguchi method
Biodiesel
Transesterication
a b s t r a c t
In this work, the optimization of transesterication process parameters for the production of Manilkara
Zapota Methyl Ester (MZME) has been studied. Molar ratio of methanol to oil, time of reaction,
temperature of reaction, and concentration of catalyst were the four parameters considered in the study.
Taguchi experimental design was used for the optimization of the above mentioned four process parameters of transesterication. The physicochemical properties and fatty acid methyl ester concentrations
were experimentally analyzed. The experimental study revealed that 50 C temperature of reaction,
90 min of time of reaction, 6:1 M ratio of methanol to oil and 1 wt% of concentration of catalyst are
the optimal process parameters. Also the study revealed that out of the four parameters considered,
methanol to oil molar ratio is most effective in controlling the optimal biodiesel production. The optimal
conditions yielded 94.83% of biodiesel. The biodiesel MZME produced with the optimized process
parameters meets the global standards for biodiesel EN 14214 and hence could be considered as a
suitable substitute for fossil diesel in unmodied diesel engine applications.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Biodiesel, a promising renewable substitute source of fuel
produced from tree born oils, vegetable based oils, fats of animals
and even waste cooking oil has been identied as one of the key
solutions for the alarming global twin problems of fossil fuel
depletion and environmental degradation [14]. Even though it
was identied in the beginning of 20th century by Rudolf Diesel,
extensive researches have been started in the tail end of 20th
century, when the demand for fossil fuel increased [58]. Biodiesel
has gained greater attention because of the advantages such as
Corresponding author at: Department of Mechanical Engineering, B.S. Abdur
Rahman University, Vandalur, Chennai 600 048, Tamil Nadu, India. Tel.: +91
9942167709; fax: +91 44 22750520.
E-mail address: sathish.rajamanickam@gmail.com (R. Sathish Kumar).
http://dx.doi.org/10.1016/j.fuel.2014.09.103
0016-2361/ 2014 Elsevier Ltd. All rights reserved.
91
Pongamia, Jatropha, rubber seed, soap seed and neem seed and
Camelina [2428].
Manilkara zapota, popularly known as sapodilla, a forest tree
with long life span is mostly found in southern Mexico, Caribbean
and Central America. It is also cultivated in larger scale in India,
Thailand, Cambodia, Malaysia, Indonesia, Bangladesh mainly for
its fruit. It is known as chikoo (chiku) in Northern India, and sapota
in southern parts of India. It is evergreen tree grows in wide range
of climatic conditions and all tropical lands like wet tropics to dry
cool subtropical areas. The soils can be slightly alkaline, well dried
with medium textured loams. Even though the tree owers and
fruits throughout the year, maximum yield occurs during the
period of March to June.
The evergreen M. zapota (sapota) is a large tree mainly cultivated for its fruit. Its normal growth can reach up to around
30 m height with the maximum diameter of trunk 1.5 m. The fruits
have a rough brownish skin with 112 seeds of color brown or
black. The seeds are covered by a juicy sweet brownish esh which
is eaten raw or made into jam and juice. The seeds are not utilized
for any major purpose except seedling. M. zapota seeds have an oil
content of 2330% and hence this underutilized oil seed can be
considered for biodiesel production.
The primary objective of this investigation is to optimize the
key parameters of transesterication process of M. zapota seed
oil (MZO). As MZO has not yet been studied for the biodiesel production, it is considered essential to optimize the key process
parameters like molar ratio of methanol to oil, concentration of
catalyst, temperature of reaction, and time of reaction. Furthermore the properties of M. zapota seed oil and its methyl ester were
estimated and compared with EN 14214 biodiesel standards.
2. Materials and methods
2.1. Materials and experimental setup
M. zapota (L.) seeds were collected. 99.9% pure analytical grade
methanol and potassium hydroxide in pellet form of above 85%
purity were used for the biodiesel production. The experimental
setup consists of a half litre four-necked batch type spherical glass
reactor, with a water-cooled condenser in one of the necks, a speed
controlled mechanical stirrer, a temperature controlled heating
mantle and a thermometer. The arrangement of the batch type
transesterication reactor used in the study is shown in Fig. 1.
2.2. Extraction of M. zapota oil and its characterization
The collected seeds were dried in sunlight for about 24 h to
remove the 10% moisture content in it. The shell was removed
manually from the dry seeds. Mechanical screw type mini expeller
manufactured by M/s. Rajkumar Agro Engineers Private Limited,
Pune, India, was used to extract oil from the raw dry seeds. The
approximate oil content of the M. zapota seed lies between
2530% of the weight of the seed. The oil was ltered and dried
at 60 C. The various important properties of raw oil and biodiesel
were estimated. Fatty acid compositions were measured using a
gas chromatograph (PerkinElmer Clarus 500 Auto System XL with
elite series PE-5 capillary column, 30 m 0.25 mm 1 lm)
coupled with a mass spectrometer (GC-MS) (Turbo; EI, 70 eV).
DB-1 (100% dimethylpolysiloxane) column with helium as the
carrier gas at a ow rate of 1 ml min1.
Kinematic viscosity was measured at 40 C using a Brookeld
DV-II Proviscometer as per the procedure of ASTM D 445. The pour
point and the cloud point were simultaneously estimated in
accordance with ASTM D 5949 and ASTM D 5773 respectively.
Flash point was measured using Pensky Martene open cup apparatus. Heating value was determined with the use of Parr 6772
bomb calorimeter. Density at 15 C was measured using a Rudolph
DDM 2909 Automatic Density Meter. The values of iodine number
and cetane number were calculated as per the standards of ASTM.
The acid value was determined using a suitable titration with
standardized KOH solution with phenolphthalein as the indicator.
2.3. Transesterication process
One of the key properties of raw oil to decide about the type of
transesterication process such as one step or two step transesterication process is free fatty acid (FFA) content. If the FFA content
of the oil is less than 2.5%, then one step transesterication process
with a base catalyst should be used and if it exceeds 2.5%, two step
transesterication process should be the choice. In this study as the
FFA content of MZO was 1.86%, single step base catalyst transesterication method has been adopted.
100 g (0.1) of MZO was placed in a four-necked batch reactor
and heated to the required temperature. The stirrer speed was
maintained at 500 rpm for constant mixing. The methoxide solution was prepared by dissolving the exactly measured quantity of
solid catalyst (KOH) in premeasured quantity of methanol. Once
the oil reached the required temperature, the prepared methoxide
was slowly poured into the reactor. The completion of pouring
instant was taken as the start of reaction. The condenser was
installed on one of the four necks to capture and reuse any
vaporized methanol. Fig. 2 shows the chemical kinetics of
transesterication process [2830]. The major inuencing
parameters considered for optimization and testing in the transesterication process are molar ratio of methanol to oil, time of
reaction, temperature of reaction, and concentration of catalyst
and selected values for these parameters are shown in Table 1.
Upon reaching the predened time of reaction, the reactor was
taken out of the heating mantle and the products of the reaction
were shifted to a 500 ml separating conical funnel. After 24 h of
settling, the heavy glycerol layer settled at the bottom of the funnel
was removed through a drainage valve. The remaining crude biodiesel produced from MZO was gently washed with distilled water
at 40 C in order to remove the unreacted methanol, catalysts and
impurities. The percentage yield of biodiesel has been calculated
using the formula:
Biodiesel yield % : Y
92
O
O
H2C
HC
(CH2)n CH3
OH
O
O
H2C
C
O
(CH2)nCH3
(CH2)n CH3
+ 3 CH 3OH
H2C
HC
OH
3 H3CO
(CH2)n CH3
H2C
O
OH
triglyceride in
vegetable oil
methanol
glycerol
Table 1
Chosen parameters and their levels.
Parameters
A
B
C
D
Levels
4:1
0.5
60
50
6:1
1
90
60
8:1
1.5
120
70
produced under optimal condition was analyzed. ASTM specications were followed to determine the properties of MZME and
the estimated properties have been compared with EN14214 biodiesel standards.
inuencing the process and the extent to which they can be varied.
The very specialty of this method is not to investigate all the possible parameters combinations but only few pairs of combinations.
This method paves way for collation of data for the determination of factors which most inuence the quality of product with
minimal number of experiments so as to reduce precious time
and resources. This method is very effective with nominal number
of parameters (350), few interactions between them and a very
few contributing signicantly.
From the Orthogonal Arrays (OA), the required number of
experiments and their conditions can be nalized. The number of
parameters and the variation levels of each parameter decide the
OA selection. The least possible number of experiments N is
decided from the number of levels L and number of design and
chosen control parameters P using the relation N = (L 1) P + 1.
Pre-treatment
Titration
FFA 2.5%
Transesterification using
base catalyst
Phase separation
Crude glycerol
Crude biodiesel
2
yi
s2i
n y2
X
j
j1
Pure biodiesel
Fig. 3. Process ow chart of biodiesel production from Manilkara zapota seed oil.
2
!
3
n
1 X
1
Larger the better SNRi 10 log
n j1 y2j
!
4
93
1
2
3
4
5
6
7
8
9
1
1
1
2
2
2
3
3
3
1
2
3
1
2
3
1
2
3
1
2
3
2
3
1
3
1
2
1
2
3
3
1
2
2
3
1
where
yi
s2i
n
1 X
y
n j1 i;j
!
mean value of response
n
X
1
y yi
n 1 j1 i;j
!
variance
% contribution of factor
SSf
100
SST
where SSf is the sum of the squares for fth parameter and SST is the
total sum of the squares of all parameters.
SSf
h
i2
n SNRL fj SNRT
3
X
j1
SST
9
X
SNRi SNRT 2
10
Content (%)
Molecular weight
13.27
2.80
64.15
17.92
1.86
256.4
284.5
282.5
280.5
278.4
Total saturated
Total unsaturated
16.07%
83.93%
i1
A conrmation test with three trials has been carried out with
the set of optimum parameters and the statistical analysis has been
validated.
3. Results and discussion
3.1. Properties of the M. zapota seed oil
Crude MZO has been used for biodiesel production without any
rening process. Its physicochemical properties and fatty acid
composition have been studied to nd the suitability as feed stock
for biodiesel production. Based on its properties and fatty acid
Table 4
Physicochemical properties of Manilkara zapota seed oil.
Parameters
Values
Density at 15 C (g/cm3)
Kinematic viscosity at 40 C (mm2/s)
Free fatty acid (% FFA as oleic acid)
Acid value (mg KOH/g)
Iodine value (g Iodine/100 g)
Peroxide value (g/kg O2)
Color
Molecular weight (g/mol)
Percentage oil content in kernel (%)
Physical state at room temperature
pH
0.887
34.75
1.89
3.79
65.02
269.54
Brownish yellow
873.95
2330%
Liquid
3.5
94
Table 5
Percentage of yield and SNR for the 9 set of experiments.
Experiment no.
1
2
3
4
5
6
7
8
9
4:1
4:1
4:1
6:1
6:1
6:1
8:1
8:1
8:1
0.5
1.0
1.5
0.5
1.0
1.5
0.5
1.0
1.5
60
90
120
90
120
60
120
60
90
50
60
70
70
50
60
60
70
50
% of Yield
Trail 1
Trail 2
Trail 3
70.8
83.5
83.3
82.4
94.4
84.5
70.1
81.4
87.2
78.4
87.8
77.8
81.8
91.8
93.4
74.4
84.3
82.8
77.6
85.6
79.5
75.2
94.6
87.0
72.2
85.3
85.6
SNR
75.6
85.6
80.2
79.8
93.6
88.3
72.2
83.7
85.2
37.57
38.65
38.08
38.04
39.43
38.92
37.17
38.45
38.61
38.32
were A (Molar ratio of methanol to oil) at level 2 (6:1), B (concentration of catalyst) at level 2 (1%), C (time of reaction) at level 2
(90 min) and D (temperature of reaction) at level 1 (50 C).
3.3. Analysis of variance (ANOVA)
The most signicant process parameter was identied by
calculating the percentage contribution of each parameter on the
biodiesel yield. The calculated SSf and % contribution were
tabulated in Table 6. From the contribution table it was observed
that concentration of catalyst was the most signicant parameter
with 67.34% contribution on the biodiesel yield from M. zapota
seed oil followed by molar ratio of methanol to oil with 25.85%
contribution. The time of reaction was the least inuencing process
parameter with 1.6% contribution followed by temperature of
reaction. It shows that the major amount of biodiesel conversion
has attained close to the start of reaction. The rate of conversion
is high during the start of reaction and it is not affected after it
reached the steady state.
Table 6
Percentage contribution of process parameters.
Parameter
SSf
% Contribution
0.3269
0.8517
0.0203
0.0659
25.85
67.34
1.60
5.21
39.0
Catalyst concentration
Mean of SN ratios
38.5
38.0
37.5
1
Reaction time
39.0
Reaction Temperature
38.5
38.0
37.5
1
95
Units
EN 14214
MZME
Diesel
Test method
Ester content
Density at 15 C
Kinematic viscosity
Acid value
Iodine value
Pour point
Flash point
Heating value
Cetane number
Sulphur content
Monoglyceride content
Diglyceride content
Triglyceride content
Free glycerol content
Total glycerol
% (m/m)
g/cm3
mm2/s
mg KOH/g
g iodine/100 g
C
C
MJ/kg
Min 96.5
0.860.90
3.55
Max 0.50
Max 120
Max 0
Min 120
Min 35
Min 51
Max 10
Max 0.8
Max 0.2
Max 0.2
Max 0.02
Max 0.25
96.8
0.875
4.67
0.15
65.28
6
174
37.2
52
0
0.52
0.13
0.12
0.00
0.17
0.861
2.96
0.18
12
48
44.8
51
350
EN14103
ASTM D4052
ASTM D445
ASTM D664
AOAC CD1-25
ASTM D97
ASTM D93
ASTM D240
ASTM D613
ASTM D5459
EN14105
EN14105
EN14105
EN14105
EN14105
mg/kg
% (m/m)
% (m/m)
% (m/m)
% (m/m)
% (m/m)
Yo 10
SNRo
5
11
96
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