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Chemical Engineering Department, Faculty of Engineering, University Malaya, 50603 Kuala Lumpur, Malaysia
Department of Chemistry, Faculty of Science, Sudan University of Science and Technology, P.O. Box 407, Khartoum, Sudan
College of Sciences and Arts-Alkamil, King Abdulaziz University, Alkamil, Saudi Arabia
d
Department of Food Science & Technology, College of Agricultural Science, Sudan University of Science and Technology, P.O. Box 407, Khartoum, Sudan
e
Unit of Research on Lipids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
f
Department of Chemistry, College of Medical Science (Turuba), Taif University, Saudi Arabia
g
Department of Mechanical Engineering, Faculty of Engineering, Erciyes University, 38039 Kayseri, Turkey
h
Erciyes Teknopark A.S, Yeni Mahalle Askveysel Bulvar Erciyes Teknopark, Tekno 3 Binas 2, Kat No: 28, 38039 Melikgazi/Kayseri, Turkey
b
c
a r t i c l e
i n f o
Article history:
Received 23 July 2014
Accepted 29 December 2014
Available online 21 January 2015
Keywords:
Moringa peregrina
Biodiesel
Fuel properties
Thermal stability
a b s t r a c t
Moringaceae is a monogeneric family with a single genus i.e. Moringa. This family includes 13 species. All
these species are known as medicinal, nutritional and water purication agents. This study reports, for
the rst time, on characterization of the biodiesel derived from crude Moringa peregrina seed oil and
its blends with diesel. The crude oil was converted to biodiesel by the transesterication reaction, catalyzed by potassium hydroxide. High ester content (97.79%) was obtained. M. peregrina biodiesel exhibited
high oxidative stability (24.48 h). Moreover, the major fuel properties of M. peregrina biodiesel conformed
to the ASTM D6751 standards. However, kinematic viscosity (4.6758 mm2/s), density (876.2 kg/m3) and
ash point (156.5 C) were found higher than that of diesel fuel. In addition, the caloric value of M. peregrina biodiesel (40.119 MJ/kg) was lower than the diesel fuel. The fuel properties of M. peregrina biodiesel were enhanced signicantly by blending with diesel fuel. In conclusion, M. peregrina is a suitable
feedstock for sustainable production of biodiesel only blended up to 20% with diesel fuel, considering
the edibility of all other parts of this tree.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Fossil fuels reservoirs around the world are declining due to
their non-renewable nature. At the same time the demand for
energy is, continuously, increasing to meet the needs of the world
population, which is growing signicantly. As a result, the prices of
fossil fuels have increased and, negatively, affected the economies
of many countries. Global warming is being caused by the greenhouse gas emissions. Reducing the dependence on fossil fuels will
be benecial, from environmental point of view, since this will
reduce the concentration of carbon dioxide in the atmosphere.
Therefore, explorations to nd new renewable, sustainable and
economically feasible sources of energy have emerged as a top priority for research to resolve all these problems.
Biodiesel is one of the most promising alternative fuels to
replace the conventional petroleum-based fuels with multiple
environmental advantages. Biodiesel, popularized as the mono
alkyl esters are derived from triglycerides (vegetable oils or animal
fats). Transesterication is the most convenient process to convert
triglycerides to biodiesel. Transesterication process involves a
reaction of the triglyceride feedstock with light alcohol in the
presence of a catalyst to yield a mixture of mono alkyl esters [1].
Currently, homogenous basic catalysis, using hydroxides of sodium
or potassium, is the common route for industrial production of
biodiesel [2].
Biodiesel industry has grown up in the world using edible
feedstock such as rape seed, soybean, sunower and palm oils.
Non-edible oils stand as new promising sources of raw materials
for biodiesel production, especially in developing countries to
satisfy their increasing energy demand [3]. Currently, Jatropha
curcas has been promoted as the most promising non-edible source
536
for bio-fuel [4]. However, all parts of Jatropha are toxic [5]. Therefore, plantation of such toxic plant for large scale and long term
production may raise risks, such as accidental consumption by
children or animals. Moreover, the situation is being worsened
by spreading Jatropha on the fertile lands in order to improve the
yields, as this will reduce water and available space for food crops
[6]. Thus, plants that can supply, simultaneously, food and fuel
should be given more attention as robust feedstock for bio-fuels.
In this respect, Moringa seed oil has emerged as a potential feedstock for biodiesel production, considering the one hundred percent usability of all other parts of this tree [7]. All nutritional
values and medicinal usage of Moringa have been comprehensively
reported [8]. After oil extraction from the seeds, the residues
remain are potential for both water purication and as a fodder [9].
Moringa is a single genus of the Moringaceae family. This family
includes 13 species. All these species originated in India and Africa
and have been distributed in many other several tropics lately [10].
Moringa oleifera [1113] and Moringa stenopetala [14] have been
reported for biodiesel production. Preliminary study [15] revealed
that crude M. peregrina seed oil is potential for biodiesel production. M. peregrina oil has high degree of unsaturation, comprised
of oleic acid as a major component [16]. Thus, other preliminary
studies [17,18], indicated the potential of M. peregrina oil for edible
purposes and other industrial application, such as hydrogenation,
shortening production and others.
M. peregrina is distributed in wide range extending from Egypt,
Ethiopia to Somalia, Sudan, the Red Sea region, Palestine and
Jordan [19]. M. peregrina as it is very fast growing tree, can reach
310 m in height during only 10 months from the plantation of
the seed. It has grayishgreen bark, long leaves, and bisexual
yellowish white to pink, showy, fragrant owers. The fruits are
elongate capsules, with a beak, glabrous and slightly narrowed
between the seeds. The seeds are globose to ovoid or trigonous
[10,19,20]. Plantations of M. peregrina have been assessed as quite
promising, with growth reasonably rapid and cultivation easy [15].
The aim of this study is to investigate the properties of
M. Peregrina biodiesel for the rst time. The oil was extracted from
M. peregrina seeds. The extracted crude oil was converted to
biodiesel by the transesterication reaction in one step, catalyzed
by potassium hydroxide. The produced biodiesel was blended with
diesel fuel No. 2. Physical characteristics of the biodiesel and biodieseldiesel blends were discussed in the light of the international
standards ASTM (American Society for Testing and Materials) D
6751. The ester content in the produced biodiesel was determined
and discussed in accordance to the European Standards EN14214
using the method EN14103.
2. Experimental
2.1. Materials
537
Table 1
GC conditions for determination of fatty acid composition.
Property
Specication
Injector
Column
Gas currier
Detector
Heating program
prepared to investigate the effect of blending on biodiesel properties at low and high blend ratios.
2.7. Fuel properties determination
Some fuel properties of the crude oil, biodiesel and biodiesel
diesel blends were examined according to ASTM D6751. These
properties include caloric value, kinematic viscosity, viscosity
index, density, cloud point (CP) pour point (PP), cold lter plugging
point (CFPP), ash point and oxidative stability. Table 2 shows the
description of the equipment and their manufactures, along with
the ASTM methods that were used to conduct these analyses in this
study. The acid values of the crude M. peregrina oil and its biodiesel
were determined by titration according to Kuntom et al. [23].
Cetane number (CN) of biodiesel is directly proportional to the
length of the carbon chain and inversely to the number of the double bonds. Therefore, it was calculated based on the iodine value
(IV) and Saponication number (SN) according to Eq. (1) as
reported by Krisnangkura [24]. IV and SN were calculated according to Eqs. (2) and (3) respectively [25]:
1
2
3
where Ai, D and MWi stand for concentration by percentage, number of double bond and molecular weight of each methyl ester.
2.8. Thermal analysis
Volatility is one of the most important properties to determine
the viability of biodiesel as a fuel regarding engine performance. In
this study thermogravimetric analyzer TGAQ500 (TA instruments,
USA) was used to investigate the thermal behavior of M. peregrina
biodiesel and the effects of blending with diesel on its volatility.
The sample (58 mg) was heated from ambient temperature to
600 C with a heating rate 10 C/min in an inert atmosphere of
Table 2
List of the equipment used in the fuel properties determination.
Property
Equipment
Manufacturer
Kinematic viscosity
SVM 3000-automatic
Anton Paar, UK
Standard method
D 445
Viscosity index
SVM 3000-automatic
Anton Paar, UK
D2270-04
Density
SVM 3000-automatic
Anton Paar, UK
D 7042
Caloric value
C2000 basiccalorimeterautomatic
IKA, UK
D 240
Normalab, France
D 2500
Normalab, France
D97
Normalab, France
D 6371
Metrohm, Switzerland
EN 14112
538
Table 3
Physical properties of crude M. peregrina seed oil in comparison to some other oils.
Property
2
M. oleifera [13]
Palm [13]
Soybean [13]
Canola [13]
Jatropha [13]
36.181
7.9707
201.1
892.8
268.5
39.916
29.255
43.4680
9.0256
195.20
897.1
263
39.762
41.7
41.932
8.4960
185.0
899.8
254.5
39.867
0.08
35.706
7.6295
223.5
907.3
280.5
39.579
6.09
35.706
8.5180
213.5
904.2
290.5
39.751
5.64
48.095
9.1039
174.1
905.4
258.5
38.961
0.32
Fig. 1. (a) FTIR spectrum of crude M. peregrina seed oil and (b) FTIR spectrum of M. peregrina methyl ester.
biodiesel [33], which indicates that the step of washing was satisfactory. The whole FTIR spectrum of M. peregrina methyl ester
obtained for this study, is similar to the spectra that were recorded
for palm, soybean and sunower methyl esters [30], indicating that
crude M. peregrina seed oil is a new feedstock potential for biodiesel production.
3.3. Ester content and composition of M. peregrina biodiesel
The yield of biodiesel was found 92.33% (v/v). The ester content
in the produced biodiesel was determined by the GC analysis
according to the EN14103 standard method. The average value of
the ester content, obtained from duplicate determination, was
97.79% with absolute difference 1.1%. EN14103 stated that the
absolute difference between two independent single test results
shall not be greater than 1.6%. Thus, the value obtained here is satisfactory regarding repeatability. This value of the ester content
(97.79%) is greater than the minimum value required by the
EN14103 (96.5%). The glycerol portion of the original vegetable
oil is usually about 10.5%, thus, values of ester content greater than
97.7% indicates that the residual total glycerol is lower than the
maximum value (0.24%) required by the ASTM D6751 [31]. It is
concluded here from the GC analysis that the obtained M. peregrina
methyl ester had high purity.
The composition of M. peregrina methyl ester as identied from
the GC analysis is presented in Table 4. For the sake of comparison
between different species in the same family, Table 4 also includes
the fatty acid composition of methyl esters derived from M. oleifera
[11] and M. stenopetala [13] oils. The prominent feature of all these
species is the presence of oleate fatty ester as the dominant component (7176%) and very low content (>5%) of polyunsaturated
fatty esters. Methyl esters that contain a high fraction of
Table 4
Fatty acid composition of M. peregrina methyl ester in comparison to M. oleifera
methyl ester and M. stenopetala methyl ester.
C16:0
C16:1
C18:0
C18:1
C18:2
C18:3
C20:0
C20:1
C22:0
C24:0
TUFEsc
TMFEsd
TPUFEse
TSFEsf
VLCFEsg
a
b
c
d
e
f
g
M. peregrina methyl
ester
M. oleifera methyl
estera
M. stenopetala methyl
esterb
9.08
2.68
4.04
71.09
4.16
0.51
2.38
1.86
3.13
1.02
80.30
75.63
4.66
19.7
8.39
6.50
4.40
72.20
1.00
4.0
2.00
7.10
75.20
74.20
1
24.80
13.10
6.10
7.50
76.0
3.80
1.70
4.40
77.70
77.7
22.3
9.90
Ref. [11].
Ref. [14].
Total unsaturated fatty esters.
Total monounsaturated fatty esters.
Total poly unsaturated fatty esters.
Total saturated fatty esters.
Very long chain fatty esters.
Table 5
Fuel properties of M. peregrina methyl ester in comparison to diesel fuel and ASTM D
6751 standard.
M. peregrina Diesel
fuel
methyl
ester
Property
Acid value
Kinematic viscosity at 40 C
Viscosity index
Density at 15 C
Iodine value
Saponication number
Cetane number
Flash point
Caloric value
Oxidative stability
Cloud point (CP)
Pour point (PP)
Cold lter plugging point (CFPP)
mg KOH/g
mm2/s
0.11
4.7658
200.3
kg/m3
876.20
mg I2/100 g 77.17
mg KOH/g 198.60
56.42
C
156.5
MJ/kg
40.119
H
24.48
C
15
C
11
C
13
3.1135
165.5
834.6
45.685
13
11
13
539
[36]. Caloric value is another fuel property that affects fuel consumption [33]. The caloric value of M. peregrina methyl ester
was 40.119 MJ/kg lower than the caloric value of the diesel fuel
(45.685 MJ/kg). The lower caloric value of biodiesel fuels because
of their oxygen content. However, the presence of oxygen in the
biodiesel leads to complete combustion of the fuel in the diesel
engine [36].
Cetane number of a fuel is inversely related to its ignition delay
i.e. the time between the initial fuel injection and ignition. Therefore, alkyl esters with high cetane numbers are favorable for the
diesel ignition engine regarding ignition quality [36]. The value
of cetane number of M. peregrina methyl ester in this study was
found 56.42 higher than the minimum value (47) that is specied
by the ASTM standard. Generally, Cetane number of biodiesel varies in the range (4867) [37]. Therefore, M. peregrina methyl ester
can be considered among biodiesel fuels that has a high cetane
number, as another indication for the suitability and potentiality
of M. peregrina for biodiesel production.
As expected, due to the low concentration of the polyunsaturated fatty esters (PUSFEs) (C18:2 and C18:3), M. peregrina methyl
ester has exhibited a high oxidative stability (24.48 h).This value is
similar to the value (26.2 h) reported for M. oleifera oil methyl ester
[12].
High ash point of biodiesel fuel is another advantage of biodiesel over petroleum-based diesel fuel. Flash point is a measure to
the ammability of the fuel, higher the ash point more safe the
fuel in handling and storage [13]. The ash point of the produced
biodiesel in this work was 156.5 C, quite satisfactory as the minimum value of the ash point prescribed by the ASTM a standard is
120 C. However, high ash point indicates low volatility properties, leading to negative effect on diesel engine performance [32].
The volatility characteristics and thermal behavior of M. peregrina
methyl ester was further investigated by the thermogravimetric
analysis (discussed in the Section 3.6)
The behavior of biodiesel during cold seasons can be evaluated
from the cold ow properties which are cloud point (CP), pour
point (PP) and cold lter plugging point (CFPP). The CP is the temperature at which smallest lump of crystals become visible when
the fuel is cooled. The PP is the lowest temperature at which the
fuel ows though the formation of gel due to the effect of cooling.
The CFPP is the temperature at which the pores of the lter start to
plug by the effect of the crystallized components in the fuel [38]. In
this study M. peregrina methyl ester has shown, signicantly, high
cold ow properties. CP, PP, and CFPP were found 15, 11, 13 C
respectively. This behavior can be explained by the considerable
concentration of saturated palmitic acid methyl ester C16:0
(9.08%) and the signicant amount of very long fatty esters (VLCFEs) (8.39) [32]. The cold ow properties of the diesel fuel used
in this study were not low as expected and fall in the range similar
to the biodiesel under investigation. This may be an indication of
its high content of parafn [39].
ASTM D
6751
0.5 max
1.96.0
880
47 min
120 min
3 min
540
b
880
5
4
3
2
1
Density (kg/m3 )
kenimatic viscosity
(mm 2/s)
840
820
800
d
48
46
44
42
40
38
36
860
180
160
140
120
100
80
60
40
20
0
16
Temperature (C)
14
12
10
8
6
Cloud point
Pour point
CFPP
Fig. 2. Effect of blending on (a) kinematic viscosity, (b) density, (c) caloric value, (d) ash point and (e) cold ow properties.
541
Table 6
Volatilization temperatures from TGA analysis.
Fuel
CMPSOa
B100
B80
B60
B40
B20
B10
B5
B0
374.69
193.36
193.31
185.04
170.56
141.94
135.06
116.62
108.86
418.12
231.14
235.48
231.56
228.18
214.61
216.97
200.13
198.37
4. Conclusions
In this study we have described a new species i.e. M. peregrina
from Moringacea for biodiesel production. The crude oil was, easily
converted to methyl esters by one step alkaline-catalyzed transesterication reaction. The physicochemical characteristics of the
produced biodiesel conformed to the major standards required
by ASTM D6751.The prominent features of M. peregrina methyl
ester were the high oxidative stability and cetane number. Moreover, the fuel properties of the M. peregrina methyl ester were
enhanced signicantly by blending with diesel fuel. The fuel properties and the thermal behavior of blends contained up to 20% biodiesel, were similar to those of diesel fuel. Therefore, with the
added advantage of the edibility of all other parts, M. peregrina is
a promising source for sustainable production of biodiesel. As such,
more research is needed to optimize the oil extraction, as well as,
biodiesel conversion and to develop a commercial production
process.
Acknowledgments
This work is a part of scientic collaboration between University of Malaya and Sudan University of Science and Technology.
The work was carried out under the Center of Separation Science
and Technology (CSST) and was supported by the University of
Malayas HIR Grant No. VC/HIR/001/2. Nile Valley University and
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