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Energy Conversion and Management 92 (2015) 535542

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Energy Conversion and Management


journal homepage: www.elsevier.com/locate/enconman

Physicochemical characterization and thermal behavior of biodiesel and


biodieseldiesel blends derived from crude Moringa peregrina seed oil
Mohammed Salaheldeen a,b,, M.K. Aroua a, A.A. Mariod c,d, Sit Foon Cheng e, Malik A. Abdelrahman b,f,
A.E. Atabani g,h
a

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

Corresponding author at: Department of Chemistry, Faculty of Education, Nile


Valley University, P.O. Box 347, Atbra, Sudan. Tel.: +249 122718984.
E-mail addresses: Salahch73@gmail.com (M. Salaheldeen), mk_aroua@um.edu.
my (M.K. Aroua), basitmariod@yahoo.com (A.A. Mariod), sfcheng@um.edu.my
(S.F. Cheng), malikabdalla@yahoo.com (M.A. Abdelrahman), a_atabani2@msn.com
(A.E. Atabani).
http://dx.doi.org/10.1016/j.enconman.2014.12.087
0196-8904/ 2015 Elsevier Ltd. All rights reserved.

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

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M. Salaheldeen et al. / Energy Conversion and Management 92 (2015) 535542

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.

2.2. Oil extraction


M. peregrina seeds were crushed by grinder and sieved to less
than 1 mm in size. The meal (500 g) was placed in a soxhlet extractor. A cotton cloth was used as a thimble to hold the sample. The
extractor was tted with round bottom ask (5 L) and a condenser.
The extraction was carried out using hexane (3 L). After 6 h extraction time, the solvent was recovered by rotary evaporator at 40 C
under vacuum. The oil was dried with sodium sulfate anhydrous
prior to biodiesel production.
2.3. Biodiesel production
The average acid value of the extracted M. peregrina seed oil was
found (0.68 mg KOH/g). It was, early, reported that the acid value
below 1.0 mg KOH/g oil, render the conversion of the vegetable
oil to biodiesel feasible by a one step base-catalyzed transesterication reaction without signicant mass loss due to saponication
[21]. The reaction was carried out in a batch reactor, which consists
of a glass jacket reactor (2 L) equipped with condenser and water
bath to control the temperature. 0.600 L of the oil were placed in
the reactor and warmed to 60 C. Simultaneously, fresh methanolic
potassium hydroxide was prepared by mixing 5.267 g potassium
hydroxide in 0.150 L pure methanol. The resultant solution was
poured into the reactor after the temperature established at
60 C. The amounts of the components of the reaction mixture
were chosen to afford 6:1 methanol/oil molar ratio and 1% (w/w)
of oil catalyst. The reaction was allowed to run under continuous
stirring for two hours. At the end, the reaction mixture was transferred to a separated funnel where two distinct layers were formed
by standing (12 h). The lower layer contained glycerol and the
upper layer contained the methyl ester of the oil. The lower layer
was drained and the layer of the biodiesel was washed gently with
warm water until the drained washing became neutral, to remove
the soaps, methanol, residual glycerol and the other impurities.
The residual methanol and water were removed by the means of
a rotary evaporator. Finally, the biodiesel was further dried with
sodium sulfate anhydrous to remove the traces of water.
2.4. Infrared spectroscopy
The conversion of the vegetable oil to biodiesel was investigated
by Fourier transform infrared spectroscopy (FTIR). Bruker tensor 27
FT-IR spectrophotometer (Germany), equipped with attenuated
total reectance (ATR) cell that has a ZnSe single crystal, was used
to obtain the IR spectra (absorbance mode) in the region 400
700 cm1 with 24 scans and 41 resolution.

2. Experimental

2.5. Ester content and fatty acid composition determination

2.1. Materials

Gas chromatography (GC Shimadzu 2010, Japan) was used to


analyze the fatty acid composition of the produced biodiesel. The
operating conditions are shown in Table 1. The retention times of
the methyl esters of the sample were compared to those of the
standard FAMEs. Quantity of each component was calculated from
the relative peak area and considered as a percentage by mass. The
ester content in the sample of biodiesel was determined according
to the EN14103 method [22], using methyl heptadecanoate as an
internal standard. All the values are reported as a mean of duplicate determination.

M. peregrina seeds were purchased from the Forest National


Corporation of the River Nile State in Sudan. The seeds were
cleaned to remove damaged seeds, sand, stones, wood and any
other foreign materials. The cleaned seeds were packed in plastic
bags and stored in a cold room until extraction. Diesel No. 2 was
purchased from a local petroleum station in Kuala Lumpur in
Malaysia, near University of Malaya. Pure analytical standards of
fatty acid methyl esters (FAME), a mixture of (C4C24) and pure
methyl heptadecanoate were purchased from SigmaAldrich
(Malaysia). All other reagent, like n-hexane 95%, sodium sulfate
anhydrous, potassium hydroxide, phenolphthalein indicator, ethanol 95%, and methanol 99.9%, were analytical grade and were purchased from Merck (Malaysia). All reagents and standards were
used as received without any further drying or purication.

2.6. Biodieseldiesel blending


Biodieseldiesel blends were prepared at ambient temperature
in glass bottles and homogenized by agitation (2000 rpm) for
30 min. Six blends (5%, 10%, 20%, 40%, 60% and 80% v/v) were

537

M. Salaheldeen et al. / Energy Conversion and Management 92 (2015) 535542

pure nitrogen at a ow rate of 100 ml/min. The obtained data were


analyzed using the universal analysis 2000 software.

Table 1
GC conditions for determination of fatty acid composition.
Property

Specication

Injector
Column
Gas currier

Split 1:50 at 240 C and 1 lL injection volume


BPX70 (30  0.32 mm ID and 0.25 mm lm thickness)
Hydrogen 64.4 K Pa, total rate ow 59.9 ml/min and
column ow is 1.1 ml/min
FID at 260 C
140 C hold 2 min, 8 C to 165
3 C/min to 192
8 C/min to 220 holding 12 min

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]:

CN 46:3 5458=SN  0:225  IV


X 560  Ai  D
IV
MWi
X 254  D  Ai
SN
MWi

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

3. Results and discussion


3.1. Crude oil properties
Extraction process revealed that M. Peregrina seed had an oil
content 26% of dry base from the whole seed. The extracted oil
had very low free fatty acid content (0.34%), equivalent to
0.68 mg KOH/g oil, eliminating the need of acid pretreatment step
as explained in the experimental part (2.3). Table 3 shows some
properties of crude M. peregrina seed oil in comparison to some
common edible and non-edible vegetable oils [13] for biodiesel
production. The kinematic viscosity of crude M. peregrina seed oil
at 40 C was found 36.181 mm2/s, which is 11 times higher than
the viscosity of diesel fuel (3.1135 mm2/s) as reported in Table 5.
Moreover, crude M. peregrina seed oil was found to have high ash
point (268.5 C). Flash point is inversely proportional to the volatility of the vegetable oils [26]. Therefore, the transesterication
reaction is necessary to improve the viscosity and volatility of
crude M. peregrina seed oil.
3.2. Infrared spectra of M. peregrina seed oil and its biodiesel
The conversion of crude M. peregrina seed oil to methyl ester
and the purity of the produced biodiesel were examined by the
FTIR spectroscopy. Fig. 1 displays the FTIR spectra of the crude M.
peregrina seed oil and its methyl ester. A comparison between
the two spectra in the region of 15001000 cm1, showed a significant differences, which are attributed to the replacement of
CH2OA group in the triglyceride by the CH3OA group in the methyl
ester. A new peak, which does not exist in the spectra of the oil,
appeared in the spectra of the methyl ester at 1435.58 cm1 due
to the deformation vibration of the methoxy group (CH3OA). This
peak represents a direct indicator for the conversion of the oil to
methyl ester [27,28]. Another, signicant, difference was observed
in the range 13001060 cm1 as a result of the esteric bond (CO)
stretching vibration. In this range, the crude oil showed strong
broad peak at 1159.63 cm1 due to the absorbance of the triple
ester group in the triglycerides [28]. Whereas, the methyl ester
showed two peaks at 1195.64 cm1 and 1169.30 cm1. The new
peak at 1195.64 cm1 is explained by the presence of the methyl
group near the carbonyl group. The peak at 1244.47 in the spectrum of the methyl ester is assigned to the asymmetrical stretching
of the group COC. The same group is noticed at 1236.47 cm1 in
the oil spectrum [29]. The absence of broad peak in the region
25003300 cm1 indicates the very low concentrations of impurities that contain hydroxyl groups such as water, methanol free
glycerol and free fatty acids [30]. Moreover, no peak was observed
in the region 16501540 cm1 indicating the absence of soap in the

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

Cloud point (CP)

Cloud and pour point tester automatic NTE 450

Normalab, France

D 2500

Pour point (PP)

Cloud and pour point tester automatic NTE 450

Normalab, France

D97

Cold lter plugging point (CFPP)

Cold lter plugging point automatic NTL 450

Normalab, France

D 6371

Oxidative stability (OS)

873 Rancimat automatic

Metrohm, Switzerland

EN 14112

538

M. Salaheldeen et al. / Energy Conversion and Management 92 (2015) 535542

Table 3
Physical properties of crude M. peregrina seed oil in comparison to some other oils.
Property
2

Kinematic viscosity at 40 C (mm /s)


Kinematic viscosity at 100 C (mm2/s)
Viscosity index (VI)
Density (kg/m3)
Flash point (C)
Caloric value (MJ/kg)
Oxidative stability (h)

M. peregrina this study

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.

M. Salaheldeen et al. / Energy Conversion and Management 92 (2015) 535542

monounsaturated fatty esters are capable to balance between the


different fuel characteristics [32]. Therefore, Moringa seed oil is a
promising feedstock to produce biodiesel fuel with high quality.
3.4. Fuel properties of M. peregrina biodiesel
The major fuel properties of M. peregrina methyl ester were
determined and compared to the diesel fuel. These results are
included in Table 5.
Acid value was reduced to very low concentration
(0.11 mg KOH/g) satisfying the ASTM standard maximum limits
(0.5 mg KOH/g).
Kinematic viscosity is related directly to the resistance of uids
to ow. Thus, it is an important property to determine the efciency of a biodiesel as a fuel. High viscosity will reduce the quality
of the liquid fuel due to poor atomization, tubing blockage and possible deposits formation in the engine causing incomplete combustion and severe fouling. As viscosity varies inversely with
temperature all these drawbacks increase at low temperature, so
fuels with high viscosities are not suitable for cold regions [33].
The effect of temperature change on the viscosity is indicated by
the viscosity index, which is an arbitrary number that can be calculated from the viscosities at 40 and 100 C according to the ASTM D
2270-4 method. The effect of temperature change on the viscosity
is minor for fuels that have high viscosity index [34]. Kinematic
viscosity of M. peregrina methyl ester, for this study, was found
4.7658 mm2/s at 40 C, signicantly lower than the Kinematic viscosity of the apparent vegetable oil (36.181 mm2/s), indicating that
the transesterication reaction was efcient at the prescribed conditions. This value falls in the range specied by ASTM standards
(1.96.0 mm2/s) and similar to the values obtained for biodiesel
fuels derived from M. oleifera (4.83 mm2/s) [11], M. stenopetala
(4.58 mm2/s) [14], J. curcas (4.723 mm2/s), palm (4.6889 mm2/s),
soybean (4.3745 mm2/s) and canola (4.5281) [13]. However, kinematic viscosity of M. peregrina methyl ester is still higher by 53.07%
than the diesel fuel (3.1135 mm2/s). M. peregrina methyl ester has,
a relatively, high viscosity index (200.3) and falls in the range that
was observed for the methyl esters of Jatropha, palm and M. oleifera (194207) and lower than the viscosity index of biodiesel that
were derived from canola (236.9) and soybean oils (257.8) [13].
The density of M. peregrina methyl ester at 15 C was found
(876.2 kg/m3), slightly greater than the density of the diesel fuel
(5%). Although the density of a fuel has less signicant effect on
the engine performance compared to the viscosity [35] the, relatively, higher density of biodiesel compared to diesel fuel will
increase the fuel consumption and consequently NOx emissions

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

3.5. Fuel properties of biodieseldiesel blends

0.5 max
1.96.0

880

47 min
120 min

3 min

As mentioned above, biodiesel investigated in this study was


observed with higher viscosity, density and lower volatility and
heating value compared to the diesel fuel. Blending biodiesel with
diesel fuel is benecial from two points of view, to improve the fuel
properties of the biodiesel and to reduce the environmental pollution [40]. Six blends were prepared (5% (B5), 10% (B10), 20% (B20),
40% (B40), 60% B60) and 80% (B80) v/v) and were examined for
their physical properties compared to diesel fuel. The effect of diesel fuel on the fuel properties of the biodiesel is depicted in
Fig. 2(ae). As expected the fuel properties of the M. peregrina
methyl ester were enhanced signicantly as the fraction of the diesel fuel increased in the blends. From Fig. 2(a), the blends of B5,

540

M. Salaheldeen et al. / Energy Conversion and Management 92 (2015) 535542

B10, and B20 showed kinematic viscosities (3.173, 3.237,


3.371 mm2/cm, respectively) very close to the diesel fuel
(3.113 mm2/s). Fig. 2(b) shows, remarkable, reduction in the density of the biodiesel on increasing the ratio of the blends. The densities of B5, B10 and B20 (836.4, 838.4, 842.7 kg/m3, respectively)
were so close to the density of the diesel fuel (836.4 kg/m3). As
illustrated in Fig. 2(c), the caloric value of the biodiesel was
increased, substantially, by increasing the diesel fuel proportion
in the blend due to the reduction of the oxygen content [41]. The
caloric values of B5, B10, B20 were (45.392, 45.110 and
44.517 MJ/kg, respectively) very close to the diesel fuel
(45.685 MJ/kg). As shown in the Fig. 2(d) signicant reduction in
the ash point of the M. peregrina methyl ester was observed even
by a small proportion diesel fuel. Moreover, B5, B10, B20 had ash
points in the range 7881 C so close to the ash point of the diesel
(77.5 C). Fuels with ash points higher than 66 C are believed to
be safe regarding hazardous ammability [41]. From Fig. 2(e) it
was, very, clear that the blending did not improve the cold ow
properties of M. peregrina methyl ester as the diesel fuel itself
had a high cloud point, pour point and cold lter plugging point.

3.6. Thermal stability of the biodiesel and the blends


The ignition quality of a fuel, basically, is affected by the thermal characteristics of the fuel [42]. TGA can be used to predict
the behavior of the fuel as the initial temperature of volatilization
can be obtained from the onset temperature (Tonset) [43]. The intercept of extrapolated horizontal line at 1% volatilization with the
tangent of the downward part of the weight curve was taken as
the Tonset [44]. Fig. 3 depicts the TGA/DGT of the M. peregrina
methyl ester whereas Table 6 shows the onset temperature and

offset temperature of the volatilization for the crude oil, biodiesel


and the blends.
From Fig. 3 it can be seen that M. peregrina methyl ester was
stable until the temperature 125 C as another evidence for the
complete removal of moisture and methanol during the purication process. The onset temperature of volatilization was observed
at 193.36 C which is very close to the boiling point of methyl
oleate (190 C) [45], the main component of M. peregrina methyl
ester as mentioned above. From the DTG curve, M. peregrina
methyl ester showed a single step of volatilization in a very narrow
range of temperature (193.36231.14 C) with a maximum rate of
mass loss (24.84.53%/min) at 220.84 C. During this stage, 97.83%
of mass loss was observed due to volatilization of M. peregrina
methyl ester. This amount of mass loss is comparable to the ester
content (97.79%) that was determined by the GC analysis.
According to Table 6, crude M. peregrina seed oil had a high
onset volatilization temperature of 374.69 C. The onset of volatilization of the crude M. peregrina seed oil was, drastically, reduced
to 193.36 C by the transesterication reaction. However, the volatility of M. peregrina methyl ester still considered low compared to
the diesel fuel. Referring again to Table 6 it can be seen that the
volatility of the biodiesel was improved, signicantly, as the fraction of diesel fuel increased in the blends. Among the blends, B5,
B10, and B20 showed volatilization behavior similar to the diesel
fuel.
From TGA analysis we can conclude that the pure methyl ester
of M. peregrina has low volatility compared to the diesel fuel, however, M. peregrina methyl ester is a promising, alternative, fuel in
term of engine performance as it showed spontaneous single step
of decomposition. The multiple step of burning usually, indicated
by more than one step of volatilization in the DTG curve, may cause
operational troubles in the engine [46].

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

Flash point (C)

Calorific value (MJ/kg)

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.

M. Salaheldeen et al. / Energy Conversion and Management 92 (2015) 535542

541

Fig. 3. TGA and DTG curves of M. peregrina methyl ester.

Sudan Higher Education Ministry are gratefully acknowledged for


allocating scholarship for the rst author.

Table 6
Volatilization temperatures from TGA analysis.

Fuel

On set temperature Ton (C)

Offset temperature Toff (C)

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

Crude M. peregrina seed oil.

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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