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DOI 10.1007/s10973-011-1861-6
M. L. S. De Melo (&)
LQF-DCFCCS, Universidade Federal da Paraba,
Campus I, Joao Pessoa, PB 58059-900, Brazil
e-mail: ladjanesodre@hotmail.com
M. L. S. De Melo P. F. Athayde Filho
LPBS-DQ-CCEN, Universidade Federal da Paraba,
Campus I, Joao Pessoa, PB 58059-900, Brazil
N. A. Santos A. G. Souza
LACOM-DQ-CCEN, Universidade Federal da Paraba,
Campus I, Joao Pessoa, PB 58059-900, Brazil
R. Rosenhaim
DEQ-CT, Universidade Federal da Paraba, Campus I,
Joao Pessoa, PB 58059-900, Brazil
Introduction
Recently, biodiesel has become the national alternative to
replace petroleum diesel and the need for rapid and
effective studies for quality control of this new biofuel
derived from several raw materials requires fast and
accurate analytical processes and techniques which highlights P-DSC and MT-DSC studies for oxidative stability
[1] and cold flow [24]. A preliminary observation of the
fatty acid composition of the raw material allows the prediction of both the physicalchemical properties and
thermo-oxidative stability of biodiesel derived. Following
ASTM PS 121-99, biodiesel must be composed of esters
with hydrocarbon chains from 12 to 22 carbons. Besides
the qualitative composition, it is important that the content
of saturated and unsaturated fatty acids leading to a biodiesel that meets the specifications of ASTM 6751 [5].
Monoalkyl esters with saturated hydrocarbon chains above
C20 and C16 chain saturated (palmitic acid) and C18
(stearic acid) have a greater tendency to become solid at
low temperature than the chains of up to 18 carbons with
one or more insaturations and therefore can make biodiesel
inappropriate for use in cold climates. This property is
measured by cloud point (CP), but the cold filter plugging
point (CFPP) is most often used to represent the behavior
of the fuel inside the engine [5]. Saturated chains, in contrast, have the advantage presenting greater resistance to
auto oxidation, i.e., oxidation stability parameters are met
more easily than in cases of massive presence of unsaturated or poly-unsaturated chains.
The high value of CP does not eliminate the possibility of
using the esters derived from oils with saturated chains (C16
and C18) for biodiesel production, but limits its use in pure
form or in blends higher than B20 for only tropical climates.
Examples are biodiesels from African palm (palm oil),
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M. L. S. De Melo et al.
Thermal analysis
The oil was extracted from dry seeds until residual moisture of about 8% in a Soxhlet system with n-hexane as a
solvent extractor. The percentage of lipid content was
determined by gravimetric calculation methodology
according to the Institute Adolfo Lutz [7].
The TG/DTG and DSC analyses were performed in nonisothermal conditions in a thermal analyzer TA Instruments, models SDT 2960 and DSC-2920, respectively,
atmosphere (air) with a flow of 110 mL min-1, heating
ratio of 10 C min-1, a temperature range of 25600 C,
and sample mass around 10 mg.
The differential scanning calorimetry curve with temperature modulation was obtained in non-isothermal conditions in a thermal analyzer, TA Instruments, DSC 2920,
coupled with a liquid nitrogen generation module, TA
Instruments, RCS 1144, in nitrogen atmosphere with flow
Synthesis of biodiesel
Methyl biodiesel was obtained by alkaline transesterification with 0.5% sodium methoxide, molar ratio, oil:methanol (1:8) at 45 C for half an hour.
123
Golden/%
Retention time/min
C(14:0)
0.2
C(16:0)
18.9
13
C(16:1)
0.3
12
C(18:0)
5.2
21
C(18:1)
69.8
20
C(18:2)
4.8
19
C(20:0)
0.4
30
C(20:1)
0.4
29
833
Table 2 Physical chemical properties of papaya biodiesel
Parameters
Biodiesel
Standard-ASTM D 6751
Density
880/kg/m3
850900/kg/m3
Viscosity
6.0/mm /s
1.96.0/mm2/s
Acid value
0.35/mg KOH/g
0.5/mg KOH/g
Iodine
65.9
Note
Saponification
174
NE
Cetane
62.83
47 min
Cloud point
Note
Pour point
-1
Note
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834
M. L. S. De Melo et al.
Electrical conductivity/S cm
200
160
80
40
0
0
10
15
20
25
30
Time/h
and last one between 500 and 600 C. Exothermic transitions at temperatures above 400 C are associated with
thermo-oxidative decomposition of biodiesel (Fig. 2b).
The initial biodiesel oxidation temperature (OT) analyzed by PDSC curve (Fig. 3a) was 155 C, and was
probably the first stage of oxidation (initiation). The OT
occurred around 200 C, where there was a first exothermic
transition attributed to the propagation step of the oxidation
process, and afterward two other exothermic peaks at 225
and 250 C. The combustion process of less stable polymers formed during the oxidation process, followed by the
combustion of stable polymers in the range 300400 C,
was observed.
The isothermal PDSC curve (Fig. 3b) indicated prolonged oxidative stability, above 10 h, justified by the high
content of esters monounsaturated (70.5%) consisting of
69.8% methyl oleate and 4.8% of polyunsaturated (methyl
linoleate) confirming the high oxidative stability, previously inferred by its intrinsic composition.
Table 3 below illustrates the results of the stability of
biodiesel compared to other papaya biodiesels.
For Table 1, note that the Rancimat test showed that
papaya biodiesel has prolonged oxidative stability when
compared to soy biodiesel, which has a high content of
polyunsaturates (61%) while papaya biodiesel is predominantly monounsaturated, rich in oleic acid (69.8%),
and presenting a saturated content of 24.1% vs. 15%
reported for soy biodiesel. However, when compared with
biodiesel from babassu, we observe that because of
babassus dominant content in saturated esters 84%, the
OIT is greater than 20 h using the P-DSC technique.
Cold flow properties
Analysis of MT-DSC curve of cooling (Fig. 4) reveals that
the solidification process (exothermic) occurred in two
events. The first event at crystallization temperature of
-1.5 C is related to saturated esters, the second event is
more intense and narrower, characteristic of purity showed
a peak of -42 C for the unsaturated esters, especially for
oleate methyl, indicating the total freezing of the fluid. This
(a)
6
4
2
0
2
4
6
8
10
12
100
60
40
20
0
0
100
200
300
400
Temperature/C
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Exo
Heat flow/mW
Mass loss/%
80
(b)
500
600
100
200
300
400
Temperature/C
500
600
(a)
(b)
1.75
Exo
Heat flow/W g
Heat flow/mW
400
2.00
1
Fig. 3 a Non-isothermal
P-DSC curve and b isothermal
P-DSC curve
835
300
200
100
Exo
1.50
1.25
1.00
0.75
0.50
0.25
0.00
0
0
0.25
100
Temperature/C
Rancimat/h
P-DSC
[25
Papaya
200
300
400
500
600
Time/h
Tc/C
CP/C
PP/C
CFPP/C
Papaya
-1.5
-1
-4
OT/C
OIT/min
Soy
-3.5 [4]
0 [14]
-2 [14]
-5 [16]
155
54
Sebo
Babassu
4.2 [4]
-4 [12]
17 [14]
15 [14]
9 [14]
-4 [12]
Soy
4.4 [16]
146 [16]
25 [16]
Babassu
180 [12]
[1200 [12]
20
Cooling
15
Tpico = 8
Heat flow/mW
10
Conclusions
Tonset = 1.5
0
5
Heating
10
(C)
Exo
15
60
40
20
20
40
Temperature/C
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