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J Therm Anal Calorim (2011) 106:831836

DOI 10.1007/s10973-011-1861-6

Use of thermal analysis techniques for evaluation of the stability


and chemical properties of papaya biodiesel (Carica Papaya L.)
at low temperatures
M. L. S. De Melo N. A. Santos R. Rosenhaim
A. G. Souza P. F. Athayde Filho

CBRATEC7 Conference Special Issue


Akademiai Kiado, Budapest, Hungary 2011

Abstract Biodiesel has the advantage of being renewable


and clean and for these reasons has been studied recently
both academically and in industry. Research in this area is
focused on developing new synthetic routes to obtain a
purer product or to find new alternative sources of food to
replace conventional oils. Papaya biodiesel is obtained
from oily residues with a fatty acid composition similar to
olive oil. It is generally discarded by the ton, considering
that Brazil is the worlds largest producer of papaya with
an annual output of 1,811 million tons, productivity of 52 t/
hectare and domestic consumption at 86.5%. This study
was designed by means of thermal analysis (TG, DSC,
P-DSC, and MT-DSC), to verify the possibility of
achieving high quality biodiesel, with oxidative stability
and flow properties previously indicated by composition
analysis of its fatty esters, physicalchemical properties
(including oxidative stability) using classical methodology,
recommended by ASTM D 6756.
Keywords

Papaya biodiesel  TMDSC  PDSC

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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832

tallow (beef), and canola oil. The wide availability of these


raw materials, despite the disadvantage of high BP, has led
scientists and engineers to investigate new methods to
improve their physicochemical characteristics [5, 6]. The
addition of unsaturated chains, for example, eases the possibility of gelling or solidification of biodiesel and therefore
the PC and CFPP become acceptable in cold climates. [3].
The content of unsaturated fatty acids from biodiesel determined by the iodine value is limited to 120 g I2/100 g oil for
vehicular use and 130 g I2/100 g for heating oil, according to
European specifications. As a result, the standard EN 14214,
the levels of linolenic acid are limited to a maximum of 12%
and polyunsaturates (with more than four double bonds) to a
maximum of 1%, which limits the use of certain raw materials for the production of biodiesel with the required quality
because the high content of unsaturated fatty acids reduces
oxidation stability [5]. The fatty acid composition of papaya
oil contains (70%) oleic acid (C18: 1), only 4% of linoleic
acid (C18: 2) diunsaturated, and 20% saturated fatty acids,
palmitic acid (C16: 0) and stearic (C18: 0) with respective
levels of 17 and 5% being the highest in content for their class
[5]. This composition meets the recommendations of ASTM
6751 D as a raw material suitable for obtaining a good quality
biodiesel, because it presents the proper proportions of fatty
acids content, both for cold flow properties or for oxidative
stability. In order to ratify these properties, evaluation of
oxidative stability and flow properties of papaya biodiesel
was employed using the normalized techniques and thermal
analysis of TG, DSC, and MT-DSC P-DSC.

M. L. S. De Melo et al.

Identification of the fatty acid composition


The identification of fatty acid profiles for papaya oil was
done using the methyl esters of the biodiesel produced in
the transesterification reaction and was performed by gas
chromatography coupled to a mass spectrometer GCMS
Model QP 2010, Shimadzu, Durabond capillary column
with stationary phase DB-5HT (30 m length, 0.319 mm
internal diameter, and 0.1-lm thick film with a temperature
range of -60 to 400 C). A 1 lL sample was injected with
the injector temperature at 290 C in split mode 1:50. The
initial column temperature was 130 C, heating rate of 2, 1,
5, and 20 C min-1, respectively, at temperatures of 170,
187, 240, and 300 C. The soaking time was 1 min for
temperatures of 130, 170, and 187 C and 2 min at temperatures of 240 and 300 C.
Physico-chemical properties of biodiesel

The seeds were obtained from Golden papaya, the Solo


group, produced at Fazenda Santa Teresa Ranch,
located on the BR-101 km, Mamanguape municipality, of
the state of Paraiba, Brazil.

The indices of acidity, saponification, and iodine were


determined according to the methodology described by the
Institute Adolfo Lutz sectionlipids [7].
The specific mass was in accordance with ASTM D
4052 using a digital densimeter DA-110 manufactured by
Mettler Toledo.
Kinematic viscosity was determined according to
ASTM D 445 with a bath viscometer (Julabo model TE
18 V) at 40 C.
The CFPP was determined according to ASTM D 6371
with equipment model AFP-102 Tanaka.
The CP and pour point were determined, respectively,
according to the rules ASTMD 2500 and ASTM D 1997
with equipment MPC-102L Tanaka.
The CI was calculated by relating the rates of saponification (NS) and iodine (NI) according to the equation:
46.3 ? (5458/NS) 0225 9 NI [8, 9], whereas the CI
increases with lengthening chain esters methyl and
decreases with increasing the number of insaturations and/
or branches in the carbon chain.

Oil extraction and determination of lipid content

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

Materials and methods


Collection of the seeds

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

Evaluation of the stability and chemical properties of papaya biodiesel

at 110 mL min-1, heating and cooling rates of 5 C min-1


in the temperature range from 25 to -50 C and -50 to
45 C with temperature modulation of 1 C min-1 and a
sample mass of about 10 mg.
PDSC curves were obtained using a differential scanning
calorimeter coupled to a pressure cell, TA Instruments Q1000
DSC, using both non-isothermal and isothermal analysis
conditions. The non-isothermal analysis was processed using
a platinum crucible with about 10 mg of sample in an atmosphere of oxygen, with pressure of 1400 kPa, and a heating
rate of 10 C in the temperature range of 25600 C. Isothermal analysis was performed at a temperature of 105 C.
The value of oxidation induction time was determined by the
difference in onset time and initial time (the time in which the
sample reached the isothermal temperature).

Results and discussion


Yield of oil
The oil content shows a good yield of 28.0 2.0 g/100 g
of seeds.
Composition in fatty acids
The fatty acid composition of methyl esters (Table 1) was
qualitatively the same as described in the literature by [10]
but differentiated by the data presented [11]. Quantitatively, the content of saturated fatty acids 23% was
slightly higher than that reported by [10, 11], respectively,
21.6 and 19.4%. The major fatty acids were palmitic acid
and stearic, with values, respectively, of 18.9 and 5.2%.
The palmitic acid content was much greater than described
by [11] (13.9%), but close to that reported by [8] (17.1%).
With regard to unsaturated fatty acids oleic acid, monounsaturated showed a high content of 69.8% (Table 1).
The content of saturated fatty acids and low content of
polyunsaturated fatty acids give papaya biodiesel an iodine
value of (65.9) (Table 2), a figure far lower than the
Table 1 Fatty acid composition of papaya biodiesel
Methyl esters

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

biodiesels of soybean, corn, canola, and sunflower seeds,


respectively, 138.7, 120.3, 103.8, and 151.9 according to
[11] and indicating greater oxidative stability in comparison. The methyl esters demonstrated a mist point of 1.0 C
and fluid point of -1.0 C, values considered to be very
good for biodiesel use nationwide, however, these values
can be improved by reducing the saturated fatty acids using
a winterization process [12]. In this process, the biodiesel is
cooled slowly and the saturated esters with high melting
point (crystallize at higher temperatures) and are separated
by centrifugation, a fact well evidenced when using the
technique described by TMDSC [12] to study the flux
properties of winterized Babassu.
Kinematic viscosity at 40 C was 6.0 mm2 s-1. This
result is in agreement with the individual values of viscosity for the principal and majority esters, methyl oleate,
methyl palmitate, and methyl stearate, respectively, 4.5,
4.4, and 5.9 mm2 s-1, being within the range determined
by ASTM D 6751 which prescribes values between 1.9 and
6.0 mm2 s-1). However, this result is slightly above the
maximum allowed by EN 14214 (5.0 mm2 s-1).
The cetane number of papaya biodiesel (62.8) calculated
with the experimental rates of saponification and iodine
number of the biodiesel in question shows the high power
ignition of this biofuel.
Thermo-oxidative stability
The thermo-oxidative stability was determined by the
Rancimat method specified by ASTM D 6751 and EN14214,
and by thermogravimetry (TG), differential scanning calorimetry (DSC), pressure differential scanning calorimetry
(PDSC) and the properties at low temperatures were evaluated by modulated differential scanning calorimetry (MTDSC). The results are shown and discussed below.
Rancimat test
In this study, we observed that the induction time for
methyl papaya biodiesel was over 25 h and during this time

123

834

M. L. S. De Melo et al.

Electrical conductivity/S cm

200

160

Methyl papaya biodiesel


120

80

40

0
0

10

15

20

25

30

Time/h

Fig. 1 Induction time by Rancimat method

there was no sudden change in electrical conductivity to


200 lS cm-1 as indicated in the standard. The results
showed marked oxidative stability considering that the
induction time obtained exceeded by four times the recommended limit minimum of 6 hEN 14214 (Fig. 1).
Thermal analysis
The thermogravimetric behavior of methyl biodiesel
(Fig. 2a) in a synthetic air atmosphere at a heating rate of
10 C min-1 showed only one significant thermal event in
the interval between 155.4 and 279.1 C, a mass loss of
95.4% compared to the initial mass, which was attributed
to volatilization, especially the methyl ester oleate majority
whose boiling point is 218.5 C.
The calorimetric analysis of the DSC curve of methyl
papaya biodiesel (Fig. 2b) showed an endothermic transition in the range 155270 C in TG corresponding to a
mass loss of 95% primarily related to the volatilization of
the methyl oleate, ester majority. After this endothermic
transition occurred, there were three exothermic transitions: one between 300 and 400 C with a peak at 350 C,
the second between 450 and 500 C with a peak at 460 C,
Fig. 2 a TG curve and b DSC
curve

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

123

Exo

Heat flow/mW

Mass loss/%

80

(b)

500

600

100

200

300

400

Temperature/C

500

600

Evaluation of the stability and chemical properties of papaya biodiesel


500

(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

100 200 300 400 500 600 700

0.25

100

Temperature/C

Table 3 Oxidative stability of biodiesel from papaya and other raw


materials
Biodiesel

Rancimat/h

P-DSC

[25

Papaya

200

300

400

500

600

Time/h

Table 4 Cold flow properties


Biodiesel methyl

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]

difficulting the accommodation of saturated organization.


All this being unlike biodiesel from tallow, which has flow
properties not recommended for use in pure form (B100)
due to its high content of saturated methyl esters, resulting
in high CP, PP, and CFPP.

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

Fig. 4 Curva de MT-DSC do biodiesel

result agrees with the freezing point of pure methyl oleate


(-40.6 0.26) [13] and demonstrates the superiority of
this ester content in relation to the saturated components.
The heating curve showed the same events with the shift of
peak temperatures to higher temperatures.
Table 4 shows the crystallization temperature and the mist
point values (CP), pour point (PP), and CFPP of biodiesel from
papaya and other biodiesels for comparison purposes.
Papaya Biodiesel showed excellent cold flow properties,
just 1 C above the values reported for methyl soybean
biodiesel [14, 15]. The results in relation to soy biodiesel
reveal that the mixture that determines the crystallization
temperature is the majority methyl esters [13]. In this case,
the unsaturated methyl esters inhibit crystallization by

The fatty acid composition of papaya oil revealed that it


has carbon chains from C14 to C20, high content of C18: 1
(69.9%), 24.1% long chain saturated fatty acids (C16 and
C18) and therefore is within the norms established by
ASTM, predicting a biodiesel with high power ignition,
low flow properties, and accentuated oxidative stability in
its purest form (B100).
The Rancimat test, standardized method, and P-DSC
technique showed high oxidative stability for biodiesel
from papaya.
The analysis of flow properties by MT-DSC is consistent
with the standard methods (CP, PP, and CFPP), indicating
the possibility of using papaya biodiesel in its pure form
(B100).
The thermal analysis techniques were very precise,
useful, and quick to reveal the thermo-oxidation events for
papaya biodiesel confirming predictions of low flow
properties, and pronounced oxidative stability.

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