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HEFAT2014

10th International Conference on Heat Transfer, Fluid Mechanics and Thermodynamics


14 16 July 2014
Orlando, Florida

METHODOLOGICAL EVALUATION OF BIODIESEL PRODUCTION AND STORAGE


CONDITIONS FROM FRIED POTATOES COOKING RESIDUAL OILS
Jimnez H.*1, Barreda M.1, and Figueiredo E.2
*Author for correspondence
1
Institute of Energy and Environment,
San Pablo Catholic University,
Campia Paisajista, Quinta Vivanco,
Arequipa, Peru
2
National Institute of Technology,
Venezuela Avenue, 82,
Rio de Janeiro, Brazil,
E-mail: hjimenez@ucsp.edu.pe

ABSTRACT
Biodiesel is composed by mono-alkyl esters, derived from
renewable sources such as vegetable oils or animal fats,
obtained by the transesterification process in which performs
the conversion from triglycerides to smaller molecules of fatty
acid , that are, esters of fatty acids.
A critical point in the production and storage of biodiesel is
the susceptibility to degradation when its exposed at
atmospheric ambient. One disadvantage of this fuel is its high
capacity to absorb moisture from the ambient, causing a
degradation process and alterations in the specifications
required for use. Studies show that biodiesel has thirty times the
hygroscopicity of the common diesel because biodiesel has
different ranges of acidity, which are very susceptible to
oxidation.
The degradation process of biodiesel includes intrinsically
corrosive molecules, process of hydrolysis and oxidation that is
why the applicability of techniques to get improved control and
monitoring of biodiesels degradation stages is investigated.
The temperature and relative humidity during storage determine
the stability and preservation of the product in different periods.
Degradation characteristics are attributed to the presence of
carbon chains with multiple unsaturations and unstable
particularly structures, causing deficiencies in the engine
performance.
The biodiesel was produced using waste oil from cooking of
fried potatoes, with a transesterification methodology with
ethanol in a basic medium and under the following rules,
Peruvian Technical Norm for Biodiesel (NTP 321.125-2008),
Resolution ANP N 7, de 19.3.2008 DOU 20.3.2008, and
European Standards. We obtain a 70% yield for a 2:1 ratio with
a method for suppressing the presence of starch, acceptable
results on stability, and 5.71 h, 4.818 mm2/s, and 0.256 KOH/g
as values for oxidation periods (OEI).

Physicochemical
characteristics
quantitatively
and
qualitatively are analyzed periodically in extreme conditions for
pure biodiesel, B50 and B20 blends, to realize a comparative
with commercial diesel S500 as reference. We obtain the
following results out of specifications for pure biodiesel, 1850
mg/kg for water presence, 5.52 mm2/s and a significant
elevation of acidity to 0.71 mgKOH/g; for B50 resulted an
acidity value out of specification with 0.58mgKOH/g, 1.92h
from degradation stability analysis and 1100mg/kg for water
presence; and for B20 we have 730.70 mg/kg, that also is out of
specification for water presence.
We concluded that exposure to temperature conditions and
moisture presence affects directly the degradation and
variability in the physicochemical properties of B100 and its
blends with common diesel; by observing stability for B20 and
its behavior, we suggest suitable thermal and moisture control
systems for long storage periods.

INTRODUCTION
The terms of traditional energy in current decades are very
controversial due to many limitations and mainly by high
contents of contamination; Traditional energy sources have
become very controversial in current decades due to several
limitations and its high rates of contamination. which drives it
leads us to seek alternative energy sources. Therefore, biodiesel
obtained from waste oil introduces a possibility makes possible
to reuse and obtain potential energy sources with low costs and
especially friendly to the environment [1].?
In Europe, projects for the production of biodiesel of
biodiesel obtention from waste oils stand out, particularly those
used by various food companies. In South America, there are
countries that several countries lead the production of biodiesel
like Brazil and Argentina. The obtained biodiesel is mixed up
added with diesel to be used in public transport vehicles.
Research Institute of Engineering (COPPE), Federal University

of Rio de Janeiro (UFRJ) and the government are experiencing


testing the development of biodiesel in a bus. the use of
biodiesel in an omnibus test. They are having good results. It is
dabbling in the Brazilian government level using biodiesel
obtained from waste oils being used for motor vehicles [2].?
Brazilian government is testing residual biodiesel
performance on vehicle motors.
Are performed Previous studies show that of
physicochemical properties of biodiesel production resulting
from waste residual cooking oil using applying the reaction of
alcohol route reaction, where the mixture of these resulting
esters has are similar to physicochemical properties with Diesel
ones derived from petroleum. For that, it is analyzed some
Research considered indicators as viscosity, density, cetane
number, ignition point and concludeds that this biodiesel is in
the parameters specificated complies with the required
parameters [1]. This good quality biodiesel must be produced
with the specifications of each country. Each country has its
own specifications In the U.S. there is applies the ASTM
D6751 norm. In Brazil, the ANP agency is the regulatory
agency.
The main variables that affect the kinetics performance of
the transesterification reaction (directly by the quality of the
raw material) are catalyst ratio, molar ratio alcohol/oil and also
the operating conditions like temperature, pressure and
homogenization [3].
The quantity of humidity and fatty acids are parameters
which that determine the conditions needed for the vegetable
oil transesterification process from vegetable oil, so it is crucial
that don't be more than they dont exceed 0.5% (w/w). The
product obtained from the formation amount of saponification
occured by the presence of humidity decreases the reaction
performance. The saponification results in causes a viscosity
increase, reaction interference and consequently the separation
of glycerol.
Therefore, if the residual frying oil has a high degree of
fatty acid, it is necessary to carry out a pre-treatment, by
esterification using acids. These acids can be sulphuric acid,
phosphoric acid and others. In the processes of alkaline
methanol the most used are potassium hydroxide and/or sodium
hydroxide [4]. The transesterification is an equilibrium
reaction, and it requires an adequate molar ratio of excess
alcohol to obtain a direct reaction where obtains a maximum
conversion to a molar ratio of 6:1 with a 98% of yield, the
value of the molar ratio of alcohol/oil affects the separation of
glycerol, due to increased glycerin solubility, it causes the
reaction is reversed and low the yield of esters.
This produced biodiesel can be used pure or mixed with oil
of 500 ppm sulphur identified as commercial Diesel S500 in
any proportion. When in the mixture there is more diesel,
exists a quantity of sulphur that increase the material corrosion,
otherwise if there is more biodiesel, we obtain better lubricity
in operation of the engine.
A globally nomenclature was adopted to identify
appropriately the concentration of biodiesel in their different
mixtures with diesel as has been normalized by the ANP
agency. These mixtures are applied to the approval of resolution
ANP No. 42/2004, now repealed by resolution ANP No.
7,19.3.2008 - 20.3.2008 DOU, for different volumetric

proportions B20, B50 and B100 and B5, this last one not
requires any adaptation for motors.
Biodiesel has high hygroscopicity. Studies reveal that is
thirty times greater than the water absorbing capacity of the
common diesel. So in mixture with the natural tendency alters
diesel oxidation catalyst because sulphur. The presence of free
water brings degradative processes such as the presence of
corrosion of engine components and storage tanks. The
formation of deposited microorganisms can cause problems
with engine parts, wear injection systems and clogging of filters
and tubes [5].
Free water is also responsible for the establishment of a
third set of processes associated with the metabolic activity of
microorganisms (bacteria and fungus). It promotes biocorrosion
and sediment formation of biological origin or biodeposits [6].
Going deeper in biodiesel studies, we observe that despite it
was not an inherently corrosive molecules, his hygroscopicity
turns the mixture with biodiesel in a corrosive liquid for some
engine materials. This characteristic is analyzed by simulating
storage for different periods of aging. It lets find information
about the material behavior and its tendency to degrade over
time. This paper studies this biodiesel production obtained from
waste cooking oil and consequently it exposes an evaluation of
performance under extreme conditions during storage.

EXPERIMENTAL PART
Materials used in the production:
Process inputs: Ethanol, sodium hydroxide, waste oil from
cooking, and diesel.
Laboratory materials: Pear of Decantation for 500ml, beaker of
500ml, digital scale, Becquer of 500ml, thermo-magnetic
stirrer, heating stove, analog multimeter, thermometer and
temperature sensors.
Production equipment: Stainless steel tank AISI 306L of fifty
liters for the ethoxide obtainment, stainless steel reactor AISI
306L of one hundred liters for the esters obtainment and a
variable mechanical stirrer controlled by a speed reducer motor
for homogenization. For parameters measurement like
temperature and conductivity, we used thermocouples type K
(Chromel-Alumel), HP Agilent 34970 data acquisition
equipment and a computer to collect the data.
Biodiesel characterization equipment: Anton Paar density
analyzer, Ostwald viscometer, Karl Fischer coulometric titrator
ASTM D6304, analyzer of Oxidative Stability Index by
Rancimat method EN 14112, potentiometric titrator of acid
number ASTM 664.
Prior procedure of feedstock:
This part is divided into the pre-treatment for solids
separation and the main stage of biodiesel production.
Pre-treatment: Stage to prepare the waste frying oil and also to
separate solids by sieve filters. Consequently were filtered
present solids of 200, 150 and 50 microns of size. Then they
were treated with chemical solutions to precipitate the mineral
salts, proteins, phosphates and other components by the method
of hydration. So water is added (0.15 v/v) to avoid increasing
acidity. Was performed finally a drying to remove water present
in the solute at 110 C of temperature for 40 minutes preventing
the raw material degrade.
Biodiesel production:

This was initially made at the laboratory to determine


parameters of the production and necessary conditions, after
that, we proceed to produce in pilot-scale plant.
Laboratory scale: The reactants are processed with chemicals in
a Bcquer of 500 mL, separately the ethoxide was prepared for
the main reaction using potassium hydroxide solution in
ethanol according to the stoichiometry. A volume of 200mL of
residual oil was pre-treated and mixed in a 500 mL Bcquer by
a magnetic stirrer with heat induction. The system was heated
to 60C until complete the dissolution, after obtaining this
ethoxide, it was slowly added to the solution of residual oil,
then it is dumped at a constant homogenization. We have
performed the conversion process for two hours, this time is
required for total conversion of esters. This oil conversion to
esters is verified by the chromatography technique in liquid
phase of thin layer, using ethyl acetate solution in the same
hexane proportion, after obtain esters, we proceed to separate
these esters each glycerin components, ethanol particles and
saponification traces. Then the washing process is done, for this
process is added 40 mL of distilled water to the Bcquer with
constant agitation for 30 minutes to consequently perform the
decantation using a decantation pear.
We performed four washes and finally the drying process to
eliminate water, alcohol, glycerin and traces of potassium
hydroxide at a temperature of 100C for one hour and a half.
For the development of the pilot plant, it is made with the same
procedure with an ethanol/oil ratio of 2:1, for a volume of 12.5
liters of ethanol to 25 liters of residual frying oil.
Storage process:
The materials used for the storage simulation:
Inputs for storage test: To determine the initial states of the
biofuel to test, we contemplated the different conditions for
B20, B50 and B100, for it was determined BX mix (%v/%v)
with Diesel addition which was calculated for 30 liters volume
of biodiesel for each condition.
Storage Equipment: We designed a stainless steel tank AISI
306L with 30 liters of capacity, breathing conditions and
income temperature control at different stages of each storage
cylinder.
For the measurement of parameters such as temperature was
performed by type K thermocouples in each phase (bottom,
middle and top), each period is processed, removing samples
for characterization. Also are controlled the external conditions
like temperature (C) and relative humidity (%RH).
Table 1 Chemical composition of stainless steel tanks AISI
306L
C
Mn
P
S
Si
Cu
Cr
Ni
(%) (%)
(%)
(%)
(%)
(%) (%) (%)
0,16 0,63 0,012 0,031 0,012 0,01 0,03 0,01
Characterization equipment for stored BX biodiesel: Relative
humidity (%RH) for each period, moisture presence analysis in
the mixtures by coulometric Karl Fischer ASTM D6304,
oxidative stability index by Rancimat method EN14112,
potentiometric titration of acid ASTM 664, determination of the
specific mass at 20 C by ABNT NBR 14065 method using a
digital densimeter Anton Parr D4500, kinematic viscosity
measurement by ABNT NBR 10441 method, using a Lauda

E200 bath 75 Cannon model, capillary type No. 100 at a 40C


temperature.
Sample procedure:
They were 500 ml samples took periodically at 30, 60, 90,
120 and 150 days, according to standard sampling and to ANP
regulation resolution No. 42 of 24.11.2004 - DOU 2004/12/09 2005/04/19 DOU. Stage sampling of bottom, middle and top,
which are then mixed tested by representative characterization
analysis and them represent tests are analyzed each sample in
different characterization analyzes, is also taken the data of
temperature and relative humidity for each period storage. The
B100 biodiesel and mixtures were stored for 150 days, then are
evaluated various parameters, both external and internal
indicators influence the storage process, such as temperature,
humidity, physical-chemical degradation, condensation of the
free water in the tanks (influenced by temperature gradient
along the storage time) and the "headspace" (free space left
within the cylindrical tank to characterize the degradation
agents in the interface during storage 150 days).

EVALUATION RESULTS
Biodiesel making process:
The obtained results determine the quality conditions. The
physical chemistry characterization of waste frying oils is
substantial as much as mass balance for biodiesel production in
laboratory and pilot-scale plant and its respective
characterization. These initial conditions of raw material
determine the conversion efficiency to biodiesel and also are
highly relevant for related costs and benefits.
Table 2 Physicochemical properties of waste frying oil.
Waste frying
oil
Density at 20 C, kg/m3
980,1 1,0%
Kinematic viscosity at 40 C, mm2/s
40,8 1,0%
Humidity index (Karl Fischer), mg/kg
310 0,1%
Acid number, mg KOH/g
0,98 1,5%
Table 2 shows the initial parameters of residual oil within
the limits set by the NTP (Peruvian Technical Norm). Hence it
is shown that a lower specific mass does greater viscosity and a
substantial reduction in acidity. It can determine that with a
higher density and viscosity, the conversion of triglycerides will
be lower, on the other hand, the greater presence of water also
means a greater possibility of saponifying.
Table 3 Mass balance of biodiesel production in laboratory and
pilot-scale from waste frying oil.
Residual frying oil
Residual frying oil
Component
(Laboratory)
(Pilot plant)
Input (g)
Output (g)
Input (g)
Output (g)
Oil
Ethanol
KOH
Glycerol
Ester

196,0
79
3

24502,5
9875
375
87,6
138,8

11972,0
16319,1

Ethanol
Excess
Lost by
manipulation
Performance

68,5%

64,4%

Total

278,1

34752,5

48,7

6086,4

3,0

375,0

Humidity
index (ppm)
IP (h)
B100

Table 4 Characterization of obtained biodiesel from waste


vegetable oil
Parameters
NTP
Method
Biodiesel
321.125from waste
2008
vegetable oil
Density at 20C, kg/m3 850 900
ASTM
874,7 1,0%
D 4052
Kinematic viscosity at
1,9 6,0
ASTM
4,8 1,0%
40C, mm2/s
D 445
Humidity index, mg/Kg Max. 500
ASTM
739,7 0,1%
D 6304
Acid value, mg KOH/g
Max. 0,5
ASTM
0,3 1,5%
D 664
Oxidative Stability
Min. 3
EN
1,5 0,5%
Index
hours
14112
In Table 4 is also observed parameters of biodiesel within
acceptable ranges, and feature the hygroscopic condition and
time of oxidative stability, which means less stability time in
the process of storage and direct relation to the bacteria growth,
with injury to reduce its quality in storage conditions.
Monitoring process:
The stability conditions of B100 and mixtures are observed
and they determine degradation reduction with external
influences and peculiar hygroscopicity conditions.
Table 5 Conditions oxidation period, during the storage time
Specification

B5

30

60

90

120

150

IP (h)

>30

16,74

15,13

11,13

11,00

9.41

Humidity
index (ppm)

72.3

87.2

90.21

92.11

98.52

100.12

13,81

6.01

5.11

3.78

3.65

3.04

14.82

5.97

5.19

3.21

3.7

3.11

13.86

6.1

5.2

4.03

3.8

3.13

150

380.2

525.7

674

731

810.5

9.14

6.72

2.95

1.99

1.92

1.29

IP (h)
B20

B50

Time (days)

Humidity
index (ppm)
IP (h)

Humidity
index (ppm)

6.45

2.91

1.91

1.18

10.59

6.62

2.88

1.93

0.53

300,0

467.9

949.3

987

1100

1350

5.61

0.54

0.17

0.01

0.51

6.02

3.05

0.64

0.17

0.07

0.3

5.51

3.09

0.64

0.13

0.35

740,0

755.32

1050

1430

1850

2543

The stability conditions of degradation are shown in the


initial evaluation for B100 and mixtures. It evidence a greater
stability at lower concentrations of biodiesel, consequently this
degradation property of hygroscopicity would be by the diesel
relation and the presence of sulphur to be catalyzed by the
presence hygroscopic biodiesel. To B100 conditions is
determined a substantial degradation at 30 days storage, for the
other mixtures remain stable.

30
25

Period of oxidation, h

Table 3 shows that the yield of residual frying oil came to


68.5% on a laboratory scale and 64.4% on a pilot scale.
Obtained biodiesel has as 86% value for input oil. It was
observed that a pilot plant scale there is an uncertainty in the
estimation of parameters of production due to the solid lines or
the moisture presence into this residual oil, this latter is
reflected in the oxidative stability values of table.

8.74

20

Monitoring of storagem

Period Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias

15
10

Accepted

5
0
B5

B20

B50

B100

Characteristic of biofuel, (B100, BX)

Figure 1 Behavior of induction period (h).


The existence of "headspace" in the reactor contributes to
run more easily the degradation processes for the various
storage periods. It was observed that during heating, cooling
and the presence of moisture in the atmosphere throughout the
day inside the containers, there is a convective transfer
coefficient which sets the mass movement. This causes multiple
variations of energy charges at molecular level in the fluid. This
property of hygroscopicity, during storage of biodiesel was
performed by the EN 14214 standard method with a
coulometric Karl Fischer titrator EN ISO 12937. According to
the regulations of the ANP to determine the moisture index is
defined for a maximum concentration of 500 mg / kg.

2.25

2750
2500

Water theor, ppm

2250
2000
1750

Monitoring of storagem

1500
1250

Tempo Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias

2.00
1.75

Acidity, mg KOH/g

Period Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias

3000

1.50
1.25
1.00

monitoring of storagem

0.75

accepted

0.50

1000
750

0.25

500

Accepted

250
B5

B20

B50

0.00
B5

B20

B50

B100

characteristic of biofuel, (B100, BX)

B100

Characteristic of biofuel, (B100, BX)

Figure 3 Acidity results for pure biodiesel and mixtures


Figure 2 Behavior of humidity presence at storage process
As shown in the graph, there is a high moisture index for
pure biodiesel at 150 days. From that, is inferred that a greater
amount of biodiesel in the mixture, it becomes more
hygroscopic. On the other hand, it is possible to consider
mixtures with an acceptable behavior, taking into account the
storage time. Acidity values are shown below in Table 6 at 150
days.
Table 6 Conditions of acidity period during storage
Storage time (days)
Specification
0
30
60
90
120
Acidity
B5
0,10 0,19 0,20 0,23 0,30
(mgKOH/g)
Acidity
B20
0,13 0.28 0,30 0,37 0.41
(mgKOH/g)
Acidity
B50
0,37 0.41 0.52 0.55 0.58
(mgKOH/g)
Acidity
B100
0.45 0,54 0.61 0,68 0,72
(mgKOH/g)

150
0.37
0.67
0.84
1.91

The importance of increasing water content determines the


acidity process. To analyze these was employed the ASTM
D974 method, using KOH in isopropanol solution as titrant and
p-naphthol benzoin as indicator, all according to the Knothe
(2006) reference, for permissible limits of 0.5 mg KOH/g
regulated by ANP.

This acidity analysis was observed during 150 days for


B100 and mixtures, suggesting that the degradation time is
caused by the presence of moisture in their molecules. The
acceptance range is between 3.0 to 6.0 mm2/s. Results of table
5 shows the viscosity, which is related with the degradation
process as increased acidity.
Table 7 Viscosity behavior at storage process
Storage time (days)
Specification
0
30 60 90 120
Kinematic
2.8
B5
viscosity
2.00 2.20
3.13 3.25
2
(mm2/s)
Kinematic
4.8
B20 viscosity
2,30 4.37
4.93 4.97
1
(mm2/s)
Kinematic
4.3
B50 viscosity
3.1 3.87
4.61 4.73
5
(mm2/s)
Kinematic
B10
5.1
viscosity
2.73 4.68
5.47 5.52
0
7
(mm2/s)

150
3.76
5.21
4.92
5.57

This high viscosity slows the flow within the combustion


injectors due to residues as glycerides (mono-, di- and
triglycerides). There is molecular interaction as the breakdown
of molecules by a high rate of shear. Most interaction occurs
due to larger chains or oxidation process by polar chains with
dipole-dipole and binding of hydrogen bonds.

Period Storagem
0- dias
30 - dias
60 - dias
90 - dias
120 - dias
150 - dias

10

Viscosity, m2/s

Physicochemical properties of biodiesel results such as


specific mass and shear rate (kinematic viscosity) show that
they are within the limits set by the European standard EN
1403. Therefore it can be concluded that the oxidative
degradation of biodiesel is more stable for mixtures according
to the analysis performed at open environments. On the other
hand the period of oxidation and humidity index for pure
biodiesel is higher at 150 days storage, indicating prevail initial
process settings.

THANKS

0
B5

B20

B50

B100

Characteristic of biofuel, (B100, BX)

We thank the support of the Ministry of Production,


CONCYTEC, INT research center and San Pablo Catholic
University.

Figure 4 Viscosity behavior for 150 days monitoring


In this comparison, is observed an increase of viscosity for
all biofuels due to the larger carbonic chain of esters, resulting
in a higher density in relation also to the number of present
unsaturations in the molecules.

CONCLUSION
Obtaining biodiesel from waste cooking oil is generally
satisfactory. Acceptable yields were achieved with the terms of
the raw material up to 64.5%. However, it needs to improve the
biodiesel production by removing the presence of water, and
reducing oxidative stability indexes by summing stability
additives.
The implementation of new methods of production would
bring great social and economic impacts. In this way we could
reuse contaminant residues and we also could optimize the
characteristics regarding their use and storage. The
physicochemical properties shown in this monitoring of
biodiesel and its mixtures B5, B20 and B50 show significant
variations throughout the storage time. Is showed the behaviors
based on the experiences and obtained results in relation to
specifications of international organizations such as ANP. The
gradual performance for the degradative stability in each
biofuel mixture is also shown.
In some cases, it was noted that oxidized fatty acid chains
may be broken to form shorter chain acids and aldehydes,
which could form gum and sediments to viscosity increase. The
existence of peroxides and hydroperoxides present in the
oxidation reaction with other radicals is caused by high molar
mass molecules as gums, acids and aldehydes.

REFERENCES
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Avaliao do Desempenho de Misturas de Biodiesel em


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Postal- 19067-CEP -81531-980, Curitiba PR,2006.
[2] Katia Moniz da Silva. Mauro Lurk Rocha. Claudia Cristina
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Oxidao do Biodiesel, Centro de Pesquisa e
Desenvolvimento Leopoldo A. Miguel de Mello,
Universidade Federal do Rio de Janeiro, Escola de
Qumica., 2007.
[3] T. Schleicher, R. Werkmeister, W. Russ, R. Meyer-Pittroff.
Microbiological stability of biodieseldiesel-mixtures.
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Universitt Mnchen, Weihenstephaner Steig 22, 85350
Freising, Germany. 14 September 2008.
[4] Azambuja S. D., Silva P. Y., Piatnicki M. C., Estudo da
Corroso de Ao Carbono em Misturas de B5 e B20,
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[5] Cavalcanti, E. Tomachuk C.R., Araujo, F. del Valle L,
Ferraz, O. Marques, L.G.C.-Controle de Estabilidade de
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[6] Lutterbach M. Barreto, A. Tomachuk, C.R., Ferraz, O.B.,
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