Fuel 158 (2015) 113121

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Fuel
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Catalytic decarboxylation of naphthenic acids in crude oils

Helosa P. Dias a, Gustavo R. Gonalves a,b, Jair C.C. Freitas a,b, Alexandre O. Gomes c,
Eustquio V.R. de Castro a, Boniek G. Vaz a,d,, Glria M.F.V. Aquije e, Wanderson Romo a,e,
a
Petroleomic and Forensic Laboratory, Department of Chemistry, Federal University of Esprito Santo, 29075-910 Vitria, ES, Brazil
b
Laboratory of Carbon and Ceramic Materials, Department of Physics, Federal University of Esprito Santo, 29075-910 Vitria, ES, Brazil
c
Petrleo Brasileiro S/A PETROBRAS, CENPES, Rio de Janeiro, RJ, Brazil
d
Chemistry Institute, Federal University of Gois, 74001-970 Goinia, GO, Brazil
e
Federal Institute of Education, Science and Technology of Esprito Santo, 29106-010 Vila Velha, ES, Brazil

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A steel slag catalyst was evaluated to

remove naphthenic acids present in
crude oils.
 A high-acidity crude oil
(TAN = 4.79 mg KOH g1 and
S = 1.022 wt%) was submitted to
thermo-catalytic process.
 The MgO contributed effectively to
promote the thermo-catalytic
decarboxylation of naphthenic acid
species.
 A reduction of TAN of 43.50%
(4.79 ? 1.89 mg KOH g1) was
observed at 350 C for 4 h.
 ESI()FT-ICR MS data conrmed an
increase in the DBE values from 15
to 518.

a r t i c l e i n f o a b s t r a c t

Article history: Naphthenic acids are recognized as the main corrosive species in acidic crude oils, although they repre-
Received 25 February 2015 sent less than 3 wt%. Alternative methods have been developed in an attempt to remove naphthenic acids
Received in revised form 23 April 2015 from the oil, however, their implementation in petrochemical industry still represents a challenge.
Accepted 5 May 2015
Herein, a sub-product of the steel industry, steel slag, is evaluated as an economic alternative catalyst
Available online 21 May 2015
and environmentally feasible to remove naphthenic acids present in crude oils. A high-acidity crude
oil (TAN = 4.79 mg KOH g1 and S = 1.022 wt%) was submitted to thermo-catalytic process at 300 and
Keywords:
350 C during 2, 4 and 6 h and its degradation products were monitored by negative-ion electrospray ion-
Naphthenic corrosion
TAN
ization (ESI) Fourier transform ion cyclotron mass spectrometry (FT-ICR MS), total acid number (TAN) and
ESI()FT-ICR MS total sulfur. The main crystalline phases detected by X-ray diffractometry in the catalyst were calcite
Catalytic decarboxylation (CaCO3), silica (SiO2) and magnesia (MgO). Among them, the MgO contributes effectively to promote
the thermo-catalytic decarboxylation of naphthenic acid species, with a TAN reduction of 43.50%
(4.79 ? 1.89 mg KOH g1) from the original oil to the degraded oil obtained after treatment at 350 C

Corresponding authors at: Petroleomic and Forensic Laboratory, Department of Chemistry, Federal University of Esprito Santo, 29075-910 Vitria, ES, Brazil. Tel.: +55 62
3521 1016 R261 (B.G. Vaz). Tel.: +55 27 3149 0833 (W. Romo).
E-mail addresses: boniek@ufg.br (B.G. Vaz), wandersonromao@gmail.com (W. Romo).

http://dx.doi.org/10.1016/j.fuel.2015.05.016
0016-2361/ 2015 Elsevier Ltd. All rights reserved.
114 H.P. Dias et al. / Fuel 158 (2015) 113121

for 4 h. Acid species with lower pKa values were selectively removed with the ESI()FT-ICR MS data con-
rming an increase in the DBE values from 15 to 518 for O2 class. Therefore, the catalyst selectively
promoted the removal of naphthenic acids via (i) neutralization reaction; (ii) cracking reaction and (iii)
MgCO3 formation from CO2 molecules produced by a previous thermal decarboxylation reaction.
2015 Elsevier Ltd. All rights reserved.

1. Introduction Most analytical methods developed for extraction or removal of

Corrosion problems in operating processes and petroleum ren-
ing concerning naphthenic acids (NAs) in crude oils have been
reported since the early twentieth century. Since then, the search
for solutions to overcome these problems has become a constant
challenge for the petrochemical industry [1,2].
Naphthenic acid are carboxylic acids characterized by the pres-
ence of a monocarboxylic group attached to an aliphatic group and
may be represented by the general formula R(CH2)nCOOH,
where R is one or more cyclopentane or cyclohexane rings.
Naphthenic acids are the main responsible for a great number of
operating problems in the petroleum rening processes, such as
emulsions stabilizers, naphthenate deposition, gum formation
and corrosion problems [3].
Alternative analytical methods have been developed by an
attempt to remove naphthenic acids from the oil. In general, these
methods can be addressed in two ways. The rst involves removal
of the carboxyl group by esterication and hydrogenation reac-
tions or thermal decomposition whereas the second involves the
separation of the naphthenic acids from the oil by means of liq-
uidliquid extractions (using an alkaline solution with alcohol
and ammonia), adsorption, membrane separation, and electrostatic
separation [4].
In 1960, Earl [5] developed an extraction process for naphthenic
acids based on solvent extraction and subsequent distillation in the
presence of alkaline materials. In the 90s, Gaikar and Maiti [6]
developed an extraction method for naphthenic acids through
absorption using ion exchange resins. Blum et al. [7] studied the
viscosity reduction and the naphthenic acid removal by thermal
decomposition processes; however, the naphthenic acid degrada-
tion mechanism was not fully explored. In the same year, Smith
et al. monitored the effect of thermal treatment on the naphthenic
acids from vacuum residues by negative-ion electrospray ioniza-
tion (ESI) Fourier transform ion cyclotron mass spectrometry
(FT-ICR MS) [8]. It was observed that the acidity of the vacuum
residue decreased as the heating temperature was increased, as
indicated by both reduction in O2 class intensity and total acid
number (TAN). In 2011 Mandal et al. [9] studied the application
of supercritical water to reduce TAN, showing an efciency of
approximately 83% at 490 C.
naphthenic acids from crude oil samples requires a large invest-
ment due to high energy consumption; thus, the implementation
of these methods in the petrochemical industry remains a
challenge.
Recently, researches on decomposing naphthenic acid species
have focused especially on the development of new catalysts with
the aim of maximizing the reaction rate using lower temperatures,
thus reducing costs. In 2006, Zhang et al. [10] showed that the cat-
alytic decarboxylation using calcium oxide or magnesium oxide is
an effective method to remove naphthenic acids at low tempera-
tures. In 2009 Ding et al. [11] studied the use of alkali metal oxides
and zinc oxide as catalysts for the naphthenic acids removal from
heavy crude oil feeds. Depending on the catalyst employed, the
thermal degradation process can be followed by decarboxylation,
neutralization or thermal cracking. In 2014, Wang et al. [12] eval-
uated the naphthenic acids removal from crude oil applying the
MgAl hydrotalcite/c-Al2O3 as a catalyst. Their results showed a
TAN reduction in the crude oils from 2.7 mg KOH g1 to less
than 0.5 mg KOH g1 with one-hour treating at 320 C and
1.013  105 Pa.
FT-ICR MS offers the highest available mass resolution, mass
resolving power, and mass accuracy, which enables the analysis
of complex petroleum mixtures on a molecular level [13].
High-resolution MS data have shown that it is possible to discrim-
inate different compounds [1416] for taking into account the dif-
ferent ionization efciencies of the crude oil constituents [17].
Accurate mass measurements [18] allow unambiguous elemental
composition (CcHhNnOoSs) assignment, enabling material classi-
cation by heteroatom content and the degree of aromaticity [19
21]. Naphthenic acids can be analyzed by ESI() coupled to
FT-ICR MS, being detected as deprotonated molecules, [MH]
[22,23]. Herein, steel slag was used as catalyst to promote the cat-
alytic decarboxylation of naphthenic acids in a sample of crude oil
with TAN = 4.79 mg KOH g1 and total sulfur content of 1.02 wt%.
Steel slag [24,25] is commercially known as a sub-product gener-
ated in large quantities during the steel industrial production
and then it can become an economic and environmentally feasible
alternative to remove naphthenic acids from crude oil. Steel slag is
composed mainly by metal oxides such as FeO, CaO, MgO, Al2O3
and SiO2, which have decarboxylation activity documented on

Fig. 1. Scheme of the thermo degradation of the crude oil subjected to treatments at 280, 300 and 350 C for periods of 26 h in the presence (An) and absence (Bn) of the steel
slag catalyst.
 H.P. Dias et al. / Fuel 158 (2015) 113121
literature [26]. The original oil and the aged oil samples were mon-
itored by ESI()-FT-ICR MS, TAN and total sulfur to investigate the
effects of the catalyst on the selective removal of naphthenic acids
during thermo-catalytic degradation process.
2. Experimental
2.1. Materials and reagents
Toluene, propan-2-ol, and potassium hydroxide, Vetec Fine
Chemicals Ltda, Brazil, all with analytical grade and purity higher
than 99.5% were used for analysis of the TAN. Methanol, ammo-
nium hydroxide (NH4OH), sodium triuoroacetate (NaTFA) and
L-arginine, SigmaAldrich Chemicals, USA, were used in the
ESI()-FT-ICR MS analysis.
2.2. Characterization of the catalyst
The X-ray diffraction (XRD) pattern of the powder sample was
recorded at room temperature in a Bruker D8 Discover X-ray
Fig. 2. SEM micrographs of the steel slag catalyst, obtained with magnication of
1800 (a) and 3000 (b), and the corresponding EDX spectrum (c).
115
diffractometer, using Cu Ka radiation (k = 1.5418 ), with the
diffraction angle (2h) varied from 15 to 90, with a voltage of
40 kV and a current of 30 mA. The XRD pattern obtained was com-
pared with the crystallographic data from JCPDS (Joint Committee
on Powder Diffraction Standards) of the International Centre for
Diffraction Data, available on PCPDFWIN software version 2.3.
Catalyst surface area was obtained by N2 physisorption at 77 K,
using a Quantachrome instrument, model Autosorb-1. The samples
were purged under vacuum during 24 h at 80 C, weighted about
0.5 g (measured after the physisorption analysis). The specic sur-
face area of the catalyst was obtained using the BET method [27].
Scanning electron microscopy (SEM) images were obtained using
a Shimadzu SS-550 instrument; the local chemical composition
of the catalyst was analyzed by energy dispersive X-ray spec-
troscopy (EDX), using a SEDX-500 instrument coupled to the scan-
ning electron microscope.
2.3. Thermo-catalytic degradation of crude oil
A crude oil with TAN and total sulfur content of
4.70 mg KOH g1 and 1.02 wt%, respectively, was employed to
study the effect of the thermo-catalytic decarboxylation of naph-
thenic acids. The thermo-catalytic decarboxylation was carried
out according to ASTM D 2892 norm [28]. Initially, 400 mL of crude
oil were heated at 300 and 350 C, for periods of 2, 4 and 6 h. The
heating procedures were performed in a closed reaction system
under reux at a reduced pressure from 760 to 0.1 mmHg. The
same procedure was repeated using 10 wt% of steel slag catalyst
added to the reaction mixture. A scheme of the thermo-catalytic
degradation of the crude oil subjected to afore-mentioned condi-
tions in the presence or absence of the catalyst is summarized in
Fig. 1. The obtained samples were named samples An (with cata-
lyst) and Bn (without catalyst), in which n ranged from 1 to 6.
2.4. Physical chemistry characterization of oils
The analysis of TAN was performed according to the technical
specications described in the ASTM D 664 standard using a poten-
tiometer Metrohm Titrando 809 [29]. The samples were dissolved
in a mixture of toluene and propan-2-ol containing a small amount
of water. For the potentiometric analysis, a membrane electrode
containing a saturated lithium chloride solution in ethanol was
used. Titrations were performed with a previously standardized
solution of potassium hydroxide at 0.1 moL L1 in alcoholic med-
ium [30]. The TAN reduction efciency for the evaluated oil sam-
ples was calculated according to Eq. (1).
Fig. 3. XRD pattern of the steel slag catalyst.
116 H.P. Dias et al. / Fuel 158 (2015) 113121

Table 1
Physicochemical characterization (TAN and total sulfur) of the An and Bn samples.

Parameters Samples Bn Samples An

1
Temperature (C) Time (h) TAN (mg KOH g ) Sulfur (wt.%) % Reduction TAN (mg KOH g1) Sulfur (wt.%) % Reduction
Original oil 0 4.79 1.02 4.79 1.02
300 2 B1 4.73 1.01 1.26 A1 3.90 0.98 17.6
4 B2 4.59 1.00 4.18 A2 3.94 0.95 14.2
6 B3 4.06 1.00 15.3 A3 3.50 0.95 13.8
350 2 B4 3.35 0.94 30.1 A4 1.89 0.94 43.6
4 B5 4.23 0.98 11.7 A5 2.94 0.91 30.5
6 B6 0.44 0.96 90.8 A6

Fig. 4. ESI()FT-ICR mass spectra for original oil and samples A15 submitted to catalytic treatment.

TANreduction% TANoriginal oil  TANaged oil =TANoriginal oil  100
1 port to the analyzer cell (ICR) through the multipole ion guide sys-
The total sulfur content (S) of the oil samples was determined
according to the method described in the ASTM D4294 standard
using an energy dispersive X-ray uorescence spectrometer
SLFA-2800, Horiba Scientic (New Jersey, USA). Initially, the cali-
bration curves were plotted and parameters such as linearity and
detection limits were obtained. The measuring time was 100 s
[31]. The total sulfur contents of samples A15 and B16 were mea-
sured in triplicate.
2.5. ESI()FT-ICR MS
The An samples were analyzed using ESI(). Briey, all samples
were diluted to 1 mg mL1 in 50:50 (v/v) toluene/methanol,
which contained 0.1% w/v of NH4OH. The obtained solution was
directly infused at a ow rate of 8 ll min1 into the ESI source.
The mass spectrometer (model 9.4 T Solarix, Bruker Daltonics,
Bremen, Germany) [29,30,3234] was set to operate over a mass
range of m/z 2001300. The ESI() source conditions were as fol-
lows: a nebulizer gas pressure of 3 bar, a capillary voltage of
3 kV, and a transfer capillary temperature of 250 C. The ion
accumulation time in the hexapole was 0.03 s, followed by trans-
tem (another hexapole). Each spectrum was acquired by
accumulating 200 scans of time-domain transient signals in 4
mega-point time-domain data sets. The front and back trapping
voltages in the ICR cell were 0.60 V and 0.65 V. All mass spectra
were externally calibrated using a NaTFA solution (m/z from 200 to
1200) followed by internal recalibration using a set of the most
abundant homologous alkylated compounds for each sample. A
resolving power of m/Dm50% 550,000, in which Dm50% is the full
peak width at half-maximum peak height, for m/z = 400 and a mass
accuracy of <1 ppm provided the unambiguous molecular formula
assignments for singly charged molecular ions.
The mass spectra were acquired and processed using a custom
algorithm developed specically for petroleum data processing,
Composer software (version 1.0.2, Sierra Analytics, Pasadena, CA,
USA). The MS data were processed, and the elemental composi-
tions of the compounds were determined by measuring the m/z
values. For each elemental composition, CcHhNnOoSs, the heteroa-
tom class, the type, and the carbon number, CN, were tabulated
to generate the class diagrams, the DBE versus CN plots, and the
DBE versus intensity histogram.
 H.P. Dias et al. / Fuel 158 (2015) 113121
Fig. 5. ESI()FT-ICR mass spectra for crude oil and degraded samples doped with stearic acid.
Fig. 6. Class distribution for heteroatomic compounds present in the original oil
and in the products obtained by catalytic degradation.
Fig. 7. DBE versus intensity histogram for O2 class of original oil and samples A15.
117
For the CN versus DBE plot, DBE was the number of rings added
to the number of double bonds in each molecular structure. The
aromaticity of a petroleum component can be deduced directly
from its DBE value according to Eq. (2):
DBE c  h=2 n=2 1 2
where c, h, and n are the numbers of carbon, hydrogen, and nitrogen
atoms, respectively, in the molecular formula.
3. Results
The catalyst microstructure was characterized by SEM/EDX,
providing information about the material morphological aspects
and its local chemical composition. The SEM images, Fig. 2a and
b, evidenced a homogeneous structure within the length scale of
observation, indicating that the phases are nely mixed and inti-
mately dispersed. Some irregularities are observed at the surface
of the catalyst particles; according to the results reported by
Leofantia et al.[35], these irregularities usually lead to an increase
in the surface area, contributing to a more efcient catalytic decar-
boxylation process. For the catalyst, a specic surface area of
18 m2 g1 was determined by N2 adsorption. The EDX spectrum
(shown in Fig. 2c) reveals the presence of Ca, Si, O, Fe, Mg, Al and
Mn.
Fig. 3 shows the XRD pattern obtained for the steel slag, from
which it was possible to identify the diffraction peaks associated
with the following crystalline phases: magnetite (Fe3O4), alumina
(Al2O3), calcite (CaCO3), silica (SiO2, as quartz), magnesia (MgO)
and manganese oxide (Mn3O4), corroborating the EDX data,
Fig. 2c. These phases present distinct degrees of crystallinity, as
indicated by the variation in the linewidths among the several
detected peaks. The SiO2 phase is the one with the narrowest
diffraction peak, pointing to a relatively large average crystallite
size. Note also that the diffraction peaks are fully dened for
SiO2, CaCO3 and MgO phases. However, for some phases (such as
Fe3O4 and Mn3O4) there is an important overlap of the diffraction
peaks due to the proximity between the corresponding interplanar
spacings, making difcult an unambiguous assignment of these
peaks. Although XRD is a semi-quantitative method, the chemical
composition of the identied crystalline phases showed that
118 H.P. Dias et al. / Fuel 158 (2015) 113121

Fig. 8. DBE versus CN plots for O2, N and NO2 classes for original oil and its degradation products (samples A1A5) submitted to catalytic degradation at 300 C during 2, 4 and
6 h.

approximately 25 wt% of the material is composed of SiO2, fol-
lowed by 19 wt% of MgO.
The physicochemical characterization (TAN and total sulfur
content) of the original oil and its degradation products (An and
Bn samples) is shown in Table 1. For the original oil sample, the
TAN and the total sulfur content is 4.79 mg KOH g1 and
1.02 wt%, respectively. Submitting the original oil to thermal
degradation process without catalyst (samples Bn), the highest
TAN reduction was observed at 350 C, reaching a maximum ef-
ciency at 6 h of aging (sample B6, with 91% TAN reduction). A
 H.P. Dias et al. / Fuel 158 (2015) 113121
Fig. 9. DBE versus CN plots for O2, N and NO2 classes for original oil and its degradation products (samples A1A5) submitted to catalytic degradation at 350 C during 2, 4 and
6 h.
similar result has been reported by Dias et al. [36]. On the other
hand, adding the steel slag catalyst to the system, a highest ef-
ciency TAN reduction was observed, reaching an optimum condi-
tion at 350 C and 2 h of aging (sample A4), Table 1. Opposing to
naphthenic acids, sulfur compounds are more stable and a maxi-
mum reduction of only 8.48% was observed (from 1.02 (original
oil) to 0.91 wt% (sample A5)), Table 1.
Aged An samples reached higher TAN reduction compared with
their referred Bn samples. This phenomenon can be explained by
the presence of basic oxides such as MgO in the catalyst chemical
composition. Zhang et al. [37] described multiple roles of MgO dur-
ing decarboxylation process of crude oil, such as its ability to
adsorb acid compounds via acid-base neutralization and promote
decarboxylation and hydrocarbon cracking. As the steel slag used
here is composed mainly by MgO, we explain the TAN reduction
describing some reactions that may occur considering the MgO
as the main constituent. The MgO is not solely responsible for cat-
alytic action, but the synergism between the various species
founded on the steel slag provides the catalytic ability observed
on this system. In Eq. (3), MgO reacts with the carboxylic acid
groups of naphthenic compounds, via acid-base reaction,
119
producing magnesium naphthenates, Mg(RCOO)2, and water.
Also, it can react with CO2 produced from thermal decarboxylation
process, Eq. (5), leading MgCO3 and thus shifting the equilibrium of
Eq. (4) for the decarboxylation reaction that produces CO2 [12]. It is
expected that the CaCO3 do not contribute to thermo-catalytic
naphthenic decarboxylation due to its higher thermal stability
when compared, for instance, to MgCO3.
MgO
2RCOOH ! MgRCOO2 H2 O 3
MgO
RCOOH ! RH CO2 4
MgO CO2 ! MgCO3 5
Fig. 4 shows the ESI()-FT-ICR mass spectra for the original oil
and the samples submitted to catalytic degradation, An, at 300 and
350 C. In general, ESI()-FT-ICR MS have proles of m/z ranges
from 200 up to 1200 with Mw centered at 440 Da for the original
oil (Fig. 4a) and 450470 Da for the degraded oils (from sample A1
120 H.P. Dias et al. / Fuel 158 (2015) 113121
to sample A5, Fig. 4bf). The main heteroatomic compounds
detected as deprotonated molecules, or [MH] ions, correspond
to naphthenic acids and pyrrole analogues.
To further demonstrate the effect of the TAN reduction over the
chemical prole of ESI()FT-ICR MS data, samples were doped
with an internal standard of stearic acid (ion of m/z 283) with a
concentration of 0.5 lmol L1, Fig. 5. Note that now, for the original
oil sample it is observed that the Gaussian prole is suppressed by
the signal of m/z 283, being this phenomenon maximized when
degraded oil samples are also doped with stearic acid (samples
A1A5, Fig. 5bf). This behavior is attributed to the lower TAN val-
ues of the treated oils [38].
Generally, petroleum samples have chemical compositions that
differ signicantly from each other. One way to display the similar-
ities or differences between the signal patterns of crude oil samples
is to construct certain types of plots, such as plots of the relative
abundances of different classes of compounds and DBE versus CN
plots [32,33,35,36].
For the class diagrams (Fig. 6), O2 class, composed mainly of
naphthenic acids, was the most abundant class. The N class (pyr-
role analogous compounds) was the second most abundant, fol-
lowed by NO2 class (pyrrole analogs or pyridine with a carboxyl
group or two hydroxyl groups). It should be noted that the relative
abundance of the O2 class compounds decreased signicantly from
the original oil to the sample A5 (80% ? 55%), treated at 350 C
during 4 h, thus conrming the data obtained from physicochemi-
cal characterization, Table 1.
Fig. 7 shows the distribution of relative abundance for the O2
class compounds in the original oil and its degradation products.
In the original oil, naphthenic acids with DBE of 45 are more
abundant, being mainly composed of three and four naphthenic
rings [30]. As a result of the catalytic decarboxylation process, their
relative intensities are reduced over aging time.
Figs. 8 and 9 show DBE vs. CN plots for N, O2 and NO2 classes for
original oil (Figs. 8ac and 9ac) and its degradation products
(Figs. 8dl and 9di) submitted to treatments at 300 and 350 C,
respectively. For O2 class of the original oil, there are compounds
with DBEs ranging from 1 to 10 and CN ranging from C23 to C50,
presenting more abundant species with DBE = 45 and CN of C32
(Figs. 8a and 9a). A signicant difference was found comparing
the O2 class of the original oil with its degradation products
(Figs. 8d, g and j and 9d and g). The increase in the relative abun-
dance of acids compounds with higher aromaticity (DBE from 5 to
20) occurs due to the ionic suppressing effect of the ESI source,
since the removal of naphthenic acids with lower pKa values
favored the ionization of other non-ionized acid species, which
have higher pKa values.
4. Conclusion
It was demonstrated in this study that the ESI()FT-ICR MS was
able to monitor the chemical composition of naphthenic acid spe-
cies on the molecular level (CcHhNnOo), allowing the evaluation of
crude oil thermo-catalytic degradation evaluating the efciency of
the thermo-catalytic degradation efciency as a function of aging
time and temperature. The efciency of the thermo-catalytic
decarboxylation of naphthenic acids was conrmed by reduction
of TAN, which showed a decrease of 43.50% (4.79 ?
1.89 mg KOH g1) from the original oil to the degraded oil obtained
after treatment at 350 C during 4 h in the presence of steel slag
catalyst. DBE versus CN plots were a useful tool for the understand-
ing of the catalytic degradation mechanism, in which an increase in
DBE values (from 15 to 518) was observed in decarboxylation
process promoted by MgO present in the structure of catalyst.
Acknowledgments
This research was generously funded by PETROBRAS/CENPES,
CNPq, FAPEG, FAPES, CAPES and FINEP.
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