Fuel 256 (2019) 115952

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Speciation of sulphur in asphaltenes and resins from Argentinian petroleum T

by using XANES spectroscopy
⁎
Yanina B. Bavaa, Mariana Geronésa, , Lisandro J. Giovanettib, Leandro Andrinib,
⁎
Mauricio F. Erbena,
a
CEQUINOR (UNLP, CONICET CCT-La Plata) Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Blvd. 120 N°1465, CC 962, La
Plata (CP 1900), Argentina
b
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA, Facultad de Ciencias Exactas, Universidad Nacional de La Plata – CONICET), Suc. 4 CC 16,
(1900) La Plata, Argentina

A R T I C LE I N FO A B S T R A C T

Keywords: Argentinian crude oil samples from different origins have been processed to separate in the four fractions
Petroleum Saturates, Aromatics, Resins, and Asphaltenes (SARA). Asphaltene and resin fractions were extracted using n-
Asphaltenes pentane and n-heptane as precipitating solvents. Sulphur contents of the samples were determined by elemental
Resins analysis and X-ray Absorption Spectroscopy at the Sulphur K-edge was used to perform sulphur speciation for
Sulphur
resin and asphaltene fractions. Reduce sulphur as sulphides, disulphides and thiophenes dominate the spectra of
XANES
asphaltenes, resins I and crude oils samples. A higher abundance of sulfoxide forms were found in the resin II
SARA
fraction. In addition, it was found that the asphaltenes are more enriched in aromatic sulphur (thiophene) when
the n-heptane solvent is employed. From the sulphur speciation determination it was possible to incorporate
different sulphur forms in the hypothetical average molecular structures for the Argentinian asphaltenes.

1. Introduction samples [9,11,12].

The molecular structures and the consequent physical properties
Petroleum consists of a very complex mixture of four main con- and chemical behaviour of asphaltenes in crude oils have been the
stituents: oils (Saturates and Aromatics fractions), Resins and subject of several studies. Nevertheless, due to the complexity of this
Asphaltenes (SARA). The asphaltene fraction is insoluble in n-alkanes, fraction their average structure remains as subject of debate [9,12].
as n-pentane, n-hexane and n-heptane. The resins can be defined as Two competing models were proposed in order to describe the as-
propane insoluble and n-pentane and n-heptane soluble fraction. In phaltene average molecular structure: the “island” or Yen-Mullins
addition, the saturate and aromatic portions are classified as the oil model [13], where one relatively big core of fused PAH containing
fractions that are soluble in n-pentane. Thus the petroleum fractions are approximately seven rings (varying between 4 and 10) is substituted by
classified by their solubility that strongly correlates with the chemical alkyl side chains (7 carbons long on average), and, on the other hand,
properties of the constituent species [1–8]. the “archipelago” model [14,15] where several smaller aromatic cores
In particular, the heaviest and most complex fraction of petroleum is (PAH) are linked by alkyl chains or naphthenic rings. Recently, the
asphaltene. The molecular structure of asphaltenes consists of a poly- combined use of ultrahigh resolution molecular imaging by atomic
cyclic aromatic hydrocarbons (PAHs) substituted by aliphatic chains. force microscopy (AFM) and scanning tunnelling microscopy (STM)
Nowadays, it is widely accepted that asphaltene fraction is composed supports that the dominant asphaltene molecular architecture is the
by molecules with high molecular weights (between 500 and 1200 Da) “island” or Yen-Mullins model for a more than 100 different coal-de-
[9,10], with high content of heteroatoms, such as oxygen, sulphur and rived and petroleum asphaltenes studied [16,17]. As is described in the
nitrogen, and smaller quantity metals, mainly vanadium and nickel. In “modified Yen model” [13] asphaltene molecules can form nanoag-
the asphaltene molecular structure, the hydrogen atoms are mostly gregates in crude oils, dictated by staking interactions of the aromatic
restricted to saturated groups while a 30–40% of the carbon atoms are cores (~6 staked PAH) leaving the alkyl chains oriented to the exterior.
condensed in aromatic structures that leads to hydrogen-to-carbon ratio These nanoaggregates join each other forming clusters of about eight
(H/C) between 1.1 and 1.3, values that are characteristic for asphaltene units. Additionally, the heaviest resins participate in the aggregation

⁎
Corresponding authors.
E-mail addresses: mgerones@quimica.unlp.edu.ar (M. Geronés), erben@quimica.unlp.edu.ar (M.F. Erben).

https://doi.org/10.1016/j.fuel.2019.115952
Received 23 April 2019; Received in revised form 1 August 2019; Accepted 2 August 2019
Available online 13 August 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
Y.B. Bava, et al. Fuel 256 (2019) 115952

constituting approximately 15% of mass fraction of the nanoaggregates sulphur chemistry the two main resin fractions, as well as the crude oils
[13]. has been also analysed. After SARA separation, the sulphur content has
Asphaltenes are considered as an undesirable fraction in petroleum been measured by elemental analysis and XANES spectra were acquired
industry because of the known problems caused along the production, around the sulphur K-edge region using synchrotron radiation. A
transportation, refining and storage of petroleum. The precipitation of comprehensive sulphur speciation analyses have been further per-
asphaltenes is responsible for the formation of solid deposit, blocking formed by linear combination fitting of the spectra using a far-reaching
wellbores or plugging pipelines, and the deactivation of catalysts used list of 14 selected sulphur reference compounds also measured using the
during refining process [9,10]. same experimental conditions. Thus, the sulphur speciation of asphal-
Generally, asphaltenes and resins fractions contain higher con- tenes, resins (type I and type II) and crude oil samples from three
centration of heteroatoms (near to 10 wt%) even greater than the ori- Argentinian oil basins have been determined.
ginal oils. These heteroatoms, present in polar and charged groups
determine, to some extent, the chemical properties of these crude oil 2. Material and methods
fractions and specially their solubility [2]. Thus, as asphaltenes are
defined by their solubility, it is of prime interest to know the het- Three Argentinian crude oils samples from San Jorge gulf basin in
eroatom speciation. Sulphur is the most abundant of all heteroatoms Comodoro Rivadavia, Loma Negra field complex on the Río Negro
present in petroleum (natural gas and crude oil), having the higher Norte Block in south-eastern Neuquen and La Salina field in La Pampa
concentrations in asphaltenes and resins fractions [18]. It is important reservoirs (C1, C2 and C3, respectively) have been processed to sepa-
to mention that the presence of sulphur-containing species has special rate the four fractions defined as Saturates, Aromatics, Resins, and
interest because of the problems it causes in the petroleum industry, Asphaltenes (SARA). A map of Argentina showing these sites are shown
such as the corrosion of pipelines, pumping, and refining equipment, as in Fig. S1 in the Supplementary Material. The geological characteristics
well as catalyst deactivation during oil processing. In addition, the of these basins have been reported elsewhere [43–45]. The American
occurrence of organo-sulphur compounds in petroleum, implies en- Petroleum Institute (API) gravities have been determined by ASTM
vironmental risks due to the production of sulphur oxides during D4052 method [46] for the crude oils samples C1, C2 and C3 showing
combustion in automobiles and industrial operations that it is re- values of 26.93°, 36.47° and 33.59°, respectively.
sponsible of the formation of acid rain [18,19]. First, the crude oil samples were separated into n-alkane insoluble
X-ray absorption near edge structures (XANES) spectroscopy is asphaltenes and the n-alkane soluble maltenes. The extraction of as-
considered as a powerful and non-invasive method to study the spe- phaltenes was done through precipitation by the addition of n-alkane
ciation for several elements in complex real samples. Sulphur presents a solvents (n-pentane and n-heptane, hereafter pent and hept, respec-
wide variety of oxidation states, ranging from −2 to +6 in a large tively) in a 1:40 wt ratio using a modified ASTM D6560 standard
variety of organic and inorganic species. The sulphur K-edge XANES method [47], as recently described [48]. The mixture was then left to
spectra are dominated by an intense peak (assigned to a 1 s → 3p equilibrate for 16 h, and the precipitated was separated by vacuum
electron transition) with an energy resonance value that strongly de- filtration through 2 μm Whatman filter paper in Buchner funnel. The
pends on the oxidation state, including a range of up to 13 eV [2,20,21]. resins co-precipitated with the asphaltenes, named Resins I, and were
Thus, sulphur K-edge XANES spectroscopy has been employed for study removed via Soxhlet extraction with boiling n-alkane during 6 h until no
speciation in complex fossil fuel samples, including the determination coloration was observed in the solvent extractor. In addition, the resins-
of the sulphur forms present in asphaltenes, crude oils, coals, kerogen, free asphaltene samples were dissolved in toluene and then filtered in
bitumen and sediments, among others [2,21–32]. order to remove the non-asphaltene species that are insoluble in n-al-
The prominent contribution of saturate and aromatic reduced sul- kane. Finally, the asphaltenes were dried in a vacuum oven at 115 °C
phur forms, as sulphide and thiophene, has been shown for asphaltene until constant weight. Thus, it is important to note that the asphaltenes
and crude oil fractions, respectively. The sulfoxide groups was found in obtained after Soxhlet extraction are solid black samples, shiny and
a smaller amount (less than 10%), as the principal oxidized component friable, having different appearances than the resins I which are dark
[21,22,26,29]. Additionally, X-ray photoelectron spectroscopy (XPS) is brown, shiny, and gummy. The n-pentane, n-heptane and toluene sol-
another technique that has also been applied to characterize the pre- vents used were of analytical grade (Carlo Erba, Italy).
sence of sulphur in bitumens, kerogens, asphaltenes and hydrotreated After precipitation of asphaltenes, maltenes were separated into
asphaltenes [33–35]. While XPS is a surface technology, XANES pro- saturates, aromatics, and resins II using the SARA technique, using a
vides averaged bulk estimates of the different forms of sulphur present modified ASTM D4124 [3,5,49–51]. Thus, the n-heptane soluble frac-
in a sample expose to X-rays. Therefore, these methods offer com- tion was concentrated by solvent evaporation and the isolation of the
plementary information about sulphur speciation [36]. The pre- three fractions was carried out by column chromatography packed with
dominance of thiophenes in petroleum asphaltenes was determined by silica gel (Merck, 70–230 mesh, 0.063–0.200 mm) activated at 120 °C
XPS sulphur 2p spectra, in concordance with the XANES results [33]. for 24 h. The maltenes were transferred into the column in the pro-
Furthermore, the sulphur speciation in crude oils and the SARA portion 1:15 w/w sample-gel and the different fractions were isolated
fractions have been studied by Fourier-transform ion cyclotron re- by sequential leaching method with different solvents. The saturate
sonance mass spectrometry (FT-ICR MS) coupled with various atmo- fraction was eluted by the addition of n-hexane; the aromatic fraction
spheric ionization techniques, including electrospray ionization (ESI) was eluted first with n-hexane-toluene (7:3) followed by toluene, and
and atmospheric pressure photoionization (APPI) [18,37–41]. It was finally the fraction corresponding to the resins II was obtained by
shown that APPI is more suitable than ESI for sulphur speciation due to washing the column with a mixture of ethyl acetate–methanol (1:1).
precludes the need for derivatization and efficiently ionizes non-polar The collected fractions were concentrated by evaporation of the elution
compounds, particularly sulphur heterocycles, that are unobservable by solvent and weighted [50]. Recoveries were 97% average (three runs),
ESI. The atmospheric pressure laser ionization (APLI) was introduced as in good agreement with similar studies previously reported [52].
other atmospheric ionization technique with up to three orders of
magnitude more sensitive than APPI for the analysis of very low-polar 3. Experimental techniques
polycyclic aromatic heterocycles in crude oil and its components
[18,42]. 3.1. Elemental analysis
In this work, the sulphur speciation in asphaltenes obtained from
crude oils from three well-known Argentinian deposits was studied by The C, H, N and S contents were obtained by the Thermo Finnigan
using XANES spectroscopy. In order to get a better understanding of the (Milan, Italy) model EA1112 Series Flash Elemental Analyzer. About

2
Y.B. Bava, et al. Fuel 256 (2019) 115952

3 mg of sample was used and a combustion temperature of 1020 °C was separated from these, as asphaltenes, resins I and resins II were mea-
applied. The oxygen content was determined by difference [53]. sured by XANES spectroscopy. Also, the untreated crude oils samples
were measure in liquid state diluted with toluene in a borosilicate ca-
3.2. X-ray absorption near edge structure spectroscopy pillary tube. The solid samples of asphaltene, resin I and resin II frac-
tions were dissolved in toluene and were deposited over carbon tape.
Sulphur K-edge XANES measurements were performed in the soft X- Small quantities of diluted solutions were used in order to minimize the
ray spectroscopy (SXS) beamline available at the Nacional Laboratory self-absorption effects.
of Synchrotron Light (LNLS) in Campinas, Brazil [54]. The set-up used
allows measurements in the chamber with pressures of the order of 10-4 4. Results and discussion
Torr. In our experiments, XANES spectra were acquired in Fluorescence
and Total Electron Yield (TEY) modes in the photon energy range from The Argentinians crude oil samples C1, C2 and C3 have been pro-
2430.0 to 2570.0 eV, using a InSb(1 1 1) double crystal monochromator cessed and separated into SARA fractions. The weight percentages of
with an energy resolution (ΔE/E) of 10-4 eV. XANES spectra were col- saturates, aromatics, resins type I, resins type II and asphaltene frac-
lected with a step of 2.0 eV in the range between 2430.0 and 2462.0 eV, tions precipitated with n-heptane solvent are shown in Table 2.
0.2 eV between 2462.0 and 2490.0 eV, 1.0 eV between 2490.0 and In order to explore the role of precipitant solvent, asphaltenes were
2520.0 eV and 3.0 eV between 2520.0 and 2570.0 eV and a dwell time also precipitated using n-pentane and the resins-free asphaltenes ob-
of 1 s. The result spectra analysed are an average of 3 scans. tained, named A1-pent, A2-pent and A3-pent, presented yields of 7.2,
Diluted samples were measured by fluorescence ensuring the ab- 2.4 and 1.7 wt%, respectively. The percentages corresponding to the
sence of self-absorption in the fluorescence spectra. Furthermore, a asphaltene fraction are higher with n-pentane than n-heptane solvent as
series of commercial standard model compounds were also measured in precipitant medium [68].
the same conditions. The reference species are sulphur-containing The percentages of atomic content obtained by elemental analysis
compounds chosen in such a way that sulphur atoms in different oxi- for asphaltenes and resins type I extracted with n-heptane are presented
dation states and chemical environments are considered with these in Fig. 2. The aromaticity character can be inferred thought the H/C
model compounds. The list of reference compounds here analysed in- ratio, having typical values between 1.19 and 1.30 for asphaltenes and
cludes: sodium thiosulphate (Na2S2O3), elemental sulphur (S8), di- between 1.61 and 1.76 for resin fractions. Thus, the resin fraction has a
benzyl disulphide (DBDS), diphenyl disulphide (DPDS), dibenzyl sul- lesser degree of aromaticity than asphaltenes. Both sulphur and total
phide (DBS), dibenzothiophene (DBT), thianthrene, dibenzyl sulfoxide heteroatoms content show lower values in resins than in the asphal-
(DBSO), diphenyl sulfoxide (DPSO), dibenzothiophene sulfone tenes fraction, as expected from the average molecular structures [8].
(DBTSO2), diphenyl sulfone (DPSO2), methane sulfonic acid (MSA), The elemental analysis of asphaltenes extracted with both n-pentane
sodium sulphate (Na2SO4) and dimethyl sulphate (Me2SO4) (see (Fig. S2 in the Supplementary Material) and n-heptane solvents result in
Table 1). The samples were purchased from Sigma-Aldrich Chemical sulphur content varying between 0.3 and 3.0%, the highest percentage
Company (Milwaukee, Wisconsin, USA) at the highest quality available. obtained for the sample A3 [48]. The asphaltenes extracted with n-
The energy calibration was done with CaSO4 with a white line peak heptane present higher proportion of heteroatoms and a major ar-
maximum at 2482.5 eV [20,55–57]. The crude oil samples and their omaticity (H/C ratio) when compared with the asphaltenes precipitated
respective fractions were analyzed by sulphur K-edge XANES spectro- with n-pentane, however no significant difference were observed in the
scopy using linear combination fitting (LCF) to determine which com- sulphur content when the precipitant solvent is changed.
bination of number and proportion of sulphur reference compounds Sulfur K-edge XANES spectra of three Argentinian crude oils sam-
represents the best fit result [58]. All XANES spectra were normalized ples and the fractions of asphaltenes, resins I and resins II extracted
by standard procedure. The LCF was carried out in the energy range from each sample with n-heptane are shown in Fig. 3. The presence of
between −20 and 30 eV around E0 energy, for all possible combina- several peaks in the range between 2470.0 and 2482.5 eV evidences the
tions (procedure details are given in the Supplementary Material). In contribution of sulphur compounds with multiple oxidation states in
both cases, normalization and LCF, were done employing the ATHENA the different fractions. It is possible to observe a significant similarity
software [59]. Linear combinations fitting method was selected for the between the XANES spectra of asphaltenes, resins I and crude oils for
spectrum deconvolution because of its accuracy and precision in de- the three samples measured, independently on the source of the Ar-
termining sulphur speciation [60]. Abundances of the sulphur species gentinian petroleum. The visual inspection of the spectra corresponding
were taken as proportional to the fitted weight from LCF procedure to resins II fraction shows slightly differences result of a major sulphur
with a relative error associated about 10% [23,30,61]. oxidation state.
Sulphur K-edge XANES spectra of model compounds are shown in The LCF analysis allows a qualitative and semi-quantitative de-
Fig. 1. The molecular structures, predicted sulphur oxidation states and termination for the oxidation state and chemical environment of the
the energy position of the sulphur K-edge white line extracted from sulphur atoms present in the different samples. The contribution of each
XANES spectra are listed in Table 1. It can be seen that the sulphur reference with the same oxidation state was added together, as shown
XANES spectra vary widely between the different compounds being a in Table S1. The results obtained for the asphaltene precipitated with n-
fingerprint of each species what makes it a powerful tool to study sul- heptane (A1-hept, A2-hept and A3-hept), as well as those present in
phur speciation [22,56]. resins I (RI1, RI2 and RI3), resins II (RII1, RII2 and RII3) and asphal-
In the Fig. 1 it is possible to observe a shift of the white line toward tenes precipitated with n-pentane (A1-pent, A2-pent and A3-pent) for
higher energy positions with the increase of the sulphur oxidation state. the three Argentinian crude oils (C1, C2 and C3) are shown Fig. 4 (more
The oxidation state for the model compounds here considered varies detailed information is given in Table S1 in the Supplementary
from −2 to +6 and the total energy range covered is 12.5 eV. The most Material).
intense feature observed in the XANES spectra corresponds to electron The sulphur speciation of the crude oil samples studied in this work
transition from 1 s sulphur orbital to vacant π* or σ* molecular orbitals is dominated by thiophene form (~50%) followed by sulphide and in
with dominant p-type character [23,25,26,56,62]. Thus, differences in less proportion sulfoxide groups. This result has a great impact in pet-
the XANES spectra are clearly observed in both inorganic and organo- roleum industry, showing the high percentage of thiophenic sulphur
sulphur compounds with different environments around the sulphur that are considered the more problematic sulphur forms being the type
atom, allowing a qualitative identification of sulphur species present in of species that remain in the crude oils even after the desulfurization
complex mixtures. treatments It is important to note that the C3 crude oil presents a higher
Three samples of Argentinian crude oils and the different fractions content of thiophene in all fractions under analysis. As was reported, in

3
Y.B. Bava, et al. Fuel 256 (2019) 115952

Table 1
Sulphur compounds, structures, predicted sulphur oxidation states and their energy position of the sulphur K-edge resonance peaks extracted from XANES spectra
reported in present work and bibliography.
Sulphur form Molecule name Molecular structure Sulphur oxidation state Resonance energy (eV)

Present work Reported Values

Inorganic thiosulphate Na2S2O3 −1, +5 2471.8 2471.7

2480.0 2481.0 [57]

Elemental sulphur S8 0 2472.8 2472.8

[23,57,63]

Organic disulphide DBDS 0 2472.4 2471.7

2472.8 [63,64]
2472.9 [23]
DPDS 0 2472.6; 2474.5 2472.6
2474.4
[63,65]
Organic sulphide DBS 0 2473.3 2473.4 [23]

Thiophene DBT 0 2473.7 2473.5 [65,66]

Thianthrene Thianthrene 0 2474.0 2474.2 [66]

Sulfoxide DBSO +2 2476.2 2476.1 [23]

DPSO +2 2479.8 2476.2 [23]

Sulphone DBTSO2 +4 2479.8 2480.1 [23]

DPSO2 +4 2480.7 2480.9 [67]

Sulphonate MSA +5 2481.2 2481.1

(NaSO3Me) [63]

Inorganic Sulphate Na2SO4 +6 2482.1 2482.6 [23,65]

Organic Sulphate Me2SO4 +6 2482.5 2482.5 [57]

Table 2
Weight percentages of saturates, aromatics, resins type I, resins type II and
asphaltene fractions precipitated with n-heptane solvent, in Argentinian Crude
Oil samples (C1, C2 and C3).
wt % Saturates Aromatics Resins I Resins II Asphaltenes

C1 57.4 36.3 1.0 4.8 0.5

C2 52.8 36.8 7.3 3.0 0.1
C3 66.8 24.2 0.5 8.3 0.3

general crude oils with greater thermal maturation are linked with
significantly higher thiophene content, perhaps as a consequence of a
conversion of sulfides to thiophenes groups during the maturating
[22,23,69].
Sulphur XANES spectra and the respective speciation for the as-
phaltene samples extracted with n-pentane and n-heptane from the
Fig. 1. Sulphur K-edge XANES spectra of a range of sulphur compounds chosen
three Argentinian crude oils are presented in the Figs. 5 and 6, re-
as references model.
spectively. A close examination of the XANES spectra reveals the oc-
currence of mixtures of reduced sulphur groups, probably sulphide and
thiophene, and sulfoxide as a minor component. Apparently, com-
pounds with higher sulphur oxidation states do not have a noticeable

4
Y.B. Bava, et al. Fuel 256 (2019) 115952

The Fig. 6 shows that the asphaltenes extracted with n-pentane have
a major contribution of sulphide and disulphide groups, amounting up
to ca. 60% of the sulphur content. On the other hand, the shift in the
white line to slightly higher energy observed in the XANES spectra
(Fig. 5) is associated with a higher contribution of thiophene in the
asphaltene samples extracted with n-heptane as compared with those
obtained with n-pentane. This result is in agreement with the higher
aromaticity of the asphaltenes obtained when n-heptane is used as the
precipitate medium, since thiophene is an aromatic heterocyclic (it has
six π electrons in a planar, cyclic, conjugated system). However, it is not
possible dismiss some uncertainty in the relative percentage of thio-
phenic and sulphidic groups due to the proximity of the respective
white lines (0.5 eV) as it was previously reported [28,60], It was also
observed that species containing sulphur in higher oxidation states (+4
and + 6) appear with low abundance in asphaltenes precipitated with
n-heptane.
Fig. 2. Percentage atomic content (%C/10, %H, %O, %N, and %S) obtained by Generally, the sulfoxide forms is the principal oxidized component
elemental analysis of asphaltenes and resins extracted from three Argentinian in asphaltenes and was observed that a higher sulfoxide abundance
crude oils samples by n-heptane addition (A1-hept, A2-hept, A3-hept, RI1-hept, correlates with small sulphide fraction [21,69]. The sulfoxide mole
RI2-hept and RI3-hept). fraction normalized by the sulphur and oxygen elemental mole fraction
obtained from elemental analysis is associated with the quantity of
contribution. Furthermore, as shown in Fig. 5, the asphaltenes extracted oxygen atoms bond to sulphur (CSO = XSO/XSXO, where Xi is the mole
with n-heptane display a shift in the white line to slightly higher energy fraction of component or group i). The plot of the CSO values versus the
when compared with those extracted with n-pentane. percentage of sulphur as sulphides (Fig. S3 in the Supplementary
The sulphur speciation study in all asphaltene samples shows that Material) allows correlating the increase in the oxygenation of sulphur
the more reduced sulphur species, mainly sulphides and thiophenes are with the decreasing of sulphide species. This are in good agreement
the dominant species. This finding is in accordance with previous stu- with previous studies that propose that the most probable source of
dies of sulphur XANES and XPS in asphaltenes samples from other sulfoxide groups is the oxidation of sulphide moieties, which is con-
origins [34]. Furthermore, as a salient contribution, our results clearly sistent with the known easy oxidation of alkyl sulphide compounds to
show that it is possible to determine and quantify the presence of both, sulfoxides and sulfones in lesser proportion [21,69].
sulphide and disulphide species in the analysed samples. Very recently, we reported a plausible average molecular structure

Fig. 3. Sulfur K-edge XANES spectra of three Argentinian crude oils and the fractions of asphaltenes, resins I and resins II extracted from each sample.

5
Y.B. Bava, et al. Fuel 256 (2019) 115952

Fig. 4. Sulphur speciation obtained by XANES in the samples: a) crude oils (C1), asphaltenes and resins fractions precipitated with n-heptane (A1-hept, RI1 and RII1)
and asphaltenes fractions precipitated with n-pentane (A1-pent); b) crude oils (C2), asphaltenes and resins fractions precipitated with n-heptane (A2-hept, RI2 and
RII2) and asphaltenes fractions precipitated with n-pentane (A2-pent) and c) crude oils (C3), asphaltenes and resins fractions precipitated with n-heptane (A3-hept,
RI3 and RII3) and asphaltenes fractions precipitated with n-pentane (A3-pent).

Fig. 6. Sulphur speciation of asphaltene fractions precipitated from three crude

oils samples with n-pentane (A1-pent, A2-pent and A3-pent) and n-heptane (A1-
hept, A2-hept and A3-hept).

Fig. 5. Sulphur K-edge XANES spectra of Argentinian asphaltenes extracted

from three samples of crude oils by precipitation with n-pentane (A1-pent, A2- aromatic cores.
pent and A3-pent), and n-heptane (A1-hept, A2-hept and A3-hept). Both resin I and II types (RI and RII, respectively) have been isolated
after Soxhlet and SARA column chromatography separation procedures.
The XANES spectra for RI and RII isolated from the Comodoro
for Argentinian asphaltenes [48]. Taken into account the current re-
Rivadavia crude oil (C1) are shown in Fig. 8. The presence of sulphur
sults, it now is possible to better define how the sulphur atom is present
groups in high oxidation states is confirmed for these resins fractions
in this average structure, including the oxidation states and chemical
(see Table S1). In effect, together with some contribution of sulphur(II),
environment, i.e. the most likely moieties together with their relative
it is apparent that S(IV) species, like sulfoxides and sulfones, dominate
abundances. Fig. 7 shows the proposed average molecular structure for
the spectra with strong absorptions at 2475.5 and 2481.0 eV, respec-
the Argentinian asphaltenes extracted with n-heptane as precipitating
tively. The RII resins extracted with methanol, the most polar solvent,
medium. The most abundant sulphur form corresponding to the thio-
showed the major contribution of the sulfoxides, in accord with the
phenic group as a part of the fused aromatic rings in the PAH core of the
Hansen Solubility Parameters (HSP) [70]. The RII resins also contain
island model, whereas the sulphide, disulphide and sulfoxide forms are
sulphur(VI) as sulfate, depending on the oil source and the polarity of
presents in the branches of aliphatic chains that substitutes the
the eluent solvent used in the SARA analysis. Thus, the presence of

6
Y.B. Bava, et al. Fuel 256 (2019) 115952

difference observed in the XANES spectra for the contribution of sulf-

oxides (the most polar group in the sulphur speciation) between the
asphaltene and the resins II fractions clearly suggest that resins are
definitely much polar than the asphaltenes.

5. Conclusion

XANES spectroscopy represents a direct, rapid and non-destructive

technique for studying the qualitative and quantitative sulphur spe-
ciation in Argentinian crude oils as well as in their asphaltene and resin
fractions. Thus, it was possible to distinguish and quantify the different
sulphur forms in all fractions from the three crude oils analyzed. The
main contribution of reduced sulphur, both aromatic and aliphatic or-
ganic sulphur, was found in the XANES spectra of asphaltenes and re-
sins, showing the last a major content of oxidized sulphur species. This
fact stressed the importance of the washing procedure for removing
resins in order to purify the asphaltene fraction.
Fig. 7. Schematic representation of possible environments of sulphur in average Interestingly, the asphaltene fractions studied in this work show
asphaltene structures, as extracted from XANES sulphur speciation. The main selective enrichment of sulphur species depending on the precipitant
groups are thiophene (40%), disulphide (21%), sulphide (16%) and sulphoxide solvents employed. The presence of reduced sulphur species has been
(14%). determined in asphaltene samples extracted with n-pentane, high-
lighting the occurrence of disulphide groups as a salient result.
Asphaltenes extracted with n-heptane are more enriched in aromatic
sulphur (thiophene) than sulphide groups, which is in agreement with
the highest aromatic carbon abundance found in these samples. In
particular, the increase in the sulfoxide content correlates with a con-
comitant decrease in sulphur bonded to aliphatic carbon, suggesting
that the oxidation of sulphide in lateral alkyl chains is a source of
sulfoxide groups present in asphaltenes.
Hence, the results of sulphur speciation obtained from XANES
spectroscopy provide clear evidences that the molecular structures of
asphaltenes need to incorporate thiophene rings in the aromatic core as
well as sulphide and disulphide groups in the lateral chains, whereas
significant amounts of sulfoxide groups should be also incorporated in
the asphaltene molecular structure.
The resin fractions are characterized by the occurrence of sulphur in
higher oxidation states. High contents of sulfoxides and sulfones char-
acterize the XANES spectra of resin type I, while the presence of sulfate
groups is evidenced for the RII resins.

Fig. 8. Sulphur K-edge XANES spectra for the resins type I (RI) and II (RII) Acknowledgements
isolated from Comodoro Rivadaviás crude oil (C1). The isolation procedure for
the different RII fractions is given in the Experimental Section. YBB is a postdoctoral fellow of CONICET, MG, LJG, LRA and MFE
are members of the Carrera del Investigador CONICET. This work has
oxidized sulphur species clearly determines the spectral features asso- been financially supported by ANPCyT (PICT 2015-2285, 2013-2130,
ciated with both, RI and RII resin fractions. 2012-1132), CONICET and UNLP. Partial support by Laboratório
In all cases, the comparison of the sulphur speciation analysis for Nacional de Luz Síncrotron (LNLS) under proposals SXS-2017-0956 and
asphaltenes and resins I reveals similar abundances of chemical species, SXS-2016-0690 is also acknowledged.
with thiophenes and sulphides as the main contributing species. By
comparing this result with the resin II fraction, smaller contribution of Appendix A. Supplementary data
thiophene species is found for RII. The lesser aromaticity of the resin
fractions leads to a major probability to found sulphur atoms as alkyl Supplementary data to this article can be found online at https://
sulphides [3]. Therefore, the three resin II fractions here analysed have doi.org/10.1016/j.fuel.2019.115952.
higher contribution of sulphur oxidized species, as sulfoxide groups,
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