Fuel 311 (2022) 122559

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Influence of asphaltene structural parameters on solubility

Ronald Nguele a, *, Albert Brandt Mbouopda Poupi b, Ghislain A. Mouthe Anombogo c,
Olalekan S. Alade d, Hakim Saibi b, *
a
Resource Production & Safety Engineering Laboratory, Kyushu University, Fukuoka 819- 0395 Japan
b
Department of Geosciences, College of Science, United Arab Emirates University, Al-Ain, 15551 Al Ain, United Arab Emirates
c
National Advanced School of Engineering of Maroua, University of Maroua, 46 Maroua, Cameroon
d
Center for Integrative Petroleum Research, College of Petroleum and Geosciences, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: This paper investigates the influence of asphaltene’s structural parameters on its solubility, including aromatic
Asphaltenes sheet diameter and aromaticity. Aromatic sheet diameter (La) was determined by integrating the D1 and G bands
Structural parameters of Raman spectra. Aromaticity was determined by the ratio of the integrated Fourier Infrared peaks of aliphatic
Asphaltene solubility
carbon relative to aromatic carbon. Asphaltenes were extracted from five dead crude oils. Two types of solubility
Asphaltene precipitation
tests were conducted, with asphaltenes dissolved in both nonpolar (aromatic hydrocarbons) and polar (cyclic
ethers and aromatic amines) solvents and re-precipitated using pentane; in addition to a scenario where
asphaltenes were dissolved in toluene and re-precipitated using nonpolar (alkanes) and polar titrants (esters).
The largest La was estimated to be 7.34 nm, while the other asphaltenes have a La within the range of 1.52–2.35
nm. La increases monotonically with aromaticity, which was inversely proportional to the hydrogen bonding
capability. In terms of dispersant polarity, π-π interactions dominated, evidenced by a better asphaltene stability,
which increased with aromatic core size. A reverse trend was recorded with nonpolar precipitants due to
hydrogen bonding. This study argues that to inhibit the aggregation of asphaltene with large La, polar inhibitors
should be used.

1. Introduction
The elemental chemistry of a typical crude oil consists of a mixture of
carbon (C, up to 87%) and hydrogen (H, up to 14%), potentially in
addition to oxygen (O), nitrogen (N), sulfur (S) and even metals (M, up
to 2%) [1]. These elements are found within the crude oil in the form of
paraffins (CnH2n+2), naphthalenes (CnH2n), and aromatics (C4r+2H2r+4),
where n and r represent the number of carbons and rings, respectively
[2]. Their concentration within the crude oil dictates its nomenclature;
for example, a crude oil rich in straight-chain or branched paraffin
would be described as a paraffinic crude oil [3]; likewise, an aromatic
crude oil is predominantly rich in aromatic compounds. Alternatively, if
the oil’s composition is dominated by asphaltenes, it is termed an
asphaltic crude.
Asphaltenes are dark brown to black friable solids with high mo­
lecular weight that have no melting point and are composed of
condensed aromatic components with variable amounts of heteroatoms
[4]. From a structural point of view, asphaltenes could be described
either by the island or archipelago model [5]. The former model de­
scribes asphaltene molecule as a central, single aromatic with unpre­
dictable alkyl chains. The archipelago approach models asphaltene as a
two fused aromatic and heteroaromatic rings, which interconnect by
alkyl bridges [6]. Fig. 1 shows a typical molecular structure of
asphaltene.
Because of the complex chemistry and nature of asphaltenes, a
simpler definition describes asphaltenes as the fraction of crude oil
soluble in aromatic solvents (e.g., benzene) and insoluble in normal
alkanes (e.g., pentane) [8]. The presence of asphaltenes in crude oil is
often detrimental to petroleum operations as their precipitation may
reduce oil-bearing matrix permeability [9,10], cause low oil production
[6], or lead to pipeline clogging[11].
The aforementioned issues are due to an imbalance between the
favorable components of the oils (i.e., asphaltene and resins) and the
unfavorable components (i.e. asphaltenes and saturates) [12,13]. The
mechanisms of asphaltene precipitation, which is a step-wise process,
are triggered by the destabilization of asphaltene monomers in

* Corresponding authors.
E-mail addresses: nguele@mine.kyushu-u.ac.jp (R. Nguele), hakim.saibi@uaeu.ac.ae (H. Saibi).

https://doi.org/10.1016/j.fuel.2021.122559
Received 21 August 2021; Received in revised form 26 October 2021; Accepted 8 November 2021
Available online 14 November 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
R. Nguele et al.
suspension in the crude oil.
The precipitation commences when the asphaltene monomers stack
up to yield nanoaggregates, whose size varies from 2 to 5 nm due to the
co-facial stacking induced by π- π bonding between the poly-condensed
cores [5,14,15]. Because of the propensity of asphaltene to self-
aggregate, the nanoaggregates cluster further to larger sizes (5–12
nm). The alteration of physico-chemical conditions of the environment
in which asphaltenes are dispersed (e.g. injecting gas in the solution)
would prompt the formation of large flocs (size > 500 nm), which lead
invariably to precipitation [16].
Wiehe et al. (2012) suggested that the asphaltene precipitation oc­
curs due to a decrease in asphaltene solubility, which is related to the
kinetics of asphaltene in a dispersed medium [17]. Consistent with the
previous studies, Adams (2014) suggested that the precipitation
occurred when there is an imbalance of the cooperative forces keeping
the asphaltene monomers in suspension, including hydrogen bonding
(H-bonding), Brønsted acid-base interactions, metal coordination com­
plexes, aromatic π- π stacking, and hydrophobic pockets [18]. In sum­
mary, previous literature indicates that both intermolecular (e.g. H-
bonding) and intramolecular forces (e.g. π- π stacking) contribute to
asphaltene precipitation and should be accounted for when considering
the thermodynamic conditions of the system [19].
Bestougeff and Byramjee (1994) showed that asphaltene solubility
could be partially understood if the polymeric nature of the asphaltene is
well-constrained [20]. Daaou et al. (2009) reported that, based on ob­
servations from the Hassi Messaould Oilfield (Algeria), asphaltene pre­
cipitation was proportional to the size of the poly-condensed aromatic
cores of the asphaltenes [21]. Riedeman et al. (2016) showed from the
structural analyses of asphaltene that the larger the aromatic diameter
sheet of the asphaltenes, the higher their likelihood of precipitating
[22]. Their findings are consistent with the conclusions of Ibrahim et al.
(2004), who showed that precipitation likelihood is higher when a
longer alkyl chain is attached to the poly-condensed aromatic core [23].
Thus, evaluating the contribution of the structural parameters of the
asphaltene is important to constrain the mechanisms of asphaltene
precipitation and, moreover, propose a potential mitigation approach.
Typically, structural parameters are determined using spectral methods
[6,24]. In this work, we applied Raman, Infrared, and X-ray spectros­
copy. Raman spectroscopy exploits the carbon structures of asphaltenes
which are similar to those of microcrystalline graphite-like substances.
Quantitatively, the position and integrated intensity of the D1 and G
bands allow the aromatic sheet diameter to be determined [22,25].
Fourier infrared (FTIR) is a complementary tool to Raman spectroscopy,
which uses the absorption of the functional groups present in the
asphaltenes to determine the aromaticity of the asphaltene.
Alhreez and Dongsheng (2019) determined the aromaticity of
Fig. 1. A typical molecular structure of petroleum asphaltenes modified from Yen-Mullin model proposed by Martín-Martínez et al. [7]
2
Fuel 311 (2022) 122559
heptane-precipitated asphaltene by computing the ratio of the inte­
grated peaks of aromatic C– – C at 1600 cm− 1 to those of aliphatic C–H
appearing at a wavelength of 1450 cm− 1 [16]. Rogel et al. (2001, 2015)
showed that the concentrations of functional groups can be estimated
from FTIR, assuming the extinction coefficient remains unchanged
[26,27]. In addition, x-ray spectroscopy (XPS) analyses the chemical
composition of asphaltene, which is expressed as a function of the
chemical states of the element. From the available literature, petroleum
and coal-derived asphaltenes consist mainly of C1s, N1s, O1s, and S2p3/2
[6]; however, differentiating aromatic carbon from aliphatic carbon is of
considerable importance, and forms an essential part of the analytical
process [28].
To help understand the contributions made by the different struc­
tural parameters of asphaltene to its solubility, in this study, we focus on
the influence of aromatic sheet diameter and asphaltene aromaticity. We
were particularly interested in understanding the behavior of asphaltene
with large aromatic sheet diameter (i.e., aromatic sheet diameter>2.1
nm) in different dispersants and titrants. For this purpose, five asphal­
tenes were precipitated from dead crude oils sampled across different
geological formations including Central and West Africa (one sample
from each geographical location), the Middle East, Asia, and North
America. Subsequently, their respective structural properties were
estimated using Raman and FTIR spectroscopy, and XPS spectrometry
was used to determine the elemental composition of the asphaltenes.
Asphaltene solubility was also evaluated in both polar and nonpolar
media using gravimetric methods.
2. Materials and methods
2.1. Materials
2.1.1. Asphaltene samples
The investigated asphaltenes were extracted from five different
crude oils sampled from the surface facilities in North America, Central
and West Africa, Northern Japan, and the Middle East. The properties of
the parent oils are summarized in Table 1.
2.1.2. Chemicals
Table 2 outlines the type, class, name, chemical structure, supplier,
and hydrogen-bonding capability of all solvents used in the present
study.
2.2. Methods
Scheme 1 shows the experimental flowchart followed in this work.
The experiments were broken down into two major groups starting
R. Nguele et al. Fuel 311 (2022) 122559

Table 1 with the extraction and the characterization of the asphaltenes from the
a
Properties of dead oil samples used to extract asphaltenes. parent oils followed by a series of solubility tests. Note that all the ex­
Code A B C D E periments were conducted at room temperature and that the solvents
were used as received.
Origin Middle Central Asia North West
East Africa America Africa
Type of crude oil Light Heavy Heavy Extra- Bitumen 2.2.1. Asphaltene sources
heavy A modified standard procedure (ASTM D3279) was followed to
API gravity (o) 33.7 17.37 16.6 7.9 7.703 extract asphaltenes from their respective parent oils [31]. One gram of
Density (g/cm3) 0.853 0.947 0.955 1.014 1.013
Total acid number 0.774 8.536 3.187 1.853 6.587
crude oil was accurately weighed and transferred to a 100 ml Erlen­
(mg-KOH/g-oil) meyer flask. The crude oil was then diluted with toluene at a volume
Total base number 0.874 0.818 1.182 0.96 0.435 ratio of 1:10 oil:toluene. The mixture was stirred at 1500 rpm using a
(mg-HCl/g-oil) magnetic stirrer (D Lab, MS H280-pro) for 2 hr and the resulting solution
a
Both total acid number and total base number were measured following was then filtered through a 0.45 µm filter paper. One volume of the
standard procedures [29] filtrate was added to 20 volumes of heptane, followed by storage

Table 2
Dispersants and titrants used in this study.
Solvent type Class Name Formula Supplier Hydrogen-bonding capabilitya

Dispersants Aromatic hydrocarbon Benzene C6H6 Junsei Poor

Toluene C6H5CH3 Junsei Poor
Xylene C6H4 (CH3)2 Junsei Poor
Ethylbenzene C6H5C2H5 Junsei Poor
Cyclic ethers Tetrahydrofuran (CH2)4O Junsei Moderate
Furan (CH)4O Sigma Aldrich Moderate
Furfural (CH)4OCO Sigma Aldrich Moderate
Aromatic amine Aniline C6H5-NH2 Sigma Aldrich Strong
Titrants Alkanes Pentane C5H12 Junsei Poor
Hexane C6H14 Junsei Poor
Heptane C7H16 Junsei Poor
Decane C10H22 Junsei Poor
Esters Methyl Acetate CH3COCH3 Junsei Moderate
Ethyl acetate C2H5COCH3 Junsei Moderate
Ethyl propionate C2H5COC2H5 Junsei Moderate
a
Hydrogen-bonding capability was extracted from Ref. [30].

Scheme 1. Experimental workflow followed in this study.

3
R. Nguele et al. Fuel 311 (2022) 122559

Table 3 2.2.3. Asphaltene solubility in different solvents

Elemental compositions of extracted asphaltenes. A gravimetric approach was employed to evaluate the interactions
Elemental composition (wt.%) between the extracted asphaltenes and different solvents following the
workflow illustrated in Scheme 2.
C1s O1s Si2p S2p Fe2p Zn2p
Two set of experiments were conducted in this study. The first set
A 51.4 42.8 3.90 1.92 – – evaluates the contribution of the dispersing medium. An asphaltene
B 57.2 39.3 2.27 1.26 – –
C 71.7 27.3 – – – 1.04
solution of 1 wt% was prepared by dissolving one gram of extracted
D 82.9 14.5 – 2.51 – – asphaltene into 100 g of either a polar (cyclic ethers) or nonpolar
E 83.0 16.7 – – 0.34 – dispersant (aromatic solvents). The asphaltenes were re-precipitated by
the addition of an excess of pentane (1:20 vol ratio) followed by filtra­
tion through a pre-weighed 0.22 µm filter paper.
overnight at atmospheric conditions. The precipitates were separated
The second set of experiments aimed to evaluate the contribution of
from the supernatant fluid by vacuum filtration using a pre-weighed
the titrant (i.e., solvent), which promotes the precipitation of asphal­
filter paper (0.45 µm). The filtered solids (asphaltenes) were then
tenes. In this series of experiments, a separate asphaltene solution
dried at ambient conditions; after this step, no further purification of the
(10,000 ppm) was prepared by dissolving the asphaltenes obtained from
precipitated asphaltenes was performed.
the parent oil into toluene. For each investigated titrant (Table 2), one
volume of the toluene solution was then added to 20 volumes of the
2.2.2. Spectral analyses
titrant. The removal of the precipitated asphaltenes was then performed
The spectral analyses used in this study included Raman, FTIR, and
per the procedure described above.
XPS spectroscopy.
The mass balance of asphaltene in the bulk solution could be written
Raman spectra were acquired using a laser Raman spectroscopy in­
as,
strument (ARAMIS, Aramis Horiba, Japan) which uses a 532 nm Lexel
Ar + Laser. The spectra were obtained in a backscattering configuration mi = mna + mcl + mpr (1)
with a 50 × long work distance objective used to focus the laser.
Fourier Transform Infrared Spectra (FT/IR) were acquired using a where mi is initial mass of the asphaltene (in g), mna is the mass of
Jasco spectrophotometer (Model 4100, Japan). All the absorption asphaltene nanoaggregates formed upon dissolving into the dispersant
spectra were acquired from 400 to 4000 cm− 1 with 48 scans and a res­
olution of 1 cm− 1; in addition, a baseline correction was performed prior
to the analysis.
X-ray photoelectron spectroscopy (XPS) was used to determine the
elemental composition of the extracted asphaltenes. The spectra were
obtained using an AXIS-ULTRA DLD instrument (Shimadzu). XPS results
revealed the photoemissions of Carbon (C1s) and oxygen (O1s) occurred
at binding energy values of 284 eV and 535 eV, respectively (Figure S1,
Supplementary file). Although less prominent, photoemission of sulfur
(S2p) at ~ 166 eV was also recorded. Additionally, transition metals
(iron, Fe2p) and metalloids (silicon, Si2p) were also photo-emitted.
Table 3 outlines the elemental composition of extracted asphaltenes.
The highest carbon content was obtained for the asphaltene extrac­
ted from bituminous crude (83%), while the lowest corresponds to the
asphaltene extracted from the Middle-Eastern heavy oil (51.7%). The
main takeaway from XPS analysis is that the total metal concentration
was too low (i.e., <3%) for their contribution to be significant to the
asphaltene solubility. A more appropriate technique i.e., ICP-Emission
Atomic Spectroscopy (AES) would provide more accurate results on
the influence of metal content to the asphaltene solubility. This point,
however, was beyond the scope of this work.
Fig. 2. Raman spectra of investigated asphaltenes.

Scheme 2. Experimental workflow used in the present study to compute the average solubility; the values 2–5 nm, 5–12 nm, and > 500 nm were extracted from
Ref. [16] and represent respectively the size of nanoaggregates, asphaltene clusters and aggregates.

4
R. Nguele et al.
(in g), mcl is the mass of asphaltene clusters formed (in g), and mpr is the
precipitated asphaltene from the bulk solution (g).
Within the scope of the present work, mpr was obtained from vacuum
the filtration experiments. Thus, the asphaltene apparent solubility (Sap)
was defined as the concentration in asphaltenes that remains in sus­
pension in the bulk solution either nanoaggregates or asphaltene clus­
ters or even both. Sap was obtained from Eq. 2,
( )
Sap = 1 − mpr /mi (2)
A value of S close to 1 would express an apparent stable asphaltene
solution, whereas a value close to 0 would imply most of the asphaltenes
had been precipitated. It is worth mentioning the asphaltene solubility,
measured using gravimetric approach, could be bias due to the poly­
dispersity of the asphaltenes. As such, the apparent solubility (Eq. 2)
expresses only a part of the dissolved sampled and it is not representa­
tive of the average concentration in asphaltenes that would precipitate.
3. Results and discussion
3.1. Structural parameters estimation
3.1.1. Raman studies and aromatic sheet diameter estimation
Fig. 2 shows the Raman spectra for all investigated asphaltenes.
Qualitatively, all acquired spectra were consistent with two shoul­
ders appearing around Raman shift values of 1350 cm− 1 and 1580 cm− 1,
termed respectively elsewhere as D1 and G bands [32]. The D1 band is
due to vibration of sp2 C–C in aromatic fused rings changed by in-plane
defects or heteroatoms. The G band, however, is attributed to stretching
of the sp2 C–C bond in ordered aromatic fused rings [33]. For most of
the extracted asphaltenes, a slight shift was observed, which could be
due to the carbon orientation within the asphaltene [6].
For all the asphaltene samples, except asphaltene (B), the G band is
sharply defined whereas the D1 band appears broad. This suggests a
poorly ordered carbonaceous asphaltene or low short-range order of the
aromatic sheet [25]. Additionally, previous literature reports that a
stronger peak intensity suggests the presence of ring strain and thus a
large aromatic sheet diameter. Quantitatively, the D1 and G bands can
be used to estimate the size of the asphaltene structure. This is achieved
by integrating the intensity of peaks at or near 1350 cm− 1 and 1580
cm− 1 and applying Eq. 3:
La = 4.4IG /ID1 (3)
where La is the aromatic diameter sheet (in nm), IG is the integrated
Fig. 3. Baseline-corrected Raman spectra for extracted asphaltenes. Approxi­
mate extent of D1 and G bands highlighted in gray.
5
Fuel 311 (2022) 122559
intensity of the G band (dimensionless), and ID1 is the integrated in­
tensity of the D1 band (dimensionless).
To apply Eq. 3, Raman spectra were first baseline-corrected (Fig. 3)
and the D1 and G bands were fitted using a Gaussian function (Fig. 4).
The area under each respective band was then estimated and La was
computed using Eq. 3. The results are summarized in Table 4.
Based on literature, the expected theoretical range of La estimated
from Raman spectroscopy is between 1.1 and 2.1 nm [22,25,34]. Our
results showed that only three of the five samples fall within this range,
namely, asphaltenes (A), (B), and (D) extracted respectively from
Middle-Eastern, Central African, and North American crude. Compared
to the aromatic sheet values from crude oils sampled in the same
geological regions [25], the La values obtained in this study were 11 and
15 % larger respectively for asphaltenes (A) and (D).
A plausible explanation would be the maturation process of the
kerogen from which the oils were sampled [35]. The largest La was
obtained from the West-African bitumen, which was threefold higher
than any other asphaltene samples in our study. Unfortunately, and to
the best of our knowledge, there are no available works at present that
report the aromatic sheet diameter of asphaltenes extracted from Afri­
can crudes. Nevertheless, these findings suggest that under the same
conditions, asphaltene (E) would be less stable than all other asphaltenes
due to rapid flocculation of the clusters formed from nanoaggregates
[19].
3.1.2. FTIR studies and asphaltene aromaticity
Fig. 5 shows the infrared spectra of the extracted asphaltenes.
Characteristic absorptions were observed in the IR band at ~ 1450
cm− 1, ~1600 cm− 1, ~1700 cm- 1, ~2900 cm- 1, and ~ 3100 cm− 1.
These peaks are attributed respectively to: (1) the bending of sp3 C–H
bonds; (2) the stretching of aromatic sp2 C; (3) a vibration stretch of
C–– O bonds from a functional group (e.g., acid); (4) sp3 C–H bonds
from aliphatic chains; and (5) vibrational stretching of O–H from an
alcohol [26,36]. Additionally, the IR spectra show a strong shoulder in
the IR band at a wavelength of ~ 2400 cm− 1 (gray shaded circles) for
asphaltenes (C), (D), and (E). This IR band is often associated with the
absorption of gaseous carbon dioxide (CO2), which would suggest that
some CO2 molecules might have been adsorbed to the sample surface
during drying, which was conducted at ambient conditions.
In order to estimate the aromaticity of the asphaltenes, the ratio of
the integrated peaks corresponding to the absorption of sp2 C– – C stretch
at 1600 cm− 1 to the absorption of sp3 C–H at 2900 cm- 1 should be used.
If the bending mode is considered, the aromaticity is computed from the
ratio of the absorption of sp2 C–
– C stretch at 600–800 cm− 1 to the ab­
sorption of sp C H at 1450 cm- 1. In this work, the structural param­
3 –
eters were determined from IR bands showing the stretching vibration
mode as it appears prominent in all the IR spectra. In addition, the in­
tegrated peak ratio 3400 cm- 1/3100 cm− 1 would estimate the likelihood
of an asphaltene to aggregate due to hydrogen bonding [16]. Lastly, the
integrated peak ratio 1700 cm- 1/2900 cm− 1 estimates the concentration
of carboxylic acid to aliphatic carbon. It should be noted that deter­
mining the aforementioned parameters assumes that the extinction co­
efficients of the functional groups do not change among the fraction
[26,37]. For each spectrum, the peaks of interest were baseline-
corrected, deconvoluted using Gaussian fit, and the integrated areas
were then computed.
The plots of the deconvoluted spectra obtained are appended in the
Supporting file of this manuscript (Figure S3, S4). The results of the
estimated parameters as a function of aromatic sheet diameter are
summarized in Table 5.
The ratio 1600 cm- 1/2900 cm− 1, an indicator of the aromaticity,
somewhat increased with increasing aromatic core size; the larger the
La, the higher the aromaticity. Nonetheless, our results are consistent
with the findings reported by Rogel et al. [26,38]. On the other hand, the
hydrogen bonding capability (3400 cm- 1/3100 cm− 1) and carboxylic-
to-aliphatic carbon ratio (1700 cm− 1/2900 cm− 1) showed opposing
R. Nguele et al.
Fig. 4. Raman raw data (white points) and baseline-corrected spectra (in black and blue) fitted with the Gaussian function of extracted asphaltenes (in red) for
samples A–E; The black line denotes D1 band, while the G band is represented by the blue line. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
trends. The former decreases with increasing La while the latter shows a
reverse trend. The observations discussed above appear true for all the
investigated samples except asphaltene D, which shows the largest
values for either parameters. These results would suggest that asphal­
tenes with large core sizes might hinder H-bonding and their aggrega­
tion might be a result of polar interactions.
3.2. Structural parameters and asphaltene solubility
Herein, the structural parameters of extracted asphaltenes will be
correlated with the apparent solubility. It is worth mentioning that the
subsequent results were found by studying one parameter at a time.
However, a multivariable analysis would be a better approach to analyze
the data than checking one parameter at a time.
3.2.1. Influence of dispersant type
To evaluate the contribution of dispersants, a total of eight solvents
were used, including four non-polar and four polar solvents. Each set of
experiments was repeated three times. The repeatability error of the
6
Fuel 311 (2022) 122559
concentration in precipitated asphaltenes was respectively ± 0.05,
± 0.67, ± 1.47, and ± 0.65 mg/g respectively for asphaltene A, C, D, and
E. A summary of the concentration in precipitated asphaltenes is pre­
sented in Table 6.
On average, the precipitate values obtained from 1 g of dispersed
asphaltene in aromatic hydrocarbons (i.e. non-polar solvents) were
24.9, 5.2, 2.4, and 3.4 mg/g for asphaltenes (D), (A), (C), and (E),
respectively. The larger the size of the asphaltene core size, the lower the
obtained precipitate value. The concentration increased with the length
of the alkyl chain attached to the phenyl group, irrespective of the core
size of the asphaltenes (Table 5). The same trend was observed in polar
solvents including cyclic ethers and aromatic amine.
In terms of asphaltene apparent solubility, we found that (1)
asphaltenes were apparently more stable in nonpolar solvents, and (2)
their solubility increases with the aromatic core size (Fig. 6).
Fig. 6 further indicates that the self-aggregation of the asphaltenes is
controlled by the nature of the dispersant. Gray et al. (2011) argued that
the process of asphaltene self-assembly is a combination of both intra-
and intermolecular forces, including π-π stacking and H-bonding [39],
R. Nguele et al. Fuel 311 (2022) 122559

Table 4 Table 6
Raman spectra analysis and calculated La Values using the Gaussian Function for Summary of the concentration of precipitated asphaltenes in different disper­
extracted asphaltenes.a sants; all concentrations are expressed in mg/g.
Sample Origin Band Raman FWHM Area La Dispersant D (2.03 A (2.07 C (2.35 E (7.34
Shift (cm− 1) (nm) nm) nm) nm) nm)
Class Name
(cm− 1)
Aromatic Benzene 0.846 2.515 1.077 0.980
A Middle East D1 1374.6 260.5 61195.9 2.07
hydrocarbon Toluene 7.793 4.780 2.041 1.148
G 1565.9 147.3 28726.4
Xylene 85.81 – 5.659 4.366
B Central D1 1403.3 183.3 78683.0 1.52
Ethylbenzene 5.324 8.272 0.745 7.283
Africa G 1576.6 174.5 27186.8
Cyclic ethers Tetrahydrofuran 11.27 2.372 1.045 0.810
C Northern D1 1363.5 85.60 4224.3 2.35
Furan 192.6 – 1.076 0.766
Asia G 1570.4 70.77 2255.7
Furfural 80.99 – 1.053 1.503
D North D1 1395.8 167.7 93852.2 2.03
Aromatic Aniline 150.6 8.691 4.042 6.074
America G 1570.5 113.7 43218.6
amine
E West Africa D1 1400.0 74.32 33068.2 7.34
G 1607.6 81.38 55168.5
Ref. Saudi Arabia D1 1343 174.6 215848.3 1.88
[25] (Middle East) G 1584 74.2 92299.5
Canada D1 1360 198.81 259549.7 1.72
(North G 1576 111.69 101401.3
America)
a
FWHM: Full width at half maximum.

Fig. 6. Influence of aromatic core size on average asphaltene apparent solu­

bility; asphaltene samples were dissolved in different dispersants and precipi­
tated using pentane.

Table 7
Fig. 5. FTIR spectra of heptane-precipitated asphaltenes. Summary of the concentration of precipitated asphaltenes in different titrants.
All concentrations are expressed in mg/g.
Titrant B D A C E
Table 5
Estimated aromaticity, hydrogen bonding propensity and carboxyl group con­ Class Name (1.52 (2.03 (2.07 (2.35 (7.34
nm) nm) nm) nm) nm)
tent as a function of aromatic sheet diameter
Alkane Pentane 28.25 7.793 4.780 2.041 1.148
La Aromaticity Carboxylic-to- Aggregation
Hexane 7.869 – 9.567 44.16 130.0
(nm) (1600 cm− 1/ aliphatic carbon ratio propensity (3400
Heptane 10.49 0.510 9.751 1.255 4.775
2900 cm− 1) (1700 cm− 1/2900 cm− 1/3100 cm− 1)
Decane 20.27 0.583 8.413 21.30 109.7
cm− 1)
Esters Methyl 73.30 45.51 8.411 9.144 1.290
B 1.52 0.119 ± 0.001 Not detected on IR Not detected on IR Acetate
D 2.03 9.960 ± 3.064 5.459 ± 2.422 0.687 ± 0.161 Ethyl acetate 45.99 1.570 12.36 15.48 0.924
A 2.07 0.505 ± 0.120 0.505 ± 0.120 10.52 ± 2.767 Ethyl 10.89 – 21.16 7.107 21.78
C 2.35 0.426 ± 0.188 0.369 ± 0.001 2.257 ± 0.503 propionate
E 7.34 1.521 ± 0.802 0.998 ± 0.694 0.371 ± 0.089

3.2.2. Influence of titrants

whose formation propensity was estimated by FTIR spectroscopy
(Fig. 5b). The solubility of asphaltene appears to be inversely propor­
tional to the H-bonding, which itself decreases with aromatic core size.
This observation validates the concept that large aromatic cores are
sterically hindered due to their aliphatic side chains and alkyl chains
[19]. These findings are also consistent with the results reported by
Shetty et al. (1996), who argued that aromatic solvents tend to decrease
π-π interactions [40]. The polarity of the solvents alters the stability of
asphaltene such that H-bonding is promoted over π-π interactions.
To investigate the influence of titrants, asphaltenes were re-
precipitated from a bulk solution consisting of 1 g of asphaltene
dispersed in 100 g of toluene. Two types of titrants were considered,
including alkanes and esters. Herein, the series of experiments were
repeated also three times and the repeatability error for asphaltene A, B,
C, D, and E was ± 0.05, ± 0.30, ± 0.68, ± 0.64, and ± 0.74 mg/g,
respectively. The results are summarized in Table 7.
Fig. 7 shows the relationship between asphaltene solubility and the
aromatic core size.

7
R. Nguele et al. Fuel 311 (2022) 122559

Fig. 7. Effect of titrant polarity on asphaltene solubility of asphaltenes; asphaltene samples were diluted in toluene.

Fig. 8. Asphaltene precipitation and solubility in the presence of different inhibitors.

As opposed to the contribution of dispersants, we found that carbon dioxide (CO2) were performed. CO2 was selected because of its
asphaltenes with large aromatic core sizes were less soluble in nonpolar reported impact on asphaltene precipitation [1,41].
solvents (Fig. 7). The average precipitation in alkanes increased mark­
edly from 16.7 to 61.4 mg/g as core size increased from 1.52 to 7.34 nm
3.3. Solvent polarity and asphaltene precipitation
(Table 6). However, an opposing trend was observed when polar sol­
vents were used. The general tendency shows that large asphaltenes’
Two oxygen-containing polar chemicals were selected based on their
cores precipitate less when polar solvents are used, suggesting that large
polarity; these included polyvinyl alcohol (PVOH) and ethylene glycol
aromatic cores are stabilized by H-bonding.
(EG). The preparation of the inhibitors as well as the experimental
It is worth highlighting that the apparent solubility, reported in
procedure are appended in the Supporting file of this manuscript. The
Figs. 6 and 7, was relatively large (>0.80 g/g). It might suggest at first
results of the analysis are shown in Fig. 8.
sight that most of the asphaltenes remained in the bulk solution either as
The general trend shows that fewer asphaltenes precipitate when the
nanoaggregates, clusters or both. This would mean that the apparent
core size is large (Fig. 8a) and consequently more stable (Fig. 8b). This
solubility should be seen as the propensity of either the dispersant or the finding is consistent with the data shown in Fig. 7. For all cases, the
titrant to promote the formation of clusters, and to floc those clusters
bubbling of CO2 initiated the self-aggregation of asphaltenes, as evi­
into large aggregates (precipitates). denced by the decrease in asphaltene solubility. The addition of EG
Nevertheless, these findings from Figs. 6 and 7 evidence the role of
caused more asphaltenes to precipitate, plausibly due to the effect of
H-bonding on asphaltene precipitation, and, furthermore, the role of π-π strong H-bonding.
bonding. Extending these observations to engineering applications (the
As an example, the concentration of precipitated asphaltenes in the
petroleum industry, for example), one can theorize that asphaltene control experiment for asphaltene (A) was calculated to be 2.29 mg/g.
precipitation from a bulk solution can be prevented if the polarity of the
Bubbling CO2 in the blank solution increased the concentration fourfold
medium is controlled. To verify this hypothesis, a series of experiments (~9.15 mg/g). The same bubbling performed in blank and EG yielded a
in which asphaltene was precipitated from a model crude oil using
concentration of 22.9 mg/g, a value tenfold larger than the initial

8
R. Nguele et al.
conditions. The same trend was also observed for larger aromatic cores.
These results validate that asphaltene solubility is inversely proportional
to the size of aromatic cores in a polar medium.
In non-polar solvents, or at least a less polar medium (i.e. PVOH in
this study), asphaltenes are likely to be more soluble due to the alter­
ation of H-bonding between the H-donor of the solvent and the alkyl
chain of the asphaltene, which is consistent with the literature [42]. As
discussed above, the inhibition of the asphaltene precipitation requires
the use of chemicals that primarily alter the H-bonding responsible for
the asphaltenes’ self-aggregation. The concentration of the inhibitor
would also be likely to have an impact, however, this aspect is beyond
the scope of the current study.
4. Conclusions
In this study, we investigate the contribution of structural parame­
ters of asphaltenes on their solubility; in particular, we explored the
effects of aromaticity and aromatic sheet diameters. Asphaltenes were
extracted from five different crude oils originating from North America,
Asia, Central and West Africa, and the Middle East. Both Raman and
Fourier Infrared spectroscopy were employed to estimate, respectively,
the aromatic sheet diameter and the aromaticity of the extracted
asphaltenes. Asphaltene solubility was further evaluated by gravimetric
analyses.
Our findings show that the aromaticity increases with the aromatic
sheet diameter, which itself is inversely proportional to the hydrogen
capability of the asphaltenes. The solubility of asphaltenes depends on
the polarity of the precipitant rather than that of the dispersed medium.
In terms of the dispersant, asphaltenes were more stable in non-polar
solvents, and their solubility increases with aromatic core size due to
π-π interactions. However, asphaltenes precipitate less when polar pre­
cipitants are used due to the effects of hydrogen bonding. From this
study, we conclude that to inhibit the aggregation of large fused cores,
polar inhibitors should be used, whereas nonpolar chemicals could be
effective for small aromatic cores.
Funding
This work was supported by United Arab Emirates University (Fund
Number 12S016).
CRediT authorship contribution statement
Ronald Nguele: Conceptualization, Methodology, Writing – original
draft. Albert Brandt Mbouopda Poupi: Formal analysis, Investigation,
Writing – review & editing. Ghislain A. Mouthe Anombogo: Re­
sources. Olalekan S. Alade: Resources. Hakim Saibi: Funding acqui­
sition, Project administration, Supervision, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors extend their gratitude to Mitsubishi Chemicals for sup­
plying the polymer used in this study. Japan Petroleum Exploration is
also acknowledged for supplying the dead oils from which asphaltenes
(C) and (D) were extracted. This research was funded by the Research
Office of United Arab Emirates University (Fund 12S016).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
9
Fuel 311 (2022) 122559
org/10.1016/j.fuel.2021.122559.
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