Journal of Petroleum Science and Engineering 208 (2022) 109611

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

A comprehensive review on the significant tools of asphaltene

investigation. Analysis and characterization techniques and
computational methods
Masoumeh Hassanzadeh, Majid Abdouss *
Department of Chemistry, Amirkabir University of Technology, P.O. Box:15875-4413, Tehran, Iran

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

Keywords: After years of research into the heavy components of crude oil, asphaltenes are still one of the most complex and
Asphaltene unknown organic molecules. During these years, asphaltene has been the subject of research by chemists,
Self-association chemical engineers, petroleum engineers, materials engineers and other sciences from various angles. Abstract of
Deposition
research on asphaltenes is a decoding of their molecular structures which is the key to solving the puzzle of
Surface activity
Analytical techniques
predicting the specific properties of asphaltenes, such as self-association, deposition, and surface activity in crude
Modeling oil. In this regard, a variety of laboratory techniques have been used to identify asphaltenes in the field of the
Simulation molecular weight, chemical structure, architecture and physico-chemical properties such as MASS, UV-VIS,
NMR, EPR, ESR, FL, IR, RA, XPS, UL, XRD, SAS, GC, AFM, STM, TEM and etc. In parallel with molecular
characterization research, engineers in this field have made great efforts to predict the properties of asphaltenes
to prevent the economic damage caused by the deposition and formation of w/o emulsions in the production
cycle (Oil well reservoir, production, transmission, storage, refinery, etc.). Numerous modeling and simulation
methods have been used to investigate these topics. In this article, a comprehensive review of laboratory
techniques for the identification of asphaltene molecules with a brief introduction of these techniques and the
most popular and most practical computational models for predicting the properties of asphaltene based on
Solubility theory and colloidal theory Has been introduced. Also Recent molecular simulation methods for the
study of asphaltenes, such as Monte Carlo and especially molecular dynamics (MD) and useful tools for the study
of asphaltene have been reviewed.

1. Introduction et al., 2014).

The oil industry has always faced many operational and economic
problems due to the deposits of asphaltene, organic wax and formation
of emulsions, which are observed in the whole process of extraction,
exploitation, production, transportation, refining and in storage tanks.
In crude oil,105-106 types of organic compounds with different mo­
lecular weights and percentages have been identified (Speight, 1999).
The most complex, polar and largest of these compounds can be found in
the molecular class of asphaltenes. They are mixed of molecules with
different weights, structures and functionalities to polydisperse form.
These molecules comprise polyaromatic units, saturated alkyl chains
and distribution of heteroatoms in heterocycles, bridging atoms and
functional groups in alkyl chains. For example, it has shown several
structures of asphaltenes models in Fig. 1 (Headen et al., 2009; Ungerer
The molecular weight of asphaltenes from different oils have been
reported from a few thousand grams to several hundred grams per mole
(Sjöblom et al., 2015). For example, 40,000 to 700, 10,000 to 7,500,> 6,
000, 3200 ± 400, 800, 300–1400 atomic mass units (Soleymanzadeh
et al., 2019). Decades of efforts have been made to identify these com­
pounds, but there are still many challenging questions to solve this great
puzzle. Related difficulties can be considered as the diversity of structure
and molecular complexity, weight range and polydispersity of asphal­
tenes, as well as the lack of analysis techniques with high resolution. The
second subject of asphaltenes which dependent on the determination of
the exact structure and molecular architecture, is to study their physical
and chemical properties and to present the mechanism of
self-association and surface activity of asphaltenes and how to predict
their behavior. Following these fundamental ambiguities, the study of

* Corresponding author.
E-mail address: phdabdouss44@aut.ac.ir (M. Abdouss).

https://doi.org/10.1016/j.petrol.2021.109611
Received 9 July 2021; Received in revised form 18 September 2021; Accepted 4 October 2021
Available online 13 October 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
M. Hassanzadeh and M. Abdouss
the properties of asphaltene has also been difficult. For this purpose,
researchers generally choose two routes to solve these problems:
1. The conventional route: after separating the whole asphaltene from
other components of crude oil, they are divided into smaller sub-
fractions according to their solubility in different n alkanes or
toluene/n-heptane volume ratio for reducing of complexity. (Fossen
et al., 2007; Marques et al., 2008). Although this method is some­
what effective, the resulting asphaltene components are still complex
and uncertain in terms of chemical structure and weight (Fossen
et al., 2011; Rashid et al., 2019; Sjöblom et al., 2015; Wattana et al.,
2005; Zheng et al., 2015).
2. The model compound route: selection and study of model molecules
similar to the structure of asphaltene that have already been syn­
thesized and their properties are similar to the average of real
asphaltene molecules. With this technique, the complexity of the
unknown structures of asphaltenes can be somewhat reduced with
the specific structures of the models, and the results of the studies can
be generalized to the tested asphaltenes with acceptable estimates
(Andrews et al., 2011; Mierau et al., 2015; Pradilla et al., 2016;
Schulze et al., 2015; Sjöblom et al., 2015).
The most important point in the critique of the first method is that
the molecular configuration of asphaltene is strongly dependent on the
extraction technique and the type of solvent. It has been a challenge to
study the self-association of asphaltene and to present models of their
mechanism in different solvents because the structure and architecture
of molecules are not clear and transparent according to this method.
This has led researchers to approach the second route, the use of model
compounds, and in addition to laboratories, have used computational
and simulation tools to investigate the properties and molecular re­
lationships between asphaltenes (Goual et al., 2014; Kuznicki et al.,
2008; Rashid et al., 2019).
In asphaltene phenomenology, there have been various tools and
techniques in finding the hard parts of this complex puzzle. The
advancement of analysis, computing power, and the development of
powerful computers have made the hidden angles of asphaltene clearer.
This review paper focuses on the important tools, “Analysis and char­
acterization techniques”, “Modeling” and “Molecular dynamic simula­
tion”, for examining asphaltene in terms of determining size, weight,
structure and molecular architecture, and the phenomenon of
aggregation.
2. Analysis and characterization techniques
Up to now, different experimental methods have been utilized to
determination of the molecular weight, chemical structure, architecture,
mechanism of aggregation, the structure of aggregates such as size,
shape and morphology that will be briefly discussed in this Section. In
Table 1, a list of these techniques and topics of investigation with their
references is Collected. It is necessary to mention that the experimental
results obtained from asphaltene studies are highly dependent on the
test conditions and the type of analysis techniques used.
O
S
A B
Fig. 1. Asphaltene molecular structures. A, B based on Headen et al. (2009), C, D from Ungerer et al. (2014).
2
Journal of Petroleum Science and Engineering 208 (2022) 109611
2.1. Spectrometry
2.1.1. Mass spectrometry
In determining the molecular weight of asphaltene, mass spectrom­
etry is the most obvious and important analysis technique. Thousands of
molecular weights have been identified from unconventional and un­
known compounds of asphaltene by MS. In addition of molecular weight
and MW distributions, this method is effective and useful in identifying
the chemical structure of asphaltenes such as the carbon number of alkyl
groups, the size of aromatic rings (core), functional groups with N, O, S,
etc. (Dalmaschio et al., 2014; Fergoug et al., 2017; McKenna et al., 2013;
Pereira, Vanini, Oliveira, et al., 2014; Pereira, Vanini, Tose, et al., 2014;
Zuo et al., 2019).with the progress of ionization technology and its
combination with mass spectroscopy, significant advances have been
made in the field of asphaltene. In this technique, gas, liquid, and dis­
solved solid samples are identified based on molecular mass and mole­
cule are converted to charged ions and vaporized, although the matrix
effect may be seen(Zuo et al., 2019). For example, Mietec Boduszynski
published results 850 g/mol as the average molecular weight
asphaltene/n-heptane with using Field ionization mass spectrometry
(FIMS), which contradicted previous conventional reports and also has
faced criticism such as the inability to obtain the gaseous form of heavy
asphaltene molecules and their fragmentation (Mullins et al., 2007). Of
course, none of the ionization techniques are able to produce ions from
all the asphaltene molecules by single ionization (Koolen et al., 2018).
Such as electrospray ionization atmospheric pressure chemical ioniza­
tion (APCI), atmospheric pressure photoionization (APPI), laser
desorption ionization and Matrix-assisted laser desorption/ionization
(MALDI)(Pereira et al., 2014b).The second major problem with all of
these techniques is the concentration of the sample in the measurement
about 255–1100 μg/mL since stable asphaltene nanoaggregates are
observed at a concentration of 50 μg/mL (m/z > 2000) (Hosseini-­
Dastgerdi et al., 2015). It is well known that the process of aggregation
occurs with solvent evaporation. The third factor in the accuracy of
these techniques is the power of the laser in using LDMS and MALDI. MW
of ~850 amu are obtained at low power and low concentration. As the
strength or concentration increases, the mass of larger molecules is ob­
tained. However, all mentioned ionizations together only gave frag­
mentary information about a subset of asphaltenes (Zuo et al., 2019) and
luckily, these techniques are in settlement with the main FIMS and TRFD
results (Mullins et al., 2007).
Recently some of these defects with the technique electrospray
ionization Fourier transform ion cyclotron-resonance mass spectrometry
(ESI-FT-ICR) resolved. In this technique, asphaltene is not evaporated,
but is measured by solvent evaporation and ionization of asphaltene
molecules in a vacuum. Molecules(M) become ions by losing proton (M-
H)– or gaining proton(M + H) +. The ions can be translocated with by
placing them in a magnetic field. One example from Venezuela heavy
crude oil shows the results of containing more than 17,000 component
species. Fig. 2 (Akbarzadeh et al., 2007).
However, mass studies and ionization methods are not yet accurate
and the use of other experimental methods is important. Time-of-flight
mass spectrometry (TOF-MS) is another mass technique that can accu­
rately measure asphaltene aggregate (Fergoug et al., 2017). TOF-MS and
FT-ICR MS can enable accurate chemical compounds, like
O O
O
S
O
S
S
C D
M. Hassanzadeh and M. Abdouss
Table 1
List of topics and Analysis and characterization techniques for Asphaltenes investigation.
Topics
Techniques
Field Ionization Mass Spectrometry
(FI MS)
Laser Desorption Mass Spectrometry
(LD MS)
Electrospray Ionization Mass
Spectrometry (ESI MS)
Atmospheric Pressure Chemical
Ionization Mass spectrometry
(APCI MS)
Atmospheric Pressure
Photoionization Mass
Spectrometry (APPI MS)
Laser Desorption laser Ionization
Mass Spectrometry (L2MS/LDI
MS)
Matrix-Assisted Laser Desorption/
Ionization Mass Spectrometry
(MALDI MS)
Surface-Assisted laser Desorption/
Ionization Mass Spectrometry
(SALDI-MS)
Laser-Induced Acoustic Desorption
Mass Spectrometry(LIAD MS)
Fourier-Transform Ion Cyclotron
Resonance Mass Spectrometry
(FT-ICR MS)
Electrospray Ionization Fourier
Transform Ion Cyclotron-
Resonance Mass Spectrometry
(ESI FT-ICR MS)
Time-Of-Flight Mass Spectrometry
(TOF MS)
Inductively Coupled Plasma Mass
Spectrometry (ICP MS)
Uv–Visible Absorption Spectrometry
(UV–VIS)
Near Uv–Visible Absorption
spectroscopy (Near UV–VIS)
Nuclear Magnetic Resonance (NMR)
Diffusion-Ordered Spectroscopy
(DOSY NMR(
Electron Paramagnetic Resonance
Spectroscopy (EPR)
Electron Spin Resonance
Spectroscopy (ESR)
Fluorescence Spectroscopy (FS)
Fluorescence Correlation
Spectroscopy (FCS)
Fluorescence Depolarization
Spectroscopy (FD)
time-resolved fluorescence
depolarization (TR-FD)
Infra-Red spectroscopy
Near Infra-Red spectroscopy
Fourier transform infrared
spectroscopy(FT-IR)
Raman spectroscopy)RA)
x-ray Raman spectroscopy (XRRS)
X-ray photoelectron spectroscopy
(XPS)
X-ray absorption near edge structure
spectroscopy (XANES)
ultrasonic spectroscopy
Journal of Petroleum Science and Engineering 208 (2022) 109611
Molecular Aggregation References
Size Weight structure architecture Phenomena critical Size&
points Shape
* (Mullins et al., 2007)
* (Koolen et al., 2018; Mullins et al., 2007; Pereira
et al., 2014b; Zuo et al., 2019)
* (Koolen et al., 2018; Mullins et al., 2007; Pereira
et al., 2014a,b; Zuo et al., 2019)
* (Jarrell et al., 2014; Koolen et al., 2018; Pereira et al.,
2014b; Zuo et al., 2019)
* (Koolen et al., 2018; Mullins et al., 2007; Pereira
et al., 2014a,b; Zuo et al., 2019)
* * * * (Groenzin and Mullins, 2000; Hosseini-Dastgerdi
et al., 2015; Jarrell et al., 2014; Koolen et al., 2018,
Pereira et al., 2014b; Sheremata et al., 2004)
* Koolen et al. (2018); Mullins et al., 2007; Pereira
et al., 2014a; Pereira et al., 2014b; Zuo et al. (2019)
* (Ghosh et al., 2016; Pomerantz et al., 2015; Rashid
et al., 2019; Sabbah et al., 2010)
* * (Borton et al., 2010; Ruiz-Morales and Mullins, 2007)
* (Dalmaschio et al., 2014; McKenna et al., 2013; Oh
et al., 2004; Pereira et al., 2014a; Pereira et al.,
2014b; Taylor, 1992)
* (Akbarzadeh et al., 2007; Hughey et al., 2002)
* * Fergoug et al. (2017)
* * (Caumette et al., 2010; Ortega et al., 2012)
* * * (Aguiar and Mansur, 2015; Evdokimov et al., 2003b;
Ghosh et al., 2007; Gray et al., 2011; Morgan et al.,
2005; Wang et al., 2013)
* * * (Evdokimov et al., 2003a; Evdokimov et al., 2003b;
Evdokimov and Fesan, 2016; Ghosh et al., 2007)
* * * * (Andrews et al., 2011; da Silva Oliveira et al., 2014;
Dutta Majumdar et al., 2013; Mullins O et al., 2012;
Poveda-Jaramillo et al., 2016; Rogel et al., 2015;
Ruiz-Morales, 2007)
* * * da Silva Oliveira et al. (2014)
* * (Ben Tayeb et al., 2015; Biktagirov et al., 2014; Cui
et al., 2017; Trukhan et al., 2014)
* * (Ben Tayeb et al., 2015; Biktagirov et al., 2014; Cui
et al., 2017; Trukhan et al., 2014)
* * * * (Abdallah and Yang, 2012; AlHumaidan et al., 2015;
Mullins O et al., 2012; Ruiz-Morales, 2002; Strausz
et al., 2002; Wang et al., 2013; Wu and Kessler, 2015)
* * * * (Andrews et al., 2006; Balou, 2014; Schneider et al.,
2007)
* * * * * (Andrews et al., 2006; McKenna et al., 2013; Mullins
O et al., 2012)
* * * * (Groenzin and Mullins, 2007; Mullins O et al., 2012)
* * (Evdokimov et al., 2017; Santos et al., 2017)
* * (Evdokimov et al., 2017; Santos et al., 2017)
* Batina et al. (2005)
* * (Abdallah and Yang, 2012; Alabi et al., 2015;
Bergmann et al., 2003; Chacón-Patiño et al., 2018;
Riedeman et al., 2016; Ruiz-Morales and Mullins,
2009)
* * (Mullins et al., 2007; Zuo et al., 2019)
* * (Li et al., 2015; Rudrake et al., 2009; Sun et al., 2015)
* (Frisch et al., 2009; Goulon et al., 1984; Rudrake
et al., 2009; Stöhr, 1992)
* * (Andreatta et al., 2005; Mullins O et al., 2012)
(continued on next page)
3
M. Hassanzadeh and M. Abdouss
Table 1 (continued )
Topics
Techniques
luminescence spectroscopy
X-ray scattering/Diffraction (XRD)
Small-Angle X-ray and Neutron
Scattering (SAXS and SANS)
Gas chromatography (GC)
High performance liquid
chromatography (HPLC)
Atomic force microscopy (AFM)
Scanning tunneling microscopy
(STM)
Scanning electron microscopy)SEM)
Tunneling electron microscopy
High-resolution transmission
electron microscopy (HR-TEM)
Vapor-pressure osmometry (VPO)
Pyrolysis
Taylor Dispersion (TD)
Ruthenium Ion Catalyzed Oxidation
(RICO)
Centrifugation
Nano-filtration
Interfacial tension measurement
(IFT)
Viscosity measurement
Calorimetric Titration
laser particle analyzer
Alternating-current conductivity
Direct-current conductivity (DC)
Fig. 2. Combined positive and negative electrospray ionization 9.4T Fourier
transform ion cyclotron resonance mass spectra of a crude oil. From Akbarza­
deh et al. (2007).
characterization of CcHhNnOoSs compounds, heteroatom quantity,
Journal of Petroleum Science and Engineering 208 (2022) 109611
Molecular Aggregation References
Size Weight structure architecture Phenomena critical Size&
points Shape
* Hosseini-Dastgerdi et al. (2015)
* * (AlHumaidan et al., 2015; Gebresellasie et al., 2013;
Tanaka et al., 2004; Yen et al., 1961)
* * * * (Adams, 2014; Amundaraín Hurtado et al., 2011;
Eyssautier et al., 2011; Hoepfner, 2013; Hoepfner
et al., 2013; Tanaka et al., 2004; Trukhan et al., 2017)
* (da Silva et al., 2014; Forsythe et al., 2015; Klee,
2012; Machado et al., 2011; Omais et al., 2012;
Omais et al., 2011; von Mühlen et al., 2010)
* (Caumette et al., 2010; Molnárné Guricza and
Schrader, 2015; Montanari et al., 2017; Rogel and
Moir, 2017)
* * * (Balestrin et al., 2017; Castillo et al., 2017; Schuler
and Meyer, 2015; Schuler et al., 2017; Zahabi et al.,
2012; Zuo et al., 2019)
* (Abdallah and Yang, 2012; Ghosh et al., 2016;
Schuler and Meyer, 2015; Zajac et al., 1994; Zuo
et al., 2019)
* * Tabatabaei-nejad et al. (2011)
* * * (Balestrin et al., 2017; Luo et al., 2010; Sharma et al.,
2002; Trejo et al., 2009; Zhang et al., 2014)
* * * (Balestrin et al., 2017; Luo et al., 2010; Sharma et al.,
2002; Trejo et al., 2009; Zhang et al., 2014)
* (Mullins O et al., 2012; Rubinstein et al., 1979;
Rueda-Velásquez et al., 2013; Sheremata et al., 2004;
Speight, 2006; Strausz et al., 2002)
* * (Karimi et al., 2011; Rubinstein et al., 1979)
* Wargadalam et al. (2002)
* * Zijun et al. (1997)
* * (Hosseini-Dastgerdi et al., 2015; Indo et al., 2009;
Mostowfi et al., 2009)
* * (Ching et al., 2010; Hosseini-Dastgerdi et al., 2015)
* * (da Silva Ramos et al., 2001; Ghosh et al., 2016; Oh
et al., 2004; Rogel, 2000; Simon et al., 2009; Sjöblom
et al., 2015; Taylor, 1992)
* * (Angle et al., 2005; Eyssautier et al., 2012; Hasan and
Shaw, 2010; Mozaffari et al., 2015)
* * (Andersen and Birdi, 1991; Andersen and
Christensen, 2000)
* * Nielsen et al. (1994)
* * (Goual and Abudu, 2010; Sheu et al., 2007; Zeng
et al., 2009)
isotopic spreading, double bond equal (Dalmaschio et al., 2014;
McKenna et al., 2013; Pereira et al., 2014a; Pereira et al., 2014b; Zuo
et al., 2019).
In addition to the techniques mentioned, in recent years, researchers
have achieved more brilliant results by connecting or stacking several
techniques and tools. For example, Multistage mass spectrometry (MSn)
is a valuable technique for detecting the molecular weight of asphaltene
that does not require an initial separation process and its molecules are
separated into ions with any fractionation or association. Connection
APCI/CS2 with MS2 created a beneficial way to discover asphaltene
structures, as alkyl length and cores size(Jarrell et al., 2014; Zuo et al.,
2019). Or Inductively coupled plasma mass spectrometry (ICP MS) has
become a favorite detector in liquid chromatography investigation of
asphaltenes (Caumette et al., 2010).
2.1.2. Ultraviolet–Visible spectrometry (UV–Vis)
Another useful and simple technique used to study the aggregation of
asphaltene is Ultraviolet–Visible spectrometry (UV–Vis), which makes it
possible to determine the degree of aggregation by measuring the
amount of asphaltene chromophore(Aguiar and Mansur, 2015; Wang
et al., 2013) Which, must be done in very dilute solution and in the
fluorescence spectrum (Ghosh et al., 2007). Because asphaltene mole­
cules are present in concentrations below 1 mg/L as monomers and
above 5 mg/L as dimers and trimmers, etc., and finally, with increasing
4
M. Hassanzadeh and M. Abdouss
concentration, lead to asphaltene deposits and also, the larger cores size
and the molecule, the lower the UV-FL intensity (Evdokimov et al.,
2003b; Morgan et al., 2005).
2.2. Spectroscopy
2.2.1. Nuclear magnetic resonance spectroscopy (NMR)
Nuclear magnetic resonance spectroscopy (NMR) is often used to
identify the chemical structure of organic compounds, and its various
regions are used to identify functional groups. This technique has been
used extensively to identify the chemical structure of asphaltene. But
asphaltenes are a complex mixture, the NMR spectra of asphaltenes do
not show a template like the template obtained for pure samples.
In more advanced methods of this technique, such as High Resolu­
tion Nuclear Magnetic Resonance spectrum (HR NMR) or a combination
of distortion less enhancement polarization transfer (DEPT) and single
pulse excitation (Andrews et al., 2011; Pereira et al., 2014a; Pereira
et al., 2014b; Rogel et al., 2015) Can be measured with good accuracy
the degree of aromatics, carbon and hydrogen distribution of asphal­
tene. With these methods, the ratio of alkyl/aromatic carbon and
chemical transfer can be obtained directly.
In addition to the above methods, Diffusion Ordered Spectroscopy
(DOSY) can also well reflect the chemical shift and molecular diffusion
in asphaltenes (da Silva Oliveira et al., 2014) Which plays a key role in
determining the diffusion coefficients of different kindes of aggregates
such as macro, micro and nanoaggregate.
The results of the NMR technique are a good complement to the
information for MS analysis (Pereira, Vanini, Tose, et al., 2014; Zuo
et al., 2019).
2.2.2. Electron paramagnetic resonance (EPR) and electron spin resonance
(ESR) spectroscopy
In recent years, Electron paramagnetic resonance (EPR) and electron
spin resonance (ESR) techniques have been used to characterization of
paramagnetic centers of asphaltenes in particular vanadium ion (VO2+)
in the porphyrin section. These techniques are so sensitive that they can
measure vanadyl ions at low concentrations with good accuracy and
provide useful information about the size of vanadium ion-containing
molecules, the aggregation, and the chemical environments around
vanadium ions (Ben Tayeb et al., 2015; Biktagirov et al., 2014; Cui et al.,
2017; Trukhan et al., 2014; Zuo et al., 2019).
2.2.3. Fluorescence spectroscopy(FS)
Fluorescence spectroscopy has been widely used to investigate the
self-association properties and to approximate the size of aromatic cores
in asphaltene molecules(Abdallah and Yang, 2012; Pereira, Vanini,
Tose, et al., 2014; Wu and Kessler, 2015). Fortunately, despite the di­
versity of asphaltene molecules, the fluorescence absorption and emis­
sion spectra are similar and Their chromophores changed slightly with
concentration changes. The onset of asphaltene aggregation occurs with
red shift and quenching of the largest peak. These shifts have also been
reported at concentrations of 50 mg/L. Fluorescence depolarization (FD)
and time-resolved fluorescence depolarization (TRFD) are belong to the
family of fluorescence spectroscopies that have shown good accuracy in
determining the size of asphaltene molecules (McKenna et al., 2013).
For example, the well-known average molecular weight of 750 Da for
asphaltene has been reported by the TRFD technique and has been
almost confirmed by other experiments(Mullins O et al., 2012; Zuo et al.,
2019).
2.2.4. Infrared spectroscopy
Infrared spectroscopy and Near-Infrared spectroscopy have been
used to identify functional groups, chemical bonds and hydrogen bonds
in asphaltene molecules. IR actually seeks from 4100 to 350 cm-1, while
NIR commonly extents from 10,000 to 4100 cm-1 (Evdokimov et al.,
2017; Santos et al., 2017). It should be noted that these techniques, like
5
Journal of Petroleum Science and Engineering 208 (2022) 109611
other methods, are sensitive to the concentration of asphaltene samples
and the phenomenon of aggregation Which cause shifts of absorption
peaks. The index features of Fourier transform infrared spectroscopy
(FTIR) are well used compared to IR and NIR in the characterization of
asphaltenes. Because it is more difficult to work with dark samples of
asphaltene in the IR transparency. With this method, more than 90% of
asphaltene hydrogens have been detected in alkyl groups (Evdokimov
et al., 2017; Santos et al., 2017).
2.2.5. Raman spectroscopy
In general, The Raman technique is used to distinguish aliphatic
chain carbon from aromatic carbon. The different frequencies of the G
and D bands are used to determine the type of carbon. Asphaltenees in
the Raman spectrum are very similar to graphite-like compounds
because they both have the chemical structure of aromatic fused rings
(Abdallah and Yang, 2012; Alabi et al., 2015; Bergmann et al., 2003;
Chacón-Patiñ;o et al., 2018; Poveda-Jaramillo et al., 2016; Rashid et al.,
2019; Riedeman et al., 2016; Ruiz-Morales and Mullins, 2009).
The x-ray Raman spectroscopy (XRRS) is a more advanced genera­
tion of Raman spectroscopy used for obtaining information about the
local structure of aromatic fused rings (Mullins et al., 2007; Zuo et al.,
2019).
2.2.6. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) is a suitable technique for
the analysis of chemical bonds of carbon, hydrogen, sulfur, nitrogen, etc.
In organic compounds, including asphaltene (Li et al., 2015). Numerous
reports on asphaltene have been presented with this technique, indi­
cating that carbon-carbon and carbon-hydrogen bonds are the most
carbon-containing compounds in asphaltene (Sun et al., 2015).More
advanced X-ray techniques such as Extended X-Ray Fine Structure
(EXAFS) and X-Ray Absorption Near Edge Spectroscopy (XANES) tech­
niques are used to obtain information on the environment and chemical
functionalities of the sulfur, nitrogen and metal elements. Studies have
shown that in asphaltene molecules, sulfur in the form of thiophenes,
sulfide, sulfoxide, sulfone, sulfonate and nitrogen in the form of pyridine
and pyrrole). Nickel and vanadium metals in the structure of porphyrins
have also been investigated by these techniques in the structure of
asphaltene (Fish et al., 1984; Goulon et al., 1984).
2.2.7. Ultrasonic spectroscopy
Most spectroscopies are based on electromagnetic waves, but
acoustic waves are also used in material analysis. Ultrasonic and High-Q
ultrasonic spectroscopy often uses a frequency range of 20 kHz to several
GHz to determine the properties of asphaltene such as formation of
micelles and aggregation (Andreatta et al., 2005; Ghosh et al., 2016;
Mullins, 2012).
2.3. Diffractometry
2.3.1. X-ray diffraction analysis (XRD)
X-ray diffraction (XRD) prepares illustration to the crystallite prop­
erties of materials and is often named “twin-technique” of Raman. The
most important basic information about the chemical structure of
asphaltene is obtained by technique XRD with measuring the inter­
lamellar spacing. XRD results for asphaltene are that the asphaltene
molecules are composed of aromatic sheets with alkyl chains sticking
out from the edges and these layers are stacked on top of each other and
have crystalline or semi-crystalline properties (Abdallah and Yang,
2012; AlHumaidan et al., 2015; Gebresellasie et al., 2013; Hosseini-­
Dastgerdi et al., 2015; Tanaka et al., 2004; Yen et al., 1961).
2.3.2. Small angle scattering
Small angle neutron scattering (SANS), small angle X-ray scattering
(SAXS) and small angle light scattering (SALS) are operated with neu­
trons, X-ray and light, respectively, all of them belong to small-angle
M. Hassanzadeh and M. Abdouss
scattering techniques that are famous and accurate techniques suitable
for length scale of 10–1000 A (Zuo et al., 2019). They have been used to
study the physical properties of colloidal systems as well as the phe­
nomenon of asphaltene aggregation (Comisarow and Marshall, 1974). In
these studies, the crystalline and semi-crystalline structure of asphal­
tene, the shape and size of asphaltene aggregates have been extensively
investigated. Reported results include: prolate ellipsoid, sphere, oblate
cylinder or fractal (Amundaraín Hurtado et al., 2011; Trukhan et al.,
2017). SAXS analysis demonstrated that the size was about 2 nm for
nanoaggregates and about 5 nm for clusters(Adams, 2014).
2.4. Chromatography
2.4.1. Gas chromatography (GC)
To identify asphaltene compounds that have hetero atoms of nitro­
gen, oxygen and sulfur, One-dimensional Gas chromatography (1D-GC)
with special detectors such as nitrogen chemi luminescence detector
(NCD), nitrogen phosphorus detector (NPD), Sulfur chemi luminescence
detector, pulsed flame photometric detector and atomic emission de­
tector Used extensively (da Silva et al., 2014; Forsythe et al., 2015; Klee,
2012; Machado et al., 2011). Despite the ease of 1D-GC technique and its
relatively good results, unfortunately there is a limit to the co-elution of
asphaltene components. To overcome this problem and increase the
sensitivity of the method, two-dimensional chromatography (GC × GC)
technique has been used by coupling non-polar × polar columns. This
improves the separation of compounds in the columns and better reso­
lution in the detectors(Omais et al., 2012).
A more advanced chromatographic technique is the coupling of two-
dimensional chromatography (GC × GC) with mass spectroscopy) MS (,
which is more complete in identifying unknown compounds by sepa­
ration. For example, using GC × GC/TOF MS, 112 types of hetero-atomic
polyaromatic compounds have been identified in coal tar(da Silva et al.,
2014; Forsythe et al., 2015; Klee, 2012; Omais et al., 2012; Omais et al.,
2011; von Mühlen et al., 2010).This technique has been used to identify
sulfur and oxygen compounds in asphaltene, which result in compounds
such as diols, phenols, benzofurans, naphthols and indoles.
2.4.2. High performance liquid chromatography (HPLC)
Simple and coupled High performance liquid chromatography
(HPLC) techniques with other techniques have been used to identify
asphaltene compounds with heteroatoms N, O, S. Such as reversed-
phase HPLC (RP HPLC), normal-phase HPLC (NP HLC), RP HPLC
accompanied by EI MS, NP HPLC-ICP MS, etc.(Caumette et al., 2010;
Molnárné Guricza and Schrader, 2015; Zuo et al., 2019).Each of these
techniques complements other techniques to help identify the heavy and
complex compounds of asphaltene in crude oil.
2.5. Microscopy
2.5.1. Atomic force microscopy (AFM)
Microscopic techniques such as Atomic force microscopy (AFM) are
used to study and analyze the morphology, heterogeneity, and surface
force of asphaltenes in micro and nanometer sizes (Balestrin et al., 2017;
Castillo et al., 2017; Zahabi et al., 2012).Coupling AFM with scanning
tunneling microscopy (STM) has obtained direct and high-resolution
images that further aid in the study of the physical properties of
asphaltene. For example, recently, Schuler and et al., in 2015, took an
interesting initiative to study the molecular structure of asphaltene.
AFM is applied to suggest a presumption of the structure, including
various side groups and If molecular orbitals are available by STM, they
can confirm or reject the presumption.so they mixed the atomic reso­
lution imaging with AFM and molecular orbital imaging with STM and
studied the chemical structure of more than Hundred asphaltenes
(Schuler et al., 2017).
6
Journal of Petroleum Science and Engineering 208 (2022) 109611
2.5.2. Scanning tunneling microscopy (STM)
Another microscopic technique is Scanning tunneling microscopy
(STM) that has developed rapidly for asphaltene molecular orbital study
and very valuable(Qi et al., 2018). One of STM’s good results is the
recording of a size of 1 nm for the core of asphaltene with 6–7 benzene
rings, which was later confirmed by the more advanced high resolution
transmission electron microscopy (HRTEM) technique (Abdallah and
Yang, 2012).
Due to the complexity of the structure, molecular diversity and self-
association of asphaltene in crude oil, coupling techniques have always
been used to obtain more accurate and detailed information. For
example, AFM/STM and FT-ICR MS concurred about size of asphaltenes
and the degree of aromatization (Zuo et al., 2019).
2.5.3. Transmission electron microscopy
TM microscopic technique is used to study the morphology and
crystal structure (ordered/disordered structure) of asphaltene. The more
advanced, HRTEM technique is well used to analyze the aggregation of
asphaltene by directly observing the stacking of sheets or the separation
of accumulated layers or destruction from nanoaggregates. For example,
Sharma and et al. showed that The spacing of the π-π stacking from cores
of 2–3 fused ring was nearly 1 nm in height, little bigger than 1 nm in
width. Other research with HRTEM has shown the effect of addition
modifiers on reducing or increasing the typical distances of PAH mole­
cules (Balestrin et al., 2017; Luo et al., 2010; Sharma et al., 2002; Trejo
et al., 2009; Zhang et al., 2014).
2.6. Others
2.6.1. Vapor phase osmometry (VPO)
The simplest and most common method for measuring the molecular
weight of materials is Vapor phase osmometry (VPO), which of course
depends on temperature and solvent (Rueda-Velásquez et al., 2013;
Speight, 2006). Unfortunately, this simple method for determining the
molecular weight of asphaltene has not received an accurate answer due
to the self-aggregation properties of asphaltene. That is, the result was a
report of the molecular weight of nano-aggregate instead of the
asphaltene monomer. Even with the adding of inhibitors, they could not
reduce the actual (or the apparent) size of the aggregates measured by
VPO and it has always been accompanied by doubt (Rubinstein et al.,
1979).To overcome this shortcoming, other techniques such as Gel
permeation chromatography (GPC) and SEC Used to determine the
molecular weight of asphaltene.
2.6.2. Pyrolysis and Ruthenium Ion Catalyzed Oxidation (RICO)
Pyrolysis and Ruthenium Ion Catalyzed Oxidation (RICO) are con­
ventional techniques for geochemists that by heating and breaking
molecular bonds, provide valuable information about the chemical
structure components of asphaltene. As with previous techniques,
valuable results regarding the chemical structure of asphaltens, both the
aromatic and the aliphatic moiety can obtain by coupling pyrolysis with
gas chromatography or mass spectroscopy (Py-GC, Py-GC/MS). For
example, the aromatic carbon in asphaltene molecules is made up of
small aromatic systems (1–5 rings) while the length of the aliphatic
chains covers a wide range up to 30–40 carbon atoms(Hosseini-­
Dastgerdi et al., 2015).
Ruthenium Ion Catalyzed Oxidation method, aromatic carbons are
converted to smaller compounds such as carbon dioxide and/or car­
boxylic acids while leaving aliphatic and aIicylic portions intact. RICO
method has been widely used to elucidate the chemical structures of
coal, kerogen, asphaltenes and other high molecular weight of petro­
leum(Zijun et al., 1997).
2.6.3. Interfacial tension measurement (IFT) and viscosity measurement
(VIS)
Due to the behavioral similarity of the self-association of asphaltene
M. Hassanzadeh and M. Abdouss Journal of Petroleum Science and Engineering 208 (2022) 109611

molecules in crude oil with the self-assembly of surfactant molecules in
solution, the tensiometer technique has been widely used to evaluate the
physicochemical behavior of asphaltene in polar organic solvents.
Numerous surface tension determinations have been reported to inves­
tigation of the self-association and surface activity of asphaltenes (Ghosh
et al., 2016; Mullins et al., 2007; Rogel et al., 2000; Sjöblom et al., 2015;
Taylor, 1992).
Second suitable technique for investigating the surface and interfa­
cial activity of asphaltene in crude oil and the model is to use a
viscometer. In a way, Viscosity measurement is similar to Interfacial
tension measurement. Another important issue in the field of asphaltene
is the study of the effect of asphaltene aggregation on the rheology of
crude oil and W/O emulsions, which has been studied in many re­
searches with this technique (Angle et al., 2005; Eyssautier et al., 2012;
Ghosh et al., 2016; Hasan and Shaw, 2010; Mozaffari et al., 2015;
Pomerantz et al., 2015).
2.6.4. Alternating-current conductivity and direct-current conductivity
(DC)
Alternating-current conductivity and Direct-current conductivity
(DC) are two other techniques such as viscometer and tensiometer, have
been used extensively to study the intrinsic properties (self-association
and surface activity) of asphaltene. The sensitivity of these techniques is
as high as their simplicity. The comparing results of AC and Dc have
shown that with the condition of choosing the right frequency range, the
AC conductivity method can be a good option for measuring floccula­
tion, precipitation, and phase separation of asphaltenes(Goual and
Abudu, 2010; Sheu et al., 2007; Zeng et al., 2009).
3. Computational methods
Subramanian et al., 2016). The most popular models of the colloidal
theory are the chemical potential, the micellization model, and the in­
verse micellization model.
A brief description of these models is shown in Table 2. (Rashid et al.,
2019). The challenge of each of these models is the extent to which they
are validated by laboratory results.
3.2. Molecular simulation
Predicting the physical and chemical properties of different materials
and examining different phenomena using the experimental test
methods and examining the results is costly and requires time, facilities
and materials, but computer simulation saves time and resources well.
Due to the structural complexity and molecular diversity of asphaltene
and consequently the diversity of properties and mechanisms, molecular
simulation has been greatly helped to understand asphaltene.
3.2.1. Molecular dynamics (MD), Monte Carlo
Today, with the development of mathematical algorithms and the
processing power of computers, simulation techniques have been used
to understand and predict the structure, physical and chemical proper­
ties, and function of molecular systems, which are a major challenge for
laboratories. In general, in the simulation literature, a trajectory is
generated for a number of system particles using known rules, and the
corresponding properties are calculated at each instant of the path and
averaged over the entire trajectory to compute estimates of desired
properties (Frenkel and Smit, 2001; Leach and Leach, 2001).
There are mainly two types of molecular simulations: Molecular
Dynamics(MD)and Monte Carlo. In the molecular dynamics method for

Today, in parallel with advances in laboratory techniques, significant Table 2

advances in calculations, methodologies of models, and simulations Important finding of the thermodynamic models base on solubility and colloidal
theory for asphaltene aggregation. Rashid et al. (2019).
have been observed to study physical and chemical phenomena in
various fields of science such as chemistry, biophysics and materials Theory Name Models Basis
science (Frigerio and Molinari, 2011). One of the biggest benefits of solubility Regular solution Hirschbery Vapor liquid phase
modeling and simulation is reducing laboratory costs and helping to Burke FHT
better design experiments and predictions. Methods of computational Novosad & Hirschberg’s model
Costain
thermodynamics modeling have been successfully used for the investi­
Rassamdana Hirschberg’s model
gation and prediction of chemical phenomena, process and etc. Different Thomas Won’s Liquid-solid model
methods of modeling and simulation are used in various asphaltene Chung Solid-Liquid equilibrium
research fields. Cimino Phase separation
De Boer Hirschberg’s model
Yarronton Solid-Liquid equilibrium
3.1. Modeling Alboudwarj Yarronton model
Buckley Refractive index
Predicting the starting point of asphaltene accumulation in the oil Wang & FHT
industry is extremely important. Many efforts have been made to Bauckley
Scot Magat Kawanaka Heterogeneous structure
improve the prediction equations using thermodynamic models to study Equation of state Gupta Solid phase fugacity
asphaltene deposits. These models are based on two approaches (1) model (EOS) correlation & Peng Robinson
solubility and (2) colloidal. Ngheim
Solubility theory believes that asphaltenes dissolve in crude oil and Sabbagh PR-Eos
Chapman Wertheim’s thermodynamic
precipitation occurs when the solubility falls below a certain threshold
perturbation theory
(David Ting et al., 2003). Using the solubility parameter, these models Gross & Perturbation theory
assume that crude oil consists of two parts: asphaltene and Sadowski
non-asphaltene parts. Any change in the solubility parameter leads to McMillan- SAFT model
the separation of these two parts into two phases with a change in their Mayer
Li & Wertheim’s thermodynamic
phase equilibrium. For example, the adsorption of gas or the increase of Firoozabadi perturbation theory & PR
alkanes in crude oil are examples of changes that improve precipitation Shirani Psudocomponents approach
of asphaltenes (Andersen and Speight, 1999). The models are based on Flory Huggins Flory Huggins Regular solutiontheory
the theory of solubility, Regular solution, Flory-Huggins, Scott-Magath, Flory Huggins- Polymer solution theory with
Zuo gravitational effect
and the state model equation.
colloidal Chemical Leontarits Colloid & suspension
Colloidal theory states that asphaltenes are dispersed in oil as Potential
colloidal particles and are stabilized by resin molecules adsorbed on Micellization Victorov & Advance thermodynamic
their surfaces (Leontaritis and Mansoori, 1987). If the amount of resins Firoozabadi
in crude oil decreases for any reason, asphaltenes become unstable and Reverse Pan & Reverse micellization
Micellization Firoozabadi
precipitate (Agrawala and Yarranton, 2001; Ashoori et al., 2009;

7
M. Hassanzadeh and M. Abdouss
particles, the equations of motion over time and path are numerically
integrated to generate a dynamical trajectory of the system, and finally
the structural, dynamic and thermodynamic properties of the system are
investigated. In the Monte Carlo method, structural and thermodynamic
properties can be calculated with the help of probabilistic rules and
sequencing of system particle states without considering time.
After selecting the type of molecular simulation, it should be
emphasized that the implementation of a successful molecular simula­
tion depends on three main factors. Precise molecular structure,
appropriate force field and optimal algorithm with powerful processor
of a computer.
3.2.2. Molecular dynamic simulation
Due to the diversity and complexity of the molecular structure of
asphaltene and the nanostructure of the processes of aggregation,
deposition and emulsification of asphaltene in crude oil, the conditions
for laboratory examination are very difficult (Lin et al., 2017; Tirjoo
et al., 2019; Zhang et al., 2010; Zhu et al., 2015). In recent decades, the
simulation of molecular dynamics and the development of methods and
the strengthening of computers has greatly provided a potential capa­
bility to expand the understanding of the knowledge of the mechanisms
(Headen et al., 2017). Another important aim of asphaltene simulations
is to be able to predict their inaccessible properties in macroscopic be­
haviors in experiments.
In all molecular simulations, especially asphaltenes, it is important to
consider several factors, which are the basic condition for the accuracy
and closeness of the simulation results to the experimental results. These
factors include: the molecular structure of asphaltenes, the effect of
solvent, appropriate force fields, the time and length scales, etc.
The molecular structure of asphaltenes: Accurate description of the
molecular structure of asphaltene in successfully simulation molecular
dynamics is vital and a challenging step. Because the molecular structure
of asphaltene in crude oil is large, diverse, complex and unknown and is
not a single molecule and there is a set of molecules in the category of
asphaltene (Headen et al., 2017).This makes the simulation method with
a major problem. If the simulation is performed with an experimental or
hypothetical molecule similar to asphaltene such as molecular weight
and heteroatom content of the molecule, it can never incorporate the
properties of a set of asphaltene molecules. On the other hand, consid­
ering polydispersity (the entire population of asphaltenes) would
complicate and lengthen computer calculations due to propose a tech­
nical difficulty in determining the actual forces that intervene in
asphaltene aggregation and is not very possible in practice.
Many studies have used model compounds that are structurally
similar to asphaltenes. This method can more accurately compare
simulation and laboratory results. In this way, the strengths and weak­
nesses of the simulation are revealed to examine the real asphaltenes
accurately and realistically, and by modifying the method, this method
can be used with more confidence. For example, Jian et al. (2013).
Simulated derivatives of violanthrone-78 as a model for asphaltene.
Another recent example is the study of alkyl-substituted hex­
abenzocoronene molecules (Costa et al., 2016). In recent years, the
study of the properties of asphaltene with MD has become more rapid
and accurate with the development of supercomputers.
The effect of solvent: In a real-world study, the properties of asphal­
tene are measured in petroleum or solvents. Therefore, in molecular
simulations, the structure-solvent relationship must be considered so
that the simulation results can be compared with experimental (Aray
et al., 2011; Tirjoo et al., 2019). However, large systems consisting of
many asphaltenes plus solvent molecules might be difficult to simulate
due to high computational cost (de León-Barreneche et al., 2015).
Force fields: after the great importance of molecular structure and
structure-solvent relationship in simulations, the third prominent issue
is the use of appropriate force fields. Because the simulations are based
on inter-molecular potentials that must be fully accredited. For example,
the Dreiding (Goddard, 1990), Universal (UFF) (Rappé et al., 1992),
8
Journal of Petroleum Science and Engineering 208 (2022) 109611
CHARMM (MacKerell et al., 1998), AMBER(Cornell et al., 1995),GRO­
MOS (Oostenbrink et al., 2004), OPLS (Jorgensen et al., 1996) and
COMPASS (Sun, 1998) are good and general force fields.
The time and length scales: to describe liquid and solid systems, the
length and time scales are very important in simulation, because we
often seek to determine the properties of molecules in the solvent such as
thermodynamic properties, dynamic behavior, orientation and accu­
mulation in solvents (Wang and Ferguson, 2016).
The all-atom simulations and coarse-grained molecular simulations
are two types of molecular simulations in which the importance of time
and length scales is clearly evident. Although significant successes have
been reported in the all-atomic method of detecting molecular details in
the early stages of asphaltene aggregation, the high computational cost
for systems larger than 50 molecules and larger than 100 nm has limited
this method (Boek et al., 2009; Greenfield, 2011; Hansen et al., 2013;
Headen et al., 2009; Mullins, 2010; Rogel, 2000; Sedghi et al., 2013). In
contrast, the coarse-grained method is a good tool for overcoming time
and length constraints compared to the all-atom method and can make
calculations up to microsecond times and hundreds of nanometer scales
at a lower cost, but fails to express molecular details along the way
(Izvekov et al., 2005; Noid, 2013).
Analysis tools of MD: Generally, several parameters and factors are
used in simulation to study the thermodynamic and macroscopic prop­
erties of molecular systems. The type of analysis depends on simulation
system plus the objective of study. In order to study the self-association
and surface activity properties of asphaltene, the attention has been paid
to the parameters of the energetics of aggregation and the solubility
parameter, …
The energetics of aggregation: The Molecular simulations investigates
to date have focused on the energetics of aggregation and the diffusion
of asphaltene molecules. Aggregation of asphaltenes actually occurs due
to the sum of the attraction and repulsion forces of intramolecular and
intermolecular interactions in the asphaltene-asphaltene molecule pair.
Much research has been done to measure the energy of aggregation and
a relatively wide range from − 89 kJ/mol (Rogel, 2000) to as high as
− 372 kJ/mol has been published, depending on the type, size and mo­
lecular structure of asphaltene (Murgich et al., 1996).
For example, Headen et al. in a series of simulations, used the SHAKE
algorithm to be a fixed distance apart of a pair of asphaltenes and
calculated the PMF (potential of mean force). In fact, PMF is equivalent
to the free aggregation energy of asphaltene (Headen et al., 2009).
Sedghi et al. used the umbrella sampling method to measure the inter­
action forces of asphaltene-asphaltene and their aggregation energy
with drawing the force-distance curve. They used harmonic-spring bias
potentials to keep constant the distance between molecules from each
other (Sedghi et al., 2013). In a more recent investigation, Pache­
co-Sánchez et al. used a more complete COMPASS force field. They re­
ported value about − 55 kcal/mol in a vacuum for dimer aggregation
energy and 3 to 4 Å for the center of mass distance of two asphaltene
molecules also the aromatic cores of the molecules are in parallel to each
other (Pacheco-Sánchez et al., 2019).
The solubility parameter: One of the important and key physico-
chemical properties of chemicals is their solubility in different sol­
vents. The solubility parameter is an easy utility method which used to
predict the attraction between the solute and the solvent(Rogel, 2011;
Stefanis and Panayiotou, 2012; Tirjoo et al., 2019).In molecular simu­
lation, the Hildebrand solubility parameter has been used extensively to
predict the solubility of asphaltenes with a series of liquids, greatly
differing either in molecular polarity or aromatic content (Belmares
et al., 2004). In fact, measuring the solubility of asphaltene is not
possible experimentally because these materials are not volatile and
decompose before boiling point and must be calculated. The solubility
parameter is demonstrated by equation (1):
Ecoh ΔHvap − RT
δ2 = = (1)
Vm Vm
M. Hassanzadeh and M. Abdouss
where Ecoh, ΔHvap, Vm, R and T are the intermolecular forces (cohesive
energy), the evaporation enthalpy, the molar volume, the general gas
constant and the temperature, respectively.
For example, Rogel obtained good results in the study of the solu­
bility of asphaltene with toluene and heptane solvents by molecular
dynamics. Several MD simulations were also conducted with 45 number
of toluene or heptane molecules. The interaction energies between
asphaltene molecules and solvent were calculated as − 160 and − 40 kJ/
mol in heptane and toluene, respectively representation qualitative
settlement with the solubility quantification. Another issue in their
research was the relationship between the size of nanoaggregates and
their solubility. The larger the particle size in the aggregation process,
the less solubility was observed(Rogel, 1995).
4. Conclusion
Due to the diversity and complexity of asphaltene structures in the
crude oil mixture, determination of the weight, structure and architec­
ture is very difficult. This principle has made it more difficult to study
and understand the physical and chemical properties of asphaltene in
crude oil. Self-association, deposition, surface activity and the formation
of emulsion in crude oil have been the subject of research by chemists,
chemical and petroleum engineers for many years.
Advances in measuring and analyzing instruments in recent decades
have greatly contributed to the advancement of asphaltene science also
studies show that test conditions play a key role in determining the
properties of asphaltene. Table 1 lists about 50 techniques for deter­
mining weight, chemical structure, molecular architecture, and inves­
tigating the self-association and surface activity mechanism of
asphaltene. Each in turn played an important role in elucidating the
asphaltene puzzle, and some techniques complemented each other.
Summary the assistance of laboratory techniques in determining the
molecular weight, chemical structure and architecture, physicochemical
properties of self-association and surface activity of asphaltenes are:
1 the weight of asphaltene molecules from different oils have been
reported from a few thousand to a few hundreds, 40,000 to 300 gr/
mol. But what is more famous and accepted the asphaltenes of pe­
troleum generally have a middle molecular weight in the span of
550–750 g/mol.
2 asphaltene molecules comprise polyaromatic units, saturated alkyl
chains and distribution of heteroatoms in heterocycles, bridging
atoms and functional groups in alkyl chains. Characterization of the
number, size, and geometry of aromatic rings in the asphaltene
molecules and how they are connected to each other in structure is a
challenging task. The results of these experiments indicate that the
fused ring system of asphaltenes have been characterized from 2 to
20 and the average number is less than 10. In recent years, more
details on the number of aromatic rings have been clarified with
capture of scanning tunneling microscopy and show that 6 to 7 fused
aromatic rings have been assumed for the aromatic section of
asphaltenes and the molecular size about 1 nm for asphaltenes.
Two essentially distinct standpoints of the asphaltene structure and
architecture are organized in the literatures where the asphaltene mol­
ecules can be classified as depending to either the island or the archi­
pelago architecture. If asphaltene has only one poly-aromatic
hydrocarbon cores per structure’s, it is named an “island” or “conti­
nental”, but it has two or more aromatic cores linked together by hy­
drocarbon bridges, it is named an “archipelago”.
3 the complexity, diversity and polydispersity of asphaltenes makes
the experimental analysis in confused, despite all the enlightenment,
there is still no acceptable community for the unequivocal answers to
the self-association of asphaltenes, and the thermodynamic driving
9
Journal of Petroleum Science and Engineering 208 (2022) 109611
force behind this phenomenon. Decades of research about the ag­
gregation of asphaltene in diverse sources have led to the suggestion
of plentiful models such as The Colloidal/micelle model, The
Yen–Mullins model and The Gray model that even contradict each
other.
4 the results of various studies have shown that asphaltenes form ag­
gregates not only in petroleum but also in toluene and benzene sol­
vents. Measurements of the surface tension of asphaltene in solvents
and determination of the break point of surface tension in terms of its
concentration is similar to the performance of surfactants in water.
Researchers in the fields of chemical and petroleum engineering
have proposed various models based on solubility and colloidal theories
for prediction of self-association and deposition. Table 2 lists 26 ther­
modynamic models according to these theories. The success rate of
predicting these models is measured by the degree to which the results of
the models match the rate of asphaltene deposition in the laboratory.
None of these models have yet been completely successful in predicting
asphaltene deposition.
In the last two decades, along with modeling, quantum chemistry
and molecular simulation methods such as molecular dynamics and
Monte Carlo have been developed to understand the mechanism of the
self-association and surface activity of asphaltenes. In all molecular
simulations, it is important to consider several factors, which are the
basic condition for the accuracy and closeness of the simulation results
to the experimental results. These factors include: the molecular struc­
ture, the effect of solvent, appropriate force fields, the time and length
scales. In addition to advances in the characterization of asphaltene with
laboratory techniques, the strengthening of computers and the devel­
opment of mathematical algorithms can be more and more involved in
the success rate of computational methods in accordance with labora­
tory results. It is safe to say that the development of computational
methods, especially the molecular dynamic simulation, complement and
fill the lack of nanoscale analysis devices.
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.
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