http://pubs.acs.

org/journal/acsodf Article

Determination of Asphaltene Stability in Crude Oils Using a Deposit

Level Test Coupled with a Spot Test: A Simple and Qualitative
Approach
Syed Imran Ali,* Shaine Mohammadali Lalji, Javed Haneef, Syed Mohammad Tariq, Muhammad Junaid,
and Syed Muhammad Aun Ali
Cite This: ACS Omega 2022, 7, 14165−14179 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: The main goal of this study is to monitor the

stability of crude oils in terms of both precipitation and deposition
magnitude with respect to time. To achieve this goal, two
experimental techniques which include a deposit level test and a
spot test were integrated and applied simultaneously. The method
was implemented using six crude oils, namely A, B, D, E, F, and G,
and tests were performed at different times which split them into
short duration tests and long duration tests. All crude oils were
found to exhibit potential for asphaltene precipitation and
subsequent deposition at different rates. Crude oils B, G, and D
were observed to have started asphaltene precipitation and
subsequent deposition relatively quicker. Similarly, crude oils B,
A, and F exhibit a higher potential for producing asphaltene deposits in terms of deposition level. Crude oil E produces relatively
fewer deposits at comparatively slower rates. The overall result indicates that crude oil B was found to be the most risky crude oil as
it produces a higher quantity of deposits at higher rates, while crude oil E proved to be the least risky. Sensitivity analysis was also
performed via the computing relevancy factor to determine the relative importance of two input parameters, namely the specific
gravity of crude oil and the time for two-output precipitation intensity and deposition level. Precipitation intensities were found by
the implementation of an image-processing tool on spot test results. The relationship between time and precipitation intensity was
found to be negligible; however, the correlation between time and deposition level was found to be strongly positive with a relevancy
factor value of approximately 0.521. Similarly, the relationship of the specific gravity of oil with precipitation intensity and deposition
level was found to be moderately negative and very close to each other, i.e., −0.228 and −0.247, respectively. The integration of the
deposit level test with the spot test allows the continuous and simultaneously reliable monitoring of both asphaltene precipitation
and deposition at different times without involving cost, complex instrumentation, or interpretation, irrespective of the type of oil.
The method enables the successful determination of stability ranking of different crude oils both in terms of precipitation and
deposition.

1. INTRODUCTION being insoluble in n-alkanes, especially n-pentane and n-

Asphaltene deposition in oil fields remains a challenging
problem for the Upstream Petroleum Industry.1 This problem
could arise anywhere in the production system, i.e., at the
reservoir or at subsurface and surface facilities.2 Asphaltene
deposition could impact oil companies technically in terms of
the deployment of complex treatment methods and econom-
ically with respect to interruption of sustainable hydrocarbon
production and implementation of expensive treatment
techniques.3−7
Crude oil is usually characterized into SARA (Saturates,
Aromatics, Resins, and Asphaltenes) fractions.8,9 Among the
SARA fractions, asphaltene is regarded as the heaviest and
most polar component of crude oil.9,10 Asphaltene, by
definition, is that component of crude oil which is found to
be soluble in aromatic solvents like xylene, toluene, etc. while
© 2022 The Authors. Published by
American Chemical Society
14165
heptane.10,11 The asphaltene molecule is composed of mainly
carbon and hydrogen and some amount of heteroatoms and
metallic compounds.6,12,13 The composition of asphaltene is
considered an important stability parameter because it
provides information regarding the asphaltene precipitation
risk in crude oils. It was reported by several researchers that
asphaltene stability in crude oils increases as the H/C ratio of
Received: February 7, 2022
Accepted: April 1, 2022
Published: April 15, 2022
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 1. (a) Archipelago asphaltene structure. Reprinted from ref 17. Copyright 2008 American Chemical Society. (b) Continental asphaltene
structure. Reprinted from ref 17. Copyright 2008 American Chemical Society. (c) Anionic continental asphaltene structure. Reprinted from ref 17.
Copyright 2008 American Chemical Society. (d) Yen−Mullins asphaltene model. Reprinted from ref 14. Copyright 2010 American Chemical
Society.

asphaltene increases and aromaticity and heteroatoms
decreases.1 Previously in the literature, various values of
asphaltene molecular weights were presented by different
researchers. However, the probable value of asphaltene was
found to be 750 g/mol.12−15
With respect to structural architecture, asphaltene does not
have a definite structure. Continental, archipelago, anionic
continental, and Yen−Mullins models are some of the most
accepted and famous structural models of asphaltene.9 Figure 1
shows the aforementioned structural models.14,17 According to
Figure 1, the archipelago model possesses several aromatic
rings joined together through various aliphatic branches.9,16,18
Alternatively, the continental model consists of a large central
cluster of aromatic rings in an asphaltene molecule that is
joined together through several aliphatic chains.9,18 The
anionic continental model has a structure similar to that of
the continental model, but the major difference lies in the
presence of a negative charge onto the aliphatic chains, which
is further joined to the main structure.9 Finally, the last, most
accepted, and recent model is the Yen−Mullins model. The
model describes asphaltene structure in terms of both size and
behavior which have an influence on crude oil properties that
asphaltene displays. According to the Yen−Mullins model, in
14166
lighter crude oils, asphaltenes exist as small polyaromatic
hydrocarbon compounds and possess an average diameter of
1.5 nm. In this scenario, the asphaltene concentration found to
comparatively low with constant asphaltene size. In black oils,
the asphaltene concentration found to be relatively high, and it
exists as nanoaggregates with an average diameter of 2 nm,
which is comparatively higher than that of the lighter oils. In
heavy oils with extremely low API gravity, the asphaltene wa
found to exist in higher concentrations with an average
diameter of 5 nm in the form of cluster.9,15
Characterization of asphaltenes requires the extraction of
asphaltene from crude oil and then utilization of various
analytical techniques.19 According to the definition of
asphaltenes, different standard protocols are developed for
the extraction of asphaltenes from crude oils. These include
ASTM D-4124-01, ASTM D-3279-07, WRI, ASTM D-4124-
09, ASTM D-6560-00, ASTM D-2007-03, etc.12 The extracted
asphaltene sample is then used for the determination of various
properties. X-ray diffraction (XRD)20 and nuclear magnetic
resonance (NMR)21,22 can be employed for the determination
of average molecular parameters of asphaltenes. Mass
spectrometry (MS) techniques, vapor pressure osmometry
(VPO), and size-exclusion chromatography (SEC) can be used
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
to determine the molecular weight distribution of asphal-
tenes.23−26 MS technology and particularly ultrahigh resolution
(UHR) mass spectrometers can be utilized for analyzing the
molecular composition and chemical properties of extracted
asphaltenes.27−29 Electrospray ionization (ESI) coupled with
Fourier transform ion cyclotron resonance−mass spectrometry
(FT-ICR−MS) can be used to analyze the composition of
heteroatomic compounds in asphaltenes and their correspond-
ing aromatics, saturates, and resin contents.30,31 Gel-perme-
ation chromatography (GPC) with inductively coupled
plasma−mass spectrometry (ICP−MS) facilitates in the
identification and quantification of sizes associated with various
Ni, V, and S compounds in asphaltenes.32 Atomic force
microscopy (AFM) is an important technique which enables
the direct observation of asphaltene molecules on an individual
scale.33
The asphaltene precipitation and its subsequent deposition
are governed by various factors. The factors mainly include
variations in pressure, crude oil composition, temperature, and
electrokinetic effects.34 The terms asphaltene precipitation,
asphaltene flocculation, and asphaltene deposition are different
in terms of mechanism and definition.35 Precipitation can be
explained as asphaltene changes its phase from the liquid to the
solid state by the process of aggregation.35 Kinetically, the
aggregation process in a colloidal system is either controlled by
an RLA (reaction-limited aggregation) process or a DLA
(diffusion-limited aggregation) process. In initial phase of
aggregation, the RLA process is found to be dominant, whereas
the later stage of aggregation is controlled by a DLA
process.36−38 After precipitation begins, these precipitated
asphaltenes grow their size to about 1 μm through the process
of clustering. This stage is referred as asphaltene flocculation.35
Lastly, a deposition phase starts after the flocculation stage
where flocculated asphaltene attains its maximum size and
starts depositing at the surface of the metal.35 It is worthy to
note here that asphaltene precipitation does not always
guarantee asphaltene deposition and is not considered as
undesirable as asphaltene deposition; however, it might
facilitate the deposition process significantly, which needs to
be controlled by implementing various treatment methods.35
The treatment methods may include operational, mechanical,
chemical, biological, ultrasonic, and thermal.34,39
For petroleum companies, it is always preferred to adopt
preventive measures rather than going for mitigation of
asphaltene deposition as it prevents them from costly
shutdowns and deployment of expensive treatment techniques.
Therefore, under these circumstances, it becomes very
important to assess the stability of crude oils. In the literature,
there are various stability assessment methods proposed to
determine the asphaltene deposition risk potential in crude
oils. Among them, one of the methods is based on determining
asphaltene stability in crude oil on the basis of crude oil SARA
values.1,40 The basic concept behind this method is that crude
oil is found to be more risky in terms of asphaltene deposition
if it contains higher contents of saturates and asphaltene and
lower contents of resins and aromatic contents.1,22 Different
models like the colloidal instability index (CII), stability index
(SI), colloidal stability index (CSI), Stankiewicz plot (SP),
ANJIS Model, qualitative−quantitative analysis (QQA), and
stability cross plot (SCP) were developed and applied in the
past, which works well on this concept.41−49 Although these
models are very easy and simple to apply as it involves less
computational work, their reliability and accuracy are
14167
Article
debatable.1,40 These indices suffer inaccuracies due to the
absence of the incorporation of other factors like asphaltene
and resins compositional and structural properties and
operational conditions such as temperature and pressure
conditions which are equally important for judging asphaltene
stability in crude oils.1 In addition, these parameters take
SARA values as input which are determined through various
techniques and found to have significant differences in values
from each other; therefore, in this context it may produce
different stability outcomes for same crude oil.1,40,41,44
Moreover, recent studies reported that these SARA-based
parameters produce biased predictions, i.e., predict certain
classes better, and because of this a significant difference is
usually found in the prediction outcomes of these models.1,40
The second way of determining asphaltene stability in crude
oils is to use thermodynamic models.1 In the literature, several
models have been reported for the modeling of asphaltene
precipitation behavior in hydrocarbon mixtures. The modeling
methods are generally categorized in five groups. These include
equation of state (EOS) models, polymer solubility models,
colloidal approaches, thermodynamic micellization models,
and molecular thermodynamic models.50 This technique is the
best method; however, it involves complex computations and
requires considerable compositional data and experimental
points for calibration.1 The experimental point can be obtained
from various high-pressure high-temperature (HPHT) exper-
imental techniques which include the gravimetric method,
acoustic resonance technique, light-scattering technique,
filtration method, and high-pressure microscopy.1 The
determination of experimental points is difficult because it
requires time and effort for performing long duration
experiments, high cost, and procurement of a high quality
pressurized bottom−hole crude oil sample free from
contamination.1,5,6 Moreover, experimental results may be
found to be different for the same oil at the same conditions
obtained from different equipment which has different
sensitivities.6 Furthermore, some of the deterministic tools
are found to be effective within particular process conditions
and depend on linear system identification models, whereas the
asphaltene precipitation and deposition mechanism is strongly
a nonlinear phenomenon with respect to the process and
thermodynamic parameters.50 Third, the quick and most
reliable methods to determine asphaltene stability in crude oil
are through experiments. The experiments include the
Heithaus parameter, toluene equivalence, Bureau of Mines
Correlation Index−toluene equivalence, oil compatibility
model, microscopy, and spot test.42,45 These experiments
involve the addition of precipitant (usually n-heptane) in crude
oils to detect the asphaltene onset point and then performance
of calculations for determining the stability. The quality of the
results depends upon the applied methodology, equipment
sensitivity, and analyst ability.42 Although, these tests are very
useful but they show a discrepancy in the results, are prone to
human error, are time-consuming, and are not continuous.1
The fourth way to judge asphaltene stability in crude oil is
through asphaltene compositional and structural character-
istics. Previous studies reported that the H/C ratio of
asphaltene,1 asphaltene solubility profile distribution,51,53
asphaltene aromaticity and density,52 polarity of asphal-
tene,54,57,58 and electrical charges on asphaltenes59 can provide
information regarding the chance for asphaltene stability in
crude oils. However, this method required the extracted
asphaltene sample, which may lead to uncertainties in results
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
due to asphaltene extraction methodology applied and the
absence of the effect of other crude oil components such as
resins, aromatics, and saturates. It was also reported that
asphaltenes collected from the field are more polar than
asphaltene extracted from the same crude under laboratory
conditions.56 Lastly, the geological settings, presence of tar
mat, and biomarker correlation of the crude oil and the source
rock also facilitate the determination of asphaltene stability in
oils.55 However, these methods are still not very common or
mature and add difficulty to the interpretations of instability
and stability from the obtained results.
In the literature, the majority of experimental stability tests
proposed were based on the determination of the onset
asphaltene precipitation point as the function of precipitant
consumption volume by crude oil.42,45,46 The crude oils are
considered to be more stable when they require a higher
volume of precipitant to trigger asphaltene precipitation.42,45,46
The interpretation of results obtained from these tests mainly
depends upon the type of methodology followed, sensitivity of
equipment, and type of precipitant used.42 Moura et al.42
recently reported that these tests could not detect onset points
for oils having lower asphaltene content (≤0.60% w/w) and
higher saturate content. Moreover, these tests do not
incorporate the magnitude of deposition and asphaltene
precipitation kinetics after the inception of the onset point,
which is extremely important for the assessment of asphaltene
stability in crude oil in terms of operational point of view. That
is why some studies could be found in the literature related to
commercial software development and implementation which
have incorporated the information on asphaltene precipitation
and deposition kinetics as key input parameters for the
modeling of asphaltene deposition.60−63 There is another type
of experiment involved in the stability determination. This
class of test requires the passing of light through the
supernatant at different times, and the magnitude of light
absorbance evaluates the dispersion efficiency.45,63 The
accuracy of these tests depends upon the light wavelength
used and offers complex instrumentation and interpretation.6
These experimental tests also do not provide information
regarding the quantity of deposition and assume that higher
dispersion efficiency offers higher deposition control, which
according to recent studies is not always true particularly
between precipitation tests and deposition tests.6 In addition,
field operators are more interested to determining stability in
terms of deposition rather than dispersion. Therefore, there is a
need for an effective extended duration experimental approach
that could incorporate both asphaltene precipitation kinetics
and magnitude of asphaltene deposition to provide reliable and
accurate results for asphaltene stability in crude oils.
In this research study, a new method is proposed, namely, a
deposit level test coupled with a spot test to monitor the
asphaltene stability in crude oil kinetically in terms of both
precipitation and deposition. The method does not involve
complex instrumentation and is flexible and continuous. The
integration of two methods not only improves the reliability of
stability results but also provides deep insight on the
mechanisms involved and the behavior of asphaltene
precipitation and deposition rates.
2. METHODS AND MATERIALS
In this research study, the stability of six crude oil samples,
namely A, B, D, E, F, and G, having a specific gravity of 0.85,
0.83, 0.84, 0.86, 0.92, and 0.81, respectively, is determined at
14168
Article
different times for 1 day. A mixture of n-heptane and a crude
oil sample in the ratio of 20:1 is prepared in a graduated
centrifuge tube having 10 mL volume. The deposit level test
and spot test are conducted simultaneously at 2, 15, 30, and 50
min as a short duration test and at 19, 22, and 24 h as a long
duration test. The description of two tests applied in this study
is given below:
2.1. Deposit Level Test. In the deposit level test, a mixture
of n-heptane and oil in a centrifuge tube at some higher
proportion is prepared. The tube is then monitored for
asphaltene deposition at different times, and finally, the level of
deposition in the tube is determined.64 Moreover, the
appearance of supernatant can also provide information
about whether all asphaltene particles have settled or if they
in the dispersed phase.64
2.2. Spot Test. This test is used for the detection of
asphaltene precipitation in crude oils. The crude oil and n-
heptane are mixed in certain proportions to initiate asphaltene
precipitation in a tube. Sample drop at the upper portion of the
supernatant is then allowed to drop at a filter paper for spot
formation.45 After drying, the spot is observed and identified
on the basis of the types as presented in Table 1:45
Table 1. Spot Reference and Its Description45,a
spot
reference
no. description of spot
1 homogeneous spot without inner ring
2 faint or poorly defined inner ring
3 well-defined thin inner ring, only slightly darker than the
background
4 well-defined thin inner ring, slightly thicker than the ring in
reference spot no. 3 and somewhat darker than the background
5 very dark solid or nearly solid area in the center; central area is
darker than the background
a
Reprinted with permission from ref 45. Copyright 2017 Elsevier.
According to the spot test, if a spot fall comes under the
category of spot reference no. 3 or higher, then it indicates that
asphaltene precipitation and flocculation have occurred and
particles of asphaltene exist in a dispersed state in the
supernatant.45 Figure 2 shows the schematic of the experiment
performed in this study.
2.3. Image Processing of Spot Test, Statistical
Analysis, and Sensitivity Analysis. After experimental
performance, the deposition level of asphaltene deposits
produced at different time intervals was noted. However, for
the quantitative determination of precipitation intensity at
different times, all spot test results were analyzed through the
image processing tool. These two obtained outputs, i.e.,
precipitation intensity and deposition level, were further used
for sensitivity analysis. The sensitivity of two input parameters,
namely specific gravity of crude oils and time, were determined
against each output using relevancy factor given below as eq
165
n
∑i = 1 (inpl , i − inpl )(out i − out)
r(inpl , out) =
n n
∑i = 1 (inpl , i − inpl )2 ∑i = 1 (out i − out)2
(1)
where inpl,i and inpl are the ith value and the average value of
the lth input variable, respectively (lth = time and specific
gravity of oil). outi and out are the ith value and the average
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 2. Schematic of experiment performed in this study.

value of the outcome (precipitation intensity and deposition

level), respectively.
The higher negative value of relevancy factor represents a
strong negative relationship between an input and output
variable, whereas the high positive value indicates a strong
positive correlation between an input factor and output
variable.65
Figure 3 shows the overall workflow followed in this research
study

3. RESULTS AND DISCUSSION

3.1. Oil Sample A. Oil A has been monitored at different
times. Referring to Figure 5a−d, the spot generated at time 2
min clearly indicates that asphaltene precipitation had started.
Qualitatively, the appearance of dark inner ring inside the spot
clearly indicates that the precipitation is intense. The same
spot was also observed at times 15, 30, and 50 min, which
depicts that precipitates are still in the solution at a dispersed
state. Looking at Figure 4a,b, the visual inspection indicates
that at 30 and 50 min the deposition has not occurred for oil A
and all of the asphaltene formed are in dispersed phase as is
evident from its dark color appearance of supernatant. It is
important to note here that the inner ring appearance in the
spot gets brighter as time progresses from 2 to 50 min because
with increasing time the asphaltene particles get bigger and
moves toward the lower portion of the centrifuge tube and the
upper portion of the supernatant where fluid has been taken
for spots that hold less precipitate. Now discussing the long
duration test at time 19, 22, and 24 h, the spot test clearly
depicts that at all times the dispersed asphaltene particles are
not in the dispersed state because of the absence of inner ring
in spots generated at these times (Figure 5e−g). The
observation seems true when we refer to Figure 4c,d, which
shows a visual appearance of fluid in centrifuge tube. It clearly
shows that before the starting time of long duration tests the Figure 3. Overall workflow followed in this research study.
total deposition has occurred as the deposition level is found to
be at a constant level, i.e., no change in deposition level. which indicates that all dispersed asphaltene particles have
Moreover, the appearance of supernatant becomes brighter, been settled at these times (Figure 4c,d).
14169 https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 4. Deposit level test results for oil A at: (a) 15 min, (b) 50 min, (c) 19 h, and (d) 24 h.

Figure 5. Spot test results for oil A at (a) 2 min, (b) 15 min, (c) 30 min, (d) 50 min, (e) 19 h, (f) 22 h, (g) 24 h.

Figure 6. Deposit level test results for oil B at (a) 15 min, (b) 50 min, (c) 19 h, and (d) 24 h.

3.2. Oil Sample B. For oil B, the spots were observed for which shows spots at the above-mentioned times, it can be
early times at 2, 15, 30, and 50 min. Looking at Figure 7a−d, clearly observed by the presence of an inner dark ring in the
14170 https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 7. Spot test results for oil (B) at (a) 2 min, (b) 15 min, (c) 30 min, (d) 50 min, (e) 19 h, (f) 22 h, and (g) 24 h.

Figure 8. Deposit level test results for oil D at (a) 15 min, (b) 50 min, (c) 19 h, and (d) 24 h

Figure 9. Spot test results for oil D at (a) 2 min, (b) 15 min, (c) 30 min, (d) 50 min, (e) 19 h, (f) 22 h, and (g) 24 h.

spot that precipitation has begun before the completion of 2
min. At the same time, deposition was also found to occur in
oil B as evident by the visual inspection of the presence of
deposits in the centrifuge tube at time 15 min (Figure 6a). The
spot test indicates that after 15 min the precipitates in the
supernatant settle at the bottom of the tube as the inner ring in
the spot was found to be brighter in appearance at times 30
and 50 min. The claim seems to hold true for the presence of
the brighter color of the supernatant and the presence of a
clear interface surface between the deposit and supernatant.
Referring to Figure 6c,d, for long duration tests at 19, 22, and
24 h, it can be clearly seen that total deposition had occurred
at time 19 h and no more deposition occurred after this time.
Moreover, these two tests also indicate that no asphaltene
particles are in the dispersed phase at later times because of the
absence of an inner dark ring from the spot and the appearance
of a brighter supernatant color (Figure 7e−g).
3.3. Oil Sample D. For oil sample D, the spot tests were
carried out at four early times. According to Figure 9a, it was
found that precipitation has begun before time 2 min as
14171
evident by the presence of an inner dark ring in the spot taken
at 2 min. At 15 min, it was observed that the inner ring
darkness was slightly increased compared to the former inner
ring spot taken at 2 min, which indicates that the precipitation
intensity has increased (Figure 9b). After 15 min, the darkness
of inner ring decreases (Figure 9c,d), which shows signs of
settling of the majority of precipitates at the bottom of the tube
due to their size growth. This interpretation was proved to be
true by observing the deposition test results which clearly show
that at a time of 50 min the deposition of asphaltene particles
has occurred in the centrifuge tube (Figure 8a,b). At later test
times (from 19 to 24 h), it was found that all dispersed
precipitated asphaltenes are deposited as is evident by the clear
appearance of supernatant (Figure 8c,d) and the absence of an
inner dark ring from the spot (Figure 9e−g).
3.4. Oil Sample E. The results of the spot test of oil sample
E as illustrated in Figure 11 clearly indicate that precipitation
in oil E progresses slowly. According to Figure 11a, the spot
contains a very bright inner ring which is a clear sign of very
low precipitation at time 2 min. However, as the time
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 10. Deposit level test results for oil E at (a) 15 min, (b) 50 min, (c) 19 h, and (d) 24 h.

Figure 11. Spot test results for oil E at (a) 2 min, (b) 15 min, (c) 30 min, (d) 50 min, (e) 19 h, (f) 22 h, and (g) 24 h.

Figure 12. Deposit level test results for oil F at (a) 15 min, (b) 50 min, (c) 19 h, and (d) 24 h.

progresses from 15 to 50 min, the inner ring of the spot get
darker, indicating that the magnitude of precipitation has
increased gradually in the supernatant (Figure 11b−d). On the
14172
other hand, the results of the deposition test indicate that
deposition of precipitates does not occur until 50 min (Figure
10a,b). The possible reason for this observation might be the
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 13. Spot test results for oil F at (a) 2 min, (b) 15 min, (c) 30 min, (d) 50 min, (e) 19 h, (f) 22 h, and (g) 24 h.

Figure 14. Deposit level test results for oil G at (a) 15 min, (b) 50 min, (c) 19 h, and (d) 24 h.

Figure 15. Spot test results for oil G at (a) 2 min, (b) 15 min, (c) 30 min, (d) 50 min, (e) 19 h, (f) 22 h, and (g) 24 h.

slow asphaltene precipitation and subsequent aggregation
kinetics in oil sample E. Oppositely, the results of long
duration tests from 19 to 24 h show the disappearance of an
inner dark ring from the spot (Figures 11e−g) and a
considerable increase in the deposition level (Figures 10c,d).
This condition clearly signifies that asphaltene particles formed
during early hour test (2 min until 50 min) do not remain in a
suspended form in the supernatant and now they are deposited
at the bottom of the centrifuge tube.
3.5. Oil Sample F. According to the Figure 13a, it can be
clearly observed that precipitation starts before 2 min as the
appearance of the inner ring is present in the spot; however,
the color is not too dark, which means that the precipitation
was not intense at this time. The color of the inner ring
appears to get darker as time progresses from 15 to 50 min
(Figure 13b−d). The visual inspection of oil sample F suggests
that no deposition occurred from 2 to 50 min (Figure 12a,b).
Oppositely, at long duration hour tests, all formed asphaltene
precipitates are deposited at the bottom of the centrifuge tube
14173
as it can be observed by the disappearance of dark inner ring
from the spot and visual monitoring of the tube (Figure 12c,d
and e−g). It is worth noting here that the supernatant
appearance of oil F is found to be quite dark as compared to
other oil samples tested particularly at long duration test. This
observation might lead to a misleading understanding of the
presence of asphaltene particles in the dispersed phase.
Therefore, spot test results found at later stages confirm that
all dispersed asphaltene particles are deposited as evident from
the absence of an inner ring from the spot at later times.
3.6. Oil Sample G. The behavior of oil G is found to be
similar to oil sample B. According to Figure 15a−d,
precipitation starts before 2 min and is found to be more
intense at time 15 and 30 min because of the darker inner ring
presence in the spot, which shows that a higher number of
precipitates are in the supernatant at these times. However, at
50 min the number of precipitates decreases in the supernatant
as the inner ring becomes brighter. The visual inspection of
sample, according to Figure 14b, suggests that deposition starts
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
before 15 min. The combination of spot test and deposit level
test results shows that both precipitation and deposition occur
at early times of the test. At long duration tests at 19, 22, and
24 h, the total precipitates formed at early times are deposited
as the inner ring of the spot at these times disappeared and the
color of the supernatant got brighter (Figures 14c,d and 15e−
g).
We now discuss the oil samples with respect to RLA, DLA,
and sedimentation mechanisms. The pictorial representation of
the mechanism is represented in Figure 16. According to
Figure 16. Behavior of reaction-limited aggregation and diffusion-
limited aggregation. Reprint from ref 38. Copyright 2019 American
Chemical Society.
Figure 16, in a colloidal system, aggregation can be generally
described by a process that is either controlled by diffusion,
which is termed as the DLA model, or by considering that
there exists an energy barrier for the process of aggregation,
which is known as the RLA model.37,38 According to the
literature, the beginning phase of asphaltene aggregation is
dominated by the RLA model, and the later stage of the
aggregation process is controlled by the DLA model, which
facilitates the increase of asphaltene aggregate size.37,38 At the
end, the aggregate size grows to the extent where it begins to
settle down, and consequently, the RLA and DLA phases are
followed by the sedimentation phase.37,38 According to Table
2, oil samples A, E, and F are found to have RLA and DLA
mechanisms that are more dominant at all stages of the short
duration tests because precipitation and aggregation of
asphaltene particles are found to start without deposition.
On the contrary, oil samples B and G are found to possess RLA
and DLA mechanisms along with a sedimentation process at
short duration tests. In short duration tests, for these oils,
precipitation and enough subsequent aggregation of asphaltene
Table 2. Mechanism Identified at Different Times of Tests for Various Oil Samplesa
short duration test
oil sample 2 min 15 min 30 min
A RLA+DLA RLA+DLA RLA+DLA
B RLA+DLA+S RLA+DLA+S RLA+DLA+S
D RLA+DLA RLA+DLA RLA+DLA
E RLA+DLA RLA+DLA RLA+DLA
F RLA+DLA RLA+DLA RLA+DLA
G RLA+DLA+S RLA+DLA+S RLA+DLA+S
a
“S” stands for sedimentation.
14174
Article
particles occur that cause deposition. Oil sample D was initially
followed by the RLA and DLA mechanisms before 15 min,
however; afterward, both the DLA and RLA mechanisms were
found at short duration tests along with sedimentation. During
long duration tests, all samples were found to have
sedimentation mechanisms.
Comparing all samples, it can be clearly stated here that
asphaltene precipitation rates were found to be higher in oil
samples B, G, A, and D and lower in samples E and F. In terms
of deposition, higher deposition occurs in B, A, and F samples,
followed by G and in the last D and E. Although asphaltene
precipitation kinetics and asphaltene deposition are compet-
itive mechanism, the higher kinetic rates do not means higher
deposition or vice versa. Deposition is the consequence of the
aggregation of asphaltene particles to a size which can settle
down. The aggregation process might be governed by factors
such as crude oil SARA composition and asphaltene
composition and properties like polarity, dielectric constant,
etc.1,51−59 On the other hand, the amount of asphaltene
deposition might depend upon the overall asphaltene weight
percent in the crude oil in the dissolved phase. An oil sample
having a higher potential of generating asphaltene deposits at
faster rates is more risky than an oil sample that produced a
lower amount of asphaltene at slower rates. In our opinion, we
believe that if oil samples are producing considerably varying
amounts of deposition then kinetics become more important.
The claim can be understood in such a way that oil that can
produce significant asphaltene deposition at lower rates can be
controlled by treatment with a reliable oil sample that can
produce considerable amounts of deposits at faster rates
because of the lower time of the treatment method
deployment. In this context, oil sample B is the most
dangerous oil sample as it produced greater amounts of
asphaltene deposits at comparatively faster rates. G and D oil
samples may be considered as the second and third most risky
crude oils, respectively, followed by A, F, and E oil samples at
the fourth, fifth, and sixth position, respectively.
4. IMAGE PROCESSING OF SPOT TEST RESULTS AND
STATISTICAL ANALYSIS
To conduct sensitivity analysis, the qualitative interpretation of
all the tests results discussed in the previous section need to be
converted in numeric value. As far as the deposition level value
is concerned, it can easily be acquired by noting the asphaltene
deposition mark on the test tubes obtained at different times.
However, the transformation of the spot test results to a
numeric value is quite challenging. Although assigning of a
numerical value to each spot on the basis of the appearance of
time
long duration test
50 min 19 h 22 h 24 h
RLA+DLA S S S
RLA+DLA+S S S S
RLA+DLA+S S S S
RLA+DLA S S S
RLA+DLA S S S
RLA+DLA+S S S S
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
Figure 17. Relevancy factor of each input parameter with (a) precipitation intensity and (b) deposition level.
inner dark ring as mentioned in Table 1 can be done, it may
lead to misleading interpretation due to human error and use
of only five numeric real values for different types of spots
produced. Therefore, a reliable and accurate technique is
needed that can determine the exact intensities of spots formed
at different time intervals.
In this research study, image processing software is
implemented on all spot test results for the evaluation of
exact precipitation intensities at different time intervals for
each oil sample. In each intensity chart, six numeric data or
information were obtained. Their description is given below:
count represents number of readings analyzed
mean represents mean color intensity
StdDev represents standard deviation
min represents minimum value of color intensity
max represents maximum value of color intensity
mode represents maximum number of repeated value
Each spot is characterized as a hill-type structure by image
processing tool having either two peaks, a rough single or
multiple shorter peaks, or a sharp single peak with smooth
dipping edges on either side. Two peaks on the intensity chart
were characterized by the presence of color with mainly two
major different intensities. This structure indicates that the
spot has a dark inner ring surrounded by a lighter bright ring
which indicates that the precipitation phase has been started
and precipitates formed a exist at the upper portion of
supernatant from where the solution is taken to produce spots.
Rough or multiple short peaks on the intensity chart indicate
that precipitation has been initiated but its intensity is not
severe. Finally, the last class, which is a sharp single peak with
smooth dipping edges on either side, indicates that either
precipitation has not yet started or precipitation phase has
been finished and all the precipitates formed were settled at the
bottom of the tube.
The outcomes of the spot test results image processing for
each oil sample at different times are shown in Figures S1−S6.
According to these figures, each image chart is placed along
with its corresponding spot marked with yellow circle which
encompasses all the readings analyzed by image processing
software. It can be clearly observed that during the early
duration tests from 2 to 50 min all oil samples image charts
show either two peaks or a rough multiple peak hill-type
structure. This means that all oil samples have started
14175
Article
asphaltene precipitation during this time period with different
intensities. Comparing the image charts of all oils, it can be
depicted that asphaltene precipitation in oil samples A, B, D,
and G has started intensely during the 2 min test as their image
chart contains a hill-type structure with two clear long
separated peaks. However, at later times, these oils show a
decrease in asphaltene precipitation because during 50 min test
time the two peaks were transformed into multiple shorter
peaks. Alternatively, in oil samples E and F, the asphaltene
precipitation trend is found to be reverse. These oil samples
image charts contain rough multiple shorter peaks during a 2
min test, whereas during the 50 min time test the appearance
of two clearly separated long peaks was observed. This
condition clearly indicates that in oils E and F the asphaltene
precipitation kinetics is slow. It is important to note here that
during the time period from 19 to 24 h all oil samples yield
image charts having hill-type structures which contain a sharp
single peak with smooth dipping edges on either side except
for one image chart obtained for oil sample B at time 22 h
having two peaks. The reason for this outcome might be the
incorrect spotting procedure due to human error. The overall
behavior of image processing results at later stages of tests
indicates that dominancy of precipitation phase has been
reduced or ceased and all the precipitates formed have been
settled down at the bottom of the centrifuge tube. This
interpretation of image processing results was found in
excellent agreement with the qualitative description of spot
test results already discussed in previous section.
5. SENSITIVITY ANALYSIS
To investigate the effect of input parameters (i.e., specific
gravity of crude oil and time) on asphaltene precipitation
intensity and deposition level, a sensitivity analysis was carried
out. For this purpose, a relevancy factor (r) was employed to
determine the influence degree of each input factor on two
outputs. To implement relevancy factor, the numeric values of
output must be known. Therefore, as discussed in previous
section, the deposition level value at different times for each oil
sample was simply obtained by noting the deposition level
mark. However, for precipitation intensity values, the data
obtained through intensity charts from spot test results
between time intervals at 2 min until 50 min were used. The
precipitation intensity at each time interval was calculated by
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
taking the difference of maximum and minimum color
intensity values. For computation purposes, it was assumed
that the minimum value of the color intensity represents the
color of the area surrounding the inner dark ring, whereas the
maximum value of color intensity denotes the color intensity of
the inner dark ring.
Parts a and b of Figure 17 show the relevancy factor results
obtained. According to Figure 17a, it can be clearly observed
that precipitation intensity has a negative relationship with
both specific gravity of oil and time. The relationship was
found to be slightly strong for specific gravity (approximately
−0.227) than time (approximately −0.0171). According to
previous studies, it was reported extensively that lighter crude
oil are more prone to asphaltene precipitation than higher
crude oils.66,67 Lighter crude oils contains more saturates and
less resins. The addition of n-alkanes in lighter crude oil
promotes destabilization at faster rates because they need to
dissolve less resin contents which act as protective shield for
asphaltene precipitation.1,8 On the other hand, the relationship
of time with precipitation intensity was found to be almost
negligible because in the majority of oils (i.e., A, D, B, and G)
both the increment and decrement in precipitation intensity
(i.e., increase followed by decrease) were observed during the
time period between 2 and 50 min. Similarly, according to
Figure 17b, it can be clearly observed that the specific gravity
of crude oil has almost the same relationship, i.e., −0.247, with
a deposition level as it has with precipitation intensity, i.e.,
moderate inverse relation. However, the time shows quite
strong positive correlation with deposition level yielding
approximately over +0.521 relevancy factor. This indicates
that with the increase of time more and more deposition will
occur.
5.1. Sources of Errors or Uncertainties. Although, this
integrated test found to be very simple, effective, cheap, and
quick but there following points need to be consider cautiously
in order to obtain quality and reliable results:
1. For the spot test, it is important to draw sufficient liquid
for producing a spot from the supernatant from the same
top portion of centrifuge tube at the required times
during all tests; otherwise, it may yield inconsistencies in
outcomes.
2. Investigators must take extra care while reading the
asphaltene deposition level, particularly in dark fluids
because in dark fluids it is often difficult to read the
deposition mark.
3. The presence of an inner dark ring in the spot could
indicate the existence of precipitation phase, intensity of
precipitation phase, or suspension of particles in the
supernatant; however, asphaltene precipitation concen-
tration could not be exactly measured by observing the
appearance of inner ring of spot.
4. The compaction of asphaltene deposits over time might
yield significant error in reading the deposit level.
5. The precipitant to crude oil ratio and underlying
conditions must be kept constant during all tests to
achieve reliable results.
6. Testing must be done on fresh and contaminant-free oil
samples. Previous studies reported that long-term
storage of samples under different conditions and oil
sample contamination might create differences in
stability results.
14176
Article
5.2. Recommendations for Future Studies. The new
experimental approach adopted in this study is quite efficient
and flexible. Future studies must be directed toward adoption
of the same methodology by involving various factors and
effects like dilution ratio and precipitant type variations,
conduction of experiments at more and equal time intervals,
blending of crude oils, and high temperature conditions. Both
asphaltene kinetics and deposition have a strong relationship
with temperature; therefore, varying temperature conditions
must affect the asphaltene stability in crude oils. Another
avenue to apply this procedure is to implement this
methodology on deposition tests carried on metallic surfaces
preferably in dynamic state and at high-pressure and high-
temperature conditions. The deposition tests are usually found
to simulate conditions close to real scenarios. In addition,
previous studies have reported that outcome yields from
deposition tests are quite different from those obtained by
precipitation tests. It is a well-known fact that asphaltene
precipitation in field conditions are usually triggered as a
function of pressure rather than through the precipitant. In this
context, the applied methodology must be implemented on live
oil under HPHT conditions where asphaltene formation
occurs due to depressurization of crude oils. Finally, the
applied methodology could easily be implemented for
evaluating the performance efficiency of chemical additives
both in terms of asphaltene deposition control as well as
retardation of asphaltene precipitation kinetics.
6. CONCLUSION
In this research study, the stability of six crude oil samples was
determined using deposit level tests integrated with spot tests.
The two tests were performed simultaneously at short time
durations (i.e., at 2, 15, 30, and 50 min) and at long time
durations (i.e., at 19, 22, and 24 h). The coupling of the two
tests allows the determination of crude stability both in terms
of precipitation kinetics and level of deposition. For
quantitative interpretation of spot test results, an image
processing was performed. According to the results, all crude
oils were found to possess potential for asphaltene precip-
itation upon addition of precipitant. Precipitation was found to
start during short duration tests at different rates for all crude
oils and all precipitates formed during early time were found to
deposit completely during long duration tests in all oil samples.
In terms of asphaltene deposition level, crude oil B, A, and F
were found to produce a higher volume of asphaltene deposits,
followed by G and in the last D and E. Sedimentation in crude
oils B, G, and D starts during the short time duration test,
while in sample A and F deposition begins after 50 min.
Alternatively, with respect to asphaltene precipitation kinetics
rates, crude oils B, G, and D were observed to destabilize
quickly and start asphaltene deposition during the short time
duration tests. Among all crude oil samples tested, crude oil B
was found to be the most risky crude oil in terms of asphaltene
problems as in these oil samples higher volumes of deposits
were produced at quick rate. Oppositely, oil sample E was
found to be the relatively least risky crude oil as it produces
asphaltene deposits at slowest rates. Moreover, sensitivity
analysis was also carried out to determine the relative
importance of input parameters which include specific gravity
and time on output variables, i.e., precipitation intensity and
deposition level. It was found that the specific gravity of the
crude oil has a negative moderate correlation with both
precipitation intensity and deposition level. Similarly, time
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
shows a negligible negative relationship with precipitation
intensity (during short duration tests) because intensity, in
most cases, increases and decreases during the test time.
Alternative, the time shows strong positive correlation with
deposition level (both short duration and long duration
reading taken). The integration of the spot test with the
deposit level test not only increases the overall strength of this
test but also allows researchers to monitor precipitation and
deposition continuously and simultaneously without involving
complex instrumentation and interpretation. The implementa-
tion of this approach is easy and flexible and can be helpful for
both the upstream and downstream petroleum industry for
evaluating the stability of crude oils under different environ-
ments and conditions.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.2c00777.
Precipitation intensity charts of all spot test results for
different crude oil samples generated through Image
processing tool (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Syed Imran Ali − Department of Petroleum Engineering, NED
University Of Engineering & Technology, Karachi 75270,
Pakistan; orcid.org/0000-0003-0133-9455;
Email: engrimran@neduet.edu.pk
Authors
Shaine Mohammadali Lalji − Department of Petroleum
Engineering, NED University Of Engineering & Technology,
Karachi 75270, Pakistan
Javed Haneef − Department of Petroleum Engineering, NED
University Of Engineering & Technology, Karachi 75270,
Pakistan
Syed Mohammad Tariq − Reservoir Services International,
Houston, Texas 77040, United States
Muhammad Junaid − Department of Petroleum Engineering,
NED University Of Engineering & Technology, Karachi
75270, Pakistan
Syed Muhammad Aun Ali − Department of Petroleum
Engineering, NED University Of Engineering & Technology,
Karachi 75270, Pakistan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.2c00777
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful for the support and encouragement
provided by members of NED Alumni Association-Houston
(NEDA-Houston) for the publication of this paper. We are
also thankful for the valuable and fruitful discussion with Ms.
Nimra Yousaf, Ms. Anum Imran, and Ms. Shahzana Zulfiqar.
■
REFERENCES
(1) Ali, S. I.; Lalji, S. M.; Haneef, J.; Ahsan, U.; Tariq, S. M.; Tirmizi,
S. T.; Shamim, R. Critical analysis of different techniques used to
screen asphaltene stability in crude oils. Fuel 2021, 299, 120874.
14177
Article
(2) Mansoori, G. A. Remediation of asphaltene and other heavy
organic deposits in oil wells and in pipelines. SOCAR Proc. 2010, 4,
12−23.
(3) Melendez-Alvarez, A. A.; Garcia-Bermudes, M.; Tavakkoli, M.;
Doherty, R. H.; Meng, S.; Abdallah, D. S.; Vargas, F. M. On the
evaluation of the performance of asphaltene dispersants. Fuel 2016,
179, 210−220.
(4) Rogel, E.; Ovalles, C.; Moir, M. Asphaltene stability in crude oils
and petroleum materials by solubility profile analysis. Energy Fuels
2010, 24, 4369−74.
(5) Abutaqiya, M. I. L.; Sisco, C. J.; Vargas, F. M. A Linear
Extrapolation of Normalized Cohesive Energy (LENCE) for fast and
accurate prediction of the asphaltene onset pressure. Fluid Phase
Equilib. 2019, 483, 52−69.
(6) Ali, S. I.; Awan, Z.; Lalji, S. M. Laboratory evaluation
experimental techniques of asphaltene precipitation and deposition
controlling chemical additives. Fuel 2022, 310, 122194.
(7) Jennings, D.; Breitigam, J.; Kim, J.; Jankowski, S.; Grutters, M.
Needs for Improving Asphaltene Treatment Programs. International
Petroleum Technology Conference, Dhahran, Saudi Arabia, 13−15 Jan
2020.
(8) Ashoori, S.; Sharifi, M.; Masoumi, M.; Salehi, M. M. The
relationship between SARA fractions and crude oil stability. Egypt. J.
Pet. 2017, 26, 209−213.
(9) Fakher, S.; Ahdaya, M.; Elturki, M.; Imqam, A. Critical review of
asphaltene properties and factors impacting its stability in crude oil. J.
Pet. Explor. Prod. 2020, 10, 1183−1200.
(10) Ali, S. I.; Lalji, S. M.; Haneef, J.; Louis, C.; Saboor, A.; Yousaf,
N. Asphaltene precipitation modeling in dead crude oils using scaling
equations and non-scaling models: comparative study. J. Pet. Explor.
Prod. 2021, 11, 3599−3614.
(11) Zhang, X.; Pedrosa, N.; Moorwood, T. Modeling Asphaltene
Phase Behavior: Comparison of Methods for Flow Assurance Studies.
Energy Fuels 2012, 26, 2611−2620.
(12) Zheng, F.; Shi, Q.; Vallverdu, G.; Giusti, P.; Bouyssière, B.
Fractionation and Characterization of Petroleum Asphaltene: Focus
on Metalopetroleomics. Processes 2020, 8, 1504.
(13) Soleymanzadeh, A.; Yousefi, M.; Kord, S.; Mohammadzadeh,
O. A review on methods of determining onset of asphaltene
precipitation. J. Pet. Explor. Prod. 2019, 9, 1375−1396.
(14) Mullins, O. C. The Modified Yen Model. Energy Fuels 2010, 24,
2179−2207.
(15) Mullins, O. C.; Pomerantz, A. E.; Zuo, J. Y.; Andrews, A. B.;
Hammond, P.; Dong, C.; Elshahawi, H.; Seifert, D. J.; Rane, J.;
Banerjee, S.; Pauchard, V. O. Asphaltene nanoscience and reservoir
fluid gradients, tar mat formation, and the oil−water interface. SPE
annual technical conference and exhibition, Louisiana, 2013.
(16) Alvarez-Ramirez, F.; Ruiz-Morales, Y. Island versus archipelago
architecture for asphaltenes: polycyclic aromatic hydrocarbon dimer
theoretical studies. Energy Fuels 2013, 27, 1791−1808.
(17) Kuznicki, T.; Masliyah, J. H.; Bhattacharjee, S. Molecular
dynamics study of model molecules resembling asphaltene-like
structures in aqueous organic solvent systems. Energy Fuels 2008,
22, 2379−2389.
(18) Zuo, P.; Qu, S.; Shen, W. Asphaltenes: Separations, structural
analysis and applications. J. Energy Chem. 2019, 34, 186−207.
(19) Pina, A.; Mougin, P.; Béhar, E. Characterisation of Asphaltenes
and Modelling of Flocculation − State of the Art. Oil Gas Sci. Technol.
2006, 61, 319−343.
(20) Eyssautier, J.; Levitz, P.; Espinat, D.; Jestin, J.; Gummel, J.;
Grillo, I.; Barré, L. Insight into Asphaltene Nanoaggregate Structure
Inferred by Small Angle Neutron and X-ray Scattering. J. Phys. Chem.
B 2011, 115, 6827−6837.
(21) Brown, J. A Study of the Hydrogen Distribution in Coal-like
Materials by High-resolution Nuclear Magnetic Resonance Spectros-
copy I-The Measurement and Interpreatation of the Spectra. Fuel
1960, 39, 79−86.
(22) Brown, J.; Ladner, W. A study of the hydrogen distribution in
coal-like materials by high-resolution nuclear magnetic resonance
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf
spectroscopy. 2. A comparison with infra-red measurement and the
conversion to carbon structure. Fuel 1960, 39, 87−96.
(23) Strausz, O. P.; Peng, P. A.; Murgich, J. About the Colloidal
Nature of Asphaltenes and the MW of Covalent Monomeric Units.
Energy Fuels 2002, 16, 809−822.
(24) Guzman, A.; Bueno, A.; Carbognani, L. Molecular Weight
Determination of Asphaltenes from Colombian Crudes by Size
Exclusion Chromatography (SEC) and Vapor Pressure Osmometry
(VPO). Pet. Sci. Technol. 2009, 27, 801−816.
(25) Hortal, A. R.; Martínez-Haya, B.; Lobato, M. D.; Pedrosa, J. M.;
Lago, S. On the determination of molecular weight distributions of
asphaltenes and their aggregates in laser desorption ionization
experiments. J. Mass Spectrom. 2006, 41, 960−968.
(26) Martínez-Haya, B.; Hortal, A. R.; Hurtado, P.; Lobato, M. D.;
Pedrosa, J. M. Laser desorption/ionization determination of
molecular weight distributions of polyaromatic carbonaceous
compounds and their aggregates. J. Mass Spectrom. 2007, 42, 701−
713.
(27) Marshall, A. G.; Rodgers, R. P. Petroleomics: The Next Grand
Challenge for Chemical Analysis. Acc. Chem. Res. 2004, 37, 53−59.
(28) Rodgers, R. P.; Marshall, A. G. Petroleomics: Advanced
Characterization of Petroleum-Derived Materials by Fourier Trans-
form Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). In
Asphaltenes, Heavy Oils, and Petroleomics; Mullins, O. C., Sheu, E. Y.,
Hammami, A., Marshall, A. G., Eds.; Springer: New York, 2007.
(29) Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the
underworld. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 18090.
(30) Shi, Q.; Hou, D.; Chung, K. H.; Xu, C.; Zhao, S.; Zhang, Y.
Characterization of Heteroatom Compounds in a Crude Oil and Its
Saturates, Aromatics, Resins, and Asphaltenes (SARA) and Non-basic
Nitrogen Fractions Analyzed by Negative-Ion Electrospray Ionization
Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.
Energy Fuels 2010, 24, 2545−2553.
(31) Klein, G. C.; Kim, S.; Rodgers, R. P.; Marshall, A. G.; Yen, A.
Mass Spectral Analysis of Asphaltenes. II. Detailed Compositional
Comparison of Asphaltenes Deposit to Its Crude Oil Counterpart for
Two Geographically Different Crude Oils by ESI FT-ICR MS. Energy
Fuels 2006, 20, 1973−1979.
(32) Gascon, G.; Negrín, J.; Montoto, V. G.; Acevedo, S.;
Lienemann, C.-P.; Bouyssiere, B. Simplification of Heavy Matrices
by Liquid−Solid Extraction: Part IIHow to Separate the LMW,
MMW, and HMW Compounds in Asphaltene Fractions for V, Ni,
and S Compounds. Energy Fuels 2019, 33, 8110−8117.
(33) Schuler, B.; Meyer, G.; Peña, D.; Mullins, O. C.; Gross, L.
Unraveling the Molecular Structures of Asphaltenes by Atomic Force
Microscopy. J. Am. Chem. Soc. 2015, 137 (31), 9870−9876.
(34) Gharbi, K.; Benyounes, K.; Khodja, M. Removal and prevention
of asphaltene deposition during oil production: A literature review. J.
Pet. Sci. Eng. 2017, 158, 351−60.
(35) Shadman, M. H.; Dehaghani, A. H. S.; Badizad, M. H. How
much do you know about the methods for determining onset of
asphaltene precipitation? Petroleum 2017, 3, 287−291.
(36) Rodahl, M.; Kasemo, B. On the Measurement of Thin Liquid
Overlayers with the Quartz-Crystal Microbalance. Sens Actuat A 1996,
54, 448−456.
(37) Yudin, I. K.; Nikolaenko, G. L.; Gorodetskii, E. E.; Kosov, V. I.;
Melikyan, V. R.; Markhashov, E. L.; Frot, D.; Briolant, Y. Mechanisms
of Asphaltene Aggregation in Toluene- Heptane Mixtures. J. Pet. Sci.
Eng. 1998, 20, 297−301.
(38) Balestrin, L. B. S.; Francisco, R. D.; Bertran, C. A.; Cardoso, M.
B.; Loh, W. Direct Assessment of Inhibitor and Solvent Effects on the
Deposition Mechanism of Asphaltenes in a Brazilian Crude Oil.
Energy Fuels 2019, 33, 4748−4757.
(39) Alimohammadi, S.; Zendehboudi, S.; James, L. A compre-
hensive review of asphaltene deposition in petroleum reservoirs:
Theory, challenges, and tips. Fuel 2019, 252, 753−791.
(40) Ali, S. I.; Lalji, S. M.; Haneef, J.; Khan, M. A.; Louis, C.
Comprehensive Analysis of Asphaltene Stability Predictors under
Different Conditions. Pet. Chem. 2021, 61, 446−454.
14178
Article
(41) Sulaimon, A. A.; Mendoza De Castro, J. K.; Vatsa, S. New
correlations and deposition envelopes for predicting asphaltene
stability in crude oils. J. Petrol Sci. Eng. 2020, 190, 106782.
(42) Moura, L. G. M.; Santos, M. F. P.; Zilio, E. L.; Rolemberg, M.
P.; Ramos, A. C. S. Evaluation of indices and of models applied to the
prediction of the stability of crude oils. J. Pet. Sci. Eng. 2010, 74, 77−
87.
(43) Kumar, R.; Voolapallia, R. K.; Upadhyayula, S. Prediction of
crude oil blends compatibility and blend optimization for increasing
heavy oil processing. Fuel Process. Technol. 2018, 177, 309−327.
(44) Pereira, V. J.; Setaro, L. L. O.; Costa, G. M. N.; Vieira de Melo,
S. A. B. Evaluation and Improvement of Screening Methods Applied
to Asphaltene Precipitation. Energy Fuels 2017, 31, 3380−3391.
(45) Guzman, R.; Ancheyta, J.; Trejo, F.; Rodriguez, S. Methods for
determining asphaltene stability in crude oils. Fuel 2017, 188, 530−
543.
(46) Asomaning, S. Test methods for determining asphaltene
stability in crude oils. Pet. Sci. Technol. 2003, 21, 581−590.
(47) Chamkalani, A. Application of LS-SVM Classifier to Determine
Stability State of Asphaltene in Oilfields by Utilizing SARA Fractions.
Pet. Sci. Technol. 2015, 33, 31−38.
(48) Stankiewicz, A. B.; Flannery, M. D.; Fuex, N. Q.; Broze, G.;
Couch, J. L.; Dubey, S. T.; Iyer, S. D. Prediction of asphaltene
deposition risk in E&P operations; AIChE: New Orleans, 2002.
(49) Saboor, A.; Yousaf, N.; Haneef, J.; Ali, S. I.; Lalji, S. M.
Performance of asphaltene stability predicting models in field
environment and development of new stability predicting model
(ANJIS). J. Pet. Explor. Prod. 2021, DOI: 10.1007/s13202-021-01407-
8.
(50) Zendehboudi, S.; Shafiei, A.; Bahadori, A.; James, L. Asphaltene
precipitation and deposition in oil reservoirs−Technical aspects,
experimental and hybrid neural network predictive tools. Chem. Eng.
Res. Des. 2014, 92, 857−875.
(51) Prakoso, A.; Punase, A.; Rogel, E.; Ovalles, C.; Hascakir, B.
Effect of Asphaltene Characteristics on Its Solubility and Overall
Stability. Energy Fuels 2018, 32, 6482−6487.
(52) Rogel, E.; León, O.; Contreras, E.; Carbognani, L.; Torres, G.;
Espidel, J.; Zambrano, A. Assessment of Asphaltene Stability in Crude
Oils Using Conventional Techniques. Energy Fuels 2003, 17, 1583−
1590.
(53) Rogel, E.; Ovalles, C.; Moir, M. Asphaltene Stability in Crude
Oils and Petroleum Materials by Solubility Profile Analysis. Energy
Fuels 2010, 24, 4369−4374.
(54) Wattana, P.; Fogler, H. S.; Yen, A.; García, M. D. C.;
Carbognani, L. Characterization of Polarity-Based Asphaltene
Subfractions. Energy Fuels 2005, 19, 101−110.
(55) Misra, S.; Abdulla, D.; Bazuhair, M.; Aboukshem, A.; Stenger,
B.; Katheeri, A. A. Management of Asphaltenes Deposition in a Giant
Carbonate Onshore Oil Field, abu Dhabi, U.A.E. SPE Middle East Oil
and Gas Show and Conference, Manama, Bahrain, 25−28 Sep 2011.
(56) Aquino-Olivos, M. A.; Andersen, S. I.; Lira-Galeana, C.
Comparisons Between Asphaltenes from the Dead and Live-Oil
Samples of the Same Crude Oils. Pet. Sci. Technol. 2003, 21, 1017−
1041.
(57) Prakoso, A. A.; Punase, A. D.; Hascakir, B. A Mechanistic
Understanding of Asphaltene Precipitation From Varying-Saturate-
Concentration Perspectives. SPE Prod. Oper. 2017, 32, 86−98.
(58) Goual, L.; Firoozabadi, A. Measuring Asphaltenes and Resins,
and Dipole Moment in Petroleum Fluids. AIChE J. 2002, 48, 2646−
2663.
(59) Hascakir, B. A New Approach to Determine Asphaltene
Stability. SPE Annual Technical conference and Exhibition, San Antonio,
TX, 9−11 Oct 2007.
(60) Kurup, A. S.; Buckley, J.; Wang, J.; Subramani, H. J.; Creek, J.
L.; Chapman, W. G. Asphaltene Deposition tool: Field Case
Application Protocol. Offshore Technology Conference, Houston, TX,
30 Apr−3 May 2012.
https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179
ACS Omega http://pubs.acs.org/journal/acsodf Article

(61) Kurup, A. S.; Wang, J.; Subramani, H. J.; Buckley, J.; Creek, J.
L.; Chapman, W. G. Revisiting Asphaltene Deposition Tool
(ADEPT): Field Application. Energy Fuels 2012, 26, 5702−5710.
(62) Kurup, A. S.; Vargas, F. M.; Wang, J.; Buckley, J.; Creek, J. L.;
Subramani, H. J.; Chapman, W. G. Development and Application of
an Asphaltene Deposition Tool (ADEPT) for Well Bores. Energy
Fuels 2011, 25, 4506−16.
(63) Xiong, R.; Guo, J.; Kiyingi, W.; Feng, H.; Sun, T.; Yang, X.; Li,
Q. Method for Judging the Stability of Asphaltenes in Crude Oil. ACS
Omega 2020, 5 (34), 21420−21427.
(64) Abrahamsen, E. L. Organic flow assurance: asphaltene dispersant/
inhibitor formulation development through experimental design; Uni-
versity of Stavanger, 2012.
(65) Chen, G.; Fu, K.; Liang, Z.; Sema, T.; Li, C.;
Tontiwachwuthikul, P.; Idem, R. The genetic algorithm based back
propagation neural network for MMP prediction in CO2-EOR
process. Fuel 2014, 126, 202−212.
(66) Alimohammadi, S.; Amin, J. S.; Nikkhah, S.; Soroush, M.;
Zendehboudi, S. Development of a newscaling model for asphaltene
precipitation in light, medium, and heavy crude oils. J. Mol. Liq. 2020,
312, 112974.
(67) Alimohammadi, S.; Amin, J. S.; Nikooee, E. Estimation of
asphaltene precipitation in light, medium and heavy oils: experimental
study and neural network modeling. Neural Comput. & Applic 2017,
28, 679−694.

14179 https://doi.org/10.1021/acsomega.2c00777
ACS Omega 2022, 7, 14165−14179