Article

pubs.acs.org/EF

A Fundamental Study of Asphaltene Deposition

Michael P. Hoepfner, Vipawee Limsakoune,,, Varun Chuenmeechao,,, Tabish Maqbool,,
and H. Scott Fogler*,

Department of Chemical Engineering, The University of Michigan, Ann Arbor, Michigan 48109, United States, and
The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand

S Supporting Information
*

ABSTRACT: Asphaltenes are a solubility class of petroleum crude oil that can destabilize and deposit in both upstream and
downstream processes. In this study, asphaltene deposits were generated in metal capillaries by heptane addition to crude oils,
and it was found that deposition is caused by submicrometer asphaltene aggregates. Deposits were generated at heptane
concentrations above and signicantly below the instantaneous onset point. Analysis of the results reveals that the governing
factor controlling the magnitude of asphaltene deposition is the concentration of insoluble asphaltenes present in a crude oilprecipitant mixture and the instantaneous onset point is irrelevant to the deposition process. Electron microscopy images of the
deposits represent the rst images and conrmation of arterial growth in laboratory generated asphaltene deposits. The axial
deposit prole was found to be highly nonuniform. In addition, deposits formed shortly after when oil and heptane mix, revealing
that the destabilization of asphaltenes occurs virtually immediately after a precipitant is added. The results were reproduced with
a second crude oil, indicating that asphaltene deposition behavior is broadly applicable.

INTRODUCTION
Asphaltenes are a complex fraction of petroleum crude oil that
are dened by their solubility in aromatics (typically toluene)
and insolubility in normal alkanes (typically n-pentane or nheptane).1 Asphaltenes are of great industrial interest and
signicance because of their tendency to deposit in porous rock
formations, well-bores, production lines, and reneries.2
Injecting miscible or immiscible compounds into a reservoir
can cause a compositional change in the crude oil and can lead
to asphaltene precipitation in the porous rock formation.35
The asphaltene molecular structure, aggregation state, and
destabilization mechanism remain as areas of intense debate
despite decades of research. High-resolution mass spectrometry
has identied the elemental composition of approximately
7,200 unique asphaltene molecules.6 Several small-angle
scattering studies suggest that asphaltenes exist either as stable
aggregates or clusters of aggregates with a radius of gyration of
approximately 10 nm or less in both crude oil and toluene.710
However, asphaltene scattering results have been successfully
analyzed by assuming asphaltene molecules exist as solid
nanoparticles and as liquidliquid concentration uctuations in
an otherwise homogeneous uid.11,12 The ambiguity of whether
asphaltenes behave as colloidal suspensions or as a liquid
liquid mixture adds to the uncertainty of understanding the
asphaltene destabilization mechanism.
To establish consistent and clear terminology, the usage of
several terms which will be used in this work are dened now.
First, the term destabilization will be used to describe the
transition an asphaltene undergoes on the nanometer length
scale from stable (not allowed to aggregate or grow in size) to
unstable (able to aggregate or grow in size). Second,
aggregation will be used to describe the generic growth
process of increasing the size of an asphaltene from the
nanometer to micrometer length scale. Finally, precipitation
2013 American Chemical Society

will refer to the entire process of asphaltenes transitioning from

stable to micrometer-sized asphaltene aggregates or precipitates. For the purpose of this investigation, assigning a detailed
description of the asphaltene precipitation process is not
necessary, and no predictive thermodynamic modeling eorts
are attempted. However for simplicity, stable asphaltenes in oil
will be referred to as nanoaggregates as most researchers agree
that asphaltenes are highly associating molecules.
Asphaltene nanoaggregates can be destabilized by changes in
pressure, temperature, and composition.3,4,1317 Pressure
depletion is the primary cause of arterial deposition in a
wellbore.2 To force asphaltenes out of solution in the
laboratory and to simulate eld conditions, a common
approach is to add an n-alkane precipitant to a sample of
stock tank or dead oil (oil that has been cooled and
depressurized to room temperature and pressure). The
problematic asphaltenes will have already precipitated by
pressure depletion during oil recovery, so adding an articial
precipitant is necessary to study asphaltene behavior unless a
high temperature and pressure recombined oil is used. A
recombined oil is a dead oil sample that has been recombined
with the dissolved hydrocarbon gases that were previously
removed and then brought to the temperature and pressure of
the reservoir. Adding a precipitant to dead oil is a widely used
technique for validating thermodynamic models and measuring
asphaltene properties and aggregation mechanisms.18,19 Unfortunately, asphaltene destabilization and behavior in systems
with low precipitant concentrations (i.e., below the instantaneous onset) has largely been ignored except for a few recent
studies.1921
Received: October 26, 2012
Revised: January 14, 2013
Published: January 22, 2013
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lighting the importance of hydrodynamics.27 At low shear rates,

Nabzar et al. states that deposition follows the colloidal
deposition scaling of diusion limited deposition. As the shear
rate increases, asphaltenes pass through a shear limited
deposition process, and at high enough shear rates, there is
no detectable deposition. Deposition under shear conditions
has promise to aid in the understanding of the deposition
mechanism; however, no attempt was made by Nabzar et al. to
measure or predict the particle size distribution in the capillary
to validate whether the shear eects are reasonable. Modeling
work by Eskin et al. estimates that asphaltene aggregates need
to have a diameter greater than 1 m before shear eects are
signicant.31 The most studied sample used by Nabzar et al. for
shear eects was a 20% toluene and 80% heptane model oil
system. With such a high heptane concentration, aggregation
will occur quickly; however, the residence time in the mixing
system was not specied. Consequently, it could be that the
shear eects observed by Nabzar et al. may be due to the
deposition behavior of large aggregates, with a diameter of
hundreds of nanometers or micrometers and thus susceptible
to shear inhibition, if the estimate by Eskin et al. is accurate.
Optical microscopy images perpendicular to the axial
direction of ow for asphaltene deposition in round glass
capillaries revealed that there is some nonuniformity associated
with the axial deposition prole, with the inlet deposit being
thicker than the outlet in a 12.7 cm long capillary.29 The
nonuniformity of the deposit could only be inferred based on
the light transmission in the micrographs, and thus the variation
in sample thickness vs axial position was not able to be
quantitatively estimated.
The experimental work associated with the model by Eskin et
al. was performed in a Taylor-Couette ow device, and
deposition was induced by pressure depletion of a recombined
oil.32 A few interesting experimental ndings resulted from this
investigation. First, it was determined that in a batch deposition
conguration, the deposition of asphaltenes ceased after a
particular period of time, suggesting that there is a size
limitation above which asphaltenes do not deposit. Second, a
crude oil was run in the apparatus one time, heated, and
pressurized back to the initial conditions for a second run. The
deposit mass collected between the rst and second experiment
was nearly identical, revealing that total amount of asphaltenes
depositing in the rst run was not sucient to signicantly alter
the deposition driving force when the experiment was repeated.
Eskin et al. modeled the deposition of asphaltenes induced
by pressure depletion by imposing a critical asphaltene
aggregate size, above which no deposition could occur and at
a size below previous estimates for shear inhibition.32 However,
a geometric population balance is successful at modeling batch
asphaltene aggregation without imposing a critical particle size
and maintaining a constant collision eciency.20 Both
aggregation and deposition after an initial layer has formed
are due to asphalteneasphaltene interactions, so there should
not be a dierent mechanism for adhesion/sticking between the
two processes. Once an initial asphaltene deposit has formed,
additional deposition can be considered to be aggregation
between a large and immobile particle and a small and mobile
one. Thus, if aggregation can occur in the bulk, deposition
should occur at the deposit interface unless shear forces, which
are largest at the deposit interface, limit either process.
Additionally, experiments designed to measure the sticking
probability of latex spheres depositing on glass beads revealed
that particle size did not alter the likelihood of adhesion.33

Slow kinetics of asphaltene precipitation have been observed

by Wang and other researchers, adding experimental diculty
in determining asphaltene behavior.1924 Maqbool et al.
questioned whether an onset point for asphaltene precipitation
exists and reported that detecting asphaltene precipitation by
optical microscopy may take 6 months or longer at suciently
low precipitant concentrations.19 Recent work suggests that
once a precipitant is added to an oil, nanometer-sized
asphaltenes are destabilized and undergo a reaction-limited
aggregation process to form larger aggregates.20 Application of
a geometric population balance model allowed Maqbool et al.
to estimate the asphaltene-asphaltene collision eciency, the
number of adhesions divided by the number of collisions, to be
on the order of 1 106 adhesions per collision.20 The collision
eciency and asphaltene aggregation rate are strong functions
of the precipitant concentration, which causes the time to
detect asphaltene precipitation to vary from nearly instantaneous to several months.19 This detection limitation is due to
the low collision eciency between growing asphaltene
aggregates and the need to increase in size from the nanometer
scale to an observable size for optically microscopy, roughly 0.5
m.
The asphaltene deposition rate is also likely to be strongly
controlled by precipitant concentration, as is the case with
asphaltene precipitation and aggregation. The work of Maqbool
et al. suggested that there may not be a critical precipitant
concentration for asphaltene stability, and as such, it is
necessary to investigate whether asphaltenes deposit at
increasingly dilute precipitant concentrations. Additionally,
asphaltene instability may be detected sooner by capillary
deposition than a batch aggregation process because of a
continuous source of destabilized nanoaggregates at the
capillary entrance. The detection mechanism, pressure drop,
does not depend on the size of asphaltene aggregates, and
submicrometer asphaltenes can deposit to contribute to the
instability detection. A capillary with a small inner diameter will
allow for sensitive detection due to the signicant increase in
the pressure drop caused by a thin deposit. The work presented
here on asphaltene deposition in dilute precipitant systems
represents a new investigative tool to better understand
asphaltene behavior.

PREVIOUS DEPOSITION STUDIES

The following literature review will focus on deposition as
measured in a capillary.2529 The capillary deposition technique
on asphaltenes was rst used to measure the solubility
parameter where asphaltenes precipitate from solution.25
Later, Wang et al. quantied the thickness and mass of material
depositing in a capillary and concluded that the deposit is
approximately uniform over a roughly 100 foot long capillary;
however, only two precipitant concentrations for each oil were
considered, near and above the instantaneous onset conditions
for asphaltene precipitation.26 Wang and Buckley have
developed a technique, called the Displacement Test, to
determine the deposit prole inside a capillary by forcing a
viscous uid out of the capillary and monitoring the mass that
exits the capillary as a function of time.30 This technique shows
promise; however, it lacks an estimate of the axial resolution
and thickness prole uncertainty, does not have any validation
of predicting a known prole, and has not undergone peer
review.
Nabzar et al. determined that there are critical shear
conditions under which asphaltenes will not deposit, high726

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The discovery of the true kinetic nature of asphaltene

aggregation at low precipitant concentrations has opened the
door for new asphaltene deposition investigations.1921 The
experimental work presented here will focus on asphaltene
deposition measured in a capillary tube. The eect of
precipitant concentration, conrmation of good mixing, and
validation of the deposit location, all of which have been largely
overlooked previously, will be explored in-depth in this
investigation.
The goal of this investigation is to relate the extent of
asphaltene deposition to a driving force, which has not been
previously accomplished. Previous asphaltene deposition
investigations have focused only on the transient pressure
drop prole to compare variations in experimental conditions,
such as the eect precipitant type (n-hexane, n-heptane,
etc.).26,29 It is doubtful signicant progress will be realized in
understanding the asphaltene deposition process until a driving
force can be related to the extent of deposition. Recent
asphaltene modeling attempts have achieved qualitative34 and
quantitative32 agreement with experiments; however, modeling
results still rely heavily on tunable parameters, and the bounds
of these parameters do not yet have experimental backing. Until
the mechanism or driving force for asphaltene deposition has
been determined, the accuracy of predictive asphaltene
deposition models is limited. However, once the driving force
for asphaltene deposition is determined, accurate modeling of
asphaltene fouling may be possible and can be improved if
combined with an aggregation and precipitation model.

Figure 1. Diagram of the primary experimental deposition apparatus

used in this study. 1: Micrometering valve (closed during experiment).
2: Mixing capillary, 5 cm long. 3: Deposition capillary, 5 or 30 cm long.
4: Microsplitter valve. 5: Back pressure regulator, 40 psi. 6: Dierential
pressure transducer. 7: Pressure relief valve (closed during normal
operation). 8: Pressure gauge. 9: Constant temperature water bath. 10:
10 m porous frits.

capillary inlet was then slowly opened to relieve the system pressure.
The deposition capillary was drained by holding the outlet against a
piece of paper towel and allowing the oil-precipitant mixture to drain.
Prior to performing deposition experiments, the oil was centrifuged at
14,000 g for 3 h to remove already precipitated asphaltenes, sand
particles, and water. The two oils used in this study, Oil A and WY Oil,
were free of any production chemicals that are commonly used to
prevent deposition or corrosion. All experiments were performed at a
total volumetric ow rate (oil + heptane) of 5 mL/h in order to keep
the residence time in the mixing capillary constant. The length of the
mixing capillary was not varied to ensure consistency between
experiments. For Oil A, the temperature was kept at 60 C for all
experiments, while the temperature was varied for WY Oil.
When starting a deposition experiment, the system was rst prelled
with only oil, and all lines were bled to eliminate air pockets. During
the prelling step, a small pocket of air was trapped between the oil
and heptane to prevent mixing of the two liquids prior to
experimentation, and oil was allowed to ow into the heptane line.
Once the system was lled with oil and back-pressure was established,
the heptane ow was started. The heptane ow pushed the air pocket
and oil into the deposition apparatus at the initial stages of the
experiment. Strictly adhering to this startup procedure will allow for
accurate measurement of when the heptane is introduced into the
system, identiable by a sharp decrease in the pressure drop due to the
lower viscosity of the uid inside the capillary with heptane added. The
time, t, when heptane enters the system is dened as t = 0. This
procedure only allows heptane to enter the system once the proper
ow rate and back-pressure have been established, minimizing error
and enhancing reproducibility. All of the generated pressure drop
proles are shifted based on the initial steady state pressure drop, Po,
which is the pressure drop of the oil-heptane mixture owing through
the apparatus before any deposition is detected. New precut capillaries
and porous frits were used as supplied from Upchurch Scientic and
replaced for each new run. All heptane in oil concentrations are
reported as volume percent heptane because the concentration in the
deposition apparatus was controlled by varying the volumetric ow
rate of oil and heptane pumps.
In order to study the eect of particle aging on the asphaltene
deposition process, a second conguration of the deposition apparatus
was used to recirculate premixed oil and heptane mixtures through a
capillary. A single peristaltic pump (Masterex #7523-20) replaced the
syringe pumps and mixing system in Figure 1. The intake for the pump
and outlet of the deposition apparatus was a continuously stirred ask
containing a premixed oil and heptane solution. The ow rate for these
experiments was 36 mL/h, and a 0.01 ID and 30 cm length
deposition capillary was used. As with the primary apparatus shown in
Figure 1, the pressure drop was monitored across the deposition
capillary to determine the extent of fouling. The recirculating

EXPERIMENTAL METHODS

Experimental Apparatus. The primary experimental deposition

apparatus consists of syringe pumps (Teledyne ISCO, 500D) lled
with DI water that are used to displace canisters of oil and n-heptane,
used as the precipitant, to pump the uids through a capillary. Toluene
(T290, >99.9%) for washing and n-heptane (H350, >99.5%) were
HPLC grade and supplied from Fisher Scientic. The oil and heptane
lines ow into a constant temperature water bath and meet in an
ultralow volume tee (Upchurch Scientic, U-428) and are forced
through a 10 m porous mixing frit (Upchurch Scientic, A-105-02) to
disrupt any interface that may form where the oil and heptane meet
and promote mixing. After the mixing frit, there is a 5 cm long stainless
steel section of 0.03 in. inner diameter capillary (0.03 ID nominal
value; Upchurch Scientic, U-115) that allows the oil and heptane to
mix and is called the mixing capillary. After mixing, the oil-heptane
mixture ows through a second 10 m porous frit that acts as a
prelter to prevent large ocs from entering the capillary test section
that could potentially be formed in the mixing section due to pockets
of high heptane concentration. The mixture then ows through
another ultralow volume tee to connect the positive side of the
dierential pressure transducer (either Sensotec, Z/741-08ZD, 100 psi
range, 0.5 psi or Sensotec, A-5/882-15, 10 psi range, 0.05 psi). The
uid then ows through the stainless steel deposition capillary test
section (Upchurch Scientic, U-101, U-111, or U-114) where the
dierential pressure is monitored, past an additional tee to connect the
negative side of the pressure transducer, through a 40 psi back pressure
regulator (BPR, Upchurch Scientic, U-469), and then into a
collection container. A diagram of the primary experimental deposition
apparatus used in this study is shown in Figure 1.
The primary experimental apparatus shown in Figure 1 was
designed to prevent removal of the deposit by shear eects during
experimental shutdown when the elevated pressure in the system was
bled to atmospheric conditions. When shutting down the experiment,
the microsplitter valve (Upchurch Scientic, P-451) at the deposition
capillary outlet was closed to prevent any uid from traveling through
the system and potentially removing the asphaltene deposit. The
micrometering valve (Upchurch Scientic, P-446) near the mixing
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Figure 3. SEM images of a clean, unused capillary (left) and control

experiment where only Oil A was owed through the system (right).
Both capillaries have a 0.02 ID.
Figure 2. Diagram of the recirculating deposition experimental
apparatus. 1: Premixed oil-precipitant reservoir. 2: Magnetic stirrer.
3: Deposition capillary. 4: Dierential pressure transducer. 5: Back
pressure regulator, 40 psi. 6: Pressure gauge. 7: Pressure relief valve
(closed during normal operation).

visible surface roughness on the inner surface of the capillary,

which can be used to aid in the identication asphaltene
deposits. The control experiment with only Oil A did not
produce any visible deposit.
The deposits shown in Figure 4 were generated by owing
mixtures of 30 vol. % heptane in Oil A through 0.02 ID and 5
cm length capillaries at 60 C. The SEM images have been
rotated to match their orientation during the deposition
experiment, and dashed circles have been drawn on the SEM
images to aid in the identication of the inner capillary wall
edge. The SEM images of the deposit at the deposition capillary
inlet (left) and at the outlet (right) are shown for three
dierent experiments (runs #13) terminated at dierent
times. Runs 1 and 2 were terminated after 4 h to visualize the
deposit, and run 3 was stopped after 2.25 h. While the run 2
deposition experiment was being performed, there was a
decrease in the measured pressure drop at approximately 3 h,
dropping from roughly 1 to 0.25 psi. This decrease in pressure
drop is believed to be caused by a deposit partially clearing
from the capillary. Runs 1 and 3 had no deposits clearing. Since
it is unknown what portion of the deposit has been removed in
run 2, it is ultimately less conclusive than the others. The
deposits shown in Figure 4 are roughly uniform radially,
indicating proper mixing is obtained in the deposition system.
The SEM images of the asphaltene deposits represent the
rst conrmation of arterially forming deposits generated in a
laboratory. For all runs, the deposit is thicker at the inlet than at
the outlet. The asphaltene deposit can clearly be identied by
the smooth surface of the deposit compared to the visible
roughness in a clean capillary or the oil control experiment
found in Figure 3. The deposition capillary outlet for run 1 in
Figure 4 shows a large particle at the bottom of the capillary. An
energy dispersive X-ray spectroscopy (EDX) unit on the SEM
instrument did not detect the presence of carbon on the large
particle, and it is consequently a contaminant that likely
adhered while draining the capillary or transportation to the
electron microscopy laboratory.
Oil Properties and Instantaneous Onset Point. After
proper mixing was conrmed in the apparatus, the concentration of precipitant needed to cause instantaneous precipitation (i.e., less than 15 min) was determined. This condition,
often called the instantaneous onset point of the oil, was
determined by controlling the composition of the oil-heptane
mixture by varying the ow rates in the deposition apparatus
and collecting samples after mixing with a short collection line.
The total ow rate for the system was 5 mL/h, and

deposition apparatus that is used to study particle aging is shown in

Figure 2.
Mixing Considerations. When the oil and heptane rst come into
contact in the primary deposition apparatus near the entrance of the
mixing capillary, shown in Figure 1, heptane will migrate to the top of
the mixing capillary because it is the less dense material. If the heptane
is concentrated at the top of the mixing capillary, the local
concentration will be greater than intended, compared to a wellmixed system, and could potentially destabilize asphaltenes to a higher
degree than desired. Computational Fluid Dynamic (CFD) calculations of the mixing process conrmed that gravitational ow is
signicant and predicted that mixing of oil and heptane will be
complete by the entrance of the deposition capillary. See the
Supporting Information for details and results of the CFD simulations.
Experimentally, the quality of the mixing in the deposition apparatus
can be determined by visualization of the deposition capillary inlet
with electron microscopy. If it is assumed that the thickest deposits
occurs in the region of greatest heptane volume fraction and oil and
heptane form a single phase, three mixing scenarios are possible:
1. A deposit observed only on the top of the deposition capillary
would suggests that mixing is poor and asphaltene deposition is due to
higher than intended heptane concentrations.
2. A deposit that is thicker on the top compared to the bottom of
the deposition capillary would suggest there is poor mixing in the
system, but asphaltenes are still depositing at a precipitant
concentration lower than the mean or bucket value (near the bottom
of the capillary).
3. A deposit that is uniform radially at the inlet conrms good
mixing due to the homogeneous concentration distribution of heptane.
To validate the mixing in the apparatus, these deposition locations
will be considered when interpreting the scanning electron microscopy
(SEM) images of the asphaltenes deposits. The SEM images were
generated using a FEI Quanta 200 3D instrument operating in the low
vacuum mode (0.5 Torr). Proper mixing is not a concern for the
recirculating deposition apparatus in Figure 2 because the reservoir is
premixed and continuously stirred.

RESULTS AND DISCUSSION

Electron Microscopy of Deposits. Before visualization of
asphaltene deposits was performed, a blank capillary and a
control experiment with only Oil A owing through the system
for approximately 4 h were viewed by SEM. Figure 3 shows two
0.02 ID capillaries with the left image being a new and clean
capillary, and the right image shows the control experiment of
only Oil A. In both of the images, it can be seen that there is
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Figure 5. Micrographs of deposition apparatus euent used for onset

determination at various heptane volume percents (0% to 40%). The
instantaneous onset point is measured to be 40 vol. % heptane.

90% vol. heptane dilution due to the low asphaltene content.

Oil viscosities were measured by the pressure drop through a
long capillary and compared to a liquid with known viscosity.
The viscosity for mixtures of oil and heptane was estimated by
volumetric logarithm mixing. The properties of each of the oils
can be found in Table 1.
Table 1. Select Crude Oil Properties used in this
Investigation. The Instantaneous Onset Concentration for
Detection of Asphaltene Instability by Microscopy is
Abbreviated as Inst. Onset

Figure 4. SEM images of the deposition capillary inlet (left) and outlet
(right) for three runs (#13) of 30 vol. % heptane in Oil A with 0.02
ID and 5 cm length capillaries. The large material found at the bottom
of the run #1 capillary outlet is a contaminant, see text for rationale.
Dashed circles are drawn to aid identication of inner capillary wall
edge.

approximately 1 mL of euent was collected for each

concentration for viewing under an optical microscope. The
total time between mixing oil and heptane and microscopy
observation was approximately 15 min for each sample. The
determination of the onset by optical microscopy for Oil A can
be seen in Figure 5.
As can be seen in Figure 5, the instantaneous onset point is
between 30 and 40% heptane. Additional experiments (not
pictured) further narrowed the onset to between 37.5 and 40
vol. %. It is unnecessary to obtain a more precise estimate of the
instantaneous onset point because it would be a function of
how much time passed between mixing and microscopy
observation, 15 min for this measurement.19 The SEM images
in Figure 4 conrm that deposition is occurring at 30% heptane,
signicantly below the instantaneous onset point. Additionally,
the lack of visible asphaltenes at the system euent reveals that
all of the asphaltene deposition is caused by submicrometer
aggregates.
Oil densities were measured using a pycnometer, and the
asphaltene content for Oil A was measured with a 40:1 heptane
dilution and a centrifugation procedure described previously.19
The total asphaltene content for WY Oil was measured with

The solubility of asphaltenes in Oil A (g of soluble

asphaltenes per 100 g of crude oil) at 60 C and various
heptane volume percents was measured by the same technique
as the total asphaltene content and is shown in Figure 6. As
expected, the solubility of asphaltenes in Oil A decreases at
increasing heptane concentrations. The dashed line at the top
of the Figure 6 represents the total heptane asphaltene content.
The solubility below 30 vol. % heptane is signicantly limited
by precipitation kinetics and was not measured, in agreement
with previous observations.19
Deposition as a Function of Precipitant Concentration. Mixtures of dierent volume fractions of heptane in oil
were owed through 0.01 ID stainless steel capillaries of either
5 or 30 cm length, and the dierential pressure, P, was
measured as a function of time. The initial pressure drop
without deposition, Po, was subtracted from the transient
dierential pressure measurement, as described in the
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Figure 8. Measured deposition detection times, td, for the rst deposit
to be detected as a function of heptane concentration for Oil A. Line
represents a linear regression of the results.

Figure 6. Asphaltene solubility in units of g of asphaltenes per 100 g of

crude oil at 60 C for heptane in Oil A. The dashed line represents the
total asphaltene content, 9.90 0.07.

The asphaltene precipitation kinetics research performed in

our lab by Maqbool et al. revealed that when an oil-heptane
solution is observed over time, asphaltenes will eventually
precipitate for concentrations lower than the instantaneous
onset point, but it may take several months or longer to detect
the precipitation.19 Slow aggregation could potentially occur
inside the capillary due to a distribution of residence times for
the uid owing through the capillary, possibly allowing for
micrometer-sized aggregates to form inside the capillary. In
order to illustrate that deposits were being formed by
submicrometer aggregates, microscopy experiments at 25 vol.
% heptane and 60 C were performed, and the onset time (i.e.,
the time for asphaltenes to grow to 0.5 m and be detected by
optical microscopy) was measured and found to be
approximately one month. Deposition in the capillary is
detected after only three hours, highlighting the sensitivity of
the deposition apparatus and revealing that all asphaltene
aggregates in the capillary are below 0.5 m. This observation
and the lack of detectable particles in the euent below 40 vol.
% heptane in Figure 5 conrms that asphaltene deposition is
dominated by submicrometer asphaltenes at low heptane
concentrations.
The deposition results at heptane concentrations as low as 20
vol. % further show that the asphaltenes are destabilized and
have the ability to deposit before the instability can be
identied by microscopy. Although it takes roughly 8 h to
detect the deposits formed at 20 vol. % heptane, the deposition
apparatus is a continuous ow process, and the asphaltenes that
are responsible for the deposit have only been in contact with
heptane for approximately 16 s, the mean residence time of the
mixing section. This nding reveals that asphaltenes are
destabilized and able to deposit virtually immediately after a
precipitant is added, and the kinetic eects detected by
Maqbool et al.19 are due to a slow aggregation process and not
a delay in when the destabilization rst occurs. Additionally, the
gradual decrease in deposition as the heptane concentration is
reduced clearly demonstrates that the def inition of an
instantaneous onset point is irrelevant with regards to asphaltene
deposition. Just as there is no well-dened onset condition for
asphaltene precipitation, asphaltene deposition also occurs
below the instantaneous precipitation onset point and at lower
precipitant concentrations that previously believed.
The axial uniformity of the deposits generated in the 0.01
ID capillaries can be assessed by comparing the pressure drop
vs time proles for experiments performed in deposition
capillaries of dierent lengths. If the deposit is nonuniform and

Figure 7. Pressure drop vs time for Oil A diluted with various heptane
volume percents in 0.01 ID capillaries of 5 and 30 cm lengths. All
runs performed at 60 C and 5 mL/h.

Experimental Methods section. There was no dierence

between the measured pressure drop in a 5 cm vs 30 cm
deposition capillary, which will be discussed later on in the
Results and Discussion section. The results shown in Figure 7
show (P Po) vs time for Oil A at a total ow rate of 5
mL/h and 60 C for various heptane concentrations. One
observes that the deposits are detected sooner at high heptane
concentrations than at lower heptane concentrations and also
have a greater rate of deposition, as indicated by the slope of
the (P Po) vs time plot in Figure 7. The time required to
detect the deposit by pressure drop will be referred to as the
deposition detection time.
For quantitative determination of the deposition detection
time, td, it is dened as the time where an upward trend in the
pressure drop is rst observed. Due to the noise in the pressure
drop measurements at the rst measurable deposit, some
degree of error is to be expected in the deposition detection
time measurement. An estimate of this error is included in the
deposition detection time measurements, shown in Figure 8.
The solid line represents a linear regression of the detection
time results. The results reveal that there is an exponential
dependence on the deposition detection time with respect to
the heptane concentration with the detection time being longer
at lower heptane concentrations, varying from 7.6 0.6 h at 20
vol. % heptane to 0.08 0.01 h at 50 vol. % heptane. It is
unclear from the experimental results in Figure 8 whether the
deposition detection time is a result of experimental detection
limitations in measuring small dierential pressures or slow
kinetics of asphaltene adsorption on the metal capillary surface.
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microscopy measurements were performed on the WY Oil

capillaries, despite the minimal pressure drop. The 0.01

exists primarily in the short capillary, the pressure drop proles

of the long and short capillaries will superimpose after shifting
by the initial pressure drop, Po. The section of the capillary at
a farther axial position from the inlet that does not have a
deposit will have a constant pressure drop vs time, and its
contribution to the pressure drop will be eliminated by
subtraction of Po. Only the section with deposition will cause
an increase in pressure over time, and if the deposition section
is entirely contained within the short capillary, the pressure
drop vs time proles will superimpose between a long and short
capillary once Po for each experiment is subtracted. The
mathematical validation of this comparison and other axial
deposit proles is found in the Supporting Information.
In order to investigate the axial deposit prole by comparing
the pressure drop between capillaries of dierent length, 30 vol.
% heptane in Oil A deposition experiments were performed in
5 cm and in 30 cm length deposition capillaries. Two
experiments were performed for each of the two capillary
lengths, and all four deposition experiments are shown in
Figure 9. The pressure drop vs time proles of the long and

Figure 10. SEM images of the deposition capillary inlet (left) and
outlet (right) for the WY Oil deposits generated in a 0.01 ID capillary
with a 5 cm length at 35 vol. % heptane at 60 C (top) and 25 vol. %
and 25 C (bottom). As with Oil A, the deposit is thicker at the inlet.

capillaries had a less circular inlet and showed some

irregularities compared to the 0.02 capillaries, likely due to
diculties in manufacturing small ID capillaries. Figure 10
shows SEM images of the deposition capillary inlet and outlet
for 35 vol. % heptane at 60 C and 25 vol. % heptane at 25 C.
The images reveal axially nonuniform deposition, thicker at the
inlet compared to outlet, as observed with Oil A. The low
pressure drop measured for WY Oil reveals that the capillary
deposition technique is most accurate when the oil has a
relatively high asphaltene content.
Deposition of Precipitated and Aged Asphaltenes.
Additional deposition experiments were performed with a
peristaltic pump to study whether crude oil containing
asphaltene particles previously precipitated with heptane
would deposit in a capillary. Oil A was diluted to 40 vol. %
heptane and a total volume of 50 mL and continuously stirred
for 95 h prior to the start of the experiment to ensure complete
precipitation. At 40 vol. % heptane, the insoluble asphaltene
fraction on a crude oil basis is 4.7 0.2 wt %, roughly half of
the asphaltenes in the oil. After 14 h of owing the premixed
mixture through a 0.01 ID capillary, no deposition was
detectable from either pressure drop measurements or SEM
images of the capillary inlet. It can be seen that in contrast to
the previous section, where heptane was added continuously
during the ow deposition experiments, there is no measurable
deposit formed with the precipitated and aged oil-precipitant
system. This nding demonstrates that asphaltenes only deposit
when they are in the process of aggregating and that aged
asphaltene aggregates do not deposit. Wang et al. also concluded
that precipitated asphaltenes do not deposit; however, the
amount of precipitated asphaltenes was not quantied in their
experiment, and the lack of observed deposition could have

Figure 9. Comparison of (P Po) vs time plot for the short (5

cm) and long (30 cm) capillaries. Two experiments for each length are
shown, and all experiments were performed with 30 vol. % heptane.
Dierences represent experimental reproducibility, and results clearly
demonstrate nonuniformity and that the deposit is occurring
preferentially near the capillary inlet.

short capillaries superimpose, within experimental reproducibility, after shifting by the initial pressure drop, Po, revealing
that the deposit is axially nonuniform and formed primarily in
the rst 5 cm of the capillary, in agreement with the SEM
images. The result does not eliminate the possibility of deposits
forming at positions farther down the capillary, but it clearly
illustrates that the rate of deposition is signicantly higher near
the capillary inlet and that the pressure drop measurement is
dominated by the deposit near the capillary inlet. If the deposits
were uniform in the long and short capillaries, the pressure
drop proles would superimpose if normalized by the capillary
length; see the Supporting Information for mathematical
validation. This is clearly not the case, because the pressure
drop in the long capillary is not six times the magnitude as the
short capillary.
Deposition of WY Oil. Deposition experiments were also
performed on a second crude oil, WY Oil, at both 60 C and at
25 C in 0.01 ID and 5 cm length capillaries. The pressure
drop for WY Oil was an order of magnitude smaller than that of
Oil A and was on the order of the error of measurement for the
transducers used, owing to the low asphaltene content and
viscosity. Consequently, it is expected for the deposit to be less
severe and more dicult to detect. Nevertheless, electron
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been due to a small precipitated fraction, which is not the case

here.26
Oil A Normalized Plot. It is common practice to convert
pressure drop measurements to an estimate of the deposit
thickness, assuming an axially uniform deposit thickness.26,29
While this is a useful procedure for visualizing the deposit in the
capillary and factoring out the inuence of viscosity or ow rate,
it does not aid in the understanding of the mechanism or
driving force for deposition. In contrast to previous approaches,
the deposition proles shown in Figure 7 will be normalized by
the insoluble asphaltene concentration, CoA (kg/m3), at the
experimental heptane volume percent. Additionally, the
experimental results will be normalized by the mixture viscosity,
, because the pressure drop for capillary ow is proportional to
viscosity. This normalization scheme will allow for a qualitative
assessment of the eect of heptane concentration on the
deposition process. Unfortunately, due to the nonuniform
deposition prole, the pressure drop cannot be simply related
to a deposit thickness. Normalization by the concentration of
insoluble asphaltenes in each oil-heptane mixture will account
for the total number of asphaltenes that can potentially deposit.
The concentration of insoluble asphaltenes as a function of
volume percent heptane can be calculated by examination of
the solubility of asphaltenes shown in Figure 6. The dierence
between the solubility measurements and total asphaltenes
content divided by 100 provides the mass fraction of
asphaltenes precipitating from the crude oil, F. The
concentration of insoluble asphaltenes, CoA, is lowered due to
the dilution of heptane and can be calculated by the following
expression

CAo = Oil OilF

Figure 11. Normalized deposition pressure drop proles for heptane

in Oil A, scaled by viscosity and the concentration of insoluble
asphaltenes in the capillary. Time is shifted by the deposition detection
time, td. Note that the entire curve for the 35% heptane result
superimposes with the 30% heptane results, as do the early times for
the 40 and 50% heptane experiments.

variations in the pressure drop proles between experiments

with dierent heptane concentrations (Figure 7) roughly
collapse to a single curve (Figure 11) when viscosity and,
more importantly, the asphaltene solubility are used to scale the
results.
The normalization procedure reveals that the deposition
behavior of asphaltenes is nearly identical at dierent heptane
concentrations when the solubility of asphaltenes is taken into
account. Qualitatively, the normalized pressure proles reveal
the relative propensity for an individual asphaltene aggregate to
deposit. Thus, the deposit that forms with 50 vol. % heptane
grows more rapidly because there are more insoluble
asphaltenes in the oil-precipitant mixture, as observed in Figure
7. Additionally, the normalized pressure drop prole reveals
that each asphaltene aggregate has a similar probability or
propensity to deposit. However, the 40 and 50 vol. % heptane
experiments begin to deviate from the normalized behavior
once the pressure drop increases signicantly, and hence, the
deposit becomes suciently thick. The deviation occurs at a
shorter time for at 50% heptane compared to the 40%
experiment, possibly indicating that at higher heptane
concentrations, asphaltenes may have a higher propensity to
deposit, as observed in previous asphaltene aggregation
modeling results.20
Normalization of the two most dilute experiments, 20 and 25
vol. % heptane, was not possible a priori because the solubility
is unknown for these heptane concentrations due to the long
times required for the equilibrium amount of precipitating
asphaltenes to be measured. For example, the solubility
measurement performed on a 30 vol. % heptane in Oil A
mixture at 60 C took approximately three weeks to reach the
equilibrium value due to slow asphaltene precipitation/
aggregation kinetics. Determining the equilibrium solubility
for concentrations below 30 vol. % heptane would take a
signicantly longer time with conventional means, such as
batch ltration or centrifugation.19 The fraction of asphaltenes
precipitating from Oil A at the two most dilute heptane
concentrations was used as the sole tunable parameter to force
the pressure proles to superimpose with the normalized
pressure drop prole. The estimated weight percent of
asphaltenes precipitating from the crude oil for the 20 and 25
vol. % heptane experiments to t the normalized deposition
curve in Figure 11 was 0.035 and 0.19 0.06 wt %,
respectively. These values can be subtracted from the total

(1)

where Oil is the mass density of the crude oil (inclusive of

asphaltenes), Oil is the volume fraction of crude oil in the
deposition experiment, and F is the mass fraction of insoluble
asphaltenes precipitating from the crude oil (g insoluble
asphaltene per g crude oil). The density of Oil A and total
volumetric ow rate do not change between experiments and
are not used in normalization. The volume fraction of oil in the
system is necessary to account for the dilution eect of heptane
on the concentration of asphaltenes. The pressure drop proles
will be divided by both the mass fraction of insoluble
asphaltenes on an oil basis (calculated from Figure 6) and
the oil volume fraction to correct for the dierences in
asphaltene solubility at various heptane concentrations.
Deposition experiments for heptane concentrations between
30 and 50 vol. % heptane can be normalized because a
measurement of the asphaltene solubility is available, thus each
pressure drop was divided by OilF. In addition, the time for
each experiment was shifted by an individually measured
detection time, td, and the dierence, t td, was used for the xaxis. Each of the multiple experiments at 30 vol. % heptane was
shifted by an individually measured deposition detection time
to account for deviations in the capillary inner diameter which
will shift the deposition detection time. A slight variation in the
capillary inner diameter will change the minimum deposit
thickness required to cause a pressure drop increase greater
than the experimental measurement noise. Thus, for a constant
ux of asphaltenes to the deposit at a given heptane
concentration, a capillary with a larger inner diameter will
have a longer deposition detection time. The scaled deposition
proles that are shifted by deposition detection time are shown
in Figure 11. The normalization results reveal that the large
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capillary. The normalization scheme revealed that the

concentration of insoluble asphaltenes is the governing factor
controlling deposition, and consequently, the depletion of
destabilized asphaltenes near the wall will reduce the deposition
ux. Thus, the axial deposition prole that will form in the
entrance region will be highly nonuniform, while the prole
that forms in the fully developed region will be more uniform.
Asphaltene deposition in the entrance region vs the fully
developed region is likely the explanation for the observed
uniform deposition prole reported previously by Wang et al. in
100 ft long capillaries.26 The length of the capillary in the
mixing section for the apparatus used by Wang et al. is
unspecied, and the mass transfer entrance region may be
entirely contained within that section. Additionally, the
deposition rate will be the highest at the entrance of the
capillary, highlighting the importance of limiting the length of
the mixing section in a deposition apparatus.
Other possible explanations for the observed nonuniform
axial deposit prole include asphaltene aggregate size eects
(i.e., asphaltenes of dierent sizes deposit at dierent rates) and
depletion of asphaltenes due to deposition. Size eects are
unlikely, because the aggregates are well below the size where
shear is expected to inuence deposition. Additionally, because
of the short residence time (1.8 s for a 0.01 ID and 5 cm long
capillary) there is likely little dierence between the inlet and
outlet particle size distributions. Depletion eects can be
investigated by calculating the capture eciency, dened as the
mass of insoluble asphaltenes that deposit compared to the
mass of insoluble asphaltenes that have entered the capillary.
For a 0.01 ID and 5 cm length capillary, the total internal
volume is 2.6 L. For a deposition experiment with 30 vol. %
heptane in Oil A, after 4 h a total of 50.7 L of insoluble
asphaltenes have owed through the capillary. Thus, the total
capture eciency must be less than 5% (otherwise the entire
capillary will be blocked), and the deposition prole is not
caused by depletion.
The detection of asphaltene deposits at dilute precipitant
concentrations has likely been overlooked previously for a
number of reasons: short experiment times, large inner
diameter capillaries, and fully developed mass transfer. First,
Broseta et al. also used 0.01 ID capillaries; however, the
precipitant concentration was increased approximately every
hour to search for the onset concentration.25 As seen in Figure
8, deposits took up to 7.6 h to detect at low precipitant
concentrations, signicantly longer than Broseta et al. waited.
Wang et al. utilized 0.02 ID capillaries, which will have a less
sensitive pressure drop response to deposit formation than the
0.01 ID capillaries used here.26 Additionally as mentioned
above, the apparatus used by Wang et al. may have deposition
occurring in the fully developed mass transfer region, and the
deposition rate in the entrance region will be greater than that
further into the capillary. Ultimately, there are a number of
factors that allowed for the detection of asphaltene deposition
at dilute precipitant concentrations that are reported here. The
high asphaltene content of Oil A was also advantageous because
even a small relative fraction of asphaltene precipitating still
represented a large total amount of asphaltenes that can
potentially deposit. Finally, not detecting asphaltene deposition
after a certain time period of ow does not eliminate the
possibility of a deposit slowly forming.
Laboratory vs Field Asphaltene Deposition. The axially
nonuniform deposit prole reported here is not directly
comparable to a deposition prole measured in a production

asphaltene content line shown in Figure 6 to extend asphaltene

solubility measurements to previously unobtainable conditions
of low heptane concentration for use in thermodynamic model
validation. Previous estimates of the critical stability point of
asphaltenes are inaccurate, and the development of more
sensitive solubility detection techniques, such as the capillary
deposition apparatus shown here, should hopefully yield more
accurate thermodynamic solubility models. In addition, the
slow rate of deposition at 20 and 25 vol. % heptane is caused by
the most unstable asphaltenes in Oil A, and the deposition
apparatus could potentially be used to capture these problematic asphaltenes for characterization.
The concentration of insoluble asphaltenes is the dominant
factor controlling the magnitude of asphaltene deposition, as
shown by the virtually identical pressure drop proles once
normalized. Generation of the normalized plot now allows one
to estimate the solubility of asphaltenes in dilute precipitant
mixtures where slow precipitation kinetics previously rendered
similar measurements impossible using conventional techniques. This new procedure is able to estimate the mass precent
of asphaltenes precipitating from Oil A over a range spanning 2
orders of magnitude, from 0.035% precipitating at 20 vol. %
heptane to 5.6% at 50 vol. % heptane. These results represent
the rst experimental evidence that the dominant inf luence on
asphaltene deposition is simply the solubility of asphaltenes. The
exact mechanism of asphaltene deposition that occurs at the oildeposit interface is still not well understood; however, the
extent of deposition can be estimated via the solubility without
knowledge of the deposition surface phenomena.
Deposit Prole and Previous Results Comparison. For
both of the crude oils investigated, the deposit was thicker near
the inlet of the deposition capillary, compared to the outlet.
This nding is in contrast to the work of Wang et al., who
reported a uniform axial deposit prole in 100 ft long
capillaries.26 The experimental evidence for a uniform deposit
came only from the mass of the asphaltene deposit, and no
comparison between capillaries of dierent length or visualization of the deposits was performed, as was done in the
investigation reported here. Additionally, Wang et al. also
reported a highly nonuniform deposit using a model system of
asphaltenes dispersed in 1-methylnaphthalene.26
The most probable cause for the observed nonuniform axial
deposition prole reported here is local mass transport
limitations. The mass transfer entrance region is where the
Sherwood number, Sh, and consequently the mass transfer
coecient, km (m/s), are functions of the axial position near the
capillary entrance.35 Recall that the Sherwood number for
internal ow through a capillary of inner diameter, a, is dened
as Sh = (kma/DA), where DA is the diusivity of asphaltene
nanoaggregates, assumed to be governed by the Stokes
Einstein equation with a diameter of 2.5 nm. The Sherwood
number is at a maximum at the entrance of the capillary and
decreases with increasing axial position until the fully developed
region is reached where it is independent of axial position. The
mass transfer entrance length for asphaltenes in the
experimental apparatus is calculated to be between 4 and 11
feet, depending on the mixture viscosity, revealing that the
deposition in the apparatus is occurring in the entrance
region.35 Larger aggregate sizes will result in a longer entrance
region due to lower StokesEinstein diusivity values.
In the mass transfer entrance region, the concentration of
asphaltenes and the concentration gradient at the capillary wall
both decrease rapidly as the mixture travels axially down the
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wellbore such as the prole reported by Haskett et al.2

Thermodynamics dictate that at a particular oil-precipitant
composition, a xed quantity of asphaltenes will precipitate.
The quantity of asphaltenes that precipitate resulting from
heptane addition to a dead oil will not vary as the mixture
travels axially down the capillary because the thermodynamic
variables of temperature and composition do not change and
the pressure only changes slightly. Additionally, the dead oilprecipitant mixture used in this investigation contains no
dissolved light ends, and the mixture properties are insensitive
to changes in pressure. In a production wellbore, the
thermodynamic conditions do vary signicantly as a function
of axial position, and the hydrostatic pressure decreases when
the oil ows vertically toward the surface, which can cause
additional asphaltenes to precipitate. Deposition, precipitation,
and aggregation all occur simultaneously in the eld.
Laboratory deposition experiments with a precipitant added
can be viewed as a simplied setup that is useful for
determining kinetic asphaltene behavior, both aggregation and
deposition, in an apparatus with dened thermodynamics.

Normalization of the deposition results revealed that the

severity of asphaltene deposition is controlled by the
concentration of insoluble asphaltenes present in an oil-heptane
mixture. Considering the eect of the insoluble asphaltene
concentration allowed for all deposition experiments with a
single oil to superimpose onto one normalized pressure drop vs
time prole. The previously unobtainable solubility of
asphaltenes at extremely low heptane concentrations can now
be estimated by the normalized deposition curve and provides
additional solubility measurements for thermodynamic precipitation model validation.

ASSOCIATED CONTENT

S Supporting Information
*

Preliminary CFD results of the mixing between oil and heptane

and derivations for the comparison of the pressure drop
between long and short capillaries for various axial deposition
proles. This material is available free of charge via the Internet
at http://pubs.acs.org.

CONCLUSIONS
In this work, a capillary deposition apparatus was used to
demonstrate that asphaltene deposition occurs before the
asphaltene precipitation can be detected by standard
techniques, such as optical microscopy. Micrographs of the
capillary euent reveal that asphaltene aggregates that grow to
0.5 m or greater are not necessary for deposition to occur.
This observation reveals that the damage from asphaltene
fouling is likely dominated by submicrometer asphaltene
aggregates and that large and mature aggregates do not deposit.
For the rst time, arterial asphaltene deposits generated in the
laboratory have been directly observed. The SEM images show
that the deposit is signicantly thicker at the capillary inlet
when compared to the outlet, and the deposition prole is most
likely caused by transport limitations of asphaltene aggregates
diusing to the deposit interface. Good mixing in the apparatus
was conrmed by SEM and supported by CFD simulations.
Contrary to previous results, there is no dierence in
asphaltene deposition when comparing experiments above and
below the instantaneous onset conditions other than the
solubility of asphaltenes. No critical precipitant concentration
was observed, and the extent of asphaltene deposition was a
smooth and continuous function of heptane concentration.
Attempting to assign an absolute set of conditions, such as an
onset point, that will dictate whether or not asphaltenes will
deposit fails to describe the complex process of asphaltene
stability and fouling. Although it takes some period of time to
detect the deposition, the asphaltenes that are responsible for
the observed deposits have only been in contact with heptane
for a short period of time, approximately 16 s. This nding
clearly illustrates that asphaltene precipitation kinetics are only
a detection limitation in observing asphaltene instability and
not a delay in when asphaltenes begin to precipitate or
aggregate. These experimental results stress the importance of
understanding asphaltene precipitation and aggregation in the
kinetic regime,1921 where asphaltene aggregates are in the
process of growing and are too small to be detected by
conventional means (i.e., optical microscopy, refractive index,
etc.). The kinetic regime for asphaltenes may be the most
critical in the deposition process and has unfortunately, largely
been overlooked.

AUTHOR INFORMATION

Corresponding Author

*E-mail: sfogler@umich.edu.
Present Addresses

School of Engineering - Biological Engineering and Small

Scale Technologies, The University of California, Merced, 5200
North Lake Rd., Merced, CA 95343, USA.

PTT Public Company Limited, Rayong Gas Separation Plant,

555 Sukhumvit Rd. Map Ta Phut, Muang, Rayong 21150,
Thailand.

ExxonMobil Research & Engineering, 1545 Route 22 East,

Annandale, NJ 08801, USA.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors would like to thank the sponsors of the University
of Michigan Industrial Aliates Program for nancial support.
Program members include the following: BP, Chevron,
ConocoPhillips, MSIKenny, Nalco, Schlumberger, Shell,
StatOil, and Total. In addition, we would like to thank Wattana
Chaisoontornyotin for performing the high-temperature
solubility measurements and Claudio Vilas Boas Favero and
Nasim Haji Akbari Balou for numerous helpful discussions.

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