Ind. Eng. Chem. Res.

2004, 43, 6861-6870 6861

Kinetics of Asphaltene Flocculation

Khashayar Rastegari, William Y. Svrcek, and Harvey W. Yarranton*

Department of Chemical and Petroleum Engineering, University of Calgary,
Calgary, Alberta, Canada T2N 1N4

The kinetics of asphaltene particle growth in model systems of asphaltenes, n-heptane, and
toluene were investigated using a particle-size analyzer. Individual precipitated asphaltene
particles were found to be on the order of 1 µm in diameter. The asphaltene particles formed
loose fractal-like flocs with volume mean diameters ranging up to 400 µm and a fractal dimension
of approximately 1.6. Asphaltene flocculation was reversible, and the flocculation rate increased
with increased asphaltene concentration, increased heptane content, and decreased shear rate.
A reversible kinetic flocculation model successfully fit the particle-size distributions and growth
in mean volume diameter over time.

Introduction
Heavy oil and bitumen resources are gaining in
prominence as conventional oil supplies are depleted.
These heavier crude oils have a high asphaltene content
and are more prone to asphaltene deposition problems.
Chemical and mechanical methods have been used to
clean up asphaltene deposits in oil wells, reservoir, and
pipelines.1,2 These remedies are not always effective,
and to better mitigate asphaltene deposition, a better
understanding of asphaltene deposition is required.
Deposition likely begins with asphaltene precipitation
caused by the introduction of diluents (for viscosity
reduction) or changes in temperature and pressure
between the reservoir, well bore, and production facili-
ties. Once asphaltenes precipitate, the precipitated
particles tend to flocculate. The size of the asphaltene
flocs is likely an important factor in asphaltene deposi-
tion because larger flocs are more likely to settle and
form deposits. However, most research has focused on
asphaltene precipitation, and there has been relatively
little work on asphaltene flocculation.
Asphaltene floc sizes from one to several hundred
microns have been reported. For dilute dispersions of
asphaltenes in mixtures of n-heptane and toluene, the
mean diameter of asphaltene flocs ranged from 0.4 µm
at the initial stage of flocculation to 12 µm after 30 h.3-6
It is believed that asphaltene flocs in the size range of
1 µm are individual particles rather than flocs.3,7,8 In
n-alkane-diluted bitumen, the asphaltene flocs were
found to be far from spherical, with diameters ranging
from 80 to 600 µm.9,10 Ferworn et al. reported unimodal
size distributions of flocculated asphaltenes, but bimodal
size distributions have been observed for two low-
viscosity oils.11
Asphaltene flocs have a loose structure, and several
researchers have attempted to determine a fractal
dimension for flocculated asphaltenes. Sheu et al.12 used
a series of time-dependent viscosity measurements to
determine that the fractal dimension of asphaltene flocs
varied from 1.49 to 1.8 depending on the types of
asphaltenes and the asphaltene concentrations. A low-
temperature electron spin-lattice relaxation technique
* To whom correspondence should be addressed. E-mail:
hyarrant@ucalgary.ca.
10.1021/ie049594v CCC: $27.50 © 2004 American Chemical Society
Published on Web 09/21/2004
showed that the fractal dimension for the three lower
molar mass fractions for five gel-permeation-chromato-
graphic fractions of Athabasca asphaltenes varied from
1.65 to 1.68 while the fractal dimension of the two
higher molar mass fractions was approximately 2.0.
These results indicate that the fractal dimension could
depend on the molar mass of the asphaltenes.13 Both
irreversible diffusion-limited and reaction-limited ki-
netic models have been used to model asphaltene
flocculation in a mixture of n-heptane and toluene.4,6,14
The fractal dimension of asphaltene flocs was treated
as a tuning parameter to correlate the experimentally
observed rate of asphaltene particle growth. The fitted
fractal dimensions varied from 1.49 to 1.77 for a
diffusion-limited flocculation model and approximately
2.0 for a reaction-limited model.
The asphaltene floc size depends on the properties of
the medium and the flow conditions, including temper-
ature, pressure, and shear rate. In general, the less
aromatic is the medium, the greater is the floc size. In
mixtures of aromatics such as toluene and n-alkanes
such as n-heptane, the asphaltene mean floc size
increases as the n-alkane content or asphaltene con-
centration in solution increases. Ferworn et al.9 and
Mason and Lin14 showed that, for n-alkane-diluted oils,
the floc size increased as the n-alkane content or
paraffinic light oil content increased. The size of the
asphaltene flocs also increased as the number of carbon
atoms in the n-alkane diluent decreased.7,10
The effect of temperature and pressure on asphaltene
flocculation is not well established. Funk7 reported that
the mean floc size of asphaltenes precipitated from tar
sand increased as the temperature increased. However,
Neilson et al.11 found that the mean asphaltene particle
size in n-alkane (n-pentane and n-heptane)-diluted
bitumen decreased as the temperature increased. Neil-
son et al.11 also found that the floc size increased slightly
with increased pressure.
The effect of shear on asphaltene flocculation is also
not well established although flocculation is known to
be shear-sensitive. Flocculation was observed to be very
unstable in toluene and n-heptane mixtures. With slight
shaking, flocs disintegrated into what appeared to be
individual particles with a diameter on the order of 1
µm.3 Ferworn et al.9 also observed that asphaltene flocs
disintegrate upon agitation.
6862 Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004
One other factor that has received little attention is
the kinetics of asphaltene flocculation. Because oil
production and processing take place in relatively short
time scales (minutes rather than hours), the kinetics of
asphaltene flocculation can have a significant impact
on the potential for deposition. In this work, the kinetics
of asphaltene flocculation are investigated in mixtures
of n-heptane, toluene, and asphaltenes. This model
system is employed because the fluid is sufficiently
transparent for particle-size analysis (at asphaltene
concentrations below 0.1 kg/m3). Also, asphaltenes are
soluble in toluene and insoluble in n-heptane. Hence,
the amount of asphaltene precipitation can be experi-
mentally controlled through both the heptane/toluene
ratio and the asphaltene concentration. The effects of
the asphaltene concentration, the heptane/toluene ratio,
and shear are considered, and a kinetic model capable
of fitting the data is developed.
Experimental Method
Material. Toluene and n-heptane of greater than 99%
purity were obtained from Aldrich Chemical Co. Hell-
manex cleaning concentrate and optical sampling cells
were obtained from Hellma Cell Inc. Athabasca coker-
feed bitumen was obtained from Syncrude Canada Ltd.
The coker-feed bitumen has been treated to remove
solids and waters. The residual water and solids con-
tents are approximately 0 and 1 wt %, respectively.
Asphaltenes were precipitated from the bitumen upon
the addition of 40 cm3 of n-heptane/g of bitumen. The
mixture was sonicated for 45 min at room temperature
and left for 24 h, and then the supernatant was filtered
using Whatman’s No. 2 (8-µm pore size) filter paper.
More n-heptane was added to the filter cake at a ratio
of 4 cm3 of n-heptane/g of original bitumen. The mixture
was sonicated for 30 min, left overnight, and again
filtered using the same filter paper. The dried filter cake
is termed the “unwashed C7 asphaltenes”.
Unwashed C7 asphaltenes may contain resinous
material and trapped maltenes. To wash out this
material and obtain “purer” asphaltenes, the unwashed
C7 asphaltenes were placed in a Soxhlet apparatus and
refluxed with n-heptane for 3-4 days. The process was
interrupted once a day to crush and mix the asphaltene
sample to increase contact between the asphaltenes and
n-heptane. The residual dried asphaltenes are termed
“Soxhlet-washed C7 asphaltenes”.15
The Soxhlet-washed C7 asphaltenes may contain non-
asphaltenic solids that coprecipitate with the asphalt-
enes.16 To remove these solids, the Soxhlet-washed C7
asphaltenes were dissolved in toluene at a concentration
of approximately 10 kg/m3. The mixture was centrifuged
at 4000 rpm for 5 min. The supernatant was decanted,
and the toluene was evaporated from the mixture in air
at room temperature overnight and then in a vacuum
oven in nitrogen at 70 °C. The dried residual asphalt-
enes are referred to as “solids-free Soxhlet-washed C7
asphaltenes”. All of the experiments presented here
were performed on solids-free Soxhlet-washed C7 as-
phaltenes, and they will be referred to simply as
“asphaltenes” hereafter.
Particle-Size Analysis. Asphaltene particle-size
distributions were measured with a Brinkmann Instru-
ments 2010 particle-size analyzer. This apparatus uses
the time-of-transition method; that is, the diameter of
a particle is determined from the time a moving laser
beam is obscured by the particle. The apparatus can be
configured with one of two lenses for different ranges
of particle sizes: lens A, 0.5-150 µm; lens B, 5-600 µm.
The particle-size measurements were performed on
samples of approximately 3.5 cm3 placed in a 1 cm × 1
cm glass cuvette equipped with a magnetic bar for
stirring. Particles could be detected at asphaltene
concentrations up to 0.1 kg/m3. At higher asphaltene
concentrations in the model systems and for heptane-
diluted bitumen, the fluid was too opaque to obtain a
measurement. At asphaltene concentrations below 0.05
kg/m3, there were too few particles to obtain an accurate
analysis. Therefore, the experiments were limited to a
narrow range of asphaltene concentrations: 0.05-0.1
kg/m3.
To prepare a sample, asphaltenes were dissolved in
toluene and sonicated for 1 h at 23 °C to ensure that
all of the asphaltenes dissolved. Note that some of the
solutions were tested in the analyzer with lens A and
no measurable particles were detected; that is, no
asphaltene particles greater than 0.5 µm in diameter
were present. At time zero, heptane was added to the
solution of asphaltenes and toluene. The mixture was
slightly shaken and then transferred to the cuvette.
Because each particle-size analysis requires 2-3 min,
the first measurement was obtained 5 min after the
heptane addition. Visual observation indicated that, in
this first 5 min, the majority of the precipitated particles
formed almost instantly and began to flocculate im-
mediately.
At each specific condition, the experiments were
repeated for three separate samples, and three observa-
tions were obtained at each time interval. The variables
and conditions investigated were as follows: heptane/
toluene volume ratio, 60:40 Heptol and 70:30 Heptol;
asphaltene concentration, 0.05, 0.08, and 0.1 kg/m3;
mixing speed, 110, 230, and 600 rpm; time, 5, 30, 45,
60, 90, 120, 150, 180, 240, 300, and 360 min.
All experiments were performed at a temperature of
23 °C. For convenience, a solution of heptane and
toluene is described as X:Y Heptol, where X and Y are
the volume fractions of heptane and toluene, respec-
tively. The mixing speeds were measured with a tacom-
eter. Because the magnetic bar is free to move in all
directions, an exact correlation for the shear rate is not
available. If we assume that the magnetic bar is
equivalent to an impeller, an approximate shear rate
for laminar and transitional flow is given by17
γ̆ ) 13N(dimp/da)2 (1)
where γ̆ is the shear rate (s-1), N is the rotational speed
(s-1), dimp is the impeller diameter (cm), and da is the
diameter of the vessel (cm). The approximate shear
rates corresponding to rotational speeds of 110, 230, and
600 rpm are 9.2, 19.2, and 50 s-1, respectively. Given
the uncertainty in the shear rate calculation, the
experimental results are reported in terms of the
rotational speed.
The laser in the particle-size analyzer focuses on a
small fixed area within the cuvette. It is possible that
the particles within this area are not representative of
the overall particle-size distribution. Therefore, the
cuvette was shifted and some particle-size analyses were
repeated at five different locations. No significant dif-
ference in the particle-size distribution was observed.
Also note that no particles were detected in the pure
toluene and pure heptane used in these experiments.

Figure 1. Kinetics of fractional precipitation of 0.5 and 1.0 kg/
m3 asphaltenes in 60:40 Heptol at 23 °C. Solid lines are a visual
aid only.
Asphaltene Precipitation. To interpret some of the
results, it was necessary to determine the amount of
precipitated asphaltenes over time. The kinetics of
asphaltene precipitation over 6 h were determined in
solutions of 60:40 Heptol at asphaltene concentrations
of 0.5 and 1 kg/m3 and at a temperature of 23 °C.
Asphaltenes were dissolved in toluene and sonicated for
1 h. Then, n-heptane was added at a 60:40 volume ratio
of n-heptane/toluene, and the mixture was slightly
shaken. After a given time, the mixture was centrifuged
at 4000 rpm for 5 min, and the supernatant was
removed. The asphaltene deposits were first dried in air
at room temperature overnight and then in a vacuum
oven in nitrogen at 70 °C. The fractional asphaltene
precipitation is the mass of the dried precipitate over
the mass of asphaltenes in the initial solution. Figure
1 shows fractional asphaltene precipitation for 0.5 and
1 kg/m3 asphaltenes in 60:40 Heptol.
Asphaltene Flocculation Model
Two characteristic time scales can govern flocculation
kinetics: the diffusion time and the reaction time. The
diffusion time, τdiff, is the typical time that it takes for
two arbitrary particles to meet each other. The reaction
time, τreact, is the typical time for two particles to
flocculate when they are held in mutual proximity.
When τdiff . τreact, the kinetics are diffusion-limited; that
is, flocculation is a diffusion-controlled process. In this
case, particles most likely flocculate on their first
encounter with a neighbor, and hence the kinetics are
largely influenced by local fluctuations in the concentra-
tion of the particles. When τdiff , τreact, flocculation is
limited by the relatively large reaction time and is
known as a reaction-limited or reaction-controlled floc-
culation. In this limit, particles may come within the
reaction range of each other numerous times before they
actually flocculate. In other words, a particle may
sample large volumes of its surrounding neighbors
before flocculating, and hence it effectively responds to
the global concentration of other particles. Stirring is a
very efficient method of shortening the characteristic
diffusion time and smoothing out local concentration
fluctuations. Hence, reaction-limited flocculation is
expected to be the dominant mechanism in the well-
mixed experiments examined here.
Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004 6863
Previous asphaltene flocculation models have consid-
ered irreversible reaction-limited kinetics.4,6 However,
the experimental data presented later suggest that
asphaltene flocculation is a reversible process.3,9 In this
case, flocs are held together with dispersion forces and
can be separated if sheared. Reversible flocculation can
be described as follows:
Fi,j
Mi + Mj {\
D
} Mi+j (2)
i+j
where Fi,j and Di+j are the reaction rates for the
flocculation and disintegration processes, respectively,
and Mi and Mj indicate the masses of species i and j,
respectively. The Smoluchowski approach is modified
to obtain a population balance equation for the kth
species,18 given by
dCk 1
dt
) ∑ (Fi,jCiCj - Di+jCi+j) -
2 i+j)k
N-k
∑ (Fk,jCkCj - Dk+jCk+j) (3)
j)1
k ) 1, 2, 3, ..., N
where the indices i, j, k, and N indicate the number of
particles in the floc; Fi,j and Di+j are the number of
reactions per unit volume per unit time (or reaction
terms) that result in flocculation and disintegration,
respectively; Ci and Ci are the concentrations of species
i and j; and t is the time.
To apply the population balance, it is necessary to
evaluate the flocculation and disintegration reaction
rates. For flocs of approximately equal mass (Mi ≈ Mj),
Ball et al.19 proposed that the flocculation reaction terms
depend on a boundary volume defined by the radii of
the two flocs. For spheres, the reaction rate expression
is given by
Fi,j ∝ Vc ) π(di + dj)2w (4)
where di and dj are the diameters of the flocs and w is
a separation distance within which flocculation can
occur. For flocs of any geometry, the radius of the
particle can be related to the number of individual
particles in a floc using a fractal dimension as follows:
dfloc ) nf1/Df dp (5)
where dfloc is the measured diameter, Df is the diameter
of gyration of the floc (approximately equivalent to the
measured spherical mean diameter), and nf is the
number of individual particles in the floc. Equation 4
can then be expressed in terms of the number of
individual particles in the flocs:
Fi,j ) Kf(ni1/Df + nj1/Df)λ (6)
where Kf is the flocculation reaction constant, ni and nj
are the number of individual particles in flocs i and j,
and λ is an adjustable parameter with a value between
2 and 3. The exponent does not necessarily equal 2
because the effective surface area of a nonspherical floc
is not necessarily proportional to the square of the
diameter.
6864 Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004

Preliminary modeling results using eq 6 could not

predict the change in the flocculation rate as the floc
size increased with time. Better predictions were ob-
tained when the reaction term was controlled by the size
of the smaller floc. Ball et al.19 argued that flocculation
between particles of different size was controlled by the
penetration of the smaller particle into the larger
particle. Such a process may be controlled by the size
of the penetrating particle. Therefore, the following
empirical expression for the overall reaction rate term
is proposed:

( nj ni
)
λ
Fi,j ) Kf ni1/Df + n 1/Df (7)
ni + nj ni + nj j

When ni ) nj, eq 7 reduces to eq 6. When ni . nj, eq 7

reduces to Fi,j ) Kfnjλ/Df; that is, the flocculation rate is
determined from the size of the smaller of the two
colliding particles.
Disintegration may occur through erosion or shatter-
ing. Erosion is the removal of individual particles from
flocs through grinding or shear. Shattering is the
fragmentation of flocs into smaller flocs of any size less
than the original floc. The experimental results dis-
cussed later suggest that shattering is the dominant
mechanism for the model systems considered here. The
shattering reaction rate is given by20

Di+j ) Si+j ) Kddi+jβ ) Kd(ni1/Df + nj1/Df)β (8)

where Kd is the shattering reaction constant and di is

the radius of the floc. The exponent β is an adjustable
parameter with a value between 0 and 3. Note that, if
required, the erosion reaction term has the same form
as the shattering reaction term except that one of the
particle numbers ni or nj must be unity.

Results and Discussion

Micrographs of asphaltene flocs in solutions of 60:40

Heptol and 70:30 Heptol are presented in parts a and b
of Figure 2, respectively. Figure 2a shows flocs of
relatively small size, and it can be seen that the
individual asphaltene particles are approximately 1-2
µm in diameter. Figure 2b shows larger flocs, and a
typical asphaltene floc is circled to illustrate its spheri-
cal diameter. The spherical diameter is similar to the
diameter measured with the particle-size analyzer.
Figure 2c shows the microscopic image of asphaltene
flocs in heptane-diluted bitumen at a 4:1 heptane/
bitumen volume ratio. The asphaltene flocs in a hep-
tane-diluted bitumen mixture resemble the flocs in the
Heptol solutions.
Typical number and volume floc size distributions for
asphaltenes in 60:40 Heptol are presented in parts a
and b of Figure 3, respectively. Figure 3a shows a large
population of particles in the 0.5-2-µm-diameter range.
A similar large population of small particles was
observed in all of the experiments in this study, and at
higher mixing rates (shear rate) or at low flocculation Figure 2. Precipitated asphaltenes 10 min after contact with
times, the bulk of the precipitated particles fell in this heptane: (a) 0.1 kg/m3 asphaltenes in 60:40 Heptol; (b) 0.1 kg/m3
range. Based on the micrographs in Figure 2, this asphaltenes in 70:30 Heptol; (c) 4:1 heptane/Athabasca bitumen
population can be interpreted to be individual asphalt- volume ratio.
ene particles. Note that, because the lower detection
limit of the particle-size analyzer is 0.5 µm, it is probable of the flocs in Figure 2 suggests that the majority of
that smaller individual particles make up part of the the individual asphaltene particles are greater than 0.5
particle-size distribution. However, a close examination µm in diameter.

Figure 3. Measured asphaltene particle distributions after 60
and 360 min for 0.1 kg/m3 asphaltenes in 60:40 Heptol at a mixing
rate of 110 rpm: (a) number frequency; (b) volume frequency.
Figure 4. Kinetics of asphaltene particle growth for 0.1 kg/m3
asphaltenes in 60:40 Heptol at a mixing rate of 110 rpm: (1) slow-
growth region; (2) rapid-growth region; (3) steady-state region.
While the particle number count is dominated by
unflocculated asphaltene particles, the majority of the
asphaltenes are, in fact, flocculated as shown by the
volume-size distribution in Figure 3b. The “particles”
greater than 2 µm in diameter are assumed to be flocs.
The 360-min volume distribution in Figure 3b shows
that more than 90% of the mass of precipitated asphalt-
enes is distributed in flocs greater than 10 µm in
diameter. These flocs are similar to those in Figure 2b.
Figure 4 shows the change in the volume mean
diameter with time for 0.1 kg/m3 asphaltenes in 60:40
Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004 6865
Figure 5. Reversibility of asphaltene particle growth for 0.1 kg/
m3 asphaltenes in 60:40 Heptol.
Heptol at a mixing rate of 110 rpm. Three distinct
regions are shown: (1) a slow-growth region, (2) a rapid-
growth region, and (3) a steady-state plateau. The period
of slow initial growth followed by rapid growth suggests
that flocculation depends on the diameter to a higher
order than unity; for example, flocculation may depend
on the surface area, cross-sectional area, or volume of
the flocs. Therefore, as the flocs grow, the flocculation
rate increases. A physical interpretation is that larger
flocs have more potential bonding sites; i.e., they grow
faster than smaller flocs. This behavior is characteristic
of reaction-limited flocculation and will be discussed in
more detail in the kinetic modeling section.
Note that the average particle size decreases in the
first 30 min. During this time, asphaltenes continue to
precipitate, as was shown in Figure 1. Either new
particles are forming or existing particles are growing
to detectable sizes. In either case, small new particles
are joining the observed particle-size distribution. There-
fore, the mean volume diameter of asphaltene flocs
decreases as the population of the particles in the
diameter range of 0.5-2.0 µm increases. After 30 min,
little further precipitation occurs and no further de-
crease in the particle-size distribution is observed.
Reversibility of Asphaltene Flocculation. Figure
4 also shows that asphaltene flocs reach a steady-state
size distribution, indicating that flocculation does not
continue indefinitely. To achieve a steady-state condi-
tion, flocculation must eventually be balanced by dis-
integration. Hence, asphaltene flocculation appears to
be reversible.
To confirm that asphaltene precipitation is reversible,
asphaltenes were allowed to flocculate at low shear,
then the shear rate was increased, and the change in
the particle-size distribution was observed. Flocculation
was initiated in a solution of 0.1 kg/m3 asphaltenes in
60:40 Heptol at a mixing speed of 110 rpm. After 2 h,
the mixing rate was increased to 600 rpm for 45 min
and then reduced back to 110 rpm. Figure 5 shows that,
as the shear rate increased, the size of the asphaltene
flocs decreased sharply while the total number count
increased. When the shear rate decreased, asphaltene
flocculation was observed again. Figure 5 demonstrates
that asphaltene flocculation is shear-sensitive and that
asphaltene flocculation can be reversed at high shear
rates.
Interestingly, the flocculation rate after the high
shear period is slower than the initial flocculation rate.
6866 Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004

Figure 6. Volume frequency distribution of asphaltene flocs Figure 7. Effect of the concentration on the asphaltene floc size
before (120 min) and after (165 min) 45 min of a high shear rate in 60:40 Heptol at a mixing rate of 110 rpm. Symbols are
of 600 rpm (0.1 kg/m3 asphaltenes in 60:40 Heptol). experimental data; lines are model predictions.

One plausible explanation is a restructuring effect

caused by the shear forces. The initial flocculation starts
from a nearly uniform particle-size distribution, takes
place at a low shear rate, and generates loose fractal-
like flocs. The higher shear rate breaks the fractal
structure of the flocs, and their size distribution ap-
proaches, but does not reach, the size distribution of the
individual particles (Figure 6). When the shear rate is
decreased, flocculation starts from a nonuniform size
distribution. It is likely that smaller flocs interpenetrate
larger flocs, increasing their fractal dimension but not
changing their diameter significantly. In other words,
the fractal dimension of the flocs increases rapidly while
their size grows slowly.
The post-shear size distribution of Figure 6 is also
characteristic of a shattering process. Erosion tends to
create a very large population of individual particles.
However, the volume fraction of individual particles in Figure 8. Effect of the heptane content on the asphaltene floc
size for 0.1 kg/m3 asphaltenes at mixing speeds of 110 and 230
Figure 6 is smaller than the volume fraction of floc- rpm.
culated particles. This distribution indicates that the
shattering mechanism is dominant in the asphaltene
disintegration process.20
Effects of the Concentration, Heptane Content,
and Shear Rate. The asphaltene concentration, hep-
tane content, and shear rate are expected to have a
significant effect on asphaltene flocculation. Figure 7
shows the effect of the asphaltene concentration on the
volume mean diameter in 60:40 Heptol. The volume
mean diameter increases as the asphaltene concentra-
tion increases. An increase in the asphaltene concentra-
tion is equivalent to an increase in the number of
individual particles. As the number of particles in-
creases, the flocculation rate also increases.
Figure 8 shows the effect of the n-heptane content on
asphaltene flocculation. Note that the volume mean
diameter of the asphaltene flocs reached the upper
detection limit of the analyzer in 70:30 Heptol at a
mixing rate of 110 rpm. Therefore, the measurement Figure 9. Effect of the mixing speed on the asphaltene floc size
for 0.1 kg/m 3 in 60:40 Heptol.
was terminated after 30 min. Figure 8 shows that the
flocculation rate increases dramatically as the heptane
content increases. The higher the n-heptane content Figures 9 and 10 show the effect of the mixing rate
precipitates, the higher the proportion of the asphalt- (shear rate) on asphaltene flocculation in solutions of
enes resulting in more particles. Also, relatively stronger 60:40 and 70:30 Heptol, respectively. The flocculation
interparticle interactions are expected because heptane rate decreases as the shear rate increases. In fact, the
is a poor solvent for asphaltenes. Both factors increase results indicate that flocculation can be reversed or even
the flocculation rate. stopped at higher shear rates. It appears that increasing

Figure 10. Effect of the mixing speed on the asphaltene floc size
for 0.1 kg/m 3 in 70:30 Heptol.
the shear rate increases the relative rate of disintegra-
tion versus flocculation.
Asphaltene Fractal Dimension. The fractal dimen-
sion of asphaltene flocs was determined indirectly from
a calculation of the mass of precipitated asphaltenes
from the measured particle-size distribution. The frac-
tional precipitation of asphaltenes on a mass basis, FA,
is given by
FA ) VT FA/mA
where FA is the asphaltene density (1.12 kg/m3), mA is
the total mass of asphaltenes in the solution, and VT is
the total volume of the flocculated asphaltenes. The total
volume of a distribution of flocs is given by
∑niVia
π sible.
VT )
6 The gravimetric measurements given in Figure 1
where nf is the number of particles in the floc and Via is
the actual volume of all of the particles in a floc. The
actual volume, Via, of a floc is given by
π di
()
Df
π
Via ) nd 3) dp3
6 i p 6 dp
where di is the measured diameter, dp is the diameter
of the individual particle, and Df is the fractal dimen-
sion. Note that eq 5 was used to relate the number of
particles in a floc to the measured diameter, giving the
final expression in eq 11. Equations 10 and 11 are
substituted into eq 9 to obtain
()
πFANf dp3 di Df
FA )
6mA ∑ fi
dp
where Nf is the total number of flocs and fi is the number
frequency of the ith floc.
The fractional precipitation of asphaltenes was cal-
culated from the number frequency distributions and
the total number count over time for three systems:
asphaltene concentrations of 0.05, 0.08, and 0.10 kg/m3
all in 60:40 Heptol at a mixing rate of 110 rpm. The
individual particles were assumed to be monodisperse
Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004 6867
Figure 11. Calculated fractional precipitation of 0.1 kg/m3
asphaltenes in 60:40 Heptol.
with a diameter of 1 µm. To illustrate the approach, the
results for a concentration of 0.1 kg/m3 are discussed
here. Figure 11 shows the calculated fractional precipi-
tation, assuming fractal dimensions of 3.0, 2.5, 2.0, 1.75,
and 1.50.
It was not possible to compare the calculated and
measured fractional precipitation directly because the
particle-size distributions could not be measured at
(9) concentrations above 0.1 kg/m3 while accurate gravi-
metric measurements could not be obtained at concen-
trations below 0.5 kg/m3. Also the total number count
of the particle-size analyzer is not necessarily accurate,
although the relative number count is accurate. In other
words, the absolute number counts may be inaccurate,
but the trends in the number count are expected to be
accurate. Hence, a qualitative comparison is still pos-
(10)
show that the fractional precipitation does not change
significantly after 30 min. Figure 11 indicates that the
fractal dimension must be below 2.0 to match this trend
and indeed to avoid unrealistic calculations of the
fractional precipitation. It is not possible to determine
the fractal dimension more accurately, although the
(11) trends best match at the lower fractal dimensions such
as 1.5.
Sheu12 measured the fractal dimension of asphaltenes
in mixtures of 70:30 and 80:20 Heptol and found that
it ranged from 1.49 to 1.8. Also, Raghunathan13 mea-
sured the fractal dimension for three gel-permeation-
chromatographic fractions of asphaltenes and obtained
values from 1.65 to 1.68. A visual inspection of the
micrographs of asphaltene flocs (Figure 2a,b) is consis-
tent with a fractal dimension of less than 2 and closer
to 1.5. Based on the calculated fractional precipitation
(12) results, the microscopic examinations, and the values
reported in the literature, the fractal dimension was
assumed to be 1.6.
As a check, the asphaltene fractional precipitation
was calculated for 60:40 Heptol after 6 h of contact
based on a fractal dimension of 1.6. The calculated
precipitation values are compared with direct gravimet-
ric measurements in Figure 12. The calculated frac-
tional precipitations fall on the same trend as measured
data, indicating that using a fractal dimension of 1.6
gives plausible results.
6868 Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004

Figure 12. Comparison of measured and calculated fractional

asphaltene precipitation in 60:40 Heptol after 360 min. The dotted
line is a curve fit provided as a visual aid.

Table 1. Concentrations of Individual Particles Input to

Flocculation Model
asphaltene fractional Ctot(actual) Ctot(model)
system concn (kg/m3) precipn (kg/m3) (kg/m3)
60:40 Heptol 0.05 0.036 0.0018 218
60:40 Heptol 0.08 0.041 0.0033 400
60:40 Heptol 0.10 0.081 0.0081 982

Note that the asphaltene flocs may not be fractals and

the fractal dimension may not remain constant at all
scales. In other words, the fractal dimension may
change as the size of the flocs changes with time,
asphaltene concentration, heptane content, and shear
rate. In this work, it was assumed that the fractal
dimension of the asphaltene flocs was constant.
Model Results. The inputs to the model are the
initial concentration of the individual particles, the
diameter of the individual particles, the fractal dimen-
sion of the flocs, the reaction constants, and the reaction
exponents. The reaction constants and exponents are
employed as tuning parameters, and the fractal dimen-
sion of the asphaltene flocs is taken to be constant at
1.6 in the 60:40 Heptol system. The diameter of the
individual particles was found to range from 0.5 to 2 µm.
For modeling purposes, the individual particles were
assumed to be monodisperse with a diameter of 1 µm.
The concentration of the individual particles was
determined from the mass of precipitated asphaltenes
at the given experimental conditions. Table 1 shows the
calculated concentrations of the individual particles for
concentrations of 0.05, 0.08, and 0.10 kg/m3 in 60:40
Heptol. Because the fractal measurement and gravi-
metric tests were performed only for the 60:40 Heptol
system, the 70:30 Heptol system was not modeled in
this study. The fractional precipitation was assumed to
be constant at its steady-state value (after 30 min).
Hence, the low initial fractional precipitation and the
increase to steady-state values over the first 30 min
were not included in the model. To minimize the
numerical error when the model is run, the total
concentration of the particles was scaled up, as indicated
in Table 1. Hence, the fitted reaction constants do not
reflect the actual concentration of the particles in the
system. Because the value of dCk/dt in eq 3 predicted
by the model at the scaled concentrations was matched
to the experimental results at the actual concentrations,
Figure 13. Flow diagram of the numerical routine for calculating
asphaltene flocculation.
the fitted reaction terms should be scaled to the
experimental conditions as follows:
Kf(corrected) ) Kf(model)[Ctot(model)/Ctot(actual)]2
Kd(corrected) )
Kd(model)[Ctot(model)/Ctot(actual)] (13)
The computer flow diagram to calculate the asphaltene
particle-size distribution is provided in Figure 13.
Equations 3, 7, and 8 were solved explicitly with a time
increment of 0.5, and the kinetics of asphaltene particle
growth were calculated over 360 min. The time step was
controlled so that the total number of individual par-
ticles remained constant. The material balance errors
were less than 3% in all cases. Note that the numerical
error from too large a time step always results in an
error in the total number of particles. The output of the
program is the number of flocs with a given number of
particles within each floc. When converted to a fre-
quency distribution, the diameter increment is not
uniform and does not match the increment of the
measured distributions. Therefore, the cumulative fre-
quency distribution was curve-fitted and subdivided into
0.5-µm increment to match the experimentally mea-
sured distribution.
The model was tuned with the inputs given in Table
2. The modeled kinetics of particle growth for asphalt-
enes in 60:40 Heptol at a mixing rate of 110 rpm are
compared with the experimental data in Figure 7. A
 Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004 6869

Table 2. Model Inputs for 0.08 kg/m3 Asphaltenes in a

60:40 Heptol System
input modeled corrected
reaction-limited reaction constant, Kf 5.2 × 10-5 7.6 × 105
shattering reaction constant, Kd 5.0 × 10-5 6.1
flocculation reaction exponent, λ 2.6
shattering reaction exponent, β 1.5
size of the individual particles (µm) 1.0
fractal dimension of the 1.6
asphaltene flocs, Df

comparison of the measured and modeled particle-size

distributions is given in Figures 14-16 for asphaltene
concentrations of 0.05, 0.10, and 0.10 kg/m3, respec-
tively. The model fits the major trends in the experi-
mental data quite well with the following exceptions:
The model did not predict the reduction in the floc
size over the first 30 min. This discrepancy likely occurs
Figure 14. Measured and fitted asphaltene particle volume
because the kinetics of asphaltene precipitation were distribution after 60 and 360 min for 0.05 kg/m3 asphaltenes in
not included in the model and the initial total concen- 60:40 Heptol at a mixing rate of 110 rpm.
tration of the individual particles was considered to be
constant at the steady-state value. It is also possible
that large flocs formed in the first 2 min, before the
solutions were placed in the cuvette and the mixer
turned on. Some time may be required to eliminate the
large flocs at the mixer shear conditions.
The model underpredicts the volume mean diameter
at higher concentration. One possibility is that the
empirical expression for the flocculation reaction is not
correct. Another possibility is that the fractal dimen-
sions of asphaltene flocs are not true fractals; that is,
the number of particles per volume may not be the same
at all length scales. For example, a larger floc may have
a less compact structure than a small floc and therefore
have a lower fractal dimension. Hence, the apparent
fractal dimension may change with time, asphaltene
concentration, heptane content, and shear rate. In this
case, a correlation of the fractal dimension to the floc
size would be required. Figure 15. Measured and fitted asphaltene particle number and
Note that the model predicted the persistent popula- volume distribution after 60 and 360 min for 0.08 kg/m3 asphalt-
tion of individual particles that was observed in the enes in 60:40 Heptol at a mixing rate of 110 rpm.
experiments. The successful prediction of the persistent
individual particle-size distribution in the model simu-
lation indicates that the shattering mechanism is suf-
ficient to model this behavior and that the introduction
of surface erosion is not required.

Conclusions
Precipitated asphaltene particles in solutions of hep-
tane and toluene are approximately 0.5-2 µm in
diameter and tend to flocculate into loose fractal-like
flocs rather than dense, spherical aggregates. The
flocculated asphaltenes in solvent solutions are quali-
tatively similar to those in heptane-diluted bitumen.
The fractal dimension of flocculated asphaltenes in
solutions of heptane and toluene is approximately 1.6.
The asphaltene floc size increased with increased as-
phaltene concentration, increased heptane content, and Figure 16. Measured and fitted asphaltene particle volume
decreased mixing rate. distribution after 60 and 360 min for 0.1 kg/m3 asphaltenes in 60:
Asphaltene flocculation is reversible, indicating that 40 Heptol at a mixing rate of 110 rpm.
flocculation is opposed by some disintegration mecha-
nism. The shape of the sheared particle-size distribu- was observed in all cases. This behavior would indicate
tions indicates that shattering is the dominant disin- that reaction-limited flocculation is the dominant mech-
tegration mechanism. It was found that the flocculation anism in asphaltene flocculation.
rate increased as the volume mean diameter of asphalt- A reversible kinetic model was proposed based on
ene flocs increased. Also, a persistent population of reaction-limited flocculation and shattering mecha-
individual particles in the diameter range of 0.5-2.0 µm nisms. The model predictions correlate well the experi-
6870 Ind. Eng. Chem. Res., Vol. 43, No. 21, 2004
mental data with percent absolute average relative
deviation of 17.8%, 14.8%, and 29.3% for concentrations
of 0.05, 0.08, and 0.1 kg/m3, respectively. The model is
suitable for relatively dilute systems with limited floc-
culation. More data are required to extend the model
to higher asphaltene concentrations where larger flocs
are created and different flocculation and disintegration
mechanisms could dominate.
Acknowledgment
The authors thank NSERC and DBR Product Center-
Schlumberger for financial support and Syncrude Canada
Ltd. for supplying bitumen samples.
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Received for review May 13, 2004
Revised manuscript received July 31, 2004
Accepted August 6, 2004
IE049594V