PAPER 2003-059

PETROLEUM SOCIETY
CANADIAN INSTITUTE OF MINING, METALLURGY & PETROLEUM

Measurement and Modelling of Asphaltene

Flocculation From Athabasca Bitumen
K. Rastegari, J. Beck, W.Y. Svrcek, H.W. Yarranton
University of Calgary

This paper is to be presented at the Petroleum Societys Canadian International Petroleum Conference 2003, Calgary, Alberta,
Canada, June 10 12, 2003. Discussion of this paper is invited and may be presented at the meeting if filed in writing with the
technical program chairman prior to the conclusion of the meeting. This paper and any discussion filed will be considered for
publication in Petroleum Society journals. Publication rights are reserved. This is a pre-print and subject to correction.

EXTENDED ABSTRACT

INTRODUCTION precipitated asphaltenes could be investigated at

Heavy crude oil production is increasing as
conventional oil supplies are depleted. However, heavy
oils are rich in asphaltenes, which can precipitate,
flocculate, and deposit during transportation and
processing. Current methods of treating the deposit are
often only partially effective. In order to better mitigate
asphaltene deposition, a better understanding of
asphaltene precipitation and flocculation is required.
This project focuses on the formation and flocculation
of asphaltene particles in solutions of n-heptane and
toluene at 23 C and atmospheric pressure. Heptane and
toluene were selected because toluene is a good solvent
for asphaltenes whereas asphaltenes precipitate in
heptane. Hence, mixtures with different proportions of
different solvent conditions.
EXPERIMENTAL METHOD
Athabasca coker-feed bitumen was obtained from
Syncrude Canada Ltd. Toluene and n-heptane were
obtained from Aldrich chemical Company with 99%+
purity. Asphaltenes were precipitated from the bitumen
with the addition of n-heptane at a 40:1 volume ratio of
heptane-to-bitumen and non-asphaltenic solids were
removed by centrifugation. Details of the precipitation
are provided elsewhere [7].
To prepare a solution of asphaltenes in heptane and
toluene, the asphaltenes were first added to toluene and
sonicated for 1 hr at 23C to ensure that all the
asphaltene dissolved. Asphaltene precipitation was
induced by the addition of n-heptane in 60:40 and 70:30
n-heptane: toluene volume ratios. Asphaltene
concentrations of 0.05, 0.08, and 0.1 kg/m_ were
considered.
The growth of asphaltene floccs was observed over 6
hours using a Brinkmann 2010 particle size analyzer.
The particle size distribution is determined from the
time of transition of the particles (or flocs) through a
laser [5]. Samples were placed in standard 1 cm x 1 cm
square optical-glass cuvettes obtained from Hellma
cells Inc. A three-speed magnetic stirrer was employed
to disperse the asphaltene particles within the cuvette.
FLOCCULATION MODEL
The probability of flocculation is a combination of
the probability of a collision (characterized by diffusion
time, tdiff) and the probability of a collision resulting in
flocculation (characterized by reaction time, trxn). In
well mixed systems, t diff <<trxn and flocculation is
reaction-limited. In this limit, particles may collide with
each other numerous times before they actually react
(flocculate). The problem can then be approached using
classical rate equations of the form:
N i + N j N i + j .............................................................. (1)
where N i denotes a floc consisting of i individual
particles.
Cluster-cluster addition is the dominant mechanism
in reaction-controlled flocculation. Flocculation is
opposed by fragmentation, which can be a combination
of surface erosion and shattering [3]. For a
monodisperse distribution of individual particles, the
derivative with respect to time of the number
concentration, n k, of flocs of diameter dk is then given
by:
1 k -1
2 ( Fi , j - S i + j - E i + j )
dn k ii +=1j = k
= ............................... (2)
dt N -k
- ( Fk , j - S k + j - E k +1 )
j =1
2
where Fi,j , S i and Ei are the number of reactions per
unit volume per unit time that result in flocculation,
shattering or surface erosion processes, respectively.
The reaction terms are defined as follows:
Fi, j = b F (vi ,v j )ni n j
Si = b S (vi )n i ..........................................................(3)
Ei = b E (vi )n i
where ni and n j are the number concentration of species
i and j, and
b F (vi, vj), bS (vi) and b E(vi) are the
collision frequency functions. The collision frequency
functions are defined as follows:
1 1
b F (vi ,v j ) = kF (N i D + N j D )3
3
b S (vi ) = kS (N i D)
...........................................(4)
3
b E (vi ) = kE (d p D )
where Ni and Nj are the number of particles in the flocs,
D is thefractal dimension of the flocs, dp is the
diameter of an individual particle and kA, k S and k E are
the reaction constants. The fractal dimension is defined
through the following relationship between the true
volume of a floc and its apparent volume based on its
measured diameter and assuming spherical geometry:
1
D d ............................................................... (5)
d floc = N floc p
where dfloc is the diameter of gyration of the floc
(approximately equivalent to the measured spherical
mean diameter) and N floc is the number of particles in
the floc.
To determine the size distribution of the flocculated
system over time, the set of differential equations
defined in Eq. 2 were solved explicitly. The time step
was controlled so that the total number of individual
particles remained constant. Note that numerical error
from too large a time step always results in an error in
the total number of particles.
RESULTS AND DISCUSSION
Typical asphaltene particle size number and volume
distributions are shown in Figures 1 and 2, respectively.
A large population of particles in the 0.5 to 2 micron
diameter range was observed in all cases as shown in
Figure 1. At high shear, the bulk of the precipitated
material fell in this range. At low shear and sufficiently
high asphaltene concentration, larger particles were
observed, as shown in Figure 2. If the shear rate was
increased, the larger particles disappeared and the 0.5-2
micron distribution was restored. The 0.5 to 2 micron
particles were considered to be individual particles
while the larger particles appear to be flocs.
Microscopic observations confirm this interpretation as
shown in Figure 4. A fractal dimension of 1.6 was
estimated for the flocs based on the microscopic
observations as well as on the correlation of the
observed volume mean diameters and particle counts to
the amount of precipitated material.
Figure 3 shows the change in volume mean diameter
with time for 0.05, 0.08 and 0.1 kg/m_ asphaltenes in
60:40 heptane: toluene at the low stirring speed. The
asphaltene flocs reach a steady state size distribution
indicating that both flocculation and fragmentation are
occurring. The persistent population of individual
particles shown in Figure 1 indicates that surface
erosion is also occurring.
To model asphaltene flocculation, an individual
particle diameter of 1.0 micron was employed and
reaction constants were fitted for the aggregation,
erosion, and shattering reactions. The model fits are
compared with experimental data in Figures 1 to 3.
Both numerical and experimental results show that
the flocculation rate increases as the characteristic floc
size grows. The numerically predicted frequency
distribution and growth rate are qualitatively in
agreement with experimental results. However, the
numerically calculated frequency distributions are
somewhat narrower than the experimental distributions
and the model underpredicts the steady state volume
mean diameter at higher concentrations. One possible
explanation for the discrepancy is that the fractal
dimension could depend on the size of the floc.
3
Accounting for this dependence could improve the
quality of the fits.
As expected, flocculation was observed to increase
with increased asphaltene concentration, increased
heptane content, and decreased shear. An attempt will
be made to correlate the reaction constants to these
variables.
ACKNOWLEDGEMENTS
The authors would like to thank Syncrude Canada
Inc. for providing bitumen samples as well as DBR-
OilPhase and NSERC for financial support.
REFERENCES
1. R.C. Ball, D.A. Weitz, T.A. Witten and F. Leyvraz,
Universal Kinetics in Reaction-Limited Aggregation,
Phys. Rev. Letters, 58 (1987).
2. P.Meakin and M.H.Ernst, Scaling in Aggregation with
Breakup Simulation and MeanField Theory, Phys.
Rev. Letters, 60, 2503-2506 (1988).
3. L.M. Popplewell, O.H.Campanella, and M.Peleg,
Simulation of Bimodal Size Distributions in
Aggregation and Disintegration Process, J. Chem. Eng.
Prog., 56-62 (1989)
4. M.Y. Lin, H.M. Lindsay, D.A. Weitz, R.C.Ball, R.
Kelein and P. Meakin, Universal Reaction-Limited
Colloid Aggregation, Phys. Rev. A, 41 (1990).
5. K.A. Ferworn, W.Y. Svrcek, and A.K. Mehrotra,
Measurement of Asphaltene Particle Size Distribution
in Crude Oils Diluted with n-Heptane, Ind. Eng. Chem.
Res., 32, 955-959 (1993)
6. V.A. Branco, G. Ali Mansoori, L.C. Xavier, S.J. Park, H.
Manafi, Asphaltene Flocculation and Collapse from
Petroleum Fluids, J. SPE, 32, 217-230 (2001).
7. H. Alboudwarej, J. Beck, W.Y. Svrcek, H.W. Yarranton,
and K. Akbarzadeh; Sensitivity of Asphaltene
Properties to Extraction Techniques; Energy & Fuels,
16,462 (2002)
8. J.A. Ostlund, J.E. Lofroth, K. Holmberg and M. Nyden,
Flocculation Behavior of Asphaltene in Solvent/
Nonsolvent systems; J. of Colloid and Interface Science
253,150-158 (2002)
 Numerical 45 min.
0.8 14
Numerical 360 min.
0.7 12
Experimental 45 min.
0.1 kg/m3
0.6 Experimental 360 min.

Volume Mean Dia.(micron)

Number Frequency

10
0.5
8
0.4
0.08 kg/m3
0.3 6

0.2 4
0.05 kg/m 3
0.1 2
0
0.1 1 10 100 0
Size(micron) 0 100 200 300 400
Time(min.)
Figure 1. Measured and fitted asphaltene particle number
distribution after 45 and 360 minutes for 0.08 kg/m3 Figure 3. Effect of concentration on the size of asphaltene
asphaltene in 60 vol% heptane and 40 vol% toluene at low flocs over time in a solution of 60 vol% heptane and 40 vol%
shear. toluene at the lowest shear rate. Dash lines are numerical
results.

Numerical 45 min.
0.3
Numerical 360 min.

0.25 Experimental 45 min.

Experimental 360 min.

Volume Frequency

0.2

0.15

0.1

0.05

0
0.1 1 10 100
Size(micron)

Figure 2. Measured and fitted asphaltene particle volume

distribution after 45 and 360 minutes for 0.08 kg/m3
asphaltene in 60 vol% heptane and 40 vol% toluene at the low Figure 4. Asphaltene flocs in a solution of 70 vol% heptane
shear. and 30 vol% toluene.