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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 different solvent conditions.
conventional oil supplies are depleted. However, heavy
oils are rich in asphaltenes, which can precipitate, EXPERIMENTAL METHOD
flocculate, and deposit during transportation and Athabasca coker-feed bitumen was obtained from
processing. Current methods of treating the deposit are Syncrude Canada Ltd. Toluene and n-heptane were
often only partially effective. In order to better mitigate obtained from Aldrich chemical Company with 99%+
asphaltene deposition, a better understanding of purity. Asphaltenes were precipitated from the bitumen
asphaltene precipitation and flocculation is required. with the addition of n-heptane at a 40:1 volume ratio of
This project focuses on the formation and flocculation heptane-to-bitumen and non-asphaltenic solids were
of asphaltene particles in solutions of n-heptane and removed by centrifugation. Details of the precipitation
toluene at 23 C and atmospheric pressure. Heptane and are provided elsewhere [7].
toluene were selected because toluene is a good solvent
for asphaltenes whereas asphaltenes precipitate in To prepare a solution of asphaltenes in heptane and
heptane. Hence, mixtures with different proportions of 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 where Fi,j , S i and Ei are the number of reactions per
induced by the addition of n-heptane in 60:40 and 70:30 unit volume per unit time that result in flocculation,
n-heptane: toluene volume ratios. Asphaltene shattering or surface erosion processes, respectively.
concentrations of 0.05, 0.08, and 0.1 kg/m_ were The reaction terms are defined as follows:
considered.

The growth of asphaltene floccs was observed over 6 Fi, j = b F (vi ,v j )ni n j
hours using a Brinkmann 2010 particle size analyzer. Si = b S (vi )n i ..........................................................(3)
The particle size distribution is determined from the Ei = b E (vi )n i
time of transition of the particles (or flocs) through a
laser [5]. Samples were placed in standard 1 cm x 1 cm where ni and n j are the number concentration of species
square optical-glass cuvettes obtained from Hellma i and j, and
b F (vi, vj), bS (vi) and b E(vi) are the
cells Inc. A three-speed magnetic stirrer was employed collision frequency functions. The collision frequency
to disperse the asphaltene particles within the cuvette. functions are defined as follows:

1 1
FLOCCULATION MODEL b F (vi ,v j ) = kF (N i D + N j D )3
The probability of flocculation is a combination of 3
b S (vi ) = kS (N i D)
the probability of a collision (characterized by diffusion ...........................................(4)
3
time, tdiff) and the probability of a collision resulting in b E (vi ) = kE (d p D )
flocculation (characterized by reaction time, trxn). In
well mixed systems, t diff <<trxn and flocculation is where Ni and Nj are the number of particles in the flocs,
reaction-limited. In this limit, particles may collide with D is thefractal dimension of the flocs, dp is the
each other numerous times before they actually react diameter of an individual particle and kA, k S and k E are
(flocculate). The problem can then be approached using the reaction constants. The fractal dimension is defined
classical rate equations of the form: through the following relationship between the true
volume of a floc and its apparent volume based on its
measured diameter and assuming spherical geometry:
N i + N j N i + j .............................................................. (1)

1
where N i denotes a floc consisting of i individual D d ............................................................... (5)
d floc = N floc p
particles.

Cluster-cluster addition is the dominant mechanism where dfloc is the diameter of gyration of the floc
in reaction-controlled flocculation. Flocculation is (approximately equivalent to the measured spherical
opposed by fragmentation, which can be a combination mean diameter) and N floc is the number of particles in
of surface erosion and shattering [3]. For a the floc.
monodisperse distribution of individual particles, the To determine the size distribution of the flocculated
derivative with respect to time of the number system over time, the set of differential equations
concentration, n k, of flocs of diameter dk is then given defined in Eq. 2 were solved explicitly. The time step
by: was controlled so that the total number of individual
particles remained constant. Note that numerical error
1 k -1 from too large a time step always results in an error in
2 ( Fi , j - S i + j - E i + j ) the total number of particles.
dn k ii +=1j = k
= ............................... (2)
dt N -k
- ( Fk , j - S k + j - E k +1 )
j =1

2
RESULTS AND DISCUSSION Accounting for this dependence could improve the
Typical asphaltene particle size number and volume quality of the fits.
distributions are shown in Figures 1 and 2, respectively. As expected, flocculation was observed to increase
A large population of particles in the 0.5 to 2 micron with increased asphaltene concentration, increased
diameter range was observed in all cases as shown in heptane content, and decreased shear. An attempt will
Figure 1. At high shear, the bulk of the precipitated be made to correlate the reaction constants to these
material fell in this range. At low shear and sufficiently variables.
high asphaltene concentration, larger particles were
observed, as shown in Figure 2. If the shear rate was ACKNOWLEDGEMENTS
increased, the larger particles disappeared and the 0.5-2 The authors would like to thank Syncrude Canada
micron distribution was restored. The 0.5 to 2 micron Inc. for providing bitumen samples as well as DBR-
particles were considered to be individual particles OilPhase and NSERC for financial support.
while the larger particles appear to be flocs.
Microscopic observations confirm this interpretation as
REFERENCES
shown in Figure 4. A fractal dimension of 1.6 was
estimated for the flocs based on the microscopic 1. R.C. Ball, D.A. Weitz, T.A. Witten and F. Leyvraz,
observations as well as on the correlation of the Universal Kinetics in Reaction-Limited Aggregation,
observed volume mean diameters and particle counts to Phys. Rev. Letters, 58 (1987).
the amount of precipitated material. 2. P.Meakin and M.H.Ernst, Scaling in Aggregation with
Figure 3 shows the change in volume mean diameter Breakup Simulation and MeanField Theory, Phys.
Rev. Letters, 60, 2503-2506 (1988).
with time for 0.05, 0.08 and 0.1 kg/m_ asphaltenes in
3. L.M. Popplewell, O.H.Campanella, and M.Peleg,
60:40 heptane: toluene at the low stirring speed. The
Simulation of Bimodal Size Distributions in
asphaltene flocs reach a steady state size distribution Aggregation and Disintegration Process, J. Chem. Eng.
indicating that both flocculation and fragmentation are Prog., 56-62 (1989)
occurring. The persistent population of individual 4. M.Y. Lin, H.M. Lindsay, D.A. Weitz, R.C.Ball, R.
particles shown in Figure 1 indicates that surface Kelein and P. Meakin, Universal Reaction-Limited
erosion is also occurring. Colloid Aggregation, Phys. Rev. A, 41 (1990).
5. K.A. Ferworn, W.Y. Svrcek, and A.K. Mehrotra,
To model asphaltene flocculation, an individual Measurement of Asphaltene Particle Size Distribution
particle diameter of 1.0 micron was employed and in Crude Oils Diluted with n-Heptane, Ind. Eng. Chem.
reaction constants were fitted for the aggregation, Res., 32, 955-959 (1993)
erosion, and shattering reactions. The model fits are
6. V.A. Branco, G. Ali Mansoori, L.C. Xavier, S.J. Park, H.
compared with experimental data in Figures 1 to 3. Manafi, Asphaltene Flocculation and Collapse from
Both numerical and experimental results show that Petroleum Fluids, J. SPE, 32, 217-230 (2001).

the flocculation rate increases as the characteristic floc 7. H. Alboudwarej, J. Beck, W.Y. Svrcek, H.W. Yarranton,
size grows. The numerically predicted frequency and K. Akbarzadeh; Sensitivity of Asphaltene
distribution and growth rate are qualitatively in Properties to Extraction Techniques; Energy & Fuels,
agreement with experimental results. However, the 16,462 (2002)
numerically calculated frequency distributions are 8. J.A. Ostlund, J.E. Lofroth, K. Holmberg and M. Nyden,
somewhat narrower than the experimental distributions Flocculation Behavior of Asphaltene in Solvent/
and the model underpredicts the steady state volume Nonsolvent systems; J. of Colloid and Interface Science
mean diameter at higher concentrations. One possible 253,150-158 (2002)
explanation for the discrepancy is that the fractal
dimension could depend on the size of the floc.

3
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.