Article

pubs.acs.org/EF

Possible Role of Asphaltenes in the Stabilization of Water-in-Crude

Oil Emulsions
Jan Czarnecki,*,† Plamen Tchoukov,†,‡ and Tadeusz Dabros‡
†
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2G6, Canada
‡
CanmetENERGY, Natural Resources Canada, Devon, Alberta T9G 1A8, Canada

ABSTRACT: Asphaltene hierarchical aggregation contributes to water-in-oil (W/O) emulsion stability by forming a network
structure within thin oil film, separating approaching water droplets. This structure changes the rheology of the film-forming oil
to non-Newtonian, which prevents the film drainage at thickness less than about 50−100 nm. It also provides a steric stabilization
mechanism to the system. Asphaltenes do not have well-defined hydrophilic heads and hydrophobic tails and, thus, do not have
amphiphilic character. Therefore, they are not similar to surfactants and cannot stabilize emulsions the way classic emulsifiers do.
The proposed stabilization mechanisms do not invoke any surfactant-like behavior of asphaltenes. Instead, they solely rely on
asphaltene aggregation propensity.

■ INTRODUCTION
Emulsions create problems and challenges in many industries,
To illustrate this point a little further, let us compare “typical”
structures of a surfactant and asphaltene molecules shown in
but it is in the petroleum industry, in particular, that these Figure 1
problems are very well-recognized and dealt with on a large
scale. Crude oil always contains some brine; it may be as little
as below 1% or as much as over 70% of the total volume of the
produced liquids. Most of the produced water is present in the
form of large drops and lenses and can be easily removed.
When the liquids start to flow from the reservoir into the well
bore or through turbulent flow on chokes and valves and on
centrifugal pump impellers, the liquids are subjected to
vigorous agitation, resulting in emulsification. Emulsification
is aided by the presence of natural surfactants, always present in
crude oils with widely varying content. The emulsified water,
often in the form of small 1−5 μm droplets, is very difficult to
separate.
Salts carried with the emulsified water pose serious corrosion
problems for pipelines and downstream refineries. Millions of
dollars are spent daily on preventing the formation of water-in-
crude oil (W/CO) emulsions or on breaking them once they
have formed. Despite the enormous industrial significance of Figure 1. (a) Typical molecular structure of a surfactant molecule
W/CO emulsions, their exact stabilization mechanism is not yet (SDS, a widely used surfactant, is shown) and (b) molecular structure
fully understood. The existing and widely accepted paradigm of an asphaltene molecule (according to the “island” model).
claims that W/CO emulsions are almost exclusively stabilized
by asphaltenes, and hundreds of papers in the scientific
literature support this claim with experimental data (see, e.g., Figure 1a shows the molecular structure of sodium dodecyl
refs 1−4 and references therein). sulfate (SDS), a widely used surfactant. A hydrophobic tail and
Asphaltenes are defined as a solubility class and not as a hydrophilic head can be easily identified. This amphiphilic
specific family of chemicals with common functional groups. molecular structure is necessary for a chemical compound to be
Individual chemical molecules in the asphaltene group differ in a surfactant.
molecular weight, composition, functionality, polarity, and just The term surfactant originates from “surface-active sub-
about any property, except their insolubility in n-alkanes. stance”. Here, surface activity is usually interpreted as the ability
However, general statements are often made referring to of a substance to decrease surface or interfacial tension of a
asphaltenes as the most heavy, polar, and surface-active liquid in which the substance is dissolved. This is a very broad
components of crude oils. Such generalizations are misleading,
especially when discussing the role of asphaltenes in the Received: May 24, 2012
stabilization of petroleum emulsions, where a specific Revised: July 28, 2012
functionality rendering them surface-active is necessary. Published: August 13, 2012

© 2012 American Chemical Society 5782 dx.doi.org/10.1021/ef300904a | Energy Fuels 2012, 26, 5782−5786
Energy & Fuels
definition, because just about any dissolved substance, with the
exception of strong electrolytes in water, would decrease
surface tension. To be more specific, it is generally accepted
that, to classify a substance as a surfactant, it must reduce
surface tension very sharply at low concentrations. It has been
suggested that, for water solutions, it must reduce the water
surface tension by about 30 mJ/m2 or more at concentrations
of 0.01 M or less.5 In this paper, we use the latter definition and
use the term “surfactant” only for substances that strongly
decrease surface tension.
Figure 1b shows the molecular structure of a typical
asphaltene molecule according to the “island” model.6 There
are several alternative models of asphaltene molecules, which
will be not discussed here. However, according to all of the
models, no hydrophilic head can be clearly identified and
asphaltene molecules consist mostly of hydrophobic moieties.
Therefore, asphaltene molecules do not have amphiphilic
character, which is necessary for strong surface activity and to
be classified as a surfactant according to our criteria outlined
above. It does not preclude weak surface activity of asphaltenes.
Before roughly 1980, asphaltenes were believed to be present
in crude oils in the form of colloidal-sized aggregates containing
several high-molecular-weight molecules. Asphaltene aggregates
were believed to be kept suspended in the parent oil by resins
of substantially lower molecular weight. This model of resins
peptizing asphaltene micelles was introduced by Nellensteyn7
and refined by Pfeiffer and Saal,8 resulting in the widely
accepted “colloidal model” of asphaltene aggregates. In this
model, asphaltene aggregates were referred to as micelles and
were considered to be similar to inverted micelles formed in
non-aqueous solutions of surfactants. Belief in the analogy
between asphaltene aggregates and surfactant micelles is so
widespread that there are numerous reports in the scientific
literature on measurements of critical micelle concentration
(cmc) for asphaltenes in organic solvents (usually from surface
tension versus asphaltene concentration). However, the cmc
concept, valid for surfactants in aqueous solutions, even with a
very liberal interpretation of the micellization term, is certainly
not applicable for asphaltenes and not even for surfactants in
nonpolar, organic solvents.9
Asphaltenes are only weakly surface-active. Therefore, they
cannot stabilize emulsions the way typical emulsifiers do.
However, as mentioned above, there are literary hundreds of
papers in scientific journals with experimental data supporting
the notion that the W/CO emulsions are stabilized by
asphaltenes. In the following, we will be trying to address this
obvious contention.
Learning from Previous Studies. Substantial new knowl-
edge on emulsion stabilization in petroleum systems was gained
from studies related to the extraction of bitumen from
Canadian oil sands in northern Alberta. Because the density
of bitumen is very close to that of water, a light hydrocarbon
solvent has to be added to bitumen to lower the oil-phase
density and viscosity, facilitating various water-removal
operations. Studies of the impact of the solvent/bitumen
ratio and solvent composition on the properties of water-in-
diluted bitumen emulsion provided important insight to W/CO
emulsion stabilization mechanisms. The most important finding
was that there is a critical solvent/bitumen ratio or critical
dilution at which properties of the system drastically
change.10−12 The critical dilution, which coincides with the
onset of asphaltene precipitation, depends upon the solvent
composition. Below the critical dilution, the oil−water interface
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is flexible and very stable water-in-oil (W/O) emulsions are
easily formed. Above the critical dilution, the oil−water
interface is rigid and W/O emulsion droplets flocculate (this
finding led to a new commercial froth treatment technology).
Composition of the material collected from the emulsified
droplets also changes at critical dilution.13,14 Above the critical
dilution (or above the onset of asphaltene precipitation), the
H/C ratio of the surface material is about 1.15, which is similar
to the H/C ratio of asphaltenes.13 However, below the critical
dilution (or below the onset of asphaltene precipitation), the
H/C ratio of the surface material is much higher than that of
asphaltenes, being about 1.32. This indicates that, under those
conditions, emulsions are stabilized by other crude compo-
nents, perhaps naphthenates, but not by asphaltenes.12 The
question remains, how asphaltenes, which are not surface-
active, act as emulsion stabilizers above or around the onset of
asphaltene precipitation. The current paper is an attempt at
answering this question based on reinterpretation of our
previously published results of thin W/O emulsion liquid film
studies.15
■
EXPERIMENTAL SECTION
Thin Liquid Film Technique. The properties of thin oil film that
separate two water droplets play a key role for the stability of emulsion
as a whole. The microinterferometric thin liquid film technique has
been widely used for studies of foams and O/W emulsions and,
recently, W/CO emulsions.16
When two water droplets approach each other, an approximately
flat thin oil film is formed between them, as shown on the left-hand
side of Figure 2. A similar film can be formed in the thin film
Figure 2. Principles of the thin liquid film technique.
apparatus, as shown on the right-hand side of Figure 2. The details of
the apparatus have been described in several books and numerous
review papers.17,18
In our case, the cell holding the studied emulsion film housed in a
thermostatted chamber (1) is placed on top of the Zeiss Axio Observer
inverted microscope (2), equipped with a Leica DFC500 charge-
coupled device (CCD) camera (3) and a Hamamatsu photodiode (4),
enabling photo-interferometric measurements of the film thickness
(see Figure 3). Pressure transducers Pg and Pr, via the pressure control
system, allow for manipulation of the film diameter and thickness as
well as provide information on the film disjoining pressure. The
National Instruments (NI) data acquisition system feeds all of the data
to a computer running NI LabVIEW custom interface, allowing for
automation of many experimental functions.
The thin liquid film technique allows for measurements of the
thickness of common thin emulsion films with an accuracy of about
2 nm or so. The dependence of the thickness upon time gives
information on the film drainage kinetics. The film thickness in
combination with the known pressure applied to the film allows for
estimation of the disjoining pressure isotherm. Our recent
dx.doi.org/10.1021/ef300904a | Energy Fuels 2012, 26, 5782−5786
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Figure 3. Thin liquid film apparatus.
modifications to the technique allow for probing of the film with direct
current (DC) and alternating current (AC) electrical signals, opening
new ways of studying W/O emulsion films, including the stability.19
■
RESULTS AND DISCUSSION
In this paper, we focus on drainage kinetics of the films made of
Athabasca bitumen dissolved in heptol (a mixture of heptane
and toluene at various solvent ratios). Figure 4 shows the
typical behavior of the films below the critical dilution (the
figure shows thinning of the film formed from 50 wt % bitumen
solution in heptol 80:20, i.e., a heptane/toluene mixture at
80:20 by volume). For heptol 80:20, the critical dilution is
about 3, corresponding to a bitumen concentration of about
25 wt %.15 As seen in the figure, shortly after formation, the
film forms a thick dimple in the center, which quickly drains to
the meniscus in one or several points, and after several minutes,
the film reaches thickness below 50 nm. The film thinning
follows theoretical predictions based on Reynold’s equation, as
shown in Figure 7a below. This behavior is well-known and
characteristic for foam and emulsion films stabilized by
surfactants. This is in agreement with the finding reported by
Czarnecki and Moran12 that, below critical dilution, the
emulsions are likely stabilized by surfactants (e.g., sodium
naphthenates).
Above the critical dilution, the film thinning is quite different.
All films prepared above the critical dilution, regardless of the
bitumen concentration or solvent composition, behave in the
way similar to that shown in panels a and b of Figure 5. Here, as
an example, thinning of a film made from 10 wt % solution of
bitumen in heptol 80:20 is shown. The film forms a thick
Figure 4. Film drainage below critical dilution (50 wt % bitumen in heptol 80:20). Stamps show the time after film formation (minutes:seconds).
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dimple as before, but contrary to typical behavior, the dimple
does not drain. The area of the film outside the dimple is filled
with discrete white dots (Figure 5a), which indicate that there
are variations in the film thickness, with dots corresponding to a
locally thicker film. Estimated thickness of those dots is about
50 nm or so. Their lateral dimensions are about a few
micrometers. Also, inside the dimple, a number of local thicker
areas become clearly visible (Figure 5b).
We believe this behavior is caused by asphaltene aggregation.
Shortly after film formation, very small aggregates are formed.
They are likely identical to nanoaggregates postulated by
Mullins.20 According to Mullins, nanoaggregates associate
further, forming nanoaggregate clusters,20 which, through
fractal-type association, eventually form an asphaltene precip-
itate. There is likely a continuous growth of asphaltene particles
from nanoaggregates to nanoaggregate clusters to even larger
assemblies of clusters, eventually leading to precipitation,
without any sharp boundaries between them.
Above the critical dilution ratio in heptane equal to about 1.6
(39 wt % bitumen),15,21 where the solubility of asphaltenes is
even lower than in heptol 80:20, irregularities of the contact
lines between the film and meniscus, non-draining lenses of
trapped liquid, and precipitated particles are clearly visible in
the emulsion film after aging the film for about 4 h (Figure 6).
The lateral dimension of the liquid lenses in the film can be as
large as tens of micrometers, and judging from several Newton
rings around them, they can be above 1 μm thick.
When the same solution (shown in panels a and b of Figure
5) was centrifuged at 20000g to remove all precipitated
asphaltenes, allowed to age until the next day, and centrifuged
again, the emulsion films prepared from this aged solution were
very stable and homogeneous (Figure 5c). The film drainage of
these films initially followed the prediction of Reynold’s law,
shown as a dashed line in Figure 7b, until the film became
about 65 nm thick, where the further drainage stopped and film
thickness did not change further for the time of our experiment
(i.e., for more than 20 min). At this stage, the film is about 3
times thicker than the final thickness of the film made from
50 wt % bitumen in heptol 80:20, which is shown in Figure 7a.
This finding is counterintuitive. After the bitumen concen-
tration was reduced and a significant amount of asphaltenes (a
potentially stabilizing agent) was rejected, the film thickness
increases. Although this result is unexpected on the basis of the
thin film literature, it agrees well with our previous studies of
the properties of the water−diluted bitumen interface. This
finding supports the notion that only a small subfraction of the
total asphaltenes is responsible for emulsion stabilization.11
Let us summarize the observations that do not fit the classical
picture: (1) Dilution of bitumen and removing some of the
“surface-active” material results in thicker and more stable films.
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Figure 5. Film drainage above the critical dilution (10 wt % bitumen in heptol 80:20). Aging: (a) 15 min, (b) 2.5 h, and (c) solution aged 24 h and
centrifuged.
Figure 6. Film drainage above the critical dilution (25 wt % bitumen in heptane). Film interfaces were aged for 4 h, and stamps show the time after
film formation in minutes:seconds.
(2) Non-draining dimples and irregular contact lines appear in
the films. Indeed, if the film liquid behaves as Newtonian, the
liquid from the dimple has to drain out because of the pressure
difference in the dimple and film meniscus.22 We speculate that
the observed behavior is due to asphaltene aggregation into
linear nano-sized aggregates, which are anchored at the water−
oil interface. The formation of asphaltene nanoaggregates and
their further assembly into larger moieties continues for a long
time.21 Such behavior is consistent with findings by Gray et al.,
who analyzed supramolecular assembly of petroleum asphal-
tenes and model compounds and found evidence for the
formation of fibrous, high pore volume, weak organic gels.23
The implications of this finding for emulsion stabilization have
not been included in ref 23 but are obvious and outlined in
more detail below.
A buildup of a network on the length scale comparable to the
film thickness must result in a non-Newtonian behavior of the
liquid forming the film. Assuming Bingham plastic fluid, there
will be a minimum thickness below which the film cannot drain.
For a Bingham plastic fluid with yield stress τB and plastic
viscosity μB, the relationship between the shear stress τ and
shear rate is τ = τB + μB(−du/dy) for τ ≥ τB and
0 = μB(−du/dy) for τ < τB. Hartland and Jeelani24 provided
asymptotic solutions to the film drainage problem when the
film thickness approaches the limiting thickness hmin. According
to eq 16a taken from ref 24, the relationship between hmin and
τB is given by hmin = πnτBRf3/3F, where Rf is the film radius, F is
the force acting on the film, and n = 2 is the number of
immobile film surfaces. In the case of free emulsion films when
the surface forces are negligible, the driving force for film
drainage is due to the capillary pressure drop in the film Plateau
border Pγ = 2γ/r (γ = 16 mJ/m2 is the interfacial tension and r
= 400 μm is the radius of the hole in the fritted glass plate
holding the film). For the film shown in Figure 7b (film radius
Rf = 100 μm), we can estimate that yield stress of 0.078 Pa is
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required to stop film drainage at hmin = 65 nm. Also, if a liquid
is characterized by a non-zero yield stress, some liquid can be
trapped in the dimple and will not drain through the
surrounding barrier ring area in the film.25 Our estimates
show that a yield stress from about 10−3 to 10−2 Pa will be
sufficient to stop dimple drainage, as shown in Figure 5a. This
Bingham yield stress may be too small to be measured by
conventional rheological instruments but large enough to
prevent further drainage of the thin oil film separating water
droplets, thus providing an effective stabilization of the
emulsion.
■
CONCLUDING REMARKS
Asphaltene hierarchical aggregation (asphaletene molecules →
nanoaggregates → aggregates → precipitate) is likely
responsible for building a gel-like structure within the oil film
separating approaching water droplets. The result of this
structure formation is 2-fold: First, it changes the fluid rheology
within the film to non-Newtonian with a very small but not
negligible Bingham yield stress. This yield stress is too small to
be measured in conventional rheometers but large enough to
prevent film drainage. Second, it forms a steric layer, providing
steric emulsion stabilization. Those mechanisms do not invoke
any surfactant-like behavior of asphaltenes. They solely rely on
aggregation propensity of asphaltenes. If correct, it calls for a
totally different emulsion breaking strategy and likely different
types of demulsifiers.
Our findings do not contradict a weak adsorption of some
asphaltene subfractions. On the contrary, asphaltene aggregates,
either formed at the water−oil interface or adsorbed as such,
are likely attached to the interface with several weak bonds.
Their removal requires breaking multiple bonds at the same
time, making it a highly improbable event. A more detailed
discussion of asphaltene attachment to the oil−water interface
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Figure 7. Film thinning of bitumen films diluted in heptol 80:20: (a)
50 wt % bitumen (below the critical dilution) and (b) 5 wt % bitumen
(above the critical dilution).
and adsorption competition with surfactant-like crude
components was presented elsewhere.12
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: 1-780-492-8826. E-mail: jc7@ualberta.ca.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We thank Dr. Zhenghe Xu for helpful discussions. The authors
express their gratitude to the Canadian government’s Panel of
Energy Research and Development (PERD) for financial
support of this project.
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