Journal of Colloid and Interface Science 241, 469478 (2001)

doi:10.1006/jcis.2001.7731, available online at http://www.idealibrary.com on

The Stabilization of Water-in-Hydrocarbon Emulsions
by Asphaltenes and Resins
Olga V. Gafonova and Harvey W. Yarranton
1
Department of Chemical and Petroleum Engineering, University of Calgary, Alberta, Canada T2N 1N4
Received February 13, 2001; accepted May 25, 2001; published online July 30, 2001
The role of asphaltenes and resins in stabilizing water-in-crude
oil emulsions was investigated by measuring the interfacial compo-
sitionand stabilityof model emulsions composed of water with mix-
tures of toluene, heptane, asphaltenes, resins, and native solids. The
interfacial composition (mass surface coverage) was determined
from a combination of emulsion surface area measurements and
concentration measurements of both the continuous and the emul-
sion phases. The emulsion surface area was calculated from drop
size distributions measured with optical microscopy. The concen-
trations were found from gravimetric analysis. The stability of the
model emulsions was assessed from the amount of water resolved
after heating and periodic centrifugation of the emulsions. Asphal-
tene surface coverage was found to increase with an increase in
the asphaltene bulk concentration until a limiting surface coverage
was achieved. Surprisingly, while asphaltenes always tend to sta-
bilize these emulsions, the stability of the emulsions decreased as
asphaltene surface coverage increased. This change in stability was
attributed to a change in the asphaltene conguration on the inter-
face. The addition of a good solvent was found to reduce both the
amount of adsorbed asphaltenes and the emulsion stability. The ad-
ditionof resins always destabilized model emulsions. It appears that
resins act as a good solvent for the asphaltenes and, at sufciently
high concentrations, are able to replace asphaltenes on the inter-
face. Naturally occurring solids that coprecipitate with asphaltenes
had little or no effect on asphaltene adsorption but dramatically in-
creased emulsion stability. The results suggest that the combination
of asphaltenes and native solids causes the most stable emulsions.
C 2001 Academic Press
Key Words: asphaltenes; resins; solids; emulsions; water-in-oil;
stability.
INTRODUCTION
The formation of water-in-crude oil emulsions is a problem
that can arise during the recovery, treatment, and transporta-
tion of crude oil. In conventional and heavy oil production,
emulsions occur when crude oil and produced water or injected
steam mix in the reservoir, well bore, or surface facilities. In
reneries, water-in-oil emulsions are deliberately created and
1
To whom correspondence should be addressed.
then broken to wash out contaminants that are present in the
produced water emulsied in the crude oil (1). In oil sands pro-
cessing, very stable water-in-oil emulsions are formed during
the hot water extraction process used to recover bitumen from
the oil sands (2). In most cases, the emulsions are undesirable
because they have higher volume and viscosity than the crude
oil and lead to increased capital and operating costs. They may
also carry contaminants such as chlorides through to a down-
stream process leading to corrosion problems (1, 3, 4). While
most water-in-crude oil emulsions can be broken with heat and
chemical additives, there are many cases where the conven-
tional treatment fails. To devise more effective treatments for
these emulsions, it is necessary to understand how they are sta-
bilized.
It is well known that the stability of water-in-crude oil emul-
sions depends mainly on a rigid protective lm encapsulating
the water droplets (59). This rigid interfacial lmis believed by
many researchers to be composed predominantly of asphaltenes,
resins, and/or ne solids (3, 68). Asphaltenes and resins are de-
ned as solubility classes of petroleum. Asphaltenes are soluble
in toluene but insoluble in alkanes, typically n-heptane or n-
pentane. Asphaltenes are large polyaromatic hydrocarbons that
consist of condensed aromatic rings, aliphatic side chains, and
various heteroatom groups. Resins are soluble in both aliphatic
and aromatic solvents but can be separated from other solubil-
ity fractions with liquid chromatography. Resin molecules are
structurally similar to asphaltenes but have lower molar mass,
higher hydrogen/carbon ratio, and lower heteroatom content.
Asphaltenes and resins both have a largely hydrophobic hydro-
carbon structure containing some hydrophilic functional groups
and consequently are surface-active (6, 7, 10, 11). Hence, both
asphaltenes and resins have the potential to accumulate on the
water/oil interface.
The formin which asphaltenes and resins adsorb on the emul-
sioninterface depends onthe format whichtheyexist insolution.
However, the behavior of asphaltenes and resins in crude oil is
still poorly understood. Asphaltenes are known to self-associate
in crude oil and form colloids or micelles (1013). Resins
are known to strongly inhibit asphaltene association (14, 15).
The resin molecules may adsorb on the asphaltene aggregates
(10, 11) or may simply act as a good solvent. Therefore,
469 0021-9797/01 $35.00
Copyright C 2001 by Academic Press
All rights of reproduction in any form reserved.
470 GAFONOVA AND YARRANTON
asphaltenes and resins may adsorb on the emulsion interface
as independent molecules or as different types of aggregates.
Eleyet al. (16) proposedthat asphaltenes stabilize water-in-oil
emulsions if they are near or above the point of incipient occu-
lation; that is, they may be solid particles. Others have suggested
that asphaltene colloids are responsible for stable emulsions
(6, 7, 17). The asphaltenes may collect on the interface in
the form of ne solid particles or asphalteneresin colloids (7,
12). However, Yarranton et al. (5) showed that, at low asphal-
tene concentrations (<0.2 wt%), asphaltenes appear to stabi-
lize emulsions as a molecular monolayer on the water/oil in-
terface. Furthermore, the examination of the interfacial lms
formed by means of the LangmuirBlodgett technique (8) and
the thin liquid lm pressure balance technique (9) indicated that
asphaltenes adsorb on the interface in molecular rather than col-
loidal form.
It is of interest to determine the interfacial composition at
higher asphaltene concentrations that are closer to realistic crude
oil compositions. It is also necessary to consider the effect of
resins as they may inuence asphaltene aggregation, adsorption
on the interface, and emulsion stability (79, 18). In this work,
the interfacial composition is measured at asphaltene concen-
trations up to 40 kg/m
3
(approximately 4 wt%). The interfacial
composition is also measured at different solvent compositions
and various asphaltene/resin ratios. Finally, the stability of the
emulsions is measured and related to interfacial composition.
While the main goal of this study is to investigate the role of
asphaltenes and resins in the stabilization of emulsions, the role
of native solids is also considered. Fine solids, such as sand, clay,
silica, and organic particles present in crude oil are also able to
stabilize water-in-crude oil emulsions (3, 19). In many cases,
polar surface-active materials present in crude oil, particularly
asphaltenes, adsorb on the solids, rendering themsurface active.
The solids can then adsorb on the emulsion interface and steri-
cally stabilize crude oil emulsions (20). It has been shown that,
when asphaltenes are extracted from bitumen by precipitating
them with a solvent, solids also co-precipitate (21). Since solids
increase emulsion stability, their presence in the asphaltene frac-
tion may overshadow the stabilization capacity of asphaltenes
and resins in emulsions. Solids may also interfere with the ad-
sorption of asphaltenes and/or resins on the emulsion interface.
Therefore, the role of native solids in emulsion stabilization is
also examined by comparing the interfacial composition and
stability of emulsions prepared with and without solids.
EXPERIMENTAL METHOD
To isolate the role of each component, the experiments were
conducted on model emulsions consisting of deionized water,
asphaltenes, resins, native solids, and toluene/heptane mixtures
in different ratios. The mixture of toluene and heptane is re-
ferred to as heptol. The composition of the heptol is indicated
as the volume percent of toluene indicated in brackets. For ex-
ample, heptol containing 75 vol% toluene and 25 vol% heptane
is denoted as heptol (75).
The effect of native solids was not tested directly; rather emul-
sions were prepared from asphaltenes together with their co-
precipitated solids or from asphaltenes that had been treated to
remove the native solids. The mixture of asphaltenes and solids
is referred to as asphaltenes, and the asphaltenes that have
been treated to remove solids are referred to as solids-free as-
phaltenes, unless otherwise noted.
Materials
Reagent-grade n-heptane and n-pentane were obtained from
Phillips Chemical Company. The 99.9%purity toluene was pur-
chased from VWR. Distilled water used for emulsions was sup-
plied by the University of Calgary water plant.
The asphaltenes and resins used in these experiments were ex-
tracted fromtwo bitumens: Athabasca oil sands bitumen (coker-
feed bitumen) and Cold Lake bitumen (recovered by steam in-
jection froman underground reservoir). Both bitumens had been
treated in the eld to remove most of the sand and water and were
ready for upgrading.
Asphaltenes were precipitated fromthe bitumens with a 40 : 1
volume ratio of n-heptane to bitumen as described previously
(22). Resins were extractedfromthe bitumenbyusinga modied
ASTM-D2007M SARA fractionation procedure (22). SARA is
an acronym for four crude oil solubility classes: saturates, aro-
matics, resins, and asphaltenes. In SARA fractionation, resins
are extracted from deasphalted oil using clay-gel adsorption
chromatography. Note that the deasphalted oil used for resin
extraction was obtained by precipitation of asphaltenes with
n-pentane not n-heptane. Saturate and aromatics can also be
extracted with this method; however, these fractions were not
required for this work. The SARA analysis of the Athabasca
and Cold Lake bitumens used in this work are given in Table 1.
Removal of Native Solids from Asphaltenes
Native solids were removed fromthe asphaltenes precipitated
from the bitumens by using two different methods: a ltration
method and a precipitation method. The ltration method in-
volves two steps. In the rst step, the asphaltene solids were dis-
solved in toluene at a volume ratio of 100 : 1 toluene : asphaltene.
The mixture was sonicated for 20 min to ensure that all of the
asphaltenes were dissolved and then centrifuged at 3500 rpm
TABLE 1
SARA Fractions and Solids Content of Athabasca
and Cold Lake Bitumens
Fraction Athabasca (mass %) Cold Lake (mass %)
Saturates 16.3 18.3
Aromatics 39.8 39.1
Resins 26.8 25.8
Asphaltenes (pentane-extracted) 17.1 16.8
Asphaltenes (heptane-extracted) 13.8 12.2
Coarse Solids
a
7.5 2.4
a
Mass percentage of heptane-extracted asphaltenes.
WATER-IN-HYDROCARBON EMULSIONS 471
(1260g) for 5 min. The supernatant liquid was decanted from
the settledsolids. Toobtainasphaltenes withonlycoarse solids
removed, the solvent was evaporated from the supernatant un-
til dry asphaltenes with ne solids remained. The size of the
coarse solids removed in the centrifuge can be estimated from
Stokes law assuming unhindered settling, spherical particles,
and a solid density of 20002200 kg/m
3
. The analysis indicates
that this method can remove solids of higher than 0.8 m diam-
eter. This value is probably too low because particles with such
a small diameter may redisperse through convection or Brow-
nian motion. Hence, asphaltenes with coarse solids removed
contain solids with a diameter less than approximately 1 m.
To obtain solids-free asphaltenes, the supernatant liquid
from Step 1 was ltered under vacuum through a 0.5 m Metri-
grad Glass ber lter (Pall Corporation). The ltrate was placed
in a vacuum oven at 45

C and left until the change in mass

of asphaltenes was less than 0.1% over a 24-h period. These
asphaltenes may still contain solids with a diameter less than
0.5 m, although smaller diameter particles may be removed as
well if they become trapped within the lter cake.
The ltration method is too slow to practically treat signi-
cant quantities of asphaltenes. Therefore, a second method based
on precipitation was tested. The native solids appear to co-
precipitate with the rst asphaltenes to come out of solution
(5, 23). Hence, most or perhaps all of the solids can be removed
by precipitating a small fraction of the asphaltenes. Here a 55 : 45
heptane to toluene volume ratio was used. At this ratio, accord-
ing to asphaltene solubility data (21), approximately 2 wt% of
Cold Lake and Athabasca asphaltenes precipitates as well as the
solids.
Initially, asphaltene solids were dissolved in toluene at a con-
centration of 1 kg/m
3
. The mixture was sonicated for 20 min to
ensure that all of the asphaltenes were dissolved and then was
centrifuged at 3500 rpm (1260g) for 5 min. The supernatant
liquid was recovered and evaporated until only dry asphaltenes
remained. This methodis suitable for the extractionof signicant
quantities of solids-free asphaltenes. However, it is not certain
if all of the solids are removed with this method. It should also
be noted that a small fraction of the asphaltenes is removed with
the solids. Both factors could inuence emulsion stability. As
will be discussed later, emulsions prepared from precipitation-
treated asphaltenes were compared with those prepared from
ltration-treated asphaltenes and nearly identical stability was
observed.
Emulsion Preparation and Drop Size Distribution
To prepare an emulsion, a known amount of asphaltenes and
resins was dissolved in toluene. The solution was stirred with a
sonic mixer for 20 min. Heptane was added after asphaltenes and
resins were completely dissolved in the toluene. The mixture
was again sonicated for ve minutes to ensure homogeneity.
The prepared oil phase was then processed with a CAT-520D
homogenizer with a 17-mm at rotor generator conguration at
17,000 rpm. During mixing a given amount of dispersed water
phase was added dropwise to the system. After all the water had
been added, the mixing continued for ve minutes at the same
speed. All the emulsions were prepared with 40 vol% water.
All of the emulsion experiments (drop size distribution anal-
ysis, gravimetric analysis, and stability tests) were performed
on settled emulsions, i.e., emulsions that were allowed to stand
for 1.5 h after preparation. In general, the emulsions settled and
separated into an emulsion layer on the bottom and a clear con-
tinuous phase on top within a few minutes. A standing time of
1.5 h was chosen to ensure that the smallest droplets had suf-
cient time to settle. There was no evidence of a change in free
water content or drop size distribution over this period.
Emulsion samples were placed in a hanging drop slide and
diluted with continuous phase to disperse the droplets for image
analysis. Drop size distributions of the settled emulsion phases
were analyzed using a Carl Zeiss Axiovert S100 inverted mi-
croscope equipped with a video camera. Images from the mi-
croscope were captured on a computer, and the drop size dis-
tributions were then measured using Image Pro image analysis
software. In the present work 400 drops were used to obtain
drop size distributions, giving an expected error of 510% ac-
cording to Dixon et al. (24). The drop size distribution is used
to calculate the Sauter mean diameter, d
32
, dened as
d
32
=

f
i
d
3
i

f
i
d
2
i
=
6V
w
A
w
, [1]
where f
i
is the number frequency of droplets with diameter d
i
,
V
w
is the volume of water in the emulsion, and A
w
is the surface
area of the emulsion (the total surface area of the water droplets).
Determination of Interfacial Composition
The asphaltenes and resin surface coverage, that is, the mass
of asphaltenes and/or resins per area of the water/oil interface of
an emulsion, can be calculated from the emulsion Sauter mean
diameter and a gravimetric analysis of the continuous phase. To
simplify the explanation, the mass of asphaltenes will be used
as an example.
The asphaltene mass surface coverage,
A
, is simply the total
mass of the asphaltenes on the interface, m
I
, divided by the
surface area of the emulsion, A
w
:

A
=
m
I
A
W
=
m
I
d
32
6V
w
. [2]
Now since asphaltenes are only soluble in the continuous hy-
drocarbon phase, m
I
can be determined from the change in con-
tinuous phase asphaltene concentration upon emulsication,
m
I
= m
t

1
C
eq
A
C
0
A

, [3]
where m
t
is the total mass of asphaltenes in the emulsion, C
0
A
is the initial asphaltenes concentration in the continuous phase
prior to emulsication, and C
eq
A
is the equilibrium asphaltene
472 GAFONOVA AND YARRANTON
concentration in the continuous phase after emulsication. Both
are measurable quantities. Substituting Eq. 3 into Eq. 2 gives an
expression for asphaltene surface coverage in terms of measur-
able quantities;

A
=
m
t
d
32
6V
w

1
C
eq
A
C
0
A

. [4]
The initial mass and concentration of asphaltenes and the water
volume are experimentally controlled variables. The measure-
ment of the Sauter mean diameter was discussed previously.
To measure the equilibrium concentration of asphaltenes after
emulsication, the continuous phase of a settled emulsion was
decanted and its volume measured. It was then placed into a
rotaryevaporator, allowingthe toluene/heptane solvent toevapo-
rate until only asphaltenes were left in the ask. The asphaltenes
were dried under nitrogen in a vacuumoven at 60

C, after which
their weight was determined gravimetrically. The balance was
accurate to 0.002 g. The concentration of asphaltenes in the
continuous phase is simply the weight of the asphaltenes divided
by the measured volume of supernatant. Fromrepeated measure-
ments, the mass surface coverage of asphaltenes on the interface
was accurate to 0.0012 g/m
2
(a 95% condence interval).
When emulsions were prepared froma mixture of asphaltenes
and resins, it was necessary to determine the mass and the ratio
of these fractions on the emulsion interface. The total mass of the
asphalteneresin mixture remaining in the continuous phase af-
ter emulsication was determined gravimetrically as described
above. Then the dry asphalteneresin mixture was dissolved in
30 cm
3
of n-heptane to reprecipitate the asphaltenes. The so-
lution was sonicated for 1 h and allowed to settle overnight.
After settling it was sonicated again for 15 min and centrifuged
for 10 min at 3500 rpm. The supernatant containing the resin
fraction was decanted, set aside until most of the heptane had
evaporated, and then placed into the vacuum oven at 45

C un-
til complete drying had occurred. The mass of the dried resins
was determined gravimetrically. The centrifuge tube containing
the precipitated asphaltenes was also placed in the vacuum oven
and the mass of dried asphaltenes was determined. The mate-
rial balance of the asphalteneresin mixture was checked. Only
results where the material balance closed to within 10% are re-
ported. The mass of asphaltenes and resins on the interface was
calculated as previously described for the asphaltenes.
One problem with this method is that the presence of resins
may affect the solubility of the asphaltenes. In other words, not
all of the asphaltenes may precipitate in heptane if resins are also
present. Therefore, the method was applied to control samples
with known amounts of asphaltenes and resins. The method gave
asphaltene masses accurate to within 17%.
Stability Tests
The stability of a given emulsion was assessed by measuring
the water separated from the emulsion as a function of time.
Samples of the settled emulsion phase (after 1.5 h of room tem-
FIG. 1. Resolved water versus time for water-in-heptol (50) emulsions sta-
bilized by Athabasca asphaltene/resin mixtures.
perature settling) were transferred into 15-cm
3
graduated cen-
trifuge tubes. The tubes were closed with caps to prevent sol-
vent evaporation, centrifuged for 5 min at 4000 rpm (1650g),
and placed in a constant temperature water bath at 60

C. After
2 h the emulsions were centrifuged for 5 min and the amount
of resolved water was measured. The centrifuge tubes were re-
turned to the heating bath for another 2 h and then centrifuged
before measuring the amount of resolved water. This procedure
was repeated until all of the water was separated. The heat-
ing/centrifuging time applied to an emulsion sample is referred
to as the destabilization time (
des
). The amount of resolved
water was reported as the percent of total water volume con-
tained in the given emulsion sample. Examples of destabiliza-
tion over time of model water-in-heptol emulsions are shown in
Fig. 1. The reported percentages of resolved water are accurate to
11 vol%. The relative stability of all of the emulsions was as-
sessed by comparing the amount of resolved water at a given
destabilization time.
RESULTS AND DISCUSSION
Before investigating the role of asphaltenes and resins, it is
necessary to consider other factors that may inuence interfa-
cial composition and emulsion stability, that is, drop size and
the presence of native solids. Larger droplets tend to coalesce
more readily than small droplets. Therefore, drop size must be
taken into account when comparing the relative stability of dif-
ferent emulsions. The mean diameter of a series of typical model
emulsions is plotted versus asphaltene concentration in Fig. 2.
The diameter decreases dramatically as asphaltene concentra-
tion increases to 4 kg/m
3
. Above 4 kg/m
3
, the mean drop size
is invariant at a value of approximately 8 m. The diameter
WATER-IN-HYDROCARBON EMULSIONS 473
FIG. 2. Effect of asphaltene concentration on the Sauter mean diameter of
water-in-heptol (50) emulsions stabilized by asphaltenes.
is invariant at high asphaltene concentrations because the as-
phaltenes quickly adsorb on the water/oil interface and stabi-
lize the droplets before coalescence can occur. Hence, 8 m is
the mean drop size created by the homogenizer. At low asphal-
tene concentrations, there are insufcient asphaltenes tostabilize
the droplets and coalescence occurs until monolayer coverage is
achieved (5). All of the emulsions presented here have a similar
relationship between mean diameter and asphaltene concentra-
tion unless otherwise noted.
As noted previously, native solids are known to increase emul-
sion stability. To assess the effect of solids, emulsions were pre-
pared fromuntreated asphaltenes, asphaltenes with coarse solids
removed by centrifugation, asphaltenes with ne solids removed
by ltration, and asphaltenes with solids removed by precipita-
tion. All of these emulsions were prepared with 5 kg/m
3
of as-
phaltene solids in heptol (50). The stability of these emulsions
is compared in Table 2. The removal of coarse solids has little
effect on emulsion stability. However, the removal of ne solids
dramatically increases the amount of resolved water; that is, it
TABLE 2
Effect of Removing Solids on Water Resolved from Emulsions
Water-in-hydrocarbon emulsions Water-in-bitumen emulsions (Ref. 3)
Organic phase (heptol (50) and Resolved water Resolved water
asphaltene-solids) (vol%) Organic phase (vol%)
Asphaltenes with solids 5.6 Bitumen (with solids) 0
Asphaltenes with coarse solids removed 9.6 Bitumen with coarse solids removed (8 m ltered) 0
(> 1 m centrifuged)
Asphaltenes with ne solids removed 48 Bitumen with ne solids removed (0.22 m ltered) 20
(0.5 m lter)
Solids-free asphaltenes (percipitated) 49
FIG. 3. Adsorption isotherms of Athabasca asphaltenes and solids-free as-
phaltenes in water-in-heptol (50) emulsions.
reduces stability. These results are consistent with Yan et al.s (3)
measurements for diluted bitumen also given in Table 2. Con-
sequently, the experiments conducted with asphaltenes were re-
peated with solids-free asphaltenes whenever possible. Also
note that the precipitation method gave the same results as l-
tering. Given its greater efciency, the precipitation method was
used for all of the other results presented here.
Asphaltene Adsorption Isotherms
Interfacial composition and structure can be illustrated
through adsorption isotherms, that is, plots of asphaltene
mass surface coverage,
A
, versus the equilibrium asphaltene
concentration in the bulk phase, C
eq
A
. The asphaltene adsorption
isotherm for model water-in-heptol (50) emulsions is shown
in Fig. 3. Isotherms for both asphaltenes and solids-free
asphaltenes are shown, and they are within 10% of each other,
indicating that solids do not signicantly affect asphaltene
adsorption.
474 GAFONOVA AND YARRANTON
As discussed above, at low asphaltene concentrations (C

A
<
4 kg/m
3
or C
eq
A
< 2 kg/m
3
), the asphaltene surface coverage
is constant at a surface coverage of 4 mg/m
2
. Above C
eq
A
<
2 kg/m
3
, the asphaltenes are essentially adsorbing onto a xed
interfacial area (constant Sauter mean diameter) and the surface
coverage follows the form of a Langmuir adsorption isotherm.
Surface coverage increases until a C
eq
A
of approximately
40 kg/m
3
and then plateaus, reaching a limiting value of ap-
proximately 11 mg/m
2
. The asphaltene adsorption isotherm is
in good agreement with asphaltene surface coverages measured
bythe LangmuirBlodgett lmtechnique. The LBsurface cover-
ages range from6 to 8 mg/m
2
at initial asphaltene concentrations
from 1 to 8 kg/m
3
(8). Ese et al. (8) also observed an increase
in the surface coverage with an increase in the bulk asphaltene
concentration.
The asphaltene adsorption isotherm has the appearance of a
Langmuir adsorption isotherm but it is not a Langmuir isotherm
because all of the adsorption is at or above monolayer coverage.
The surface coverage of 4 mg/m
2
observed at lowconcentrations
appears to be a monolayer coverage (5). When an emulsion is
created with interfaces partially covered with asphaltenes, the
emulsion coalesces until this coverage is achieved. As well, the
estimated thickness of the interfacial layer is consistent with a
monlayer of asphaltenes. There are several possible explana-
tions for the increase in the asphaltene surface coverage above
a monolayer value:
1. At higher bulk phase concentration, asphaltene molecules
undergo a conguration change. At low concentrations, they
spread out on the interface in a planar form, and at high con-
centrations, they align into a more compressed vertical con-
guration allowing more compact packing of molecules on the
interface, as shown in Fig. 4. This leads to a higher surface cover-
age. The observed plateau at high C
eq
A
indicates that asphaltenes
achieve the maximum packing on the interface.
2. Larger asphaltene molecules adsorb preferentially. At low
concentrations, there are insufcient large molecules to saturate
the interface. At higher concentrations, the interface becomes
saturated with large molecules and the mass surface coverage
plateaus.
3. The asphaltenes adsorb as multilayers on the interface. The
plateau might arise because the adsorption of a second layer is
energetically favorable, but the adsorption of additional layers
is less favorable as the separation distance between the interface
and the adsorbed molecules increases.
As will be seen, observations on emulsion stability suggest
that the increase in surface coverage is likely due to a confor-
mation change rather than to multilayer formation or selective
adsorption.
Effect of Asphaltene Adsorption and Solids
on Emulsion Stability
The stability of different emulsions can be compared at any
given destabilization time (
des
). The data given below is re-
FIG. 4. Possible congurations of asphaltene molecules on the emulsion
interface.
ported at a destabilization time of 16 h for more stable emul-
sions and 6 h for less stable emulsions. These times were found
to provide data that best illustrated the trends in emulsion stabil-
ity discussed below. However, the same trends were detectable
at all times prior to complete destabilization.
A plot of resolved water versus the concentration of as-
phaltenes in the water-in-heptol (50) emulsion is given in Fig. 5.
As concentration increases up to 510 kg/m
3
, the emulsions
FIG. 5. Correlation between Sauter mean diameter and emulsion stabiliy
(heptol (50),
des
=16 h).
WATER-IN-HYDROCARBON EMULSIONS 475
FIG. 6. Comparison of the stability of emulsions stabilized by asphaltene
solids or solids-free asphaltenes (heptol (50),
des
= 6 h).
become more stable. This increase in stability correlates rea-
sonably well with the decrease in mean diameter also shown in
Fig. 5. Above 10 kg/m
3
, the amount of resolved water (stabil-
ity) does not change signicantly. However, these asphaltenes
contain solids, which may enhance emulsion stability.
The resolved water for emulsions stabilized with solids-
free asphaltenes are compared with asphaltene solids stabilized
emulsions in Fig. 6. As discussed previously, the removal of
solids signicantly decreases emulsion stability. The removal
of solids also reveals an unexpected trend. For the solids-free
emulsions, as asphaltene concentration increases above 5 kg/m
3
,
emulsion stability decreases. Clearly, the solids mask this be-
havior in the asphaltene solids stabilized emulsions. But why
does stability decrease as the concentration of the asphaltenes,
an emulsion stabilizer, increases?
This unexpected behavior contradicts the argument that the
accumulation of asphaltenes on the interface leads to the creation
of a stronger, thicker interfacial barrier that increases emulsion
stability. Hence, the reduction in stability argues against the for-
mation of asphaltene multilayers on the interface or the satura-
tion of the interface with larger molecules. One remaining inter-
pretation is that there is a change in the asphaltene conguration
on the interface.
At low asphaltene concentrations and consequently low
surface coverage, molecules may be spread out on the interface.
In this position, the molecules may have many points of attach-
ment on the interface, as shown in Fig. 4a. At high asphaltene
concentrations, the molecules may adsorb in a more vertical
alignment on the interface so that they become attached at one or
only a few points per molecule. Lateral interaction between the
asphaltenes may preserve this conguration even if multiple at-
tachments are energetically favorable. In the vertical alignment
much more material can be attached to a given surface area, as
shown in Fig. 4b. When molecules are attached to the interface
at only one point, they are more extended into the continuous
phase and may be more mobile than when attached at several
points. This more mobile interface may present less of a barrier
to coalescence. When molecules are attached at several sites,
the interface may be more rigid and the emulsion more stable.
Effect of Solvent Composition
The effect of solvent composition on the interfacial adsorption
of asphaltenes and emulsion stability is shown in Fig. 7. The two
solvents compared are heptol (50) and heptol (75). In the better
solvent (heptol (75)), the asphaltene adsorption is approximately
20% less for the whole range of measured concentrations. This
trend is consistent with Ese et al.s (1998) LangmuirBlodgett
lm results. The stability is also less (more resolved water) for
the heptol (75) system over the entire measured range of as-
phaltenes concentrations.
Figure 8 compares the Sauter mean diameter of the emulsions
from Fig. 7. At C
eq
A
less than 510 kg/m
3
, the mean diameter of
the water-in-heptol (75) emulsion is higher than in the emulsion
made with heptol (50). Above this C
eq
A
, the mean diameters of
both emulsions are almost identical. Once again, at low asphal-
tene concentrations, emulsion stability appears to be governed
by emulsion drop sizes and the larger droplets formed in heptol
(75) lead to less stable emulsions.
At higher asphaltene concentrations, the reduction in stabil-
ity of emulsions containing 75 vol% toluene may be related
to the reduction in asphaltene adsorption on the emulsion in-
terface. As shown in Fig. 4c, good solvent molecules tend
to solvate (surround) the asphaltenes to a higher degree. The
solvated molecules are more loosely packed on the interface,
thus decreasing the effective surface coverage. Furthermore, in
a better solvent, the strength of asphaltenesolvent interactions
FIG. 7. Effect of solvent composition on the asphaltene solids adsorption
isotherm and emulsion stability (
des
= 16 h).
476 GAFONOVA AND YARRANTON
FIG. 8. Effect of solvent composition on the Sauter mean diameter.
approaches that of the asphalteneasphaltene interactions.
Therefore, in a better solvent, asphaltenes may be more mobile,
the interface less rigid, and the emulsion less stable.
Emulsion stability for a broad range of toluene/heptane com-
positions is shown in Fig. 9. First consider toluene contents
greater than 50%. As expected, when the amount of heptane in-
creases and the solvent becomes poorer, the emulsion stability
increases. However, at a toluene content of approximately 45%
the trend reverses. This reversal corresponds to the precipitation
of asphaltenes. As demonstrated by Yarranton et al. (5), the pre-
FIG. 9. Effect of solvent composition and the presence of solids on emul-
sion stability (C
0
A
=5 kg/m
2
;
des
= 6 h).
cipitated asphaltenes do not participate in stabilizing emulsions,
and as more asphaltenes precipitate, fewer asphaltenes are avail-
able to stabilize the emulsions. Hence belowa toluene content of
45%, the addition of heptane reduces emulsion stability. Similar
results were obtained by McLean and Kilpatrick (7). Emulsions
stabilized by solids-free asphaltenes exhibit trends that are the
same as those shown in Fig. 9. Note that once the asphaltenes
begin to precipitate the solids are removed as well and both as-
phaltene solids and solids-free asphaltene stabilized emulsions
have identical stability.
Effect of Resins
Emulsions containing resins are quite unstable. Emulsions
prepared with resins and no asphaltenes broke completely upon
centrifuging(withinminutes of preparation). Inthe case of emul-
sions containing mixtures of resins and asphaltenes, the only
emulsions that did not coalesce during the measurement pe-
riod contained a 1 : 3 resin/asphaltene (R: A) mass ratio dis-
solved in heptol (50). In emulsions with higher R: A ratios and
in all solids-free emulsions, drop rupture was observed during
microscopy measurements. Nonetheless, gravimetric measure-
ments were performed for these emulsions keeping in mind that
the measured interfacial compositions for these emulsions are
rough estimates.
Figure 10 shows the adsorption isotherms of asphaltenes (with
solids) in emulsions containing 1 : 3 and 1 : 1 R: A ratio versus
C
eq
A
in a range fromabout 5 to 30 kg/m
3
. The adsorption isotherm
of pure asphaltene solids is also shown for comparison. The ad-
dition of resins decreases the amount of asphaltenes adsorbed on
the interface. The decrease in asphaltene adsorption is relatively
small at lowresin concentrations or lowresin/asphaltenes ratios.
Furthermore, when the interfacial composition was determined,
FIG. 10. Adsorption isotherms of asphaltene/resin mixtures in water-in-
heptol (50) emulsions.
WATER-IN-HYDROCARBON EMULSIONS 477
no resins were found on the emulsion interface at resin concen-
trations below approximately 20 kg/m
3
. It appears that, at low
resin concentrations, the resins merely act as a good solvent to
the asphaltenes.
At a 1 : 1 R: A ratio, the resins completely replace the as-
phaltenes on the interface once the resin concentration reaches
20 kg/m
3
. It appears that the total resin: concentration is a more
signicant factor than the resin-asphaltene ratio. This suggests
that, at sufciently high concentration, resins may act more as
competitive surfactants than as a mediator of asphaltene adsorp-
tion. In any case, they appear to replace the asphaltenes with a
lmof resins that is likely more mobile and less likely to prevent
coalescence.
The resolved water in emulsions containing 1 : 3, 1 : 2, 1 : 1,
and 2 : 1 R: A ratios in the continuous phase are compared with
resin-free emulsions in Fig. 11. Here, all of the asphaltenes con-
tain solids. Stability tests were performed for the same set of
emulsions with solids-free emulsions as shown in Fig. 12. Note
that Figs. 11 and 12 are both plotted versus initial asphaltene
concentration rather than equilibrium asphaltene concentration
because many of the resin-containing emulsions were too un-
stable to measure an accurate equilibrium concentration.
The emulsions containing solids are more stable as expected.
However, consistent patterns are observed in emulsions prepared
with and without solids. As asphaltene concentration increases
to approximately 5 kg/m
3
, emulsion stability increases. Above
5 kg/m
3
, the stability of the emulsions decreases. The initial
increase in stability is caused by a decrease in the mean diameter,
as discussed previously. The subsequent decrease in stability is
likely caused by resins solvating the asphaltenes and, at high
resin concentration, replacing asphaltenes on the interface.
The stability of emulsions at all the R: A ratios is much less
than in emulsions stabilized only by asphaltenes for the whole
FIG. 11. Effect of resins on emulsion stability (heptol (50),
des
= 6 h).
FIG. 12. Effect of resins and solids removal on emulsion stability (heptol
(50),
des
= 4 h).
range of measured concentrations. Furthermore, the emulsions
become less stable as the R: Aratio increases, especially at high
resin concentrations. Resins appear to act as demulsiers in all
cases.
Comparison of Athabasca and Cold Lake Asphaltenes
To determine if the observations made on Athabasca as-
phaltenes extend to asphaltenes from other sources, some ex-
periments were repeated with Cold Lake asphaltenes. The ad-
sorption isotherms of Cold Lake and Athabasca asphaltenes are
compared in Fig. 13. The Cold Lake asphaltenes adsorb in lesser
FIG. 13. Comparison of adsorption isotherms and stability of emulsions
containing Athabasca or Cold Lake asphaltenes (heptol (50),
des
= 6 h).
478 GAFONOVA AND YARRANTON
amounts than the Athabasca asphaltenes at the same asphaltene
concentration. However, the shapes of the adsorption isotherms
are identical. The resolved water for emulsions stabilized by the
Athabasca and Cold Lake solids-free asphaltenes are also com-
pared in Fig. 13. The stability of the two emulsions is identical.
The similarity in stability curves and in adsorption isotherms
indicates that Cold Lake and Athabasca asphaltenes exhibit the
same general behavior.
CONCLUSIONS
Fine solids, asphaltenes, and resins all play a signicant
role in the stabilization of water-in-hydrocarbon emulsions. As-
phaltenes and native solids act as emulsion stabilizers while
resins destabilize emulsions. The asphaltenes appear to adsorb
as a monolayer with interfacial congurations (or packing den-
sities) that depend on the asphaltene concentration. The highest
packing density occurred at high concentrations but led to less
stable emulsions. The most likely explanation is that there are
fewer points of attachments to the interface per molecule at
higher packing density and, hence, the interface is more uid
and the emulsions less stable.
Emulsion stability increased in poorer solvents unless as-
phaltenes precipitated. Inpoor solvents, the asphaltenes are more
difcult to displace from the interface and consequently the
emulsions are more stable. Upon precipitation, emulsion sta-
bility decreased as more asphaltenes precipitated. Precipitated
asphaltenes do not participate in stabilizing emulsions. Hence, in
effect, precipitation removes stabilizing asphaltenes. Resins are
interfacially active but do not stabilize emulsions. In all cases,
resin addition decreased emulsion stability. Resins are a good
solvent for asphaltenes and also, at high concentrations, they
replace asphaltenes on the interface.
Naturally occurring solids were found to have no effect on
asphaltene adsorption but signicantly increased emulsion sta-
bility. The increased stability was attributed to solids less than
1 min diameter. These solids were found to precipitate with as-
phaltenes. Hence, they may obscure the stabilization effect of as-
phaltenes in emulsion studies. The presence of solids should al-
ways be accounted for when investigating asphaltene-stabilized
emulsions.
The above results suggest that appropriate surfactant or sol-
vent addition can be an effective treatment for water-in-crude
oil emulsions stabilized by asphaltenes. However, native solids
may be the key factor in problem emulsions that persist after
conventional treatment methods. Future research may best be
targeted toward the role of solids.
ACKNOWLEDGMENTS
We thank Imperial Oil Ltd. and NSERC for nancial support. We are also
grateful to Ms. D. Sztukowski for assistance with the experimental work and
Dr. B. McGarvey for helpful advice.
NOMENCLATURE
A
w
surface area of an emulsion (m
2
)
C
0
A
initial concentration of asphaltenes in the continuous
phase before emulsication (kg/m
3
)
C
eq
A
concentration of surface-active asphaltenes in the
continuous phase after emulsication (kg/m
3
)
d
i
diameter of ith water droplet (m)
d
32
Sauter mean diameter (m)
f
i
number frequency of water droplets of diameter d
i
m
I
mass of asphaltenes on the interface (mg)
m
t
mass of asphaltenes in the emulsion (mg)
V
w
total volume of water phase (m
3
)

A
asphaltene mass surface coverage on the water
hydrocarbon interface (mg/m
2
)

des
destabilization time (h)

w
volume fraction of water in emulsion
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