Review

pubs.acs.org/EF

Water-in-Crude Oil Emulsion Stabilization: Review and Unanswered

Questions
Peter K. Kilpatrick*
Department of Chemical and Biomolecular Engineering, University of Notre Dame, 257 Fitzpatrick Hall of Engineering, Notre Dame,
Indiana 46656, United States

ABSTRACT: Emulsions of oil droplets in water but more typically water droplets in oil are common in the production,
transportation, and refining of petroleum and related products. Emulsions of water in petroleum or petroleum-derived liquids can
be stabilized by a variety of surface-active compounds and components present in petroleum and also with which petroleum
comes into contact. These include asphaltenes, carboxylic organic acids of various types, fine inorganic particles, and
combinations of these three types of materials. Several of these means of emulsion and thin-film stabilization of emulsions in
petroleum−water mixtures are reviewed here, as well as some of the key physical and chemical means of characterizing both the
materials that stabilize the emulsions and the means of characterizing the oil−water interface and the emulsion films themselves.
Some of the key unanswered questions surrounding the study of emulsion stability in petroleum systems are also reviewed.

■ INTRODUCTION
An emulsion is a mixture of two immiscible liquids in which
droplets of one of the liquids become stably suspended in the
other liquid because of either very slow coalescence or a barrier
to coalescence.1−4 An emulsion is thus thermodynamically
unstable but kinetically stable. Emulsions are common in a host
of industrial products, such as foods, cosmetics, agricultural
products, paints and coatings, and pharmaceuticals. Emulsions
are also common in the petroleum industry, where they are
typically (although not always) undesirable. Because emulsion
droplets can dramatically increase the viscosity of a liquid,
water-in-petroleum emulsions can dramatically increase pump-
ing costs. Water in oil emulsions also enhance corrosion
(because of the inclusion of salt and brine in the petroleum),
reduce throughput, and can lead to equipment failure.
Understanding their causes, both physically and chemically,
and predicting their formation and how to mitigate them are,
thus, very important objectives in the petroleum industry.
There are a number of different physicochemical mechanisms
whereby petroleum emulsions are stabilized, and we briefly
summarize these here before describing in more detail in the
main body of this paper.
It has been well-appreciated for many decades that
asphaltene-containing and related heavy crude oils often
combine with water or brine to produce stable water-in-oil
(W/O) emulsions, and this has led to the widespread and
popular notion that asphaltenes are one of the primary causes
of emulsion stability in petroleum mixtures.5−34 Indeed, there
are many hundreds of papers on the topic, and a great effort has
been made to characterize the properties of asphaltenic films
and emulsions prepared in model systems in which the
asphaltenes are isolated from the crude oil by alkane
precipitation and then used to prepare emulsions in the
laboratory. Asphaltenes are defined as the toluene-soluble but
heptane- or pentane-insoluble fraction of petroleum. Therefore,
the definition is as a solubility class, and, as a result, asphaltenes
contain hundreds of thousands if not millions of chemically
distinct molecules.35 Many of these molecules that report to the
asphaltene fraction are surface-active, although many actually
destabilize W/O emulsions, while others stabilize them.
Therefore, it is clear that not all asphaltene molecules are
responsible for emulsion stabilization but rather a subfraction.
Of course, a key unanswered goal in crude oil emulsion
research is to elucidate the nature of that subfraction, how to
predict its presence in petroleum, and to predict the nature and
severity of possible emulsion challenges in the processing of a
particular petroleum feedstock.
Many of the molecules in crude oil are acidic and can ionize
at the oil−water interface to form the anion of the acid and
dramatically lower the interfacial tension (IFT). This can lead
to stabilized interfaces and emulsion stability.36−55 Some of
these acid components are simple alkyl carboxylic acids; some
are alkylbenzene carboxylic acids; some are naphthenic acids;
and some are fused aromatic ring acids. In addition, some may
be large molecular species with a combination of fused aromatic
rings, alkyl side chains, and other chemical moieties with
carboxylic acid pendant groups. It is well-appreciated that a
number of these chemical species will “report” to the
asphaltene fraction when the crude oil is precipitated with an
alkane, but it is more precise and informative to describe the
stabilization of water in oil emulsion droplets by these acids and
their anions as crude oil acid stabilization rather than asphaltene
stabilization. Indeed, some of these acids are known to be
relatively high-molecular-weight acidic species. In addition, a
mechanism whereby precipitates of high-molecular-weight
acidic species form calcium soaps at the oil−water interface
has been definitively demonstrated to cause severe emulsion
challenges over the past 5−8 years. The tetra-acids of carbon
Special Issue: Upstream Engineering and Flow Assurance (UEFA)
Received: February 25, 2012
Revised: May 28, 2012
Published: May 30, 2012

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Energy & Fuels
number 80 that have been given the name ARN acids are a
particular case in point of this mechanism.56−61
A third mechanism for stabilizing crude oil emulsions is
actually probably an enhancement mechanism, namely, by the
surface modification of very small inorganic solid particles, such
as clay fines, silicas, iron oxides, and other inorganics, through
the adsorption of polar species from the crude oil, such as resins
or asphaltenes, to render the surface-modified inorganic
particles interfacially active.62−69 This mechanism can lead to
dramatically enhanced emulsion stability, and indeed, this
particle mechanism can play a dominant role in some systems
in which there is a substantial inventory of such particles that
are suitably modified.
A final emulsion stabilization mechanism that is very closely
related to the crude oil acid mechanism is the formation of
lamellar liquid crystalline films and possibly other smectic liquid
crystalline phases at the oil−water interface.43−46,70−73 It is
well-known that acids and their soaps form these phases at
sufficiently high concentrations and that adsorption at the oil−
water interface serves as a means to concentrate these species.
Many reports in the last several years have documented this
mechanism, and it appears to occur with a very broad range of
different types of acids and their soaps.
■ ROLE OF ASPHALTENES AND THEIR
SUBFRACTIONS IN WATER IN CRUDE OIL
EMULSION STABILIZATION
Definition, Composition, and Molecular Aggregation
of Asphaltenes. As mentioned above, asphaltenes are defined
as the toluene-soluble and n-heptane-insoluble fraction of
petroleum [American Society for Testing and Materials
(ASTM) and IP-143; see ref 74]. The great irony of this
definition is that there are individual molecular species in
asphaltenes that are known to be insoluble in toluene75 and
there are molecular species that report to the asphaltene
fraction that are actually soluble in n-heptane.76 However,
because the physical state of the asphaltenes in toluene,
heptane, and the crude oil itself is as an aggregated, molecularly
self-assembled, lyophilic (solvent-loving) colloidal aggregate,
the solubility behavior of the individual molecular species
comprising the asphaltenes does not become apparent unless
they are either diluted to very high dilution or separated from
the other asphaltenic species. Thus, even with the solubility
definition, which yields a very large number of molecular
species, there are individual molecules that do not fit the
definition. Nonetheless, the molecular and functional group
composition of asphaltene fractions suggests that at least a
substantial proportion of the molecules in such fractions are
highly aromatic (with hydrogen/carbon atomic ratios in the
range of 1−1.2), possess heteroatoms (N, S, and O) in
amounts varying from 2 to 10% (w/w), possess a range of polar
functional groups capable of hydrogen bonding (including
pyrrole, pyridine, carboxylic, quinone, thiophene, sulfhydryl,
sulfonyl, and related functional groups), possess trace amounts
[parts per million (ppm) to parts per trillion (ppt)] of
vanadium, nickel, and iron, suggesting porphyrin and
porphyrin-like functional groups, and alkyl bridges and pendant
groups.3 This molecular composition can be modeled with
small numbers of particular molecules only to provide a sense
of the types of molecules likely to be present in asphaltenes.77
Recent high-resolution mass spectrometric experiments using
Fourier transform ion cyclotron resonance (FT-ICR) at high
field and with high resolving power hold promise that precise
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molecular structures may soon be forthcoming, at least for
portions of asphaltene fractions.78−80
The molecular aggregates formed by asphaltenes, depending
upon the solvent conditions and concentrations, vary all of the
way from small oligomeric aggregates (a few to several
molecules) to very large microparticulates (containing hun-
dreds of thousands of molecules). Barre and co-workers have
summarized nicely the recent work in characterizing asphaltenic
aggregates in solution, much of it by small-angle X-ray
scattering (SAXS) and small-angle neutron scattering (SANS)
work.81 The nanoscale aggregates (3−10 nm in characteristic
dimension) are typically ellipsoidal and polydisperse and
entrain significant solvent within the aggregate interior.81−91
A careful recent study by Barre and his collaborators at IFP and
Grenoble confirm the oblate cylindrical model.91 The scattering
curves of asphaltenic aggregates in solution are well-fit by mass
fractal models with dimensions on the order of 1.8−2.3,
suggesting roughened surfaces. There has been less work
characterizing the microparticulates formed by asphaltenes,
although it is known that both diffusion- and reaction-limited
aggregation to form microparticulates occurs under conditions
in which asphaltenes aggregate and precipitate and the
crossover in the kinetics is sensitive to the asphaltene
concentration.92−94
From SANS studies on emulsion droplets formed by
asphaltenic solutions and crude oils, the stabilizing interfacial
film in asphaltenic emulsions is on the order of the size scale of
the asphaltenic aggregates, typically 7−20 nm.95−97 These
studies also revealed that there is significant oil and water
entrained in the interfaces and that the volume fraction of
asphaltenes in the interface can vary substantially from 0.1 to
0.3. Asphaltenic emulsion films formed in “poorer” solvents,
such as decalin, appear to lead to denser interfaces and more
stable emulsions.96 There is also clear evidence of densification
and molecular rearrangement of asphaltenic molecules once
adsorbed at an oil−water interface.98−101 This evidence comes
from many sources, including the many dozens of hours
required for many properties of oil−water interfaces, to which
asphaltenes have adsorbed to reach a steady state, including
IFT, dilatational elastic modulus, interfacial shear modulus, and
other properties. These properties continue to change over this
time scale, even when all of the bulk asphaltenes in the oil
phase have been replaced by pure solvent, indicating that the
change is attributable to the consolidation or molecular
rearrangement of the adsorbed asphaltenes. These asphaltenic
films are also observed, by the same experimenters, to be very
strongly adsorbed. This suggests that the asphaltenes are firmly
anchored to the interfacial film and to each other, likely through
multiple intermolecular interactions per asphaltene molecule.
Considering the chemical composition of asphaltenes, the
intermolecular interactions are likely π bonds between aromatic
groups, hydrogen bonds, charge-transfer interactions, multi-
polar forces, and van der Waals interactions. These interactions
confer on adsorbed asphaltenic films elasticity, rigidity, and
enhanced emulsion stability.
Role of Solvency and Chemical Structure in Asphal-
tene Emulsion Stability. Asphaltene nanoscale aggregates are
mostly surface-active under solvent conditions in which they
are still soluble but close to a precipitation phase behavior.23,24
Dependent upon the chemical identity of the individual and
collective asphaltene molecules, this precipitation phase
boundary can occur at Hildebrand solubility parameters varying
from 16 to 18 MPa1/2. Moreover, the amount of asphaltenes
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that precipitate from solution can vary appreciably from crude
oil source to source. It is common to lower the solubility
parameter (or equivalently the refractive index of the solvent)
by adding n-alkane (typically an alkane longer than 4−5 carbon
atoms). Gawrys et al.102 studied the variation in elemental
composition, trace metal content, and aggregation potential of
asphaltene fractions precipitated in narrow bands of solvent
space between a composition of n-heptane and toluene of 90%
toluene/10% n-heptane (v/v) and 0% toluene/100% n-heptane
(v/v). The variations in the hydrogen/carbon and heteroatom/
carbon ratios were relatively complex for asphaltenes isolated
from three different asphaltenes from three differing crude oils.
Asphaltenes isolated from Canadon Seco, an Argentine crude
oil, were fairly aromatic (overall H/C ratio of 1.11), contained
relatively low metal concentrations, and could be judged to be
less polar than other crude oil asphaltenes studied. Con-
sequently, emulsions formed from Canadon Seco asphaltenes
(and from Safaniya or Arab Heavy asphaltenes, another
nonpolar asphaltene fraction) were relatively less stable than
those formed from polar asphaltenes, such as B6, Hondo, or
Athabasca bitumen asphaltenes. This is shown in Figure 1,103 in
Figure 1. Emulsion stability as judged by percent water resolved versus
percent toluene in the oil phase for asphaltenes from four different
crude oils: Arab Heavy (AH), Canadon Seco (CS), B6, and Hondo
(HO). Emulsions were prepared by emulsifying mixed equal volumes
of water and oil, with the oil comprising a mixture of n-heptane and
toluene into which 0.5% (w/w) of the asphaltenes has been added.
The emulsions were prepared, and their stability was gauged by the
centrifugal separation method described by Spiecker et al.33 The
solubility limit of the asphaltenes is roughly 45−50% toluene, although
the precise phase boundaries for three of the asphaltenes can be found
in the study by Gawrys et al.102
which the percent water resolved profiles (a measure of inverse
emulsion stability; i.e., the higher the percent water resolved by
centrifugation, the lower the emulsion stability) versus heptane
and toluene concentrations for these four crude oil
asphaltenes103 are presented. The polar asphaltenes (B6 and
HO) form very stable emulsions (by this test) up to nearly
100% toluene, as judged by the low percent water resolved
(10−20%) over a large range of solvent conditions. Thus, even
in a very good solvent, such as pure toluene, these polar
asphaltenes adsorb strongly at the oil−water interface and
stabilize emulsion. The relatively nonpolar asphaltenes (AH
and CS) form weak emulsions at high toluene concentration
and only stabilize emulsion with any efficacy at toluene
concentrations close to the solubility boundary for the majority
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of the asphaltenes (40−50% toluene). It is thus clear from these
data what a crucial role the chemistry of the specific asphaltenes
plays in stabilizing emulsion. Indeed, it is clear from a variety of
recent studies that only a select small fraction of the asphaltenes
and associated acids play key roles in stabilizing emul-
sion.104−108 Thus, a important goal of current and future
research in crude oil emulsions is the clear elucidation of those
asphaltenic structures responsible for the stability of emulsions.
The work on fractionating asphaltenes into fine fractions of
very differing properties, the observation that asphaltenes of
differing chemistry behave very differently in stabilizing
emulsion, and the observation that some asphaltene molecules
are actually insoluble in toluene but are only solubilized by a
very different fraction of the asphaltenes suggest that there are
specific chemistries and chemical functional groups (and
possibly topologies) in asphaltene molecules that engender
not only interfacial activity at the oil−water interface but may
also be primary, perhaps essential, in facilitating the stability of
W/O emulsions by asphaltenes. Clearly, there are polar,
relatively insoluble asphaltene molecules that are more prone to
self-assemble and aggregate that appear to be the most
interfacially active. These molecules likely have multiple
functional groups in each molecule that are capable of forming
intermolecular bonds with neighboring asphaltene molecules.
In addition, those intermolecular bonds of greatest importance
are undoubtedly those with the greatest temporal lifetime, such
as hydrogen bonds and metal−multipole intermolecular bonds.
Indeed, there are a number of researchers who have recognized
that interconnecting asphaltene molecules must be present to
explain the rheological and emulsion-stabilizing potential of
adsorbed asphaltenic films.98−101 What is the precise chemistry
of these polar, emulsion-stabilizing asphaltenes? Recent work
by Stanford et al.106,107 and commentary by Czarnecki108
suggest that these asphaltenes may contain oxygen-rich acidic
functional groups, be of relatively low double bond equivalent
(DBE) values, and contain multiple sites for binding to other
asphaltene molecules. One might imagine that these oxygen-
rich molecules contain more than one chemical moiety for
hydrogen bonding. One might also imagine that these
molecules contain a topological structure for assuming many
configurations to bind to multiple nearby molecules. This last
point seems consistent with the low DBE value of the
interfacially active material identified in the study by Wu104
and discussed by Czarnecki.
Interfacial Properties of Asphaltenic Emulsion Films.
The interfacial properties of asphaltenic films at the oil−water
interface have been probed by dynamic IFT, interfacial shear
rheology, interfacial dilatational rheology, SANS and SAXS, and
a number of other methods.5,8,29,95−101,105−115 The picture that
emerges is that (1) asphaltenes rearrange their conformation at
a molecular and intermolecular level over time scales of hours
to days, (2) the interfacial rheology gradually approaches that
of an elastic solid if the inventory of asphaltenes is sufficiently
high, (3) the stability of emulsions correlates with the
dilatational elastic modulus, and (4) the thickness of
asphaltenic emulsion films is on the order of 8−20 nm, and
the composition of those films is denser (less entrained
solvent) than the corresponding nanoscale aggregates that
adsorbed to comprise the film. As mentioned above, these
learnings do not speak to the precise chemistry of the adsorbing
molecules, which is still being understood through a variety of
experiments using both the Wu D2O droplet method104−107
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Energy & Fuels
and a variety of chemical and molecular characterization
methods.
■ STABILIZATION OF W/O EMULSIONS BY
CARBOXYLIC ACID, NAPHTHENIC ACIDS, AND
THEIR SOAPS
Another important mechanism whereby emulsions are
stabilized in crude oil systems is through the adsorption of
carboxylic acids and their anions, depending upon conditions of
pH. It has long been known that acids in crude oil can adsorb
to a crude oil−water interface and dramatically lower the
IFT.36−40 Indeed, this mechanism has been exploited by many
to devise enhanced oil recovery processes, using either simply
added alkali or a combination of surfactant-assisted and/or
polymer-assisted alkaline flooding.36,41,42 What has also been
observed in experiments in which crude oil or model oils with
components from petroleum are contacted with water phases of
varying pH is that, following a dramatic reduction in IFT,
sometimes to values as low as from 10−2 to 10−3 mN/m, the
tension often rises again. This has been interpreted as a transfer
of interfacially bound material, presumably the anion or the
acid of the carboxylic acids in the crude oil that has adsorbed
from the interface into the aqueous phase. Indeed, researchers
have observed the buffering effect that this interfacial transfer
has on the water phase emulsified into an acidic crude oil
following resolution of the emulsion into a bulk water phase.
The carboxylic acids capable of lowering IFT and stabilizing
emulsion appear to vary quite broadly in chemical structure and
molecular weight. While some crude oils have a modest
concentration of linear n-alkanoic acids, it is more common to
find what are sometimes collectively known as naphthenic acids
in crude oil. These acids are called naphthenic because they
have at least one cylic alkane functional group, sometimes more
than one, and alkyl side chains onto which the carboxylic acid
functional group is often attached.116−120 A number of excellent
recent studies have described in great detail the chemical
structure of naphthenic acids and the distribution of such
structures, in particular crude oils (see ref 117 and references
cited therein). One well-studied analogue of a naphthenic acid
is 5-β(H)-cholanic acid, a steroidal acid that is commercially
available. Ostlund et al. performed pulsed field gradient spin-
echo nuclear magnetic resonance (NMR) diffusion measure-
ments and determined that β-cholanic acid interacts with
asphaltenes.119 Ese and Kilpatrick demonstrated that β-cholanic
acid can stabilize both oil-in-water (O/W) and W/O
emulsions, depending upon the pH and concentration and
appears to do so through the formation of a lamellar liquid
crystalline phase.48 Horvath-Szabo, Masliyah, and Czarnecki
have demonstrated that both commercial sodium naphthenates
as well as naphthenates formed by contacting Athabasca
bitumen with alkaline solutions from lamellar liquid crystalline
phases, which stabilize water-in-crude oil emulsions,43−46
similar to the liquid crystalline stabilizing mechanism reported
earlier by Friberg and co-workers in surfactant−oil−water
mixtures.70−72
Another important mechanism whereby emulsions are
stabilized by naphthenates is through the formation of the
alkaline earth soaps, particularly calcium naphthenate, by
polyvalent acids. Among these are tetra-acids of roughly 1230
atomic mass units that have come to be known as ARN
acids.56−61 These acids and their calcium soaps adsorb at oil−
water interfaces, yielding IFTs of 11−19 mN/m and dilata-
tional elasticities of 30−60 mN/m, and appear to be common
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in a number of West African and North Sea crude oils. Baugh
and co-workers,56,57 Sjoblom and co-workers,58−61 and others
have studied these materials, and while they appear to be
common, they are not ubiquitous and are certainly not the sole
cause of emulsions in the oil field by acids and their soaps.
Nonetheless, they are an important means whereby actual
petroleum emulsions are stabilized.
There are also acidic components of asphaltenes, that are
very effective at both adsorbing to water−oil interfaces and
being capable of dramatically stabilizing W/O emulsion films.
Verruto, Le, and Kilpatrick101 have probed the effective pKa of
asphaltenes from two distinct heavy petroleum sources: Hondo,
an offshore Californian crude oil, and bitA, an Athabasca
bitumen, by dynamic IFT. Hondo asphaltenes have an effective
pKa close to 7, and bitA asphaltenes have an effective pKa closer
to 3 (i.e., more acidic). Thus, under alkaline conditions with
both Hondo and bitA asphaltenes, these researchers observed
interfacial transfer from the interface to bulk water of the anions
of some of the asphaltenic acids. They also observed an initial
maximum in dilatational elasticity at short times in the
adsorption of both bitA and Hondo asphaltenes at alkaline
pH in pure water, followed by a decline in elasticity over time.
In contrast, with added electrolyte, there was less evidence from
dynamic IFT of interfacial transfer into the aqueous phase of
charged anions of asphaltenic acids and, over a long time period
and after an initial decay in elasticity with added salt, a slow
growth in elasticity, indicating asphaltenic consolidation at the
interface. It thus appears that, under appropriate conditions of
charging of acids, typically pH values in excess of 9 or 10, acidic
species in the asphaltene fraction compete with other less
charged or amphoteric asphaltenic species for the interface. The
presence of salt screens electrostatic repulsion between anions
at the interface and enables the mixture of anionic and less
charged asphaltenes to interact and consolidate slowly over
time, rendering a stronger emulsion interface.
In summary, linear alkanoic acids, naphthenic acids, tetra-
acids (such as ARN), and asphaltenic acids can all adsorb
strongly at water−oil interfaces to aid in the stabilization of
both O/W but more commonly W/O emulsions. In the case of
naphthenic acids, the mechanism appears to be, at least in the
strongest emulsion interfaces, through the formation of layered
lamellar liquid crystalline films. There is growing evidence for
this. In the case of ARN acids, the mechanism appears to be
through the formation of a cohesive film that can be strongly
anchored to the interface through the binding of divalent
cations, such as calcium. Finally, it appears that acids and
asphaltenes can interact strongly with each other and, under
appropriate conditions, form integrated films of high dilata-
tional elasticity.
■
STUDIES ON INTERACTIONS OF ASPHALTENES
AND ACIDS IN THE STABILIZATION OF W/O
EMULSIONS
The interactions of asphaltenes and either naphthenic acids,
linear acids, or fused aromatic ring acids are an area of research
that is garnering increased attention. Pauchard et al.55 and
Muller et al.120 describe a recent study of a low total acid
number (TAN)/high asphaltene crude oil that forms
particularly stable and troublesome emulsions. By carefully
isolating the interfacially adsorbed material and characterizing it
by Fourier transform infrared (FTIR) spectroscopy, FT-ICR
mass spectrometry, and other means, these researchers
determined that the strongly bound interfacial material that
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Figure 2. Emulsion stability as judged by percent brine resolved using the centrifugal separation method described by Spiecker et al.33 The emulsions
were prepared by emulsifying equal volumes of water and oil, with the oil phase containing equal volumes of n-heptane and toluene into which 0.5%
(w/w) Hondo asphaltenes have been dissolved. Varying amounts of β-cholanic acid were also included in the oleic phase, and the pH of the aqueous
phase was adjusted to the designated pH using NaOH as described in the study by Ese and Kilpatrick.48
would not dissolve or wash off in toluene comprised a
dicarboxylic acid of varying chain length, while weaker bound
material appeared to be very similar to asphaltenes (almost
certainly some fraction of the asphaltenes). Therefore, it
appears from their work that integrated films of diprotic acids
and asphaltenes can form particularly troublesome field
emulsions.
There has also been work showing both the enhancement
and diminution of the stability of asphaltene-stabilized W/O
emulsions upon the addition of model carboxylic acids of
varying H/C ratios.121 As mentioned above, Ese and Kilpatrick
demonstrated that β-cholanic acid (with an H/C ratio of 1.696
and a model naphthenic acid molecule) can stabilize both O/W
and W/O emulsions depending upon the concentration of acid
and the pH of the oil.48 In subsequent work,121 they showed
that W/O emulsions stabilized by Hondo asphaltenes could be
destabilized upon the addition of a very small amount of β-
cholanic acid (see Figure 2), as little as a few hundred ppm. In
this experiment (Figure 2), Hondo asphaltenes (0.5%, w/w)
were dissolved in a mixture of n-heptane and toluene (50:50, v/
v), varying amounts of β-cholanic acid were added (0−1.5%, w/
w), and the entire oleic phase was emulsified with water, which
had been pH-adjusted with NaOH to have an aqueous phase
pH between 10.0 and 13.2. The emulsion stability was then
assessed by the centrifugal separation method.33 As shown in
Figure 2, very small amounts of β-cholanic acid (300−1000
ppm or 0.03−0.1 wt %) at pH 12.0 significantly destabilize the
Hondo asphaltene-stabilized emulsions. This indicates that the
charged soap of β-cholanic acid is much more surface-active
than the HO asphaltenes and tiny amounts can adsorb at the
W/O interface and prevent Hondo asphaltenes from anchoring
in that interface and stabilizing the emulsion droplets. However,
when the β-cholanic acid concentration was increased from a
few hundred ppm to 1−2% (w/w) and when the range of pH
of the water phase was between 11.5 and 12.5, the liquid
crystalline mechanism described above dominates and W/O
emulsions are again very stable. Thus, two clearly different
mechanisms of W/O emulsion stabilization are seen in the
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same system, as well as antagonism between the two that
results in destabilization.
Somewhat similar experiments were performed121 in which
two blended crude oils, EB and GCB, known to stabilize W/O
emulsions by forming asphaltenic films, were modified by the
addition of 0.5% (w/w) of a carboxylic acid of varying
molecular structure and then the stability of emulsions prepared
from these modified crude oils by emulsifying them with water
of two differing pH values were measured by the critical electric
field (CEF) method.122 Both of the crude oils contained
substantial amounts of asphaltenes (C7 insolubles for EB = 4.7
wt % and for GCB = 9.1 wt %) and very small amounts of acids
(TAN for EB = 0.15 and for GCB = 0.12). At neutral pH of the
water phase, the addition of acid had no effect on emulsion
stabilization as judged by CEF for the most alkane-like acids
(high H/C ratio): β-cholanic acid, undecylenic acid, and
pentane−cyclohexanoic acid. However, for fused aromatic ring
acids, such as anthracene carboxylic acid, naphthoic acid, and
tetrahydro-naphthoic acid, the addition of 0.5% acid was able to
double or triple the value of the CEF (see Figure 3), suggesting
a dramatic increase in the emulsion stability. In identical
experiments but with the pH elevated to 12 in the water phase,
the addition of the asphaltene-like acids (lower H/C) to the
oils yielded W/O emulsions of dramatically higher CEF and
stability, while the addition of naphthenic acids, such as β-
cholanic acid, heptylbenzoic acid, and pentane−cyclohexanoic
acid, to the oils yielded greatly destabilized W/O emulsions as
gauged by CEF.121 These results indicate that both neutral and
charged asphaltene-like acids can integrate with asphaltenes at
water−oil interfaces to form even more stable emulsions than
with the original asphaltenes. It should be noted that, in the
experiments performed in Figure 3 and described in this
paragraph, the water also contained 1% sodium chloride.
These results are consistent with the interfacial rheology
experiments reported by Verruto et al.101 and described above
for Hondo and bitA asphaltenes at water interfaces and at
alkaline pH with added electrolyte. Therefore, the emerging
picture of the ways in which both asphaltenes and naturally
occurring acids of varying chemical structure interact at
dx.doi.org/10.1021/ef3003262 | Energy Fuels 2012, 26, 4017−4026
Energy & Fuels
Figure 3. Emulsion stability as judged by critical electric field (CEF) as
described in the study by Sullivan et al.123 The oleic phase was either
EB (blend of European oils) or GCB (a blend of Gulf Coast oils). Into
each oil, 0.5% of an acid was dissolved, and then the oil was emulsified
according to the procedure by Spiecker et al.,33 in which the water/oil
ratio was 30:70. The higher the CEF, the more stable the W/O
emulsion. The acid with the lowest H/C (0.64) was 2-anthracene−
carboxylic acid, with the order of increasing H/C: naphthoic acid
(0.70), tetrahydronaphthoic acid (1.1), 1-heptylbenzoic acid (1.46), β-
cholanic acid (1.696), undecylenic acid (1.90), and pentane−
cyclohexanoic acid (1.91). Note that the H/C ratio is computed
only for the hydrophobic portion of the acid molecule and does not
include the carboxylic moiety.
interfaces suggests that naphthenic acids can modestly enhance
asphaltene emulsion stability at neutral pH and dramatically
decrease that stability at alkaline pH. Asphaltene-like acids, in
contrast, containing fused aromatic ring moieties, appear to
enhance the stability of W/O emulsions stabilized by
asphaltenes at all pH, whether charged or not. Similarly, di-
and multiprotic acids can significantly enhance the stability of
asphaltenic interfaces. Indeed, one wonders if these various
acids (aromatic, fused ring aromatic, and multiprotic) naturally
report to the asphaltene fraction and are typically intimately
associated with asphaltenes in the crude oil medium. One could
well imagine that the polar and hydrogen-bonding capability of
these acids and the π-bonding capability of aromatic acids make
them natural bridging agents and intermolecular cross-linkers of
the other asphaltenes.
■
ROLE OF INORGANIC SOLID PARTICLES IN
STABILIZING W/O EMULSIONS
Among the inorganic fine solid particles that arise naturally in
the production and processing of petroleum are silicas, clays,
and metal oxides, such as iron. Early in the 20th century,
researchers discovered the ability to stabilize emulsions of water
and oil with finely divided solid particles. Finkle et al.124 were
the first to relate this to the solid−liquid−liquid contact angle,
observing that the phase that wets the solid better (i.e., for
which the contact angle is less than 90°) is the continuous
phase of the emulsion. Gelot et al.62 studied the emulsification
of water in oil by the clays Ca−bentonite and Ca−kaolinite, as
well as carbon black. They found that they could enhance the
emulsion stability and change the wettability of the particles by
adding the surfactant sodium dodecyl sulfate (SDS). Thus, the
principles that emerged from this work and prior work was that
surface modification of the solid particles by adsorption of
4022
Review
surface-active materials can alter the wettability of the particles
and the stability of the emulsions.
Sullivan and Kilpatrick66 described in detail the ways in
which asphaltenes and resins can adsorb and modify inorganic
solid particles and then studied the modification of fine
particles (0.026−1.45 μm size) of iron oxide, the clay kaolin,
and the clay montmorillonite by the adsorption of surface-
active materials (asphaltenes and resins) from three crude oils.
They concluded that W/O emulsions could be very strongly
stabilized by these fine inorganic particles when suitably
modified through asphaltene and resin adsorption. They also
demonstrated the strong role that particle size plays in
emulsion stability, with the smallest particles yielding the
most stable emulsions. They also demonstrated the role that
the solubility state of the asphaltene plays in its ability to adsorb
to fine solids by varying the resin/asphaltene ratio, which, in
turn, varies the size of the asphaltenic aggregates in solution.
Sztukowski and Yarranton studied the role of clay platelets
and other oil sand solids in enhancing the emulsion stability of
water-in-model oil (heptane and toluene) droplets stabilized by
asphaltenes and resins.67 They found that clay platelets of 100−
500 nm were very effective at enhancing stability and occupied
up to 50% of the interfacial area of the droplets. They also
determined that the clay platelet thickness at the interface was
on the order of asphaltenic film thicknesses (8 nm). Hannisdal
et al. elegantly reaffirmed the critical role of the adsorption of
crude oil components (resins and asphaltenes) in modifying the
wetting and interfacial adsorption properties of nanoscale silica
and the subsequent role in stabilizing both O/W and W/O
emulsions.68 The mechanism of stabilization of water-in-crude
oil emulsions by inorganic solid particles thus appears to be
primarily through the enhancement of asphaltene and/or resin
or crude oil acid-stabilized emulsions through the adsorption of
surface-modifying components in the crude oil to the particles
that render them interfacially active. There appears to be a limit
to the surface coverage of inorganic particles that can effectively
stabilize micrometer-sized droplets, with particles in the tens to
hundreds of nanometer size scale being most effective.
■ SUMMARY AND SOME KEY UNANSWERED
QUESTIONS
It seems clear from the evidence in the literature that
asphaltenes play an unambiguous and important role in
water-in-crude oil emulsion stabilization. Even with the most
nonpolar asphaltenes, it appears possible to create relatively
stable emulsions, although it is also clear that asphaltene
polarity and chemistry strongly impact the stability of W/O
emulsions. It also seems clear that there are subfractions of
asphaltenes that appear primarily responsible for emulsion
stability. From a number of studies, the chemistry of those
asphaltenes most responsible for W/O emulsion stability
appear to be acidic, of relatively low DBE or aromaticity, and,
by inference, highly flexible molecules. Recent studies also
suggest that the acidity in these “key” molecules may be
multiprotic, which further suggests that their role may be to
anchor the stabilizing film in the interface or possibly to serve
as intermolecular cross-linking agents for the asphaltenes. It is
still a very important chemical, functional question to try and
resolve the precise range of molecular identities of these
molecules.
Crude oil acids are also known to play an unambiguous and
important role in water-in-crude oil emulsion stabilization. We
have reviewed the stabilization of these emulsions by
dx.doi.org/10.1021/ef3003262 | Energy Fuels 2012, 26, 4017−4026
Energy & Fuels
naphthenates, which often appear to stabilize by a lamellar
liquid crystalline mechanism. Multiprotic acids, such as ARN
acids, also appear to stabilize W/O emulsions well, apparently
by being multiply anchored in the interface, particularly when
saponified and precipitated by alkaline earth counterions. As
mentioned, there are apparently strong interactions between
and among asphaltenes and multiprotic acids in the stabilizing
interfacial film that can enhance emulsion stability. Similarly,
aromatic and polyaromatic acids (presumably asphaltenic acids)
can also greatly enhance the stability of asphaltene emulsions,
again, likely through multiple points of interaction with the
asphaltenes. It stands to reason that, if the stability of water-in-
crude oil emulsions is typically accompanied by high dilata-
tional interfacial elasticity (as well as shear interfacial elasticity),
any molecules that are able to enhance multiple intermolecular
bonds among asphaltenes in the interface would also serve to
enhance the stability of the emulsion droplet films.
Interestingly, as shown in the review, acids can under alkaline
conditions, in which they form anions, dramatically destabilize
asphaltenic interfacial films. This has been shown for a host of
monoprotic naphthenic acids. Is interfacial dilatational elasticity
or gel strength an appropriate measure of emulsion stability?
Recent data on this question seem to be mixed. If not elasticity,
what is the best measure or predictor of emulsion stability?
This question remains elusive for the full range of water-in-
crude oil emulsions observed. If multiprotic acids appear to be a
common means of cross-linking asphaltenes in water-in-crude
oil emulsions, to which functional groups in the asphaltenes are
they binding? Other acidic or Lewis base groups? Answers to
these questions might yield measures of functional groups or
asphaltene chemistry that could correlate with TAN and a
modified multiprotic TAN, which could provide important
clues to emulsion stability.
Finally, it seems clear that inorganic solid fines, particularly
clays, silicas, and iron oxides, can play major roles in enhancing
water-in-crude oil emulsion stability, particularly when modified
through the adsorption of resins and asphaltenes to render
them strongly interfacially active. Inorganic particle size and
wettability are key variables in dictating how effective inorganic
solids are in enhancing this stability, with the most effective
particles being in the range of a few hundred nanometers in
size.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: peter.kilpatrick@nd.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Parts of this work were supported by grants from Exxon Mobil
Research and Engineering [National Science Foundation
(NSF) Grant TSE0124760] and an industrial consortium
comprising ExxonMobil, Nalco, ConocoPhilips, Shell, and
PetroBeam. The author gratefully acknowledges their support.
■
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