Article

pubs.acs.org/EF

Study of the Cation and Salinity Effect on Electrocoalescence of

Water/Crude Oil Emulsions
Carlos Eduardo Perles,*,† Pedro Luiz Onófrio Volpe,‡ and Antônio J. F. Bombard†
†
Institute of Exact Sciences, Federal University of Itajubá − UNIFEI, Itajubá, MG, Brazil
‡
Institute of Chemistry, University of Campinas - UNICAMP, Campinas, SP, Brazil

ABSTRACT: The resolution of water-in-crude oil (W/O) emulsions formed during extraction or desalinaton processes of crude
oil is still a problem for the oil industry. Among the main separation processes used today, electrostatic separation induced by the
application of DC or AC electric fields is the most interesting because it is ecologically correct. However, the electroseparation
efficiency is still limited by the current lack of knowledge concerning the mechanism that is behind this process. Stabilization of
the water/crude oil emulsion is guaranteed, mainly, by resins and asphaltenes that are present at the W/O interface, forming a
rigid cross-linked film that wraps the droplets. The influence of salts and the salinity of the aqueous phase on the stability of
emulsions is poorly known because most researchers use, as the aqueous phase, a complex saline solution composed of a mixture
of chlorides and sulfates of mono- and divalent cations to simulate the composition of seawater. Thus, the isolated effect of each
type of cation may not be known. In this work, we used the rheology technique to study the effect of cation type and salinity of
the aqueous phase on the stability of water/oil emulsions, under application of a DC electric field. It was verified that the stability
of the emulsions follow this order: H2O ≪ Na+ ∼ K+ < Ba2+. It was also observed that the presence of salts increases the stability
of the emulsions up to a critical value of ionic strength (∼0.1−0.3 mol L−1, depending on the system), above which the stability
decreases, tending to that observed for the emulsion produced with water.

I. INTRODUCTION According to Fordedal et al.,12 when an electric field is

Crude oil is a complex mixture composed mainly by
hydrocarbons (up to 90%), with small amounts of sulfur,
nitrogen, and oxygen compounds. This mixture can be
classified based on the composition of saturated compounds,
aromatic compounds, resins, and asphaltenes, known as the
SARA classification.1,2
Asphaltenes and resins are polyaromatic and heteroatomic
macromolecules which have complex and poorly known
structures. They have molar masses greater than 500 g mol−1
and significant surface/interfacial activities, which are respon-
sible for stabilizing the water/crude oil interface by reducing the
interfacial free energy and also by the formation of a strong
interfacial film with viscoelastic properties.3−7 Sjöblom et al.6
suggested that resins act by solubilizing asphaltenes, allowing
their migration to the water/crude oil interface to stabilize the
emulsion.
This strong stabilization promoted by asphaltenes and resins
makes the resolution of these emulsions an arduous task for the
oil industry. That justifies investment in research focused on
the development of methods and/or on the improvement of
methods that are already applied in order to reduce the costs of
oil extraction and processing.
Although it is already applied by the oil industry, electrostatic
separation still has low efficiency due to the lack of knowledge
about the mechanism behind this phenomenon.8−10 According
to Less et al.,8 Atten et al.,9 Eow and Gadhiri,11 and Aryafar and
Kavehpour,10 progress in electrostatic separation techniques is
limited by actual scientific knowledge about the phenomenon.
They also believe that technological improvements will only be
possible by elucidating the electrocoalescence mechanism.
applied through the emulsion, the water drops align with the
electric field, forming linear chains. These chains are formed by
electrostatic attraction between the electric field-induced
dipoles of the droplets. This dipole arises due to ionic and
molecular polarization inside the droplet.
Less et al.8 reinforced this mechanistic proposal, observing
that the viscosity increases proportional to the intensity of the
electric field applied perpendicular to the direction of flow.
According to Less et al. the overall process can be correlated
with electrorheological curves. The flow resistance increased as
a consequence of the formation of the linear aggregates aligned
to the electric field. The viscosity increases until a critical value
of the electric field (Ec) from which the droplets coalesce,
forming a continuous path that connects the two electrodes and
causes a short-circuit. From this point, the viscosity decreases
sharply and the electrical current increases abruptly. The critical
value of the electric field represents the field intensity needed
for water droplets to form linear aggregates and to coalesce.
The Ec is a function of the properties of the continuous phase
as well as of the W/O interface stabilizing mechanisms.13,14
Rheology is a technique increasingly applied to the study of
electrocoalescence because it allows obtaining significant
macroscopic information about the systems by changes in
flow resistance as a function of the electric field.15
The present work aims to contribute to the mechanistic
understanding of the electrocoalecense process, so that the
knowledge generated can be used to optimize this process,
Received: September 1, 2012
Revised: October 29, 2012
Published: November 1, 2012

© 2012 American Chemical Society 6914 dx.doi.org/10.1021/ef301433m | Energy Fuels 2012, 26, 6914−6924
Energy & Fuels
Table 1. Physical Properties and Composition of Interfacially Active Compounds (Asphaltenes and Resins) for the Crude Oil
Used in This Work
°API d/g cm‑3 (60 F) % asphaltenesa
19.8 ± 0.3 0.932 ± 0.005 5.0 ± 0.3
a
Methodology of Fordedal et al.12
having impact on improving the quality of the crude oil that
arrives at the refineries.
II. EXPERIMENTAL SECTION
2.1. Determination of Water Content. A solution of the crude
oil (50% w/w) was prepared using as solvent a system composed (4:1)
of toluene/methanol. Approximately 200 mL of this solution was
titrated with Karl Fisher reagent (Merck). The water content of the
solvents was subtracted from the results obtained by titration.
2.2. API Gravity of the Crude Oils. The API (American Petroleum
Institute) gravity was obtained by using a vibrating tube densimeter
(Anton Paar, DMA 4500), according to standard ASTM - D4052.16
This ASTM standard defines that the API values must be obtained at
60 °F (15.56 °C).
2.3. Quantification of Asphaltenes. Asphaltenes were precipi-
tated by dissolution of the crude oil in hexane (99.5%, Synth) in a ratio
of 1:40 (4 g of crude oil in 160 g of hexane), inside of a round
bottomed flask.12,17 These samples were kept under magnetic stirring
for 24 h at approximately 25 °C. After this period, this solution was
filtered under vacuum through a nylon membrane (pore diameter of
0.45 μm). The asphaltene retained in the membrane (black solid) was
washed with small aliquots of hexane, dried at a temperature of ∼60
°C, and weighed on an analytical balance. The filtrate, known as the
maltene fraction (deasphalted oil), was saved for extraction and
quantification of resins.
2.4. Quantification of Resins. The quantification of resins was
made according to methodology described by Fordedal et al.12
The resins were directly extracted from the maltene fraction,
obtained from the extraction process of asphaltene. To extract the
resin, silica gel (Merck) was slowly added to the maltene fraction,
under gentle agitation, until the solution become clear and slightly
yellowish.
The resin adsorbed on silica gel was extracted by using a mixture of
1,2-dichloroethane with 7% methanol, under magnetic stirring for 1 h.
This mixture was filtered in order to remove the silica gel, and the
solvent (dichloroethane/methanol) was removed under vacuum with
slight warming (∼60 °C). After removing the solvent, a dark and
highly viscous liquid was obtained.
2.4.1. Wax Appearance Temperature (WAT). A mass of
approximately 10 mg of crude oil sample was weighed into a DSC
sample holder of (crucible), which was sealed and inserted into a
Q100 TA-Instruments DSC. An empty crucible of the same
dimensions was used as reference. A cyclic sweep in the range of
+30 to −50 °C at a rate of 2.0 °C min−1 was made under argon
atmosphere.
2.5. Preparation of Emulsions. The water/crude oil emulsions
were prepared by adding a defined amount of each phase and mixing
them with an Ultra Turrax homogenizer (IKA, T-18), using a rotor/
stator (IKA-S18N-19G) at 18000 rpm for 2 min. The emulsions were
aged for 20 min before the rheological and electrocoalescense
measurements. This aging time is important because the adsorption
and stabilization of the interfaces is a kinetic phenomenon and,
therefore, depends directly on the contact time between phases.
2.6. Mean Diameter and Size Distribution of Drops. The
W/O emulsions were prepared by mixing the water and crude oil
phases in defined proportions and ionic strength values. A small
amount of sample was put on a microscope slide by using a
micropipet. This drop was deposited on a thin glass coverslip to
produce a thin emulsion film. The images were obtained by using a 1.3
megapixel camera (Moticam 1000), and the drop diameter was
measured by using the Motic Image Plus 2.0 software, calibrated with a
standard scale of microscopy.
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% resinsa WAT/°C η/Pa s % H2O
22 ± 2.5 15.5 0.353 0.4
2.7. Rheological and Electrocoalescense Study. In the
rheologic studies, an Anton Paar MCR-301 rheometer, equipped
with an electrorheological accessory and voltage source (FüG-
elektronik, HCP14-12500), was used. The studies were made by
using concentric cylinders geometry (ϕcell = 28.921 mm; ϕbob = 26.660
mm), with a gap of 1.131 mm.
All rheological experiments were made at 25.00 °C, and the
rheological behavior was studied in a 0−500 s−1 shear rate range (γ̇).
In this system, the electric contact occurs in the bob, through the
contact of a steel wire pressed against the bob. This friction affects the
shape of the rheological curves at low shear rate. In a systematic study,
it was defined that 50 s−1 is the lowest value of shear rate in which the
influence of the steel wire is negligible. This value was fixed in the
electrocoalescense studies.
The electrocoalescense studies were made with a constant shear rate
(50 s−1), and the DC voltage was swept in the range of 0 and 3000 V,
with a scan rate of 2.0 V s−1. All accessories are connected to the
rheometer so that the control and data acquisition is realized through
the Rheoplus software.
III. RESULTS
In this work a crude oil from Marlim Field, located in the Bacia
de Campos (coast of the state of Rio de Janeiro, Brazil), was
used. The main characteristics of this crude oil are shown in
Table 1.
The content of “native” water dispersed in this crude oil is
lower than 0.5% and, therefore, can be neglected in the
calculation of mass fraction (Xaq) of the emulsions studied.
According to the API grade scale, this crude oil is classified as
heavy.18
Mean Size and Size Distribution of Droplets. For the
studies, two samples of the same oil reservoir were used. The
properties shown in Table 1 do not differ between samples, but
the rheological and electrocoalescense properties are a bit
different. The microscopic observations (Table 2) and the
Table 2. Mean Size and Size Distribution of Droplets in the
Emulsions W/O, Obtained by Optical Microscopy Images
emulsion systema (S1) mean diameter/μm size distribution range/μm
20H2O 1.3 0.7−4.0
20Na0.60 1.0 0.2−2.8
20K0.60 1.0 0.3−3.0
20Ba0.60 0.8 0.2−2.9
a
The composition of emulsions is abbreviated as follow: XYZ, where X
= mass fraction of water, Y = composition of the aqueous phase, and Z
= ionic strength of the aqueous phase (omitted when the aqueous
phase is composed of distilled water).
study of the mass fraction of the aqueous phase were made with
the crude oil sample defined as “S1” and the study of the effect
of salinity and cation type were made with the sample defined
as “S2”.
The mean size and size distribution of droplets of the
aqueous phase dispersed in crude oil were obtained from
optical microscopy digitalized images. For this study, a droplet
of emulsion was put on a glass slide and compressed with a
coverslip to form a thin and translucent film of emulsion.
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Energy & Fuels
Figure 1. Rheological curves (η × γ̇) of the W/O emulsions obtained between 0.5 and 500 s−1 for emulsions with Xaq = 0.10, 0.20, and 0.35 and
saline solutions of NaCl, KCl, and BaCl2 with ionic strength of 0.6 mol L−1. These curves were obtained without friction of the contact wire on the
bob.
The micrographs obtained were analyzed by sof tware
calibrated with a microscopy scale to obtain the droplet
diameters. The data are shown in Table 2.
The results show that the mean diameter of droplets as well
as the range of size distribution is lower for the emulsions with
saline solutions when compared to distilled water. This result
suggests a better stabilization of the emulsions when the
aqueous phase contains dissolved salts.
Comparing the emulsion systems produced with saline
solutions, it can be observed that the mean diameter of the
droplets is slightly smaller when the aqueous phase contains
Ba2+, though the range of distribution is approximately the
same. This lower droplet diameter indicates a better
stabilization with Ba2+ cation, compared to the monovalent
cations Na+ and K+.
The study of stability will be made by using the
electrorheological technique, and the results will be compared
to those shown in Table 2.
Rheological Study. Deviations of Newtonian behavior are
frequently observed in suspensions/emulsions because of the
interaction/aggregation of particles or droplets dispersed in the
continuous phase. Therefore, it is necessary to rheologically
characterize the emulsion systems that will be studied. In this
study the emulsions had mass fractions of the aqueous phase
between 10 and 35%, and the shear rate was swept between 0.5
and 500 s−1.
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The experimental results, shown in Figure 1, indicate that
only the emulsion with Xaq = 0.35 of distilled water (Figure 1a)
behaves as a non-Newtonian f luid, presenting a characteristic
deviation known as shear-thinning. This behavior is common for
high mass fraction colloidal emulsions/suspensions. Shear-
thinning rheological profiles for high mass fraction water/crude
oil emulsions were previously described by Steinborn and
Flock.19
Significant differences of the rheological behavior were not
observed within the ionic strength range studied (0.05−1.20
mol L−1). Thus, only the rheological curves for ionic strength
0.60 mol L−1 are presented for each emulsion system.
The deviation from Newtonian behavior, observed only for
the distilled water in the Xaq = 0.35 emulsion, can be a result of
droplet deformation as well as an effect of breakdown of
droplet clusters due to the force applied by the flux of the
continuous phase. The extent of droplet deformation depends
on some properties such as surface tension, stiffness of the
interfacial film, size of the droplet, and the difference of
viscosity between the phases.20
Figure 1b-d shows that, independent of the ion in the
aqueous phase (Na+, K+, or Ba2+), the emulsions behave as
Newtonian fluids in the experimental conditions. Furthermore,
the ionic strength of the aqueous phase had no direct effects on
the rheological behavior of the emulsions (data not presented).
dx.doi.org/10.1021/ef301433m | Energy Fuels 2012, 26, 6914−6924
Energy & Fuels
Figure 2. Curves of relative viscosity as functions of aging time of the emulsions produced with distilled water and aqueous saline solutions of NaCl,
KCl, and BaCl2 at different values of ionic strength. a) NaCl; b) KCl, and c) BaCl2; d) variation of viscosity as functions of the ionic strength for each
salt.
There are reports21−23 that indicate interfacial adsorption as
the main cause of stabilization of water/crude oil emulsions. It
is believed that surfactant molecules (asphatenes and resins)
form a protective interfacial film which has viscoelastic
properties, building a physical barrier which hinders the
aggregation followed by coalescence of the emulsions.24−26
This interfacial film could be responsible for the difficulty of
removing the water produced in the extraction of crude oil,
which impacts on the quality of crude oil and its production
costs.
Interfacial Film. The interfacial film is progressively
constituted over time, and this process can be separated into
two elementary steps. In the first step, the accumulation of
asphaltenes and resins at the water/crude oil interface occurs, a
process that directly depends on the kinetics of migration of
these molecules to the W/O interface. The second step can be
described as a “reticulation” process which consists in the
spacial reorganization of the molecules in this interfacial film,
resulting in maximization of intermolecular forces. Thus, this
film becomes stronger with the contact time between the
phases.
The kinetics of constitution of the interfacial film was
monitored by its physical manifestations on the emulsion
viscosity over 20 min from its preparation. To make the
comparison between the emulsions systems studied easier, the
viscosity data in Figure 2 are shown as relative viscosity (ηr),
using the viscosity measured at 5 min as reference.
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In Figure 2a-c an increase of the viscosity with time for all
emulsion systems can be observed, i.e., this behavior is
independent of the aqueous phase composition (distilled
water or saline solutions).
It is possible to observe clearly that the increase of viscosity
with time is more significant for the saline solution emulsions
than for the distilled water one. It can also be observed that
there is a close relationship between ionic strength and the
emulsion viscosity (Figure 2d). For emulsions with saline
solutions, increases of viscosity up to 20% (depending on the
salt and the ionic strength) were observed, while with distilled
water the maximum increase was ∼10%.
Mohammed et al.21 made an interesting study of interfacial
rheology between water and crude oil and concluded that the
increase of viscosity of the interface with time occurs due to
adsorption of surfactant molecules in the interface. According
to these authors, the adsorbed molecules form a “molecular
network” around the droplets making them more resistant to
deformation. Based on these ideas, it is possible to establish a
relationship between the increase of emulsion viscosity over
aging time and its stability.
In recent papers, Moradi et al.26 and Wang et al.27 studied
the effect of salinity (ionic strength) on water/crude oil
emulsions using only two concentration levels of saline
solutions with mono- and divalent cations. Wang et al.
concluded that the stabilities of the emulsions decrease when
the salinity is increased, while Moradi et al. showed that the
mean diameters of the droplets decrease when salinity is
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Energy & Fuels
increased, suggesting an opposite conclusion, i.e., an increase of
stability proportional to the ionic strength of the aqueous
phase.
However, in this study, it was experimentally verified, with at
least 4 levels of ionic strength for each salt (NaCl, KCl, and
BaCl2), that the viscosity increases to a limiting value of ionic
strength from which new increments result in reduction of the
viscosity. Based on the model in which the viscosity of the
emulsion is related to the formation of aggregates and the
rigidity of interfacial film, it is expected that the stability of these
emulsions (which will be studied by electrocoalescence) have a
similar behavior to that observed for viscosity as a function of
the ionic strength. The results shown in Figure 2 indicate that
Wang et al. and Moradi et al. may have explored different ionic
strength ranges, i.e., Moradi et al. may have studied salinities in
the range in which the stability increases, while Wang et al.27
made his studies in the range in which the stability decreases.
Electrostatic Coalescence. The stability of the water/
crude oil emulsion systems immersed in an electric field was
studied by electrorheological technique. Here, two variables of
these systems will be explored: mass fraction and ionic strength
of the aqueous phase. The studies of each will be shown below.
a). Mass Fraction of Water. The water/crude oil emulsions
were prepared with a water mass fraction between 0.05 and
0.35. These emulsions were subjected to a ramp of electric
potential of 2 V s−1 in a gap of 1.013 mm.
As described in the Experimental Section, the friction of the
contact wire on pressed against the bob affects the rheological
curves at low shear rate. To define a value of shear rate in which
the influence of contact wire on the rheological curves is
negligible, it was realized a shear rate scan of 0.5−500 s−1 with
and without electrical field (with and without friction of the
steel wire). The curve of shear stress vs shear rate was
presented in Figure 3.
Figure 3. Effect of the pressure of the steel wire on the rheological
experiments on electrical field.
As can be seen in Figure 3, deviations resulting from the
pressure of the contact wire on the rheological curve are no
longer observed from the shear rate of 50 s‑1. Therefore, the
shear rate value of 50 s−1 was fixed for all rheological
experiments under electrical field. The results are shown in
Figure 4.
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The curve in Figure 4b indicates an inversely proportional
ratio between Ec and Xaq, so that a higher intensity of the
electric field is needed to promote the coalescence in smaller
mass fraction of the aqueous phase.11,27
The curves in Figure 4a were presented as a function of Δη,
i.e., the difference between each viscosity point and the first
point, without electrical field (0 V mm−1). In the region of low
intensity of electric field (initial portion of the curve), it can be
observed that viscosity is virtually unaffected by the electric
field. In a specific value of the electric field, which depends on
the mass fraction of the aqueous phase, among other factors,
the viscosity of the emulsion starts to increase at an
approximately constant rate, until it reaches an intensity of
electric field at which the viscosity undergoes an abrupt
increase, reaching the critical electric field (Ec) and the peak
viscosity (ηp), followed by a sharp drop in the emulsion
viscosity.
According to Less et al.,8 the droplets are randomly
distributed in the continuous phase when an electric field is
absent, as described by Stokes law and the Brownian motion.
When a DC electric field is applied through emulsion, the
dispersed droplets are polarized, and these dipoles are aligned
parallel to the electric field lines.
In water, in addition to molecular polarization, with the
alignment of water dipoles, ionic polarization due to electro-
phoretic migration of ions to the edges of the droplets also
takes place. These ions are produced in the self-dissociation of
water (H3O+ and OH−).
According to Fordedal et al.12,28 and Wang et al.,27 the short-
circuit occurs through the “channels” of water formed by the
linear aggregates which electrically connects the electrodes.
Also according to these authors, the short-circuit must occur
when the aligned droplets reach a critical distance between
them, in a condition of “pre-coalescence”.
According to Less et al.,8 the reduction of the Ec value when
the mass fraction of the aqueous phase is increased, as observed
in Figure 4, occurs due to the reduction of mean spatial
distance between droplets and to the smaller path that each
droplet must travel to align with the electric field and form
aggregates.
Furthermore, when the mass fraction of aqueous water
increases, the thickness of continuous phase layer between two
droplets becomes thinner, and, therefore, less oil must be
drained from this interdroplet region before two droplets come
into contact and coalesce. The drainage of the oil between two
droplets is considered the first physical barrier to be overcome
for coalescence to occur.12
An interesting characteristic of the rheological curves as a
function of electric field is the amplitude of viscosity at the
maximum, Δηp, which occurs in the Ec value. This parameter
can be related to the number and the complexity of the
aggregates formed in the gap because, when the droplets are
aligned with the electric field, the aggregates formed are
disposed perpendicular to the flux lines of the fluid imposed by
rotation of the bob. The stability of the emulsion should also
influence Δηp because the more stable is the emulsion, the
higher will be the value of electric field needed to break it and,
consequently, the higher will be the dipole forces and the
electrostatic attraction between droplets. The increase in the
resistance to emulsion flow occurs until the Ec, when some of
these aggregates coalesce and sediment by gravity, promoting
an abrupt reduction in viscosity of the emulsion due to partial
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Energy & Fuels
Figure 4. a) Rheological curves as a function of electric field for water/crude oil emulsions with Xaq between 0.05 and 0.35; b) curve of Ec as a
function of Xaq; and c) curve of Δηp as a function of Xaq.
removal of the dispersed phase and, consequently, in the
reduction of friction between the phases.
As reported by McLean and Kilpatrick,5,29 in crude oil,
asphaltenes are solvated and solubilized by the resins. The
nonaromatic components of oil (major components) are poor
solvents for asphaltenes. According to Mohammed et al.21,22
and Yang et al.,30 when the asphaltenes are solvated by resins, a
reduction of the interfacial activity of the asphaltenes occurs. As
McLean and Kilpatrick5 reported, a reduction in stabilization of
the emulsion was observed when an aromatic solvent, which
solvates the asphaltene molecules similar to resins, was added
to it. However, when poor solvents (nonaromatics) are added
to the emulsion, aggregation of the asphaltenes in colloidal
particles occurs, and a significant increase in their stability is
observed.
This experimental information reinforces the theory that the
stabilization of the water/crude oil emulsions occurs by
adsorption of asphaltene aggregates at the interface and not
by its surfactant action in molecular form.
b). Mass Fraction of Saline Solutions. The main constituent
of seawater is sodium chloride in a concentration of
approximately 0.6 mol L−1. The effects of salinity on the
electrocoalescence of W/O emulsions are still poorly known.
This work aims to improve this knowledge using a mechanistic
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understanding of the phenomenon, allowing optimizations in
the electrocoalescence process.
The study of the electrocoalescence process was carried with
emulsions whose aqueous phase was composed of sodium,
potassium, or barium chlorides with ionic strengths of 0.6 mol
L−1, a value based on the ionic strength of NaCl found in
seawater.
In Table 3, the electrocoalescense parameters, critical electric
field (Ec) and amplitude of peak viscosity (Δηp), are presented
for each emulsion system. Different from those made with
distilled water, the saline solution emulsions with Xaq = 0.05
showed no effect on the ER curves. This observation indicates a
better stabilization of the W/O emulsions when sodium,
potassium, or barium ions are present in the aqueous phase.
However, the rheological curves as a function of electric field
for saline solution emulsions with Xaq > 0.05 show a profile
similar to that of the emulsion with distilled water, as reported
above. The electrocoalescense parameters obtained from the
ER curves (Figure 5) are presented in Table 3.
Using the Ec parameter as stability criteria, it can be observed
in Table 3 that the W/O emulsions are generally more stable
when there are dissolved salts in the aqueous phase.15 Also, it
can be observed that this increase in stability is independent of
the mass fraction of the aqueous phase and also of the cation in
this phase. Furthermore, it is evident that the Δηp values for
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Energy & Fuels Article

Table 3. Electrocoalescense Parameters of the Curves Shown The higher stability and lower Δηp value observed for
in Figures 4 and 5, for Each Emulsion System emulsions with saline solutions, compared with those produced
with distilled water in the same Xaq value, can be explained by
emulsion system (S1) Ec/V mm‑1 Δηp/Pa s
the formation of an interfacial film, possibly thicker and/or
5H2O 751 0.082 more rigid than that formed at the distilled water/crude oil
10H2O 491 0.097 interface. This increase of the stiffness or thickness could act to
20H2O 348 0.153 hinder the deformation of the droplets by the electric field and
35H2O 231 0.189 cause a reduction of the cohesive force between them, which
10Na0.60 577 0.074 leads to the experimentally observed lower Δηp values (data in
20Na0.60 364 0.083 Table 3). A schematic representation of a proposed model is
35Na0.60 237 0.069 shown in Figure 6. The Newtonian behavior observed in the
10K0.60 561 0.068
20K0.60 364 0.087
35K0.60 212 0.052
10Ba0.60 550 0.079
20Ba0.60 425 0.152
35Ba0.60 248 0.077

emulsions with saline solutions are always lower than the

respective values for emulsions with distilled water in the same
values of Xaq.
As already mentioned, the Δηp is probably related to the
structural complexity of the linear droplet aggregates formed by
electric field action and also to the cohesive forces between the
droplets in these aggregates. The aggregates are oriented Figure 6. Schematic representation of the proposed model, emphasiz-
perpendicularly to the direction of the fluid flow. Thus, the ing the probable cause of variations in Δηp with Xaq.
more cohesive and structurally complex are these aggregates,
the greater will be the resistance to flow (viscosity).

Figure 5. a,b,c) Rheological curves as a function of electric field for the W/O emulsions produced with aqueous solutions of NaCl, KCl, and BaCl2
in mass fractions between 0.10 and 0.35; d) curves of Δηp as a function of Xaq.

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Energy & Fuels
Figure 7. Rheological curves as a function of electric field and the related electric current curves for W/O emulsions with saline solutions in various
ionic strengths. a, b) NaCl; c, d) KCl; e, f) BaCl2.
rheological study of emulsions with saline solutions at all Xaq
values, compared to the non-Newtonian behavior observed for
the distilled water emulsion with Xaq = 0.35, indicates that the
thickness of the interfacial film or the resistance of droplets to
deformation increase when ions are in the aqueous phase. Since
the mechanism of stabilization of W/O emulsions is based on
the steric interaction and the mechanical resistance of the
interfacial film, consisting of resins and asphaltenes adsorbed at
the interface, the conclusions of the rheological studies agree
with the trend of higher stability for emulsions with saline
solutions as the aqueous phase.
In data shown in Table 3, it can be observed that the Δηp
value increases proportionally with the mass fraction of the
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aqueous phase for distilled water emulsions. However, when
saline solutions were used as the aqueous phase, the Δηp value
increases when Xaq is increased from 0.10 to 0.20, and a slight
reduction was observed when Xaq was increased from 0.20 to
0.35, as seen in the Δηp as a function of Xaq curves, Figure 5d
and Table 2. The cause of decrease in the Δηp value from 0.20
to 0.35 of Xaq can be associated with physical changes in the
interfacial film. Thus, understanding of the phenomena will
require future studies about physical and chemical properties of
this interfacial film.
The mean diameter and size distribution of the droplet data
corroborate the electrocoalescense observations about the
increase of stability promoted by dissolved salts in the aqueous
dx.doi.org/10.1021/ef301433m | Energy Fuels 2012, 26, 6914−6924
Energy & Fuels Article

phase. The data shown in Table 3 indicate that the presence of more with saline solutions than with water, indicating the
dissolved salts causes a reduction in the mean diameter and formation of a more rigid and/or thickened interfacial film in
range of size distribution of the droplets, suggesting increased the presence of the ions, which act to increase the resistance to
stability of emulsions with saline solutions. droplet deformation and/or impose a higher energy barrier to
c). Ionic Strength of the Aqueous Phase. Electrocoalecense coalescence of the droplets.
was studied with W/O emulsions in which the aqueous phase A possible explanation for the increased stabilization
was constituted of solutions of sodium, potassium, or barium phenomenon could be the formation of complexes between
chlorides with various ionic strengths (salinity). the acidic groups (phenols, carboxylic acids) present in the
As previously observed in the kinetic curves (Figure 2), the structures of the molecules of asphaltenes and resins and the
ionic strength of the aqueous phase affects the viscosity of the
metal ions present in the aqueous phase. The complexation
emulsion in a possible macroscopic manifestation of physical
properties of the interfacial film. Here, the goal is to study the increases the affinity of these molecules for the interface of the
effect of ionic strength on the electrocoalescence process. water drop.15,26 Based on this proposal, it can be suggested that
The experimental curves of Δη as a function of intensity of the increase in ionic strength causes an increase in the amount
the electric field are presented in Figure 7, and the respective of strongly adsorbed compounds on these interfaces. According
electrocoalescense parameters are presented in Table 4. To Guo et al.,31 the number of acid groups is different between
resins and asphaltenes, being considerably higher for the
Table 4. Electrocoalescense Data from the Curves Presented asphaltenes. Considering the hypothesis that the interfacial
in Figure 8 for Each Emulsion System As Functions of the “skin” which surrounds the droplet is formed by interactions
Ionic Strength of the Aqueous Phase between resins and asphaltenes, while chemical and/or
structural changes of this film can directly affect the stability
emulsion system (S2) Ec/V mm‑1 Δηp/Pa s
of the emulsions.
20Na0.05 402 0.143 The observed relationship between Ec and the emulsion
20Na0.10 418 0.140
stability indicates that the structure of this film undergoes
20Na0.30 481 0.174
changes in the presence of ions in solution. It is possible that
20Na0.60 428 0.107
20Na1.20 391 0.083
asphaltenes or resins interact more strongly with the interface,
20K0.05 439 0.162
due the complexation with ions, and this difference of energy of
20K0.10 476 0.180 adsorption can promote changes in the ratio of this species in
20K0.30 418 0.120 the constitutions of interfacial films and, as a consequence, can
20K0.60 402 0.086 form thicker films, more compact and/or rigid, improving the
20K1.20 375 0.076 stability of the emulsion.
20Ba0.12 476 0.182 After a certain ionic strength the proportion of surfactant
20Ba0.30 550 0.206 species in the interface can result in destruction of the film
20Ba0.60 460 0.149 since a decrease in stability is experimentally observed (Figure
20Ba1.20 444 0.115 2).
It is also possible that the acid groups in the structure of the
make an easy visual comparison of the Ec parameter, the resin and asphaltene molecules dissociate on contact with the
respective curves of electrical current vs electric field are also interface, producing a negative charge associated with anions.
presented. The breaking of the emulsion occurs due to an When the ionic strength is increased, more molecules of
abrupt rise of the electrical current, forming a nearly vertical asphaltene and resin adsorb at the interface forming more
line. compact and rigid films, increasing the stability of the
Figure 8 shows a comparison of rheological curves as a emulsions. However, above a certain ionic strength the degree
function of electric field for the emulsions produced with saline of compression of the interfacial film reaches a critical value,
solutions of different salts at the same value of ionic strength and repulsion begins to occur between the charges of adsorbed
and permits evaluating the effect of the cation on the stability of molecules at that interface. With this repulsion, the interfacial
W/O emulsion. film is gradually destructured as more molecules adsorb at this
In Figure 9, the curves of Ec as a function of ionic strength of interface. This proposed mechanism explains the experimental
the aqueous phase are shown for all salts used in this study. observations. In Figure 7, when the rheological curves are
Comparing the experimental data for the saline solution compared with their current curves as a function of the electric
emulsions with that for distilled water emulsions (Figure 9), an field, for the same values of Xaq (0.20) and ionic strength (0.60
increase in the Ec and Δηp values can be observed up to a and 1.20 mol L−1), it can be observed that the emulsions
critical value of ionic strength, after which the Ec and Δηp values
produced with a solution of BaCl2 are considerably more stable
decreases as the ionic strength increases. Experimental
observations suggest that the presence of ions in the aqueous than those produced with solutions of NaCl and KCl under the
phase increases the stability of emulsions at low concentrations, same conditions.
but, at high concentrations, the ions seem to hinder the The complexation of bivalent cations and acidic groups
stabilizing mechanism. The rheological curves presented in (carboxylate, for example) in the molecules of resins and
Figure 2 show a similar trend for viscosity (viscosity at t = 20 asphaltenes is stronger than with monovalent cations.15 This
min) as a function of ionic strength, i.e., the viscosity increases information supports the idea advocated that the stability of
with the ionic strength up to a given value and then starts to emulsions is directly related to the adsorption energy of the
decrease, tending to the viscosity value of the emulsion with interfacially active molecules of the crude oil at the interface of
water. Generally, it was observed that the viscosity increases the aqueous phase and oil.
6922 dx.doi.org/10.1021/ef301433m | Energy Fuels 2012, 26, 6914−6924
Energy & Fuels
Figure 8. Rheological curves as a function of electric field and the related electric current curves, comparing emulsions prepared with aqueous
solutions of NaCl, KCl, and BaCl2 at same ionic strength, Xaq = 0.20. a,b) ionic strength of 0.60 mol L−1; c,d) ionic strength of 1.20 mol L−1.
Figure 9. Curves of Ec as a function of ionic strength of the aqueous
phase for solutions of NaCl, KCl, and BaCl2, with Xaq = 0.20.
IV. CONCLUSIONS
Based on the rheological and electrorheological studies it was
possible to conclude that the presence of salts dissolved in the
aqueous phase of emulsion water in crude oil directly affects the
mechanism of stabilization of these emulsions.
However, it was expected that with the ionic polarization of
the droplets of saline solutions, the difference in the interfacial
potential would increase and the electrocoalescence would
6923
Article
occur at lower electric fields. The electrocoalescense data show
an opposite effect, in which the salt dissolved in the aqueous
phase induces an increase in the stability of these emulsions,
suggesting that the dissolved ions, mainly the cations, act in the
interface by changing the physical properties of the interfacial
film buildup between the droplets and continuous phase.
The comparison of the rheological curves of the profile
(without application of electric field) of the emulsions with
those with distilled water and saline solutions also indicates a
decrease in the interaction between droplets and/or an increase
in mechanical resistance to deformation of such drops when
there are ions dissolved in the aqueous phase. The reduction in
range size distribution and average diameter of dispersed
droplets corroborate the conclusions about the stability
observed in the emulsions with salt solutions. Based on these
experimental observations it is possible to suggest that metal
ions present in the aqueous phase form complexes with polar
groups present in these surfactant molecules, increasing the
strength of adsorption at the interface and the compression of
the film, resulting in a greater rigidity of this ″film″. With
increasing energy of adsorption at the interface, the thickness of
film can also be increased, increasing the approximation of the
droplets, contributing also to the steric stabilization of the
emulsion.
It was also possible to conclude that the ionic strength of the
aqueous phase considerably affects the stability of emulsions.
The results show that the stability is increased up to a certain
ionic strength value, which depends on the emulsion system.
From this value of ionic strength, the stability of the emulsion
dx.doi.org/10.1021/ef301433m | Energy Fuels 2012, 26, 6914−6924
Energy & Fuels
begins to decrease tending toward that of the corresponding
emulsions with distilled water.
The conclusions of this work can contribute to the
understanding about the chemical and physical characteristics
of the water/crude oil interface when salts are present in the
aqueous phase. This interface has serious implications on the
stability of water/crude oil emulsions, so a good understanding
of its characteristics is necessary to improve the efficiency of
electrostatic separation techniques.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: ceperles@gmail.com.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Carlos E. Perles thanks FAPEMIG − Fundaçaõ de Amparo à
Pesquisa do Estado de Minas Gerais, Brazil, for the postdoc
fellowship BPD 00286-10. Antonio Bombard acknowledges
FAPEMIG for the Grants: APQ-00531-08; APQ-00463-11, and
REDE-113-10. We deeply acknowledge Professor Carol
Hollingworth Collins for critical review.
■
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