Journal of Petroleum Science and Engineering 86–87 (2012) 137–143

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Journal of Petroleum Science and Engineering

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Emulsification of heavy crude oil in water by natural surfactants

S.N. Ashrafizadeh ⁎, E. Motaee, V. Hoshyargar
Research Laboratory for Advanced Separation Processes, Department of Chemical Engineering, Iran University of Science and Technology, Narmak, Tehran 16846-13114, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The factors affecting the stability of a heavy crude oil-in-water emulsion stabilized by sodium carbonate
Received 24 June 2011 (Na2CO3) as a natural surfactant were studied. An Iranian heavy crude oil, namely West Paydar, was used
Accepted 14 March 2012 as the oil phase of the emulsions. Tap water was used as the aqueous phase. Various concentrations of sodium
Available online 28 March 2012
chloride were employed to study the effect of aqueous phase salinity on the stability and interfacial tension of
the emulsions. The stability and viscosity of O/W emulsions and their viability for the transportation of heavy
Keywords:
heavy crude oil
crude oil through the pipeline were investigated. The diverse factors affecting the properties of emulsions
emulsion were investigated.
natural surfactant The study reveals that the stability of the oil-in-water emulsions was increased versus surfactant concentra-
interfacial tension tion due a decrease in the crude oil–water interfacial tension. The natural surfactant was responsible for the
viscosity very low values of interfacial tensions observed and for the stabilization of the viscous crude oil-in-water
stability emulsions. By increasing the surfactant concentration in the aqueous phase, as well as the speed and duration
of homogenization, the emulsion stability was increased. There was a limit of 60 vol.% for the crude oil content
in the emulsions, beyond that the emulsions were inverted into water-in-oil emulsions. Zeta potential
measurements revealed that the zeta potential of emulsion droplets decreased by the concentration of sodium
carbonate in the aqueous phase.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction Conventional pipelining is not suitable for transporting these

Heavy crudes account for a large fraction of the world's potentially
recoverable oil reserves. The viscosity of these crudes at 25 °C varies
from 1000 to more than 100,000 cP (Schumacher, 1980). These
viscous crudes account for 25% of the economically recoverable oil in
the United States (Riva, 1983). Production of heavy crudes is expected
to increase significantly in the near future as low viscosity crudes are
depleted (Plegue et al., 1989).
Canada, Venezuela, and South America account for 90% of all
known heavy oil reserves, according to Alberta Research Council,
as reported by the Canadian Society of Exploration Geophysicists.
Venezuela has the largest Deposits, and by 2015 heavy or “unconven-
tional” oil could make Canada the world's fifth largest producer (Gerez
and Pick, 1996; Safinya, 2008). Some reports claim that U.S. heavy
oil resource approaches 100 billion barrels of original oil in-place
(OOIP) (California Department of Oil Gas and Geothermal Resources,
2006). The increasing importance of heavy crudes in the outlook of
world energy demands has been repeatedly announced in numerous
recent references (Emadi et al., 2010; Hasan et al., 2010; Nunez and
Rivas, 1998).
⁎ Corresponding author. Tel.: + 98 21 77240496; fax: + 98 21 77240495.
E-mail address: ashrafi@iust.ac.ir (S.N. Ashrafizadeh).
heavy crudes from the reservoir to the refinery because of the high
viscosities involved. Generally, crude viscosities less than 200 cP are
desired for pipelining (Messick, 1982). Several alternative transporta-
tion methods have been proposed including dilution with lighter
crudes, preheating the crude with subsequent heating of the pipeline,
and injection of a water sheath around the viscous crude (Saniere
et al., 2004). Each of these methods may have logistic, technical, or
economic drawbacks for a given application.
Another favorable pipeline technique is the transport of viscous
crudes as concentrated oil-in-water (O/W) emulsions (Marsden and
Raghaven, 1972; Sifferman, 1981; Simon and Poynter, 1970). The
technical viability of this method was demonstrated in an Indonesian
pipeline in 1963 and in a 13-mile long, 8-inch diameter pipeline in
California (Ahmed et al., 1999).
The use of surfactants and water to form stable O/W emulsions
with crude oils is the subject of a series of patents (Titus, 1973). The
development of an adequate technology aimed at handling very viscous
hydrocarbons through their emulsification in water has been studied
over the past two decades by several researchers. However, not very
much information on crude oil-in-water emulsions stabilized by natural
surfactants has been published so far (Acevedo et al., 2001).
The objective of the current research is to investigate the various
factors affecting both the stabilization and destabilization of a heavy
crude oil-in-water emulsion. West Paydar crude oil, one of the Iranian

0920-4105/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2012.03.026
138 S.N. Ashrafizadeh et al. / Journal of Petroleum Science and Engineering 86–87 (2012) 137–143
viscose crude oils provided to Kermanshah refinery, was used as the
heavy crude oil. The study investigates the effect of Na2CO3 concen-
tration as a natural surface active reagent, as well as the salinity of
water, and the time and speed of homogenization on the stability
(and instability), interfacial tension, and viscosity of the emulsion.
Several important issues related to the behavior of natural surfactants
as the emulsifying reagents along with the methods used for destabi-
lization of this system through variation in pH and/or addition of
other emulsifiers have been discussed. The main properties of the
crude oil-in-water emulsions stabilized by the mentioned reagent
have been reported and discussed. The present work is novel for
emulsification of heavy crude oil in water by using a natural chemical
as a surfactant although a similar work has been done for stabilization
of bitumen in water by Acevedo et al. (2001).
2. Materials and methods
2.1. Materials
West Paydar crude oil, one of the Iranian viscose crude oils from
western provinces of Iran, provided to Kermanshah refinery was used
as the oil phase. The crude is classified in heavy crude oils because of
its API gravity (18.89°) and its viscosity which is equal to 2700 cP at
25 °C. According to U.S. Geological Survey (USGS) considerations such
crude oils with viscosities higher than 100 cP are classified as heavy
crude oils (Veil and Quinn, 2008). The physical and chemical properties
of West Paydar crude oil are given in Table 1.
The sodium carbonate was supplied by Merck© (Art No.: 6392,
99.5% pure, less that 0.5% other metallic substances). The alkaline
solutions of carbonate salts were chosen because they produce a
buffer solution, which is capable to keep the pH of the solution practi-
cally constant at around 11.3 ± 0.3 over a wide range of carbonate
concentrations (see Fig. 1). Various concentrations of Na2CO3 in the
aqueous phase, in the vicinity of 500–15000 ppm, were used.
2.2. Experimental methods
Emulsions were prepared by mixing the West Paydar crude oil
with an aqueous phase containing different concentrations of sodium
carbonate. A polytron homogenizer model PT-1200C supplied by
Kinematica AG (Switzerland) was used for the emulsification of the
crudes. After conducting some preliminary experiments to find the
optimum mixing time (ranging from 5 to 25 min) and the optimum
mixing speed (ranging from 6000 to 12000 rpm) for the best stability,
it was indicated that 10 min of mixing time and 6000 rpm of mixing
speed were the optimum conditions for emulsification. Therefore, all
the experiments were conducted at the aforementioned conditions
while the volume fraction of oil phase (ϕ) was 0.6 and T = 25 °C.
Although the temperature would slightly affect the interfacial
tension as well as emulsification, there was no control on temperature
during the emulsification and the process was conducted at room
temperature. Except in some cases that homogenizer was used with
mixing times more than 10 min, during which small temperature
variations had been sensed, the temperature of the mixture maintained
almost constant at room temperature.
Table 1
Physical and chemical properties of West Paydar crude oil.
Specification Unit Value Test method
Saturates wt.% 34.22 SARA
Aromatics wt.% 38.82 SARA
Resins wt.% 19.96 SARA
Asphaltenes wt.% 6.58 SARA
Wax temperature °F 122 Viscosity
Wax quantity wt.% 3.56 BP-237
Fig. 1. pH of the aqueous solution as a function of Na2CO3 concentration at 25 °C.
The O/W emulsions which were prepared at various conditions
were tested for their stability by transferring the emulsion into a
60 mL cone-shaped glass tube graduated to 0.5 mL graduations
and tightly stoppered with a PTFE lid. The ratio of the volume of the
separated water to the total volume of water was measured as a
criterion of instability every 24 h for five days.
The equilibrium interfacial tension of crude oil–aqueous solution
containing various concentrations of carbonate and chloride salts
was measured. A Du Noüy ring interfacial tensiometer model Sigma-
700 was used for the measurement of interfacial tension.
Viscosity of the emulsions was determined using a Kinematica
Viscostar viscometer. Of course, this method of viscosity measure-
ment, does not provide exact information about the rheology of
emulsions and it is just useful to compare the emulsions at various
conditions. Exact data from the rheology of emulsions are produced
when rotary viscometers are used. They can apply shear rate ðγ_ Þ in
a wide range and measure shear stress (τ). Final results for these
rheometers are flow curves. One can calculate viscosity (apparent
viscosity) by dividing τ to γ_ at any point. These curves illustrate
complete information about non-Newtonian or Newtonian (in some
cases) behavior of the system.
Zeta potentials of the emulsions were measured with a Zetasizer,
model ZEN3600 supplied by Malvern. The Zetasizer Nano Series calcu-
lates the zeta potential through determination of the electrophoretic
mobility and then applying the Henry's equation. The electrophoretic
mobility is obtained by performing an electrophoresis experiment on
the sample and measuring the velocity of the particles using Laser
Doppler Velocimetry (LDV). Zeta potentials reported here are the
average values obtained by tracking at least 20 different particles.
The data reported in this article for interfacial trension, zeta
potential, and viscosity are mean values of replications, e.g. each
interfacial tension data is indicated by at least 15 times measurement
by the respective apparatus. The mentioned data were purely deter-
mined by the instrumental apparatus and did not need any further
processing.
3. Results and discussions
3.1. Interfacial properties
The effect of pH on the interfacial tension of the systems formed
by crude oil containing organic acids or acid bitumen/aqueous
solutions of NaOH has been discussed in a number of references
(Minana et al., 1986; Rodriguez et al., 1987; Rudin and Wasan,
1993; Rivas et al., 1997; Saniere et al., 2004). The proposed mecha-
nism relies on the interfacial reaction among the carboxylic acids
present in the oleic phase and the alkali in the aqueous phase. This
reaction produces carboxylate ions, which are the ionized forms of
 S.N. Ashrafizadeh et al. / Journal of Petroleum Science and Engineering 86–87 (2012) 137–143
acids (soaps). The adsorption of these soaps at the interface signifi-
cantly lowers the interfacial tension (Saniere et al., 2004).
For these systems, the interfacial tension decreased very rapidly
at pH values above 9, reaching values lower than 0.1 dyn/cm in the
range of pH between 10.5 and 12. Ultra low values of interfacial
tensions were achieved at a pH of 11.5. At this point, an adsorbed
monolayer of ionized and non-ionized acid molecules should be
adsorbed at the interface (Saniere et al., 2004).
A further increase in the pH up to 13 or higher, promotes an in-
crease in the interfacial tension, attributed to the complete ionization
of the carboxylic acids, followed by the formation of insoluble salts of
sodium carboxylate.
It is thus evident that pH is a very important parameter in con-
trolling the phase behavior of crude oil/alkaline aqueous solution
systems. However, we believe that the ionic strength should also play
an important role. Thus, experiments were carried out using Na2CO3
as the alkaline reagent. In fact, Na2CO3 generates a kind of buffer
solution, whose pH remains practically constant at around 11.3 ± 0.3
over a wide range of carbonate concentrations (Fig. 1).
The reason that pH values above 9 are of dominant interest is
due to the fact that asphaltenes or resins and somewhere waxes,
are activated at this range of pH and play the role of a surfactant
(Acevedo et al., 2001). They would help making stable emulsions by
reducing the interfacial tension. Using Na2CO3 as an alkaline reagent
also allows investigation on the effect of Na + concentration on the
interfacial tension in crude oil/water systems. Fig. 2 shows the effect
of Na2CO3 concentration on the interfacial tension in a two phase
system consisting of West Paydar crude oil and aqueous solutions of
Na2CO3. As it is shown, as the Na2CO3 concentration increases from
500 to 1000 ppm, a sharp decrease in the interfacial tension is ob-
served. In the range of concentrations between 1000 and 2000 ppm,
lower interfacial tensions developed. Interfacial tension increases
with any further increase in the concentration of Na2CO3.
With accordance to the main purpose of the present work, i.e.
to develop an economic emulsification method viable for the trans-
portation of heavy crudes, 2000 ppm is gratefully an acceptable
concentration of sodium carbonate. From an economic point of view,
it would not much affect the economy of the process to use Na2CO3
concentrations up to 2000 ppm.
The presence of NaCl in the aqueous phase demonstrated an
increase in the interfacial tension at each and every concentration
of Na2CO3 studied (Fig. 3). In all of these experiments, the pH of the
aqueous phase remained constant at around 11.3 ± 0.3, while the
sodium (Na +) concentration was increased progressively. It is evi-
dent that under conditions of constant pH, the impact of the ionized
carboxylic acids on reducing the interfacial tension depends much
Fig. 2. Interfacial tension, at 25 °C for the crude oil/water system, as a function of the
Na2CO3 concentration in the aqueous phase.
139
Fig. 3. Interfacial tension at 25 °C for the crude oil/water system, as a function of the
NaCl at the presence of 2000 ppm of Na2CO3 in the aqueous phase.
more on the concentration of Na+ ion. Since the concentration of Na +
would be increased by addition of NaCl, according to the Le Chatelier
principle the equilibrium would act against dissociation of sodium
carbonate (Eq. 14) —known as “common ion effect”. The latter would
suppress the ionization of carboxylic acids which further decreases
interfacial tension; as it has been already said.
The mentioned behavior can be explained by the adsorption–
desorption mechanism proposed in Fig. 4. It should be noticed that
the first point of Fig. 3 is indeed the minimum point of Fig. 2. At a
particular Na2CO3 concentration of 500 ppm, the concentration of
hydroxyl ions (OH −) is enough high to promote the ionization of
the carboxylic acids (HA) present at the crude oil/water interface,
forming the carboxylate ions (A −), whose interfacial activity is well
known (Saniere et al., 2004; Titus, 1973).
Since the crude oil contains a mixture of carboxylic acids, with
different molecular structures and molecular weights (Simon and
Poynter, 1970), a fraction of the carboxylate ions remain adsorbed
at the interface, while the rest diffuse to the aqueous phase.
As the concentration of Na2CO3 increases, the pH of the aqueous
phase tends to remain constant, while the concentration of Na +
increases. This increase in Na + concentration makes the carboxylate
ions, which are dissolved in the aqueous phase, more and more
hydrophobic, promoting its diffusion and adsorption at the interface,
with a subsequent decrease in the interfacial tension. A point is reached
(between 1000 and 2000 ppm of Na2CO3) where very low interfacial
tensions were detected. Further increase in the Na2CO3 concentration
Fig. 4. Adsorption–desorption mechanism for carboxylate ions.
Regenerated from Acevedo et al. (2001).
140 S.N. Ashrafizadeh et al. / Journal of Petroleum Science and Engineering 86–87 (2012) 137–143

introduced into the system, the required Na + concentration, promoted
the formation of insoluble sodium carboxylate salts (NaA). Under these
conditions the interfacial tension increased again.
The interfacial behavior discussed above could be understood
better using a simple model, deduced from the system chemistry
shown in Fig. 4. Thus, these are the following reactions: partitioning
of carboxylic acids (HA) between the crude oil and the aqueous
sublayer,
HAo ↔HAw :
With a partition coefficient, Kp, defined as
½HAw 
Kp ¼ : ð2Þ
½HAo 
If the pH of the aqueous phase remains constant, Eq. (12) can be
rewritten as
− −
½As  ¼ K ½Aw −½NaA: ð13Þ
According to Eq. (13), the concentration of carboxylate ions
adsorbed at the interface decreases as the concentration of sodium
carboxylate (NaA) increases. There is a critical concentration of Na +,
given by Eq. (8), at which the precipitation of sodium carboxylate
ð1Þ (NaA) starts. Once the NaA starts to precipitate, the excess of Na +
added to the aqueous phase only contributes to the removal of the
carboxylate ions adsorbed at the interface by further formation of
NaA. Consequently, as it was observed experimentally, the interfacial
tension increases with increase in the concentration of Na + ions in
the aqueous phase.

Dissociation of the carboxylic acid at the aqueous side of the inter- 3.2. Stability of the emulsions
face according to the reaction
Emulsification of heavy and extra-heavy crude oil and bitumen-in-
− þ
HAw þ H 2 O↔Aw þ H 3 O : ð3Þ water, has facilitated its production and transportation (Ashrafizadeh
and Kamran, 2010; Chirinos et al., 1990; Layrisse et al., 1978; Nunez et
Whose ionization constant is given by al., 1996) since the viscosity of these concentrated emulsions, contain-

ing volume fractions (ϕ) of hydrocarbon on the order of 0.6–0.7, is
þ
½A −
w  H3 O several orders of magnitude lower than the viscosity of the hydrocarbon
Kd ¼ : ð4Þ
½HAw  itself. Although viscosity reduction of a heavy crude-in-water emulsion
for ϕ = 0.8 was 35% (Hasan et al., 2010) but in some cases viscosity re-
Adsorption of the carboxylate ions at the crude oil/water interface, duction is about 90% (Yaghi and Al-Bemani, 2002).
according to the equilibrium All the O/W emulsion samples were examined for their stability
every 24 h in a manner described in Section 2.2. Fig. 5 shows the
− −
Aw ↔As : ð5Þ separated water from the emulsions after a total settling time of
four days. As it is shown, the amount of separated water of West
With an adsorption constant, Ks, defined by Paydar crude oil-in-water emulsions with ϕ = 0.6, decreases as the
concentration of Na2CO3 in the aqueous phase increases.
½A −
s  All of these emulsions were prepared under the same conditions,
Ks ¼ : ð6Þ
½A −
w namely, stirring rate at 6000 rpm for 10 min. Crude oil-in-water
emulsions which were prepared at Na2CO3 concentrations of
Precipitation of the carboxylate ions, as sodium carboxylate, 2000–10000 ppm were stable. At concentrations below or above
whose reaction is given by this range, emulsions were completely unstable. As shown in Fig. 5,
increasing the Na2CO3 concentration to 2000 ppm, increased the
− þ
Aw þ Na ↔ANa: ð7Þ stability of emulsions, for which 60% of the water was removed from
the emulsions after 4 days. Further addition of Na2CO3 decreased the
Which is governed by the following constant (solubility product stability. The presence of NaCl in the aqueous phase demonstrated a
constant): reduction in the stability at each and every concentration of Na2CO3
studied (Fig. 6).
1 Emulsions prepared in the presence of various concentrations of
Kc ¼ þ : ð8Þ
½A −
w ½Na 
 NaCl, in excess of Na2CO3, showed higher values of separated water
than those formed in the absence of NaCl.
All those equilibria are affected by the water ionization The process of the formation of crude oil-in-water emulsions sta-
bilized by natural surfactant can be better understood if the chemical
þ −
2H 2 O↔H3 O þ OH ð9Þ

and its constant Kw, or the ionic product of water, given by

h i
þ −
K w ¼ H3 O ½OH : ð10Þ

The total concentration of carboxylic acids in the system is given

by the following mass balance:
− −
½HAo  ¼ ½HAw  þ ½Aw  þ ½As  þ ½NaA: ð11Þ

Rearrangement of Eq. (11), with the use of the equilibrium rela-

tionships, yields the following equation:
! !
− − Kw 1
½As  ¼ ½Aw  −1 −1 −½NaA: ð12Þ Fig. 5. Separated water versus time at different concentrations of Na2CO3 with ϕ = 0.6
K d ½OH−  K p
at 25 °C.
 S.N. Ashrafizadeh et al. / Journal of Petroleum Science and Engineering 86–87 (2012) 137–143
Fig. 6. Separated water versus time at various concentrations of NaCl in presence of
2000 ppm Na2CO3 at 25 °C.
reactions occurring in both of the solutions as well as at the interface
are taken into account. Thus, when Na2CO3 is dissolved in water,
ionization occurs according to:
þ 2−
Na2 CO3 →2Na þ CO3
followed by the alkaline hydrolysis of carbonate ions and formation
of a buffer solution, which maintains a constant pH of the aqueous
phase,
2− − −
CO3 þ H 2 O↔CO3 H þ OH :
Subsequently, the formation of carboxylate ions and its adsorption
at the interface occurs:
− −
HAw þ OH ↔Aw þ H2 O
− −
Aw ↔As :
When the concentration of Na2CO3 is increased, while pH main-
tains constant, more carboxylate ions are formed in the aqueous
phase (Eqs. (15) and (16)). As such, more carboxylate ions will be
available for the adsorption at the interface of crude oil/water
(Eq. (17)). If the concentration of surface active reagent increases
in the aqueous phase, at constant ϕ, a larger interfacial area can be
saturated by its molecules and thus the mean droplet diameter of
the formed emulsions should decrease.
The presence of NaCl in the continuous phase of the emulsions
promotes a decrease in the stability of the emulsions prepared at
Na2CO3 concentration of 2000 ppm (Fig. 6). In fact, an increase in
the salt concentration, up to a certain level, causes compression of
the electrical double layer and also results in increased binding of
the sodium ions to the adsorbed carboxylate ions. This means that
the carboxylate ion concentration at the interface increases, which
in turn, allows an increase in the interfacial area or a decrease in the
mean droplet diameter of the emulsions. On the other hand, an excess
amount of sodium ions in the aqueous phase completely destabilizes
the emulsion due to the precipitation of carboxylate ions as sodium
carboxylate. Thus, emulsions containing more than 10,000 ppm of
Na2CO3 were completely unstable; the same behavior was observed
in emulsions prepared in the presence of various concentrations of
NaCl and 2000 ppm of Na2CO3.
3.3. Viscosity of the emulsions
Each emulsion has a viscosity more than that of its continuous
phase. Comparing the viscosity of water with that of heavy crude
rationalizes why emulsification should be used (Urdahl et al., 1997;
141
Zaki, 1997). In one instance, by using O/W emulsions, up to 80% of
reduction in drag forces was achieved. It was also found that hydraulic
pressure gradient could be decreased to 30% of that for heavy crude
(Zhang et al., 1991). Using drag reducing additives, by reducing
39.5% of drag where 100 ppm of that was used, could not compete
with the emulsification (Martínez-Palou et al., 2011). The application
of emulsification represented saving of energy when compared with
the other available options considering the facilities available in the
reservoir area (Guevara et al., 1998). The hydrodynamic forces during
drop collisions govern the viscosity behavior. When the emulsion is
subjected to a shear flow, hydrodynamic forces cause two drops to
make a doublet rotating around their mutual center of mass (Krieger
and Dougherty, 1959; Lee, 1969). The rotating doublet dissipates
more energy than hydrodynamically isolated drops. To quantitatively
characterize the polyhedral structure of the emulsions, a number of
authors (Princen and Kiss, 1986; Weaire and Fu, 1988; Yoshimura and
Prud'homme, 1988) have used the volume-surface or Sauter mean
diameter, dSV, defined as
∑ni D3i
dSV ¼ : ð18Þ
∑ni D2i
ð14Þ
Since dSV is simply related to the total interfacial area per unit
volume, it is useful in correlating the drop size and the rheology
of concentrated emulsions; where Otsubo and Prud'homme (1994)
reported a simple relation between viscosity and Sauter mean diame-
ter, as shown in Fig. 7.
ð15Þ Viscosity of the emulsions, at 25 °C, was slowly increased when
the concentration of Na2CO3, in the continuous phase, was increased
from 2000 to 6000 ppm (Fig. 8). This increase in the viscosity should
be attributed to a decrease in the mean diameter of droplets and to the
thinning of the thin liquid films separating the oil droplets. In fact, as
ð16Þ the mean diameter of droplets decreases, the interfacial area increases
and the number of interactions among droplets becomes larger.
ð17Þ Emulsions containing 8000 ppm of Na2CO3 showed a viscosity which
is at least 6 times higher than that of emulsions having 6000 ppm
of Na2CO3. This difference in the viscosity should be attributed to a
difference in the mean diameter of droplets, but especially to the total
energy of interactions among the droplets. In fact, emulsions with
6000 ppm of Na2CO3 show a repulsion energy barrier high enough to
avoid droplet flocculation in the primary minimum; however, crude
oil droplets in those emulsions containing 8000 ppm of Na2CO3, with
a very low repulsive energy barrier, can easily overcome this barrier
and flocculate in the primary minimum. The situation is even more
apparent in emulsions, stabilized with 10,000 ppm of Na2CO3; the
very high values of viscosity observed in these emulsions indicate that
oil droplets have been flocculated in the primary minimum. These
Fig. 7. Relation between viscosity at γ_ ¼ 1 s−1 and the reciprocal of the volume–
surface mean diameter (Otsubo and Prud'homme, 1994).
142 S.N. Ashrafizadeh et al. / Journal of Petroleum Science and Engineering 86–87 (2012) 137–143
Fig. 8. Viscosity of bitumen-in-water emulsions as a function of Na2CO3 and NaCl
concentrations at 25 °C.
results suggest that emulsions containing more than 8000 ppm of
Na2CO3 are mainly stabilized by only short-range repulsive forces.
A similar situation of increasing viscosity with Na2CO3 concentra-
tion was also observed in the emulsions prepared in the presence
of NaCl; all of the samples showed higher viscosity values than the
emulsions formed in the absence of NaCl (Fig. 8).
Fortunately, pressure gradients and drag forces which are expe-
rienced in pipelines are less than those of our experiments; the
migration of particles away from regions of high shear near the pipe
walls actually creates a high viscosity region in the center of the pipe
(Nunez and Rivas, 1998).
3.4. Zeta potential of the emulsions
The zeta potential values (ζ) for the West Paydar crude oil-in-
water emulsions, with ϕ = 0.6, as a function of Na2CO3 concentration
are presented in Table 2 and are shown in Fig. 9. All these emulsions
were prepared under the same conditions, namely, stirring at
6000 rpm for 5 min. A decrease in ζ is observed when the concentra-
tion of Na2CO3 is increased from 2000 to 6000 ppm. It is notable that
where the concentration of Na2CO3 increases from 2000 to 6000 ppm,
the charge density of the emulsion droplets remains constant due to
complete saturation of the interface by the carboxylate ions. Further
increase in the concentration of Na2CO3 up to 15000 ppm promoted
a decrease in the zeta potential. This effect should be attributed to
the precipitation of some of the carboxylate ions, as ANa, adsorbed
on the surface of the crude oil droplets. Although there is no direct
relationship between effective droplet diameters and zeta potential
(Wia˛cek and Chibowski, 1999), but here is a rough conclusion
according to principle concepts provided by Soltys et al. (1997). At
any particular conditions (such as pH, temperature, Na2CO3 and oil
content), the only internal variable which can vary is droplet size
distribution (DSD). If mean droplet size decreases due to any reason,
at such conditions, number of droplets would increase. That would
produce much more interface. Hence, each droplet is surrounded by
fewer charges because of constant amount of that. Electrical field
will be weaken (droplets had no charge), so electrical potential is
Table 2
Zeta potential as a function of Na2CO3 concentration.
Na2CO3 concentration in aqueous phase Zeta potential
(ppm) (mV)
2000 0.798
4000 0.512
6000 0.350
9000 0.283
12,000 0.218
15,000 0.203
Fig. 9. Zeta potential as a function of the Na2CO3 concentration in the aqueous phase of
crude oil-in-water emulsions with ϕ = 0.6.
sequenced to decrease. Finally, it is evident that droplet size may be
directly related to zeta potential.
4. Conclusions
The interfacial properties of natural surface active reagents in the
production of West Paydar crude oil-in-water emulsions were studied.
It was found that the interfacial tension of the crude oil/water system
is very much affected by the concentration of Na2CO3 in the aqueous
phase. The interfacial tension is decreased with Na2CO3 concentration
until very low values are reached at concentrations between 1000 and
2000 ppm. Further increase in the concentration of Na2CO3 promoted
an increase in the interfacial tension. At any particular concentration
of Na2CO3, the interfacial tension was lower than that of a similar case
where 5000 ppm of NaCl was added to the aqueous phase.
The properties of the crude oil-in-water emulsions stabilized by
natural surfactants were also studied. Stable emulsions were prepared
using various concentrations of Na2CO3 in the aqueous phase between
2000 and 10,000 ppm. The separated water from the emulsions
decreased as the concentration of Na2CO3 in the system increased.
The results indicate that emulsions containing up to 6000 ppm
Na2CO3 were stabilized by the interactions of double layer repulsions.
However, those emulsions containing 8000 and 10,000 ppm of Na2CO3
were probably stabilized by only short-range interaction forces, as
deduced from the measured values of viscosities.
The advantages of using Na2CO3 are very promising. From the
economic point of view, use of a mineral salt brings the benefit of
eliminating chemical surfactants which are too expensive to be used
in commercial scale. On the other hand, no environmental drawbacks
would occur by discharging the effluent. Moreover, since no surfactant
remains in the oil phase, the problems encountered in the refining
process of the crude oil such as foaming etc. are also prevented.
Acknowledgments
National Iranian Oil Engineering and Construction Company
(NIOEC) as well as the research council of Iran University of Science
and Technology (IUST) is highly acknowledged for their financial
support during the course of this project.
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