SPE-190377-MS

Nanoparticle-Fortified Emulsification of Heavy Oil

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Danial Arab, Apostolos Kantzas, and Steven L. Bryant, University of Calgary

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE EOR Conference at Oil and Gas West Asia held in Muscat, Oman, 26-28 March 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Chemical flooding has been suggested as an efficient conformance control technique to develop many of
thin post-CHOPS heavy oil reservoirs in Western Canada. In-situ formation of oil in water emulsions due to
the effect of surfactant/natural soap has been reported as the main mechanism behind chemical EOR. In this
work, the effect of surface-modified silica NPs to enhance the efficiency of surfactant to emulsify heavy oil
(14,850 mPa.s and 980 kg/m3 at 25 °C, from the Luseland field) in water has been investigated.
Bulk fluid screening experiments were conducted using different surfactants and surface-modified silica
NPs for selecting the best heavy oil emulsifier. Complementary experiments such as interfacial/surface
tension, NP zeta potential and size measurements, and elemental analysis were conducted to understand the
interactions between NPs and surfactant molecules.
In the absence of NPs, concentration of both anionic and cationic surfactants should be tuned within
a narrow window, near CMC, to create stable heavy oil in water emulsions. It was found that there is a
threshold for IFT, obtained at the CMC, which should be met to have stable oil in water emulsions. The
created oil in water emulsions break easily at surfactant concentrations higher than the CMC, yielding
IFTs higher than the threshold. This observation was also seen in a system containing dodecane. At the
CMC of both anionic and cationic surfactants, the IFT between dodecane and an aqueous phase is negative,
producing stable dodecane in water emulsions for over three months.
In the presence of surface-modified silica NPs heavy oil emulsification is achieved at surfactant
concentrations much lower than the CMC. In this case, IFT is remarkably (54 %) reduced, well below the
threshold value, due to the combined effect of 2 wt. % negatively-charged silica NPs and only 0.1 wt. %
anionic surfactant. These results suggest that the repulsive interaction between negatively-charged NPs and
anionic surfactant may result in pushing the surfactant molecules back towards the oil-water interface to
enhance IFT reduction.

Introduction
Chemical enhanced oil recovey (EOR) has been widely reported as an efficient alternative to thermal and
solvent-based processes in many post-CHOPS heavy oil reservoirs in Western Canada (Bryan and Kantzas.,
2007; Liu et al., 2007; Mai et al., 2009). Two main mechanisms have been suggested for the improvement
in oil recovery by chemical floods: one is improvement in macroscopic/volumetric sweep efficiency, and
2 SPE-190377-MS

the other is enhancement in microscopic oil displacement efficiency at pore scale level (Olajire, 2014). The
former is caused by emulsion-assisted plugging of the fingered pathways formed after water flooding and
the resultant conformance control and the latter is caused by residual oil entrainment in the form of oil in
water emulsions with viscosities much lower than the originating heavy oils. Considerable research has been
done to improve these mechanisms either by boosting emulsion stability to sustain conformance control or
generating emulsions with low viscosity and ease of flow.

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In chemical EOR floods, surfactant is injected into the reservoir to either generate low interfacial
tension (IFT) with the hydrocarbon in place providing a condition to overcome capillary forces and allow
hydrocarbon to flow (Barnes et al., 2008) or alter rock wettability towards less oil-wet (Kamal et al.,
2017). These surfactant-based processes suffer surfactant loss/adsorption on the rock (Olajire, 2014), early
breakthrough of the injected surfactant slug (Kamal et al., 2017; Salehi et al., 2014), high cost, and surfactant
precipitation in high-temperature high-salinity environment (Kamal et al., 2017). Addition of alkaline to the
surfactant solution was introduced in 1980s to reduce the amount of required expensive synthetic surfactant
(Hirasaki et al., 2008). Furthermore, alkaline can react with the acidic crude to create in-situ natural
surfactant (soap) to further reduce IFT and promote oil emulsification (Farouq Ali, 2006). In addition, it
is reported that injection of alkaline along with surfactant decreases surfactant adsorption on the rock by
increasing negative charge density of the rock's surface (Manrique et al., 2007).
This experimental research is aimed to combine the effect of surfactants with various surface-modified
silica NPs, with different alkalinity, to produce heavy oil in water emulsions. We show that oil in water
emulsions can be generated due to the effect of 2 wt. % surface-modified silica NP along with only 0.1 wt.
% surfactant. Comprehensive IFT measurements, NP zeta potential and hydrodynamic size measurements,
and elemental analysis were conducted to understand the effect of different NPs to enhance the efficiency
of different surfactants to reduce IFT.

Materials and methods

Dodecane (reagent grade, ≥ 99%, Sigma-Aldrich) and Luseland heavy oil (14,850 mPa.s and 980 kg/m3
at 25 °C, total acid number (TAN) of 1.72 mg KOH/g, and asphaltenes content of 14.6 wt. %) were used
in the emulsification tests. A vortex mixer, operating at 1,000 rpm for three minutes, has been used to
make an emulsion. It was desired to produce oil in water emulsions and so, the water oil ratio (WOR)
was kept constant and high enough (9:1). All the batch mixing experiments were conducted at room
temperature (23° C). NanoPlus HD (zeta/nano particle analyzer) was used to measure NP zeta potential and
hydrodynamic diameter. The solutions were bath ultrasonicated for 20 minutes before these measurements,
which took 5 minutes during which no sign of NP precipitation was observed. Inductively coupled plasma
mass spectrometry (ICP-MS) was used to measure the elemental content of mixtures of NP dispersions
and surfactants. The solutions were bath ultrasonicated for 20 minutes and then vortexed at 2,000 rpm
for 5 minutes immediately prior to ICP-MS analysis. There was no visual NP precipitation during these
experiments. IFT and surface tension (SFT) measurements were done using the Wilhelmy plate technique.
Different surfactants including dodecyl trimethyl ammonium bromide (DTAB, ≥ 98%, Sigma-Aldrich)
(cationic), sodium alkane sulfonate (Bio-terge PAS-8S, Stepan) (anionic), and polyoxyethylenesorbitan
monopalmitate (Tween 40, contains approximately 90 % Palmitic acid based on GC, Sigma-Aldrich) (non-
ionic) were used to emulsify oil in water. These surfactants were selected based on their reported effects on
either emulsifying heavy oil in water or having enhanced interactions with silica NPs to emulsify simple
hydrocarbon (decane) in water. Due to the lack of work investigating the effect of NPs to emulsify heavy
oil, we trusted on the literature done with simple hydrocarbons. Table 1 incorporates the properties of the
surfactants used in this study. Sodium carbonate (Na2CO3) was used as an alkaline. This alkaline has been
widely used over other alkaline chemicals due to its lower sensitivity to water chemistry (Bryan and Kantzas,
2007).
SPE-190377-MS 3

Table 1—characteristics of the surfactants used in this study

Surfactant name Type CMC (mg/L) Reason to be selected

Bio-terge PAS-8S Anionic 10,3041 Good heavy oil emulsifier (Bryan and Kantzas, 2007; Atkinson,
2004)

DTAB Cationic 4,500 – 4,9002 Good interaction with silica NP to stabilize decane in brine
emulsion (Kim et al., 2016a)

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Tween 40 Non-ionic 27-291 Good interaction with silica NP to stabilize decane in DIW
emulsion (Xu et al., 2016)

1.These values are nominal CMCs, reported by the manufacturers.

2.Aguiar et al., 2003

Two types of colloidal silica NPs, EOR-5XS (20 wt. %, pH = 10.6, 5 nm, negatively-charged, from
Nissan Chemical (Houston, TX)) and Ludox CL (30 wt. %, pH = 4.5, 12 nm, positively-charged, from
Sigma-Aldrich) were used as received. Silica NPs in Ludox CL NP dispersion are coated with alumina,
which imparts a positive charge. EOR-5XS NP dispersion has been reported to produce stable decane in
brine emulsions (Kim et al., 2016b). EOR-5XS NP dispersion contains 10 wt. % ethylene glycol (EG)
as cosolvent. This colloidal silica NPs were surface treated for brine stability. The surface treatment is
covalently bonded to the silica surface. The manufacturer did not release any information about the nature of
surface treatment. In addition, Ludox CL NP was reported to remarkably enhance the efficiency of anionic
surfactant, sodium dodecyl sulfate (SDS), to stabilize n-dodecane in water emulsion (Binks and Rodrigues,
2007).

Results and discussion

Surfactant CMC determination
Critical micelle concentration (CMC) of surfactants was determined by the procedure specified by standard
documentation (IS0 431 1-1979 (E)) to measure SFT, using a plate, stirrup or ring, of the purified or
unpurified surfactants. Based on this standard documentation there may be three different behaviors
for a plot of SFT versus logarithm of surfactant concentration; 1) a sharp change in a slope where
corresponds to CMC 2) a minimum on the curve where SFT is notably lower than that at higher surfactant
concentrations, which corresponds to the range of CMC 3) a gradual decrease in SFT with increasing
surfactant concentrations which may indicate experimental errors or particular phenomena. In the last case,
if the behavior was still observed in different repetitions the CMC cannot be determined. As can be inferred
from Fig. 1, for anionic and cationic surfactants the second behavior exists and there is a range for CMCs of
between 1 and 1.5 wt. % for the anionic surfactant and between 0.3 and 0.4 wt. % for the cationic surfactant,
which are consistent with the nominal CMCs presented in Table 1.
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Figure 1—CMC of different surfactants used in this study is a) between 1 and 1.5 wt. % for anionic surfactant (sodium
alkane sulfonate) (Arab et al., 2018a) b) between 0.3 and 0.4 wt. % for cationic surfactant (dodecyl trimethyl ammonium
bromide) c) 0.0854 wt. % for non-ionic surfactant (polyoxyethylenesorbitan monopalmitate) at room temperature (23 °C)

Different conjectures have been postulated to explain the existence of minima in surface tension curves;
some early researchers claim that this should be due to experimental errors to measure surface tensions
(Clayton, 1943; Miles and Shedlovsky, 1944), while others attributed this rarely observed behavior to the
probable occurrence of abrupt changes in colligative characteristics of some certain surfactant solutions
(Powney and Addison, 1937). In this regard, Miles and Shedlovsky reported a marked minimum in
SFTconcentration curve when there is a mixture of SDS and alcohols (Miles and Shedlovsky, 1944). They
attributed this observation to the presence of more than one surface-active materials in the solution. They
reported no minimum in a case of pure SDS. In their experiments, they used a platinum-iridium ring and Du
Noṻy tensiometer to measure SFT of a mixture of SDS with different surface-active materials like dodecanol
and sodium hexadecyl sulfate. Their results seem to be in some agreement with the results presented by
Adam (Adam, 1938) who pointed out that the minima in SFT-concentration curve may be caused by an
SPE-190377-MS 5

increase in the amount of solute adsorption at the interface at certain concentrations which in turn, may
resulted from the presence of either more than one capillary-active component in the system or a small
amount of an impurity. In addition, Miles and Shedlovsky reported a minimum in the curve when the solution
contains a mixture of two surface-active materials one of which is only slightly water soluble (Miles and
Shedlovsky, 1944). This mixture may be comparable with surfactant solutions which contain molecules
with high and low water-solubility. In a more recent study, Ashraf et al., also reported a minimum in a

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curve of SFT for a pure anionic surfactant (sodium cholate) (Ashraf et al., 2015). Miles and Shedlovsky
(Miles and Shedlovsky, 1944) also speculated that a minimum in SFT-surfactant concentration curve may
also be appeared in case of some cationic surfactants, which is reported many years later by Bouchal et al.,
(Bouchal et al., 2016) and also in the current manuscript (Fig. 1b).
Furthermore, Powney and Addison reported well-defined minima in SFT-surfactant concentration curves,
which were as much as 5 mN/m lower than that at higher surfactant concentrations (Powney and Addison,
1937). They used Du Noṻy tensiometer using a platinum-iridium alloy. They used pure sodium alkyl
sulphates with twelve to eighteen chain lengths of carbon atoms. In our case, SFT measurements were
repeated four times to investigate an experimental error as a source of the minimum point. As shown in Fig.
1, the error bars are very small. The surface tension at the minima points (CMC) in Fig. 1a and b are 6.5 and
11.3 mN/m lower than that at 5 wt. % concentration of anionic and cationic surfactant, respectively, which
is comparable with what was reported by Powney and Addison (Powney and Addison, 1937).
In the case of the non-ionic surfactant, the first behavior suggested by the standard documentation was
observed (Fig. 1c). Based on least square fitting to the data points of SFT-concentration curve the CMC is
854 ppm, which is much higher than that reported by the manufacturer (Table 1). This discrepancy between
the measured CMC of non-ionic surfactants and the nominal values is also addressed by Patist et al., (Patist et
al., 2000), who reported the sensitivity of SFTs, measured by Wilhelmy plate, to the presence of impurities.
To investigate the validity of the CMC value obtained by the SFT technique, the CMC of the non-ionic
surfactant was determined based on an electrical conductivity technique. Based on least square fitting to
the data points of electrical conductivity the CMC of the non-ionic surfactant was 1245 ppm, which is even
higher than that obtained by the SFT technique. Since the purity of the non-ionic surfactant was reported as
90 % Palmitic acid, it seems that the CMC of this surfactant is remarkably influenced by impurities.

Bulk fluid screening experiments

Surfactants. This section includes the results of bottle experiments conducted at room temperature (23 °C)
to screen surfactants, NP dispersions, and their mixtures for selecting the best heavy oil emulsifier. So, first
the best/optimum concentration of each of these chemicals were found and then, they were mixed to screen
the best cocktail. Fig. 2 incorporates the photographs of the vials containing increasing concentrations of
different types of surfactants. The surfactants’ concentrations are shown in the text boxes above each vial.
In all cases, no emulsion is formed at low surfactant concentrations. In cases of both anionic and cationic
surfactants, there is only emulsion at around CMC (Fig. 2a and b), specified with the red rectangle in the text
boxes above the vials. In these cases, at surfactant concentrations far from CMC, these oil in water emulsions
break and 24 hours after vortexing there is no emulsion (Fig. 2a and b). This phase separation starts 2 hours
after vortexing. However, at around CMC although there is some degree of oil droplets coalescence the
lower phase contains emulsified oil droplets, as can be inferred from the observed brownish lower phase.
The type of emulsions in both lower and upper phases were oil in water emulsions, confirmed with the
drop method. For the anionic surfactant, only right at CMC low viscosity heavy oil in water emulsions are
produced (Arab et al., 2018a). I n the presence of the precise concentrations of anionic surfactant heavy
oil components adhere to the glass above the fluid level much less than that in the presence of cationic
surfactant (see the glass above the fluid level in vails shown in Fig. 2a and b).
6 SPE-190377-MS

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Figure 2—Photographs of vials at 23 °C, captured 24 hours after vortexing, containing Luseland heavy
oil and increasing concentrations (text boxes above vials) of different surfactants in the absence
of NP dispersion: a) anionic surfactant (sodium alkane sulfonate), b) cationic surfactant (dodecyl
trimethyl ammonium bromide), c) non-ionic surfactant (Polyoxyethylenesorbitan monopalmitate)

When using the cationic surfactant at low concentrations, below 0.2 wt. %, heavy oil cannot be washed
from the vial wall and there is no mixing at all. This indicates that at these concentrations the energy
produced by vortexing (1,000 rpm for 3 minutes) is not sufficient to mix the oleic and aqueous phases.
When there is no surfactant (i.e., the aqueous phase contains only DIW) energy generated by a vortexer can
mix the oil with DIW. This mixture is not stable and breaks immediately after vortexing. However, at low
cationic surfactant concentrations (below 0.2 wt. %) there is even no mixing during vortexing and the oil can
just slide on the vial edge without complete mixing (see Fig. 2b at concentrations below 0.2 wt. %). At the
cationic surfactant's CMC, there is a layer of oil on the glass wall even immediately after vortexing, which
was not observed with anionic surfactant. For the non-ionic surfactant, at all the concentrations the energy
generated by a vortexer is sufficient to mix the heavy oil with an aqueous phase, unlike the observations
with low concentrations of cationic surfactant. However, after 18 hours complete phase separation occurrs
in all the cases. Based on these observations, the anionic surfactant was selected for further experiments
in the presence of NP dispersion.
To further investigate the effect of the precise concentration of both cationic and anionic surfactants
required to emulsify heavy oil in water, the bottle tests were repeated using dodecane. These tests were
performed with WOR of 9. However, since there was a considerable amount of foam created due to vortexing
of surfactant solutions it was not possible to distinguish this agitation-created foam from the milky emulsion.
Therefore, these tests were repeated with WOR of 1 to have the foam on top and the milky emulsion in the
middle (Fig. 3). For both cationic and anionic surfacants, the highest degrees of emulsification occur at the
CMC (Fig. 3a and b). The type of these emulsions was confirmed to be oil in water using the drop method.
These observations with a simple hydrocarbon (dodecane) also indicate the formation of emulsions only at
the narrow surfactant concentrations and are consistent with what observed with the Luseland heavy oil.
SPE-190377-MS 7

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Figure 3—Photographs of vials at 23 °C, captured 24 hours after vortexing, containing dodecane and
increasing concentrations (text boxes above vials) of different surfactants in the absence of NP dispersion:
a) anionic surfactant (sodium alkane sulfonate), b) cationic surfactant (dodecyl trimethyl ammonium bromide)

This oil in water emulsion destabilization at high surfactant concentrations has been reported in some
earlier studies (Cockbain, 1952; Pal, 1993; Aronson, 1989; Aronson, 1991; Fairhurst et al., 1983). Cockbain
pointed out the striking flocculation and creaming of oil in water emulsions above the CMC of ionic
surfactants (Cockbain, 1952). This free surfactant-induced destabilization of emulsions has been also
reported by Fairhurst et al., who reported a rapid creaming of oil in water emulsions at surfactant
concentrations above a critical flocculation concentrations (CFC) which is higher than CMC (Fairhurst et
al., 1983). They used different types of commercial/unpurified non-ionic surfatants. In this regard, Aronson
reported the same observations with different water-soluble surfactants: three types of non-ionic surfactants
and one type of anionic surfactant (Aronson, 1989). He reported a very rapid creaming of paraffin oil in
water emulsions stabilized by the four types of surfactants when their concentrations exceeded CFC (in
the range of 0.5 – 4 wt. % for different surfactants). He concluded that this emulsion breakage occurs
due to flocculation of approaching oil droplets resulted from micelles exclusion. Below CFC discrete oil
droplets move independently since the micelles are positioned between approaching oil droplets to prevent
their flocculation. However, above CFC the micelles exclusion happens allowing flocculation of the two
approaching droplets. Based on this study, the magnitude of CFC decreases with increasing droplet size
and is a function of surfactant structure. In continuation of this study, Aronson pointed out this observation
is not due to the impurities existing in commercial surfactants or oils and reported the exactly same
observations with highly purified oils (tetradecane and hexadecane) in water emulsions stabuilized by
monodispersed nonionic surfactants (alcohol ethoxylates) and a pure cationic surfactant (alkyl trimethyl
ammonium bromide) (Aronson, 1991). I n addition, Pal reported flocculation of oil in water emulsions due
to the excess of non-ionic oil-soluable surfactant (sorbitan trioleate) (Pal, 1993). Therefore, free-surfactant-
induced flocculation of droplets seems to be a general phenomenon, which can occur in a variety of
conditions with different types of either pure or unpure water or oil-soluble surfactants (non-ionic, anionic,
and cationic) and different types of emulsions i.e., oil in water versus water in oil. Therefore, surfactant
concentrations should be tuned to just the right concentration stabilizing the emulsions with no concern
8 SPE-190377-MS

about free-surfactant-induced droplets flocculation. In this study, this happens around CMC (Fig. 2 and 3)
at which IFT is minimum, as will be discussed later.
As discussed, high concentrtaions of surfactants (between 1 and 1.5 wt. % for the anionic surfactant
and between 0.3 and 0.4 wt. % for the cationic surfacatnt) is required to achieve the desired heavy oil
emulsification. However, these high concentrations are not cost-effective and more importantly, since
there is surfactant adsorption/loss during flow in porous media, it seems impractical to keep surfactant

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concentrations exactly as these optimum values (equal to CMC) during surfactant floods. Therefore, we
combined the effect of different silica NPs along with low concentration (0.1 wt. %) of anionic surfactant
to emulsify heavy oil in water.
Anionic surfactant + silica NP. Fig. 4 is a photograph of the vials, captured immediately after vortexing,
containing different chemicals: only DIW (the leftmost vial), only 0.1 wt. % anionic surfactant (second vial
from the left), only 2 wt. % Ludox CL NP dispersion (third vial from the left), and a mixture of 0.1 wt.
% anionic surfactant and 2 wt. % Ludox CL NP dispersion (the rightmost vial). In all the cases, there is
no heavy oil emulsification in an aqueous phase. As will be discussed later, none of these chemicals lower
heavy oil-water IFT below the threshold IFT required for the Luseland heavy oil emulsification and as a
result, no emulsion was observed in Fig. 4.

Figure 4—Photograph of vials, captured immediately after vortexing, at 23 °C containing different chemicals:
only DIW (the leftmost vial), only 0.1 wt. % anionic surfactant (sodium alkane sulfonate) (second vial
from the left), only 2 wt. % Ludox CL NP dispersion (third vial from the left), and mixture of 0.1 wt. %
anionic surfactant (sodium alkane sulfonate) and 2 wt. % Ludox CL NP dispersion (the rightmost vial)

Fig. 5 depicts a photograph of the vials, captured immediately after vortexing, to show the effect of
EOR5XS NP dispersion either alone or along with 0.1 wt. % anionic surfactant to emulsify Luseland heavy
oil in water. Unlike Ludox CL NP dispersion, heavy oil is mixed with an aqueous phase in the presence of
only 2 wt. % EOR-5XS NP dispersion (see Fig. 5, third vial from the left). This effect was enhanced when an
aqueous phase contains 2 wt. % EOR-5XS NP dispersion along with 0.1 wt. % anionic surfactant (see Fig.
5, the rightmost vial). In addition, the glass above the fluid level in the presence of 2 wt. % EOR-5XS NP
dispersion and 0.1 wt. % anionic surfactant is clean (see Fig. 5, the rightmost vial), indicating no adhesion
of oil components to the glass. This is also observed in the presence of 2 wt. % Ludox CL NP dispersion
and 0.1 wt. % anionic surfactant (see Fig. 4, the rightmost vial), suggesting the combined effet of silica NP,
regardless of its surface treatement, and the used anionic surfactant to prevent adhesion of oil components
to the glass. The pH of 2 wt. % EOR-5XS NP dispersion is 10.3. Therefore, the NPassisted emulsification,
observed in Fig. 5, may be because of one or a combination of the following factors: surface treatment
of silica NP in EOR-5XS NP dispersion, the presence of EG in EOR-5XS NP dispersion, or alkalinity of
EOR-5XS NP dispersion. To investigate the effect of alkalinity, the following bottle tests were conducted.
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Figure 5—Photograph of vials, captured immediately after vortexing, at 23 °C containing different chemicals:
only DIW (the leftmost vial), only 0.1 wt. % anionic surfactant (sodium alkane sulfonate) (second vial from
the left), only 2 wt. % EOR-5XS NP dispersion (third vial from the left), and mixture of 0.1 wt. % anionic
surfactant (sodium alkane sulfonate) and 2 wt. % EOR-5XS NP dispersion (the rightmost vial) (Arab et al., 2018a)

Alkaline only. The effect of increasing alkaline (sodium carbonate) concentration to emulsify Luseland
heavy oil in water is depicted in Fig. 6a. The pH values of the aqueous phases in Fig. 6a are shown in
Fig. 6b. As shown in Fig. 6a, even the lowest concentration of sodium carbonate (0.1 wt. %, with pH
of 11.3) produces a uniform/homogeneous mixture of heavy oil and water. These results suggest that the
heavy oil emulsification due to the effect of EOR-5XS NP dispersion with pH of 10.3, observed in Fig, 5,
may be due to the alkalinity of EOR-5XS NP dispersion. This speculation should be verified by: repeating
the experiments with sodium carbonate solution whose pH adjusted to the pH of 2 wt. % EOR-5XS NP
dispersion (i.e., 10.3), investigating the effect of EG on the enhancement in heavy oil emulsification, and
probing the nature of silica NP surface treatment, which are subjects to our future studies. As shown in
Fig. 6a, the oil components tend to adhere to the glass above the fluid levels in the presence of all the
sodium carbonate concentrations studies. This is observed in all the bottle tests (Figures 4 to 6) with all
the chemicals except when there is a mixture of silica NP dispersion and anionic surfactant (see Fig. 4 and
5, the rightmost vials).

Figure 6—(a) Photographs of vials, captured immediately after vortexing, at 23 °C containing

increasing concentration of alkaline (sodium carbonate) (text boxes above vials) in the absence
of surfactant and NP dispersion, (b) pH of the aqueous phases in the vials depicted in (a) at 23 °C

Interfacial interactions quantification

Surfactant only. This section incorporates the results of surface tension and interfacial tension
measurements to understand the presented emulsification behaviors. Fig. 7 shows the interfacial tension
between Luseland heavy oil and aqueous phase containing different surfactants. As shown, IFT drops to a
minimum at the CMC. This behavior was observed for both anionic (Fig. 7a) and cationic surfactants (Fig.
10 SPE-190377-MS

7b) and seems to explain the results of batch mixing tests presented in Fig. 2 a and b. Above CMC, IFT
increases and since at these concentrations there is no heavy oil emulsified in water (Fig. 2a and b) it seems
that there is a IFT threshod below which emulsification occurs. This threshold is around 30 mN/m and
20 mN/m for anionic and cationic surfactant, respectively. As shown in Fig. 7, the IFT between Luseland
heavy oil and aqueous phase containing cationic surfactant is lower that than in the presence of the same
concentrations of anionic surfactant. However, the anionic surfactant tends to produce low viscosity oil in

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water emulsions (Arab et al., 2018a), which was not observed with the cationic surfactant.

Figure 7—IFT between Luseland heavy oil and different concentrations of a) anionic surfactant (sodium alkane sulfonate)
(Arab et al., 2018a) b) cationic surfactant (dodecyl trimethyl ammonium bromide), in the absence of NP dispersion

Fig. 8 shows the IFT between dodecane and different surfactants. The IFT value for the reference case
containing dodecane and DIW is 51.5 mN/m, which is in good agreement with literature (Rodriguez, et
al., 2016; Zeppieri, et al., 2001). As shown in Fig. 8a and b, IFT decreases with increasing surfactants
concentrations up to CMC and then starts to increase. These trends agree with the trends in SFT data
presented in Fig. 1a and b and, with heavy oil IFT data (Fig. 7a and b). As shown in Fig. 8a and b, at
the CMC of both anionic and cationic surfactants the IFT is negative. To make sure the validity of these
results, each measurement was repeated four times and the error bars are miniscual (Fig. 8). The negative
value for IFT was also previously reported (Bialké et al., 2015; Davies and Rideal, 1963; Kaptay, 2017;
Kimball, 1917; Leal-Calderon et al., 2007; Lee, 1999; Miller et al., 1977; Patashinski et al., 2012; Prince,
1967; Prince, 1969; Schulman and Montagne, 1961; Sharma and Shah, 1985; Shah et al., 1972; Solans et al.,
2016) and interpretd as a condition where the interface of the two initially immiscible fluids is expanding
rather than contracting to facilitate mixing and spontaneous emulsification. To experimentally meaure a
negative IFT the interface needs to be supported by exerting a counter tension onto the interface to prevent
surface breakage/spontaneous emulsification. The Wilhelmy plate technique was cited as a method to exert
this counter tension and measure negative IFT (Schulman and Montagne, 1961).
SPE-190377-MS 11

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Figure 8—IFT between dodecane and different concentrations of a) anionic surfactant (sodium alkane
sulfonate) b) cationic surfactant (dodecyl trimethyl ammonium bromide), in the absence of NP dispersion

In the absence of surfactants, interfacial molecules of one liquid in contact with another one tend to
contract towards their own bulk part to minimize net free energy of the system. However, when there is a
surfactant in the system, surfactant molecules with hydrophilic head and hydrophobic tail tend to pack at
the interface where they can form a monolayer. In this case, this tendency to pack at the interface must be
taken into account along with the interfacial area contraction for pure systems i.e., without any surfactant
(Davies and Rideal, 1963). To consider this, the total IFT can be calculated through the following equation
(Davies and Rideal, 1963; Lee, 1999; Prince, 1967; Schulman and Montagne, 1961):
(1)
Where γ is total IFT, γ0 is IFT in the absence of any surfactant, and π is spreading pressure of the surfactant
monolayer adsorbed at the oil-water interface. Eq. 1 shows that when γ0 > π IFT is positive and the oilwater
interfacial area tends to shrink and finally phase separation occurs. However, when the adsorbed monolayer/
film of surfactant at the interface is so compressed (high spreading pressure (π)) γ0 is less than π and IFT
would be negative. In this case, an interfacial area expands due to the existence of available energy – γdA
(A is surface area) to create microemulsion on one or both sides of the interface leading to miscibility
(Davies and Rideal, 1963; Prince, 1967). Momentary negative IFT of the system containing xylene due
to strong adsorbance of detergent (dodecylamine ions) on the interface is also reported by Kaminski and
McBain (Kaminski and McBain, 1949). Spontaneous emulsification and mixing results in transferring of
the oil into aqueous phase and reduction in the amount of free detergent ions at the interface up to a level
where the adsorption of amphiphilic compounds at the interface is not sufficient to keep π high enough
sustaining negative IFT values (Kaminski and McBain, 1949; Davies and Rideal, 1963). In this regard,
Prince pointed out that the actual concentration of alcohol at the interface which is a function of oil type,
rather than the total concentration in the bulk, affects raising of π to make IFT negative (Prince, 1967). In
this work, soap and long-chain alcohols were used as emulsion stabilizers. He reported three stages for film
pressure development based on the relative importance of the forces acting among the components adsorbed
at the interface. These forces include electrostatic, coulombic, hydrpgen bonding, and van der Waals forces
which are functions of the interfacial concentration of alcohol and soap.
Prince reported the maximum film pressure at intermediate concentration of alcohol (Prince, 1967). This
implies that at intermediate concentration of alcohol high film pressure may result in negative IFT. In
our case negative IFT values in Fig. 8a and b were obtained at CMC which may be called intermediate
concentration. The spontaneous emulsification is reported to start slightly at IFT values equal to a few tenths
of mN/m below zero and is enhanced when IFT = -1 mN/m (Davies and Rideal, 1963). Our results are in
good agreement with the mentioned range for IFT values to embark emulsification. As shown in Fig. 8a
12 SPE-190377-MS

and b, IFT between dodecane and surfactant solutions is - 0.7 and - 1.7 mN/m at the CMC of anionic and
cationic surfactants, respectively. At these concentrations, dodecane in water emulsions are stable for more
than three months. Davies and Rideal emphasized that the true spontaneous emulsification, where there is
no energy required to create an emulsion, should be distinguished from an easy emulsification which can
occur by very low IFT (Davies and Rideal, 1963). So, since in our system without applying any energy
there is no emulsion easy emulsification may be a better term for the phenomenon we observed in Fig. 3.

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Surfactant + NP. The combined effect of NPs and surfactant to change interfacial properties has been
reported as a governing factor controlling stability of particle-stabilized emulsions (Arab et al., 2018b;
Horozov and Binks, 2006; Lan et al., 2007). To better understand the effect of EOR-5XS NP dispersion
along with anionic surfactant to emulsify heavy oil in water (Fig. 5), SFT and IFT were measured. Fig.
9 shows SFT data measured in different systems containing pure surfactant or mixtures of surfactant and
different NP dispersions. It is noteable that 2 wt. % EOR-5XS NP dispersion, in the absence of surfactant,
decreases SFT from 72 mN/m to 70 mN/m (3 % reduction in SFT) suggecting these NPs possess some
degrees of surface activity per se. This surface activity should be due to their surface modification. On the
contrary, the SFT of Ludox CL NP dispersion without surfactant is the same as pure DIW, suggesting that
although these NPs also possess alumina surface coating they are not surface active per se and show no
tendency to adsorb at the air-water interface. This has been reported in previous studies: Ma et al., reported
72.71 mN/m for SFT of the system containing 20 wt. % additive-free and negatively-charged hydrophilic
silica NP (Ma et al., 2008) and Binks et al., reported SFT of the system containing negatively-charged
silica NP (Ludox HS-30) equal to that of pure water (Binks et al., 2007). As can be inferred from Fig. 9,
a combination of both Ludox CL and EOR-5XS NP dispersions with anionic surfactant improves the SFT
reduction obtained by only surfactant in all the surfactant concentrations studied. According to the data
in Fig. 9, this enhancement in SFT reduction is more pronounced at very low surfactant concentrations.
Furthermore, this enhanced effect to reduce SFT is stronger when the aqueous phase contains 2 wt. %
Ludox CL NP dispersion compared to when it contains 2 wt. % EOR-5XS NP dispersion. This will be more
investigated in the next section.

Figure 9—SFT at different concentrations of anionic surfactant (sodium alkane sulfonate) in the
absence and presence of either 2 wt. % EOR-5XS NP dispersion or 2 wt. % Ludox CL NP dispersion
SPE-190377-MS 13

IFT between heavy oil and aqueous phase was measured for the three systems pure 0.1 wt. % anionic
surfactant, mixture of 0.1 wt. % anionic surfactant and 2 wt. % Ludox CL NP dispersion, and mixture
of 0.1 wt. % anionic surfactant and 2 wt. % EOR-5XS NP dispersion. These chemical concentrations are
consistent with the concentrations used in batch mixing tests presented in Fig. 4 and 5. In the absence of
NP dispersion the initial IFT between heavy oil and DIW is 58.6 ± 0.9 mN/m which decreases to 50 mN/
m in the presence of only 0.1 wt. % anionic surfactant, which is higher than the threshold IFT for heavy oil

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emulsification in the presence of the used anionic surfactant (i.e., 30 mN/m). Therefore, there is no emulsion
in the presence of only 0.1 wt. % anionic surfactant (Fig. 4 and 5). In the absence of surfactant, addition
of 2 wt. % Ludox CL NP to DIW has no effect on IFT, while addition of 2 wt. % EOR-5XS NP has a
striking effect (Fig. 10). These results explain observations in the batch mixing tests: there is no mixing
of heavy oil with an aqueous phase due to the presence of only 2 wt. % Ludox CL NP dispersion (see
third vial from the left in Fig. 4), but in the presence of only 2 wt. % EOR-5XS NP dispersion heavy oil is
easily mixed with an aqueous phase (see third vial from the left in Fig. 5). The latter yields IFT of 29 ± 1
mN/m, which is lower than the threshold IFT, which should be met to emulsify heavy oil. In the cocktails
containing NP dispersions along with anionic surfactant, there is much more noteable change in IFT due to
the combined effect of Ludox CL NL dispersion along with anionic surfactant than that of EOR-5XS NP
dispersion. These results are qualitatively consistent with SFT data suggesting Ludox CL NP dispersion
can interact with anionic surfactant more efficiently than EOR-5XS NP dispersion. These interactions are
investigated in the next section.

Figure 10—IFT between Luseland heavy oil and different concentrations of anionic surfactant
(sodium alkane sulfonate) in the absence and presence of different NP dispersions

IFT in the presence of only 2 wt. % Ludox CL NP dispersion is 58 mN/m which declines to 40 mN/m
(31 % reduction in IFT) in the presence of 2 wt. % Ludox CL NP dispersion along with 0.1 wt. % anionic
surfactant. In this case, although there is 31 % reduction in IFT, the IFT is still higher than the threshold
value justifying no emulsification due to the combined effect of Ludox CL NP dispersion along with 0.1 wt.
% anionic surfactant (see Fig. 4 the rightmost vial). However, IFT in the presence of only 2 wt. % EOR-5XS
NP dispersion is 29 ± 1 mN/m which declines to 27 mN/m (7 % reduction in IFT) in the presence of 2 wt.
% EOR-5XS NP dispersion along with 0.1 wt. % anionic surfactant. As discussed, a cocktail of 2 wt. %
EOR-5XS NP dispersion and 0.1 wt. % surfactant produces a homogeneous/uniform mixture of heavy oil
with an aqueous phase (see Fig. 5 the rightmost vial), which is not observed in the presence of only 2 wt. %
14 SPE-190377-MS

EOR-5XS NP dispersion (see third vial from the left in Fig. 5). Keeping in mind these observations in batch
mixing experiments, IFT results suggest that a reduction in IFT values below the IFT threshold remarkably
affects heavy oil emulsification. The IFT between Luseland heavy oil and aqueous phase containing 0.1
wt. % sodium carbonate, in the absence of surfactant and NP dispersion, is 25 mN/m which is lower than
the IFT threshold explaining the emulsification observed in Fig. 6a. This alkaline-assisted IFT reduction
should be due to the reaction of alkaline with acidic components of heavy oil to form natural surfactant

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(soap), as widely reported previously (Farouq Ali, 2006). This effect may also contribute to the heavy oil
IFT reduction obtained by only 2 wt. % EOR-5XS NP dispersion with pH of 10.3. This speculation can
be supported by the fact that the only 2 wt. % EOR-5XS NP dispersion remarkably reduces heavy oil IFT
(51 %), which is notably larger than the reduction in SFT due to the effect of only 2 wt. % EOR-5XS NP
dispersion (3 %). The other possibilities to explain the remarkable effect of EOR-5XS NP dispersion to
reduce Luseland heavy oil IFT are the nature of surface treatment of these silica NPs or existence of EG in
NP dispersion, which are subjects to our future studies.

Mechanism explaining interactions between anionic surfactant and NP dispersions

Different authors suggested different mechanisms to explain the interactions between anionic surfactants
and either positively-charged or negatively-charged NP dispersions. Here we report the enhanced
interactions in systems containing anionic surfactant along with both positively-charged NP (Ludox CL
NP) and negatively-charged NP (EOR-5XS NP) dispersions, each one will be dealt with in the following
subsections.
Anionic surfactant + positively-charged Ludox CL NP dispersion. In previous studies, the combined
effect of positively-charged NPs along with different types of anionic surfactants has been reported. Cui et
al., reported an enhanced effect of positively-charged CaCO3 NP on the capability of anionic surfactant such
as SDS and Dioctyl sodium sulfosuccinate (Aerosol OT, AOT) to reduce SFT (Cui et al., 2010). They tried to
quantify the electrostatic attraction btween positivelycharged CaCO3 NP and anionic surfactants using zeta
potential analysis. They reported a decrease in absolute value of NPs zeta potential suggesting monolayer
adsorption of anionic surfactant molecules at the particle-water interface. They pointed out in the presence of
NPs there should be lower surfactant molecules available at the air-water interface compared to the particle-
free system. On the other hand, the hydrophilicity of particles decreases due to the monolayer adsorption
of anionic surfactants and surfactantcoated particles show more tendency to sit at the interface compared to
bare particles. It seems that there should be a competition between the amount of free surfactant available
at the interface and the number of partially-hydrophobized NPs capable of reaching the interface to reduce
interfacial tension. It seems that in Cui et al.,'s (Cui et al., 2010) work the presence of NPs at the interface
is more prominent in reducing IFT compared to the amount of free surfactant molecules at the interface.
This is also reported by Moghadam and Azizian (Moghadam and Azizian, 2014). Based on their results,
anionic surfactant (SDS) adsorption on the surface of positively-charged ZnO NP and the resultant decrease
in NPs hydrophilicity provides a driving force for migration of NPs to the interface further enhancing the
capability of SDS to reduce IFT between water and n-decane.
Contrary to the results presented by Cui et al., (Cui et al., 2010) and Moghadam and Azizian (Moghadam
and Azizian, 2014), it seems that in the Sun et al.,'s (Sun et al., 2015) work the presence of free SDS
molecules at the interface is more efficient than the presence of SDS-coated NPs to reduce SFT. In Sun
et al.,'s work (Sun et al., 2015), at SDS concentrations above 0.01 wt. %, SFT in the presence of both
surfacemodified silica NPs (1 wt. %) and SDS is higher than that of pure SDS solutions. They attributed this
increase in SFT to the depletion of interface from free surfactant being replaced by SDS-coated NPs due to
the excessive adsorption of SDS molecules on the surface of NPs. In this case, SDS molecules are adsorbed
on the surface of positively-charged partially hydrophobic silica NPs through hydrophobic interaction. At
SDS concentrations lower than 0.01 wt. %, SFT is lower in a system containing SDS and 1 wt. % surface-
SPE-190377-MS 15

modified silica NP compared to the system containing pure SDS. They did not mention anything to explain
this enhanced SFT reduction due to the combination of SDS and NPs. Based on their results, at these SDS
concentrations, specifically smaller than 0.003 wt. %, there is no notable change in zeta potential of silica
NP indicating lack of electrostatic attraction between SDS and positively-charged NPs.
In this regard, Saien and Bahrami reported 16 % reduction in IFT between n-hexane and water due to
the effect of 0.01 wt. % surface-modified silica NP (11 – 14 nm) in the absence of surfactant (Saien and

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Bahrami, 2016). They concluded that surface-modified silica NPs with long alkyl chains on their surface are
less hydrophilic and can migrate towards the interface to reduce IFT. They also reported an enhancement
in IFT reduction due to the combined effect of 0.01 wt. % surface-modified silica NP along with SDS.
They hypothesized that SDS molecules can adsorb on the surface of hydrophobic NPs through hydrophobic
tail interaction to leave the hydrophilic head of surfactant molecules pointed outwards. This combination
tends to diffuse into n-hexane-water interface more than hydrophobic NPs and so the IFT is further reduced
compared to the system containing only either NP or SDS (Saien and Bahrami, 2016).
In the discussed studies, the authors tried to attribute the combined effect of NPs and surfactants to
enhance IFT reduction to the number of NPs, NP-coated surfactant molecules, or free surfactant molecules
at the interface in the cocktail compared to pure systems (containing only NP or surfactant) and the relative
importance of surfactant-coated NPs compared to only NP or free surfactant as surface-active agents. We
used different techniques to quantify the amount of anionic surfactant and positively-charged Ludox CL
NP in solution to understand the remarkable NP-assisted enhancement in efficiency of anionic surfactant
to further reduce SFT/IFT. As shown in Fig. 9, this enhanced effect is maximum in a system containing
2 wt. % Ludox CL NP and 0.01 wt. % anionic surfactant yielding 42 % reduction in SFT compared to
the pure 0.01 wt. % anionic surfactant. NP hydrodynamic diameter and zeta potential in the presence of
different concentraions of anionic surfactant were measured (Fig. 11). Zeta potential of Ludox CL NP (2
wt. %) in the absence of surfactant is + 43 mV, which agrees with literature value for the same particles
(Binks and Rodrigues, 2007). As shown in Fig. 11, zeta potential of NP dispersion in the presence of
different concentrations of anionic surfactant does not significantly change, indicating a lack of electrostatic
attraction between NPs and surfactant molecules even with opposite charges. In addition, there was no NP
precipitation in the presence of different surfactant concentrations even after 7 days. This Ludox CL NP
stability in the presence of anionic surfactant is resulted from high enough zeta potential of NPs providing
sufficient repulsion between colloiding NPs of similar charge in solution. However, size of Ludox CL NP
increases at 0.1 wt. % an anionic surfactant indicating some degrees of NP flocculation at this surfactant
concentration. At this surfactant concentration, there was also no visual NP precipitation.

Figure 11—Zeta potential and hydrodynamic diameter of Ludox CL NP at

different concentrations of anionic surfactant (sodium alkane sulfonate)
16 SPE-190377-MS

To further confirm NP stability in solution, ICP-MS was used to measure the amount of Ludox CL NP
in a mixture of Ludox CL NP and anionic surfactant. Since Ludox CL NP is an alumina-coated silica NP,
we tracked Si and Al. As shown in Fig. 12, the amount of Al and Si seems to be approximately constant
at different anionic surfactant concentrations. These results along with zeta potential analysis indicate the
stability of Ludox CL NP in the presence of anionic surfactants at the concentrations studies.

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Figure 12—ICP-MS elemental (Si and Al) analysis of Ludox CL NP dispersion
at different concentrations of anionic surfactant (sodium alkane sulfonate)

Since the amount of Ludox CL NP in solutions of different surfactant concentrations and possibly at the
air-water interface is approximately similar, the reduction observed in SFT due to the combined effect of
Ludox CL NP and anionic surfactant should not be due to the effect of NPs alone. To further understand this
effect, the amount of Sulphur, as a componet of anionic surfactant (sodium alkane sulfonate), was tracked
in two systems: pure surfactant solutions and mixture of surfactant and 2 wt. % Ludox CL NP dispersion.
As shown in Fig. 13, the amount of Sulphur is approximately unchanged up to 0.01 wt. % anionic surfactant
concentrations. However, at higher surfactant concentrations it seems that higher amount of surfactant was
detected in the presence of NP, equivalently as if there is higher surfactant concentration in the system.
Further understanding of this observation is subject to our future studies.

Figure 13—ICP-MS elemental (Sulphur) analysis of different concentrations of anionic surfactant

(sodium alkane sulfonate) in the absence and presence of 2 wt. % Ludox CL NP dispersion
SPE-190377-MS 17

Although these results fail to explain the remarkable reduction in SFT due to the combined effect of
Ludox CL NP dispersion and low concentrations of anionic surfactant (≤ 0.01 wt. %), they provide some
explanation for the enhanced SFT and IFT reduction at surfactant concentrations higher than 0.05 wt. %
(Fig 9 and 10). This effect was also reported elsewhere (Binks and Rodrigues, 2007), where remarkable
enhancement in n-dodecane in water emulsion stability (for 6 months) was reported due to the combined
effect of the same NP as we used here and anionic surfactant (SDS). They also reported the emulsions

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prepared with only 2 wt. % Ludox CL NP dispersion broke within several minutes. They did not measure
IFT, and although they used different anionic surfactant from what we used here, the IFT data presented here
may explain their emulsification behavior: i.e., no SFT/IFT reduction due to the effect of only Ludox CL
NP, while enhancement in tension reduction in system containing both Ludox CL NP and anionic surfactant.
Anionic surfactant + negatively-charged EOR-5XS NP dispersion. As shown in Fig 9 and 10, IFT
and SFT is further reduced due to the combined effect of EOR-5XS NP dispersion and anionic surfactant
compared to when there is only either EOR-5XS NP dispersion or anionic surfactant. Zeta potential of 2
wt. % EOR-5XS NP dispersion alone is – 35 mV. So, one possible mechanism can be repulsive interactions
between NPs and anionic surfactants to deplete the bulk from surfactant molecules pushed back to the air-
water or heavy oil-water interface, as if higher concentrations of surfactant exist in the system to further
reduce SFT and IFT. This mechanism to explain the combined effect of negatively-charged NPs along with
anionic surfactants to enhance surfactant capability to reduce SFT/IFT has been previously reported (Ahualli
et al., 2011; Biswal et al., 2016; Ma et al., 2008; Moghadam and Azizian, 2014; Zargartalebi et al., 2015).
This effect was reported at surfactant concentrations well below CMC (Biswal et al., 2016; Ahualli et al.,
2011; Ma et al., 2008; Vatanparast et al., 2017; Zargartalebi et al., 2015), which agrees with our results. At
higher surfactant concentrations, it seems that the interface is already saturated with surfactant molecules
and there is no enhanced interaction between NPs and surfactant molecules. To investigate the possibility of
this mechanism in our system, the amount of Sulphur, as a componet of anionic surfactant (sodium alkane
sulfonate), is measured in two systems: pure surfactant solutions and mixture of surfactant and 2 wt. %
EOR-5XS NP dispersion (Fig. 14). As shown in Fig. 14, the amount of Sulphur in the presence of EOR-5XS
NP is higher than that in the pure surfactant solutions, confirming the possible repulsive interactions between
negatively-charged silica NPs and anionic surfactant to force surfactant molecules migrating towards the
interface enhancing SFT/IFT reduction.

Figure 14—ICP-MS elemental (Sulphur) analysis of different concentrations of anionic surfactant

(sodium alkane sulfonate) in the absence and presence of 2 wt. % EOR-5XS NP dispersion
18 SPE-190377-MS

Conclusions
Batch-mixing experiments show that in the absence of NPs, concentration of both anionic (sodium alkane
sulfonate, with CMC between 1 and 1.5 wt. %) and cationic (dodecyl trimethyl ammonium bromide, with
CMC between 0.3 and 0.4 wt. %) surfactants should be tuned at the very narrow window, near CMC, to
obtain stable (minimum 24 hrs) emulsions. Higher surfactant concentrations yield complete phase separation
24 hours after preparation. This is true for the systems containing both Luseland heavy oil and dodecane.

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Maintaining surfactant concentrations at the CMC during surfactant flood is neither costeffective nor
practical due to the surfactant adsorption/loss during flow in porous medium. I n the presence of negatively-
charged surface-modified silica NP, heavy oil in water emulsification is achieved at much lower surfactant
concentrations (0.1 wt. %).
In the absence of NP dispersion, the IFT between Luseland heavy oil and an aqueous phase decreases to a
minimum at the CMC. IFT increases with a further increase in surfactant concentrations above CMC. This is
also observed in a system containing dodecane having a minimum/negative IFT at the CMC, facilitating easy
emulsification. In the presence of negatively-charged surface-modified silica NPs and only 0.1 wt. % anionic
surfactant, the IFT between heavy oil and an aqueous phase is remarkably (54 %) reduced, explaining
the enhanced emulsification behavior observed in batch-mixing experiments. The repulsive interactions
between negatively-charged NPs and anionic surfactant to force surfactant molecules migrating from the
bulk towards the oil-water interface, as if there is a higher number of surfactant molecules at the interface,
may be the reason behind the NP-assisted IFT reduction. In the presence of positively-charged surface-
modified silica NPs and 0.1 wt. % anionic surfactant, although IFT is also notably reduced (32 %) it is still
higher than the threshold required for heavy oil emulsification, justifying why no heavy oil emulsification
was observed in this system.

Acknowledgements
Support for this research came from the Canada Excellence Research Chair program in Materials
Engineering for Unconventional Reservoirs. The authors gratefully acknowledge the financial support of
the FUR program from NSERC, AITF, and the sponsoring companies: Athabasca Oil Corporation, Devon
Canada, Foundation CMG, Husky Energy, Brion Energy, Canadian Natural, Suncor Energy, as well as the
Schulich School of Engineering (University of Calgary).

References
Adam, N. K. (1938). The Physics and Chemistry of Surfaces, 2nd Edition, pp. 113,115. Oxford, University Press, London.
Aguiar, J., Carpena, P., Molina-Bolıvar, J. A., Ruiz, C. C. (2003). On the determination of the critical micelle concentration
by the pyrene 1: 3 ratio method. Journal of Colloid and Interface Science, 258 (1), 116-122.
Ahualli, S., Iglesias, G. R., Wachter, W., Dulle, M., Minami, D., Glatter, O. (2011). Adsorption of anionic and cationic
surfactants on anionic colloids: supercharging and destabilization. Langmuir, 27, 9182–9192.
Aminzadeh, B., Hoang, V., Inouye, A., Izgec, O., Walker, D., Chung, D., Dwarakanath, V. (2016). Improving Recovery
of a Viscous Oil Using Optimized Emulsion Viscosity. SPE 179698 presented at the SPE Improved Oil Recovery
Conference held in Tulsa, Oklahoma, USA, 11-13 April.
Arab, D., Kantzas, A., Bryant, S. L. (2018a). Nanoparticle-enhanced Surfactant Floods to Unlock Heavy Oil, SPE 190212
will be presented at the SPE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, USA, 14-18 April.
Arab, D., Kantzas, A., Bryant, S. L. (2018b). Nanoparticle stabilized oil in water emulsions: A critical review. Journal of
Petroleum Science and Engineering, 163, 217–242 https://doi.org/10.1016/j.petrol.2017.12.091.
Aronson, M. P. (1989). The role of free surfactant in destabilizing oil-in-water emulsions. Langmuir, 5(2), 494-501.
Aronson, M. P. (1991). Flocculation of Emulsions by Free Surfactant in Purified Systems. Colloids and Surfaces. 58,
195-202.
Ashraf, U., Chat, O. A., Maswal, M., Jabeen, S., Dar, A. A. (2015). An investigation of Pluronic P123–sodium cholate
mixed system: micellization, gelation and encapsulation behavior. RSC Advances, 5 (102), 83608-83618.
Ashrafizadeh, S. N., Motaee, E., Hoshyargar, V. (2012). Emulsification of heavy crude oil in water by natural surfactants.
Journal of Petroleum Science and Engineering, 86, 137-143.
SPE-190377-MS 19

Atkinson, I. (2004). Interfacial phenomena and phase behavior using alkali-surfactant-polymer enhanced recovery
methods in medium and heavy crude oils, MSc. Thesis, University of Calgary, Canada, pg. 122.
Barnes, J. R., Smit, J., Smit, J., Shpakoff, G., Raney, K. H., Puerto, M. (2008). Development of surfactants for chemical
flooding at difficult reservoir conditions. SPE 113313 presented at the SPE Symposium on Improved Oil Recovery,
Tulsa, Oklahoma, USA, 20-23 April.
Bera, A., Kumar, T., Ojha, K., Mandal, A. (2014). Screening of microemulsion properties for application in enhanced oil
recovery. Fuel, 121, 198-207.
Bialké, J., Siebert, J. T., Löwen, H., Speck, T. (2015). Negative Interfacial Tension in phase-separated active brownian

Downloaded from http://onepetro.org/SPEOGWA/proceedings-pdf/18OGWA/2-18OGWA/D022S002R002/1239617/spe-190377-ms.pdf/1 by University of Calgary user on 26 January 2023

particles. Physical review letters, 115 (9), 098301.
Binks, B. P., Rodrigues, J. A. (2007). Enhanced stabilization of emulsions due to surfactant-induced nanoparticle
flocculation. Langmuir, 23, 7436-7439.
Binks, B. P., Rodrigues, J. A., Frith, W. J. (2007). Synergistic interaction in emulsions stabilized by a mixture of silica
nanoparticles and cationic surfactant. Langmuir, 23 (14), 3626–36.
Binks, B. P., Rodrigues, J. A. (2007). Enhanced stabilization of emulsions due to surfactant-induced nanoparticle
flocculation. Langmuir, 23, 7436-7439.
Biswal, N. R., Rangera, N., Singh, J. K. (2016). Effect of different surfactants on the interfacial behavior of the n-hexane–
water system in the presence of silica nanoparticles. The Journal of Physical Chemistry B, 120, 7265–7274.
Bryan, J., Kantzas, A. (2007). Enhanced Heavy-Oil Recovery by Alkali-Surfactant Flooding. SPE 110738 presented at
the SPE Annual Technical Conference and Exhibition held in Anaheim, California, 11-14 Nov.
Chen, L., Zhang, G., Ge, J., Jiang, P., Tang, J., Liu, Y. (2013). Research of the heavy oil displacement mechanism by using
alkaline/surfactant flooding system. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 434, 63-71.
Clayton, W.: The Theory of Emulsions and their Technical Treatment, 4th Edition, pp. 6-12, 53-55. The Blaliiston Co.,
Philadelphia (1943).
Cockbain, E. G. (1952). Trans. Farad. Soc. 48, 185.
Cui, Z. G., Cui, Y. Z., Cui, C. F., Chen, Z., Binks, B. P. (2010). Aqueous foams stabilized by in situ surface activation of
CaCO3 nanoparticles via adsorption of anionic surfactant. Langmuir, 26 (15), 12567–12574.
Davies, J. T., Rideal, E. K. (1963). Interfacial Phenomena. 2nd edition, Academic Press, New York.
Fairhurst, D., Aronson, M. P., Ohm, M. L., Goddard, E. D. (1983). Some comments on non-ionic surfactant concentration
effects in oil-in-water emulsions. Colloids and Surfaces, 7(2), 153-159.
Farouq Ali, S. M. (2006). Practical heavy oil recovery.
Hirasaki, G. J., Miller, C. A., Puerto, M. (2008). Recent Advances in Surfactant EOR. SPE 115386 presented at the SPE
Annual Technical Conference and Exhibition, Denver, 21-24 September.
Horozov, T. S., Binks, B. P. (2006). Particle-stabilized emulsions: A bilayer or a bridging monolayer?. Angewandte
Chemie, 118, 787-790.
IS0 4311-1979 (E). Anionic and non-ionic surface active agents - Determination of the critical micellization concentration
- Method by measuring surface tension with a plate, stirrup or ring (1st edition, 1979/06/01).
Kamal, M. S., Hussein, I. A., Sultan, A. S. (2017). Review on Surfactant Flooding: Phase Behavior, Retention, IFT, and
Field Applications. Energy & Fuels, 31(8), 7701-7720.
Kaptay, G. (2017). On the negative surface tension of solutions and on spontaneous emulsification. Langmuir, 33 (40),
10550-10560.
Kim, I., Worthen, A. J., Lotfollahi, M., Johnston, K. P., DiCarlo, A., Huh, C. (2016a). Nanoparticle-Stabilized Emulsions
for Improved Mobility Control for Adverse-Mobility Waterflooding. SPE-179644-MS presented at the SPE Improved
Oil Recovery Conference held in Tulsa, Oklahoma, USA, 11–13 April.
Kim, I., Worthen, A. J., Johnston, K. P., DiCarlo, D. A., Huh, C. (2016b). Size-dependent properties of silica
nanoparticles for Pickering stabilization of emulsions and foams. Journal of Nanoparticle Research, 18 (4), 1–12.
http://doi.org/10.1007/s11051-016-3395-0.
Kimball, A. L. (1917). Negative Surface Tension. Science, 45 (1152), 85-87.
Kaminski, A., McBain, J. W. (1949). Spontaneous Emulsification of Pure Xylene in an Aqueous Solution through Mere
Adsorption of a Detergent in the Interface. In Proceedings of the Royal Society of London A: Mathematical, Physical
and Engineering Sciences (Vol. 198, No. 1055, pp. 447-454). The Royal Society.
Lan, Q., Yang, F., Zhang, S., Liu, S., Xu, J., Sun, D. (2007). Synergistic effect of silica nanoparticle and cetyltrimethyl
ammonium bromide on the stabilization of O/W emulsions. Colloids and Surfaces A: Physicochem. Eng. Aspects,
302, 126–135.
Lee, L. H. (1999). Relevance of film pressures to interfacial tension, miscibility of liquids, and Lewis acid–base approach.
Journal of colloid and interface science, 214 (1), 64-78.
20 SPE-190377-MS

Lopez, F., Cinelli, G., Ambrosone, L., Colafemmina, G., Ceglie, A., Palazzo, G. (2004). Role of the cosurfactant in
water-in-oil microemulsion: interfacial properties tune the enzymatic activity of lipase. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 237(1), 49-59.
Liu, Q., Dong, M., Ma, S., Tu, Y. (2007). Surfactant enhanced alkaline flooding for Western Canadian heavy oil recovery.
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 293 (1), 63-71.
Ma, H., Luo, M., Dai, L. L. (2008). Influences of surfactant and nanoparticle assembly on effective interfacial tensions.
Phys. Chem. Chem. Phys., 10, 2207–2213.
Mai, A., Bryan, J., Goodarzi, N., Kantzas, A. (2009). Insights into non-thermal recovery of heavy oil. Journal of Canadian

Downloaded from http://onepetro.org/SPEOGWA/proceedings-pdf/18OGWA/2-18OGWA/D022S002R002/1239617/spe-190377-ms.pdf/1 by University of Calgary user on 26 January 2023

Petroleum Technology, 48 (03), 27-35.
Manrique, E. J., Muci, V. E., Gurfinkel, M. E. (2007). EOR field experiences in carbonate reservoirs in the United States.
SPE Reservoir Evaluation & Engineering, 10(06), 667-686.
Martin, F. D., Oxley, J. C. (1985). Effect of various alkaline chemicals on phase behavior of surfactant/brine/oil mixtures.
Presented at the SPE International Symposium on Oilfield and Geothermal Chemistry held in Phoenix, Arizona, April
9-11.
Miller, C. A., Hwan, R. N., Benton, W. J., Fort, T. (1977). Ultralow interfacial tensions and their relation to phase separation
in micellar solutions. Journal of Colloid and Interface Science, 61 (3), 554-568.
Miles, G. D., Shedlovsky, L. (1944). Minima in Surface Tension–Concentration Curves of Solutions of Sodium Alcohol
Sulfates. The journal of physical chemistry, 48 (1), 57-62.
Moghadam, T., Azizian, S. (2014). Effect of ZnO nanoparticles on the interfacial behavior of anionic surfactant at liquid/
liquid interfaces. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 457, 333–339.
Olajire, A. A. (2014). Review of ASP EOR (alkaline surfactant polymer enhanced oil recovery) technology in the
petroleum industry: Prospects and challenges. Energy, 77, 963-982.
Patist, A., Bhagwat, S. S., Penfield, K. W., Aikens, P., Shah, D. O. (2000). On the measurement of critical micelle
concentrations of pure and technical-grade nonionic surfactants. Journal of Surfactants and Detergents, 3 (1), 53-58.
Patashinski, A. Z., Orlik, R., Paclawski, K., Ratner, M. A., Grzybowski, B. A. (2012). The unstable and expanding interface
between reacting liquids: theoretical interpretation of negative surface tension. Soft Matter, 8 (5), 1601-1608.
Pal, R. (1993). Rheological behaviour of surfactant-flocculated water-in-oil emulsions. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 71(2), 173-185.
Powney, J., Addison, C. C. (1937). The properties of detergent solutions. Transactions of the Faraday Society, 33,
1243-1260.
Rodriguez, A. M. B., Binks, B. P., Sekine, T. (2016). Novel stabilisation of emulsions by soft particles: polyelectrolyte
complexes. Faraday discussions, 191, 255-285.
Prince, L. M. (1967). A theory of aqueous emulsions I. Negative interfacial tension at the oil/water interface. Journal of
Colloid And Interface Science, 23 (2), 165-173.
Prince, L. M. (1969). A theory of aqueous emulsions: II. Mechanism of film curvature at the oil/water interface. Journal
of colloid and interface science, 29 (2), 216-221.
Saien, J., Bahrami, M. (2016). Understanding the effect of different size silica nanoparticles and SDS surfactant mixtures
on interfacial tension of n-hexane–water. Journal of Molecular Liquids, 224, 158–164.
Salehi, M. M., Safarzadeh, M. A., Sahraei, E., Nejad, S. A. T. (2014). Comparison of oil removal in surfactant alternating
gas with water alternating gas, water flooding and gas flooding in secondary oil recovery process. Journal of Petroleum
Science and Engineering, 120, 86-93.
Schulman, J. H., Montagne, J. B. (1961). Formation of microemulsions by amino alkyl alcohols. Annals of the New York
Academy of Sciences, 92 (1), 366-371.
Sharma, M. K., Shah, D. O. (1985). Introduction to macro-and microemulsions. American Chemical Society Symposium
Series: Washington, DC.
Shah, D. O., Tamjeedi, A., Falco, J. W., Walker, R. D. (1972). Interfacial instability and spontaneous formation of
microemulsions. AIChE Journal, 18 (6), 1116-1120.
Sharma, M. K., Shah, D. O. (1985). Introduction to macro and microemulsions, theory and applications. ACS Symposium
Series, 1–18.
Sahni, V., Dean, R. M., Britton, C., Kim, D. H., Weerasooriya, U., Pope, G. A. (2010). The role of co-solvents and co-
surfactants in making chemical floods robust. SPE 130007 presented at the SPE Improved Oil Recovery Symposium
held in Tulsa, Oklahoma, USA, 24-28 April.
Solans, C., Morales, D., Homs, M. (2016). Spontaneous emulsification. Current Opinion in Colloid & Interface Science,
22, 88-93.
Sun, Q., Li, Z, Wang J., Li, S., Li, B., Jiang, L., Wang, H., Lü, Q., Zhang, Ch., Liu, W. (2015). Aqueous foam stabilized
by partially hydrophobic nanoparticles in the presence of surfactant. Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 471, 54–64.
SPE-190377-MS 21

Vatanparast, H., Samiee, A., Bahramian, A., Javadi, A. (2017). Surface behavior of hydrophilic silica nanoparticle-SDS
surfactant solutions: I. Effect of nanoparticle concentration on foamability and foam stability. Colloids and Surfaces
A: Physicochem. Eng. Aspects, 513, 430–441.
Xu, K., Zhu, P., Tatiana, C., Huh, C., Balhoff, M. (2016). A Microfluidic Investigation of the Synergistic Effect of
Nanoparticles and Surfactants in Macro-Emulsion Based EOR. SPE-179691-MS presented at the SPE Improved Oil
Recovery Conference held in Tulsa, Oklahoma, 11–13 April.
Zargartalebi, M., Kharrat, R., Barati, N. (2015). Enhancement of surfactant flooding performance by the use of silica
nanoparticles. Fuel, 143, 21–27.

Downloaded from http://onepetro.org/SPEOGWA/proceedings-pdf/18OGWA/2-18OGWA/D022S002R002/1239617/spe-190377-ms.pdf/1 by University of Calgary user on 26 January 2023

Zeppieri, S., Rodríguez, J., López de Ramos, A. L. (2001). Interfacial tension of alkane+ water systems. Journal of
Chemical & Engineering Data, 46 (5), 1086-1088.