Industrial Crops and Products 43 (2013) 6–14
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Industrial Crops and Products
journal homepage: www.elsevier.com/locate/indcrop
Formulation, optimization and application of triglyceride microemulsion
in enhanced oil recovery
Z. Jeirani a , B. Mohamed Jan a,∗ , B. Si Ali a , I.M. Noor a , C.H. See b , W. Saphanuchart b
a
b
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
BCI Chemical Corporation Sdn. Bhd., Lot 7, Jalan BS 7/22, Taman Perindustrian Bukit Serdang, Seksyen 7, 43300 Seri Kembangan, Selangor Darul Ehsan, Malaysia
a r t i c l e
i n f o
Article history:
Received 24 April 2012
Received in revised form 3 July 2012
Accepted 3 July 2012
Keywords:
Microemulsion
Enhanced oil recovery
Chemical flooding
Palm oil
Triglyceride
a b s t r a c t
This paper presents the determination of an aqueous phase composition of a new triglyceride microemulsion in which the triglycerides constitute the whole oil-phase of the microemulsion. Palm oil was used
as the oil phase of the microemulsion. Experimental results indicate that the optimum triglyceride
microemulsion was achieved when equal mass of palm oil and the aqueous phase containing 3 wt%
sodium chloride, 1 wt% alkyl polyglycosides, 3 wt% glyceryl monooleate, and 93 wt% de-ionized water
were mixed. The formulated composition of the aqueous phase was able to form translucent Winsor
Type I microemulsion with palm oil at ambient conditions. The measured interfacial tension between
the optimum microemulsion and the model oil, which is n-octane in this study, was 0.0002 mN/m. The
maximum tertiary oil recovery of 71.8% was achieved after the injection of the optimum microemulsion
formulation to a sand pack. The significant increase in total oil recovery (87%) suggests the effectiveness of the triglyceride microemulsion formulation for enhanced oil recovery. Its capability in recovering
additional oil (4.3% of the trapped oil after water flooding) compared to a typical polymer in tertiary oil
recovery indicates the efficiency of the optimum triglyceride microemulsion formulation.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction
Chemical flooding, one of the most successful techniques to
enhance oil recovery (Austad and Milter, 2000), involves the injection of a chemical to displace the oil remaining in the reservoir after
waterflooding. Microemulsion is one type of formulation, which
consists of oil, water, and an amphiphile mixture (Paul and Moulik,
2001). Amphiphile is a substance containing both hydrophilic and
hydrophobic parts in its molecular structure. Surfactants and cosurfactants are two examples of amphiphiles. Microemulsion has
been used in tertiary oil recovery since the 1970s (Putz et al.,
1981; Purwono and Murachman, 2001; Bouabboune et al., 2006;
Santanna et al., 2009). A microemulsion slug mobilizes the remaining oil by reducing the interfacial tension (IFT) between oil and
Abbreviations: APG, alkyl polyglycoside; NaCl, sodium chloride; IPA, isopropyl
alcohol; IBA, isobutyl alcohol; NBA, normal butyl alcohol; FA8, fatty alcohol C8;
FA810, fatty alcohol C8/C10; FA1214, fatty alcohol C12/C14; SA, stearyl alcohol; CA,
cetyl alcohol; EGEE, ethylene glycol mono-ethyl ether; TWN20, Tween20; TWN80,
Tween80; GLY, glycerol; SM, sorbitan monooleate; GM, glyceryl monooleate; SAP,
saponin; GC, gas chromatography; FID, flame ionization detector; IFT, interfacial
tension; PIT, phase inversion temperature; CMC, critical micelle concentration;
HLB, hydrophilic–lipophilic balance; PV, pore volume; IOIP, initial oil in place; wt%,
weight percent.
∗ Corresponding author. Tel.: +60 379676869; fax: +60 379675319.
E-mail address: [email protected] (B. Mohamed Jan).
0926-6690/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.indcrop.2012.07.002
water. Microemulsion flooding has been conducted in two distinct
ways. In the first method, a microemulsion system is prepared by
mixing water, oil, and amphiphile(s) on the surface prior to its injection (Putz et al., 1981; Santanna et al., 2009). In the second method,
a microemulsion slug is prepared in the porous media from the formation brine, residual oil, and the injected amphiphile and water
(Zhao et al., 2008; Wang et al., 2010).
In the 1980s chemical flooding was considered uneconomical due to low oil price, which caused a major halt in scientific
publications. On the other hand, in 1990 researchers started to
embark on chemical flooding due to the higher oil prices accompanied with the first gulf war. However, at that time microemulsion
flooding was not considered as a common chemical flooding.
Only recently numerous researchers have started conducting tests
to improve microemulsion flooding efficiency by modifying the
existing microemulsions in the market or developing a new
microemulsion (Iglauer et al., 2009; Wu et al., 2010).
It is evident that altering the chemical nature or amount of
any component in a microemulsion may result in drastic changes
in the IFT, type of microemulsion, and amount of the recovered
oil (Kahlweit et al., 1995a; Sottmann and Strey, 1997; Sottmann
and Stubenrauch, 2009). New microemulsions were formulated
to enhance oil recovery by altering the surfactants and/or cosurfactants (Wang et al., 2010; Iglauer et al., 2010a,b); however, the
oil-component in the microemulsion prepared on the surface plays
an important role not only in the cost of microemulsion preparation
Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
but also in the efficiency of the microemulsion flooding due to
changes in the IFT. Some researchers in literature used a specific
crude oil or a fraction of petroleum such as n-octane as the oil phase
of the microemulsion (Putz et al., 1981; Bouabboune et al., 2006).
Despite extensive attempts made on the formulation of
microemulsions with n-alkane or hydrocarbons, there is another
attractive option; using triglycerides for the oil phase of the
microemulsion. It is not a very common practice in enhanced oil
recovery because microemulsions have typically been prepared
in situ from the injected chemical slug and the remaining oil
in the reservoir. However, microemulsions can be prepared outside before the injection and the oil component of the prepared
microemulsion can be either hydrocarbons or triglycerides. The
application of a triglyceride microemulsion in tertiary oil recovery was once tested by Santanna et al. (2009) with the use of pine
oil (a kind of vegetable oil) as the oil phase of a microemulsion.
A great number of triglyceride-based microemulsion formulations have also been carried out in the last decades in
applications other than enhanced oil recovery (Kunieda et al., 1988;
Joubran et al., 1993; Kahlweit et al., 1995a,b; Hecke et al., 2003;
Komesvarakul et al., 2006; Engelskirchen et al., 2007; Do et al.,
2009; Fanun, 2010; Phan et al., 2011). Triglycerides are esters of
glycerol and three fatty acids. Triglycerides are the major components of palm oil. Triglycerides in palm oil are a mixture of
mono-unsaturated, poly-unsaturated, and saturated triglycerides.
Compared to n-alkane oil, saturated triglycerides are among the
hardest oil to microemulsify since saturated triglyceride molecules
have a bulky polar head and three long hydrocarbon chains (Phan
et al., 2011). Therefore, the presence of unsaturated triglycerides in
palm oil reduces the possibility of forming microemulsion. However, if an effective surfactant and a suitable co-surfactant are
selected in the microemulsion formulation, an efficient triglyceride
microemulsion with low to ultra-low interfacial tensions and a high
solubilization parameter could be achieved easily. Various types
of surfactants and co-surfactants such as alcohols were used to
formulate triglyceride microemulsions in the literature (Kunieda
et al., 1988; Joubran et al., 1993; Kahlweit et al., 1995a,b; Hecke
et al., 2003; Komesvarakul et al., 2006; Engelskirchen et al., 2007;
Do et al., 2009; Fanun, 2010; Phan et al., 2011).
The main objective of this paper is to formulate an efficient
triglyceride microemulsion on the surface to improve oil production in a tertiary recovery process after its injection. Alkyl
polyglycosides were used as the surfactant of the triglyceride
microemulsion. In this paper, an attempt has been made to screen
and select the most effective co-surfactant from various kinds of cosurfactants such as alcohols and non-ionic surfactants. The highest
cumulative tertiary oil recovery and the lowest interfacial tension between the formulated microemulsion and the model oil
are the two essential criteria considered in the selection of the cosurfactant. After the co-surfactant screening, the composition of the
aqueous phase of the triglyceride microemulsion was optimized
to ensure minimum interfacial tension and maximum cumulative
tertiary oil recovery are achieved. Finally, the efficiency of the optimum triglyceride microemulsion formulation was compared to a
common commercial polymer solution in tertiary oil recovery by
conducting a sand pack flooding. In all these steps, the type of
the formulated triglyceride microemulsions used is Winsor Type
I microemulsion, which exists in equilibrium with the excess palm
oil.
2. Experimental tests
2.1. Materials
The surfactant used in this work was Glucopon 650EC, a mixture of alkyl polyglycosides (APGs) having an average alkyl chain
7
Table 1
Some properties of the palm kernel oil.
Composition (wt%)
Monounsaturated fat
Polyunsaturated fat
Saturated fat
Density (g/ml)
Viscosity (cP)
43.33
12.22
44.45
0.8142
65.39
length of 11, hydrophilic–lipophilic balance (HLB) of 11.9, and critical micelle concentration (CMC) of 0.073 g/L at 37 ◦ C (Jurado et al.,
2007). It was provided by Cognis (Malaysia) Sdn. Bhd. which is
now part of BASF Chemical Company. The active percentage of the
surfactant solution is 50–53 wt%.
Sodium chloride (NaCl, A.R. grade) and lower alkanols such as
isopropyl alcohol (IPA), isobutyl alcohol (IBA), and normal butyl
alcohol (NBA) were supplied by LGC Scientific, Malaysia. In addition, fatty alcohol C8 (FA8), fatty alcohol C8/C10 (FA810), fatty
alcohol C12/C14 (FA1214), stearyl alcohol (SA), cetyl alcohol (CA),
and ethylene glycol mono-ethyl ether (EGEE) were provided by BCI
Chemical Corporation Sdn. Bhd. Furthermore, n-octane, Tween20
(TWN20), Tween80 (TWN80), glycerol (GLY), sorbitan monooleate
(SM), glyceryl monooleate (GM), and saponin (SAP) were supplied
by Sigma–Aldrich. Palm kernel oil was purchased from Delima Oil
Products Sdn. Bhd. in Malaysia. Some properties of the palm kernel oil are tabulated in Table 1. All of the materials were used as
supplied without further purification.
2.2. Triglyceride microemulsion preparation
A triglyceride microemulsion was prepared by mixing 230 g
of the oil phase with 230 g of the aqueous phase. The aqueous
phase comprised surfactant, co-surfactant, sodium chloride, and
de-ionized water at various compositions. The oil phase was pure
palm oil. After adding all the components at their desired fractions,
the sample was shaken with orbital shaking motion. Lab Companion SI-300 Benchtop Shaker at low shaking frequency of 100 rpm
was used to avoid the appearance of emulsion phase. The triglyceride microemulsion sample was shaken for at least an hour to
ensure a well-mixed and uniform mixture because of quite low
aqueous solubility of APG, low frequency of mixing, and the relatively large volume of the samples. The sample was then poured
into a separating funnel and left undisturbed for at least one week
for equilibrium. Since palm oil is a natural component, to avoid the
possibility of degradation, sample bottles used during the mixing
were sealed with Viton lined screw caps. In addition, separating
funnels used in the resting step were sealed with tight lubricated
Teflon stopper. The microemulsion phase formed after the equilibrium was Winsor Type I or lower phase microemulsion. Then the
microemulsion phase was separated from the upper (excess oil)
phase in the separating funnel and was used in the next measurements.
2.3. Methodology of IFT measurements
Prior to IFT measurements, the density or specific gravity of
both the light and heavy phases was determined. The heavy phase
was a microemulsion, which is prepared based on the aforementioned methodology and separated from the excess oil phase. The
light phase was n-octane, which represents the crude oil in reservoirs (Green and Willhite, 1998). In density measurements, about
1.0 cm3 of sample was filled into the oscillating U-tube capillary
of a Density/Specific Gravity Meter DMA 4500/5000 (Anton Paar,
Austria) via syringe at 30 ◦ C. Measurement was repeated for all
samples of the heavy and light phases.
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Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
Fig. 1. Set-up of the experimental flooding system.
In the next step, interfacial tensions between the heavy and
light phases were measured using a Spinning Drop Tensiometer
SITE 4 (KRUSS, Germany) at 30 ◦ C. As a general procedure, 10 ␮l of
the light phase was injected into the rotating capillary filled with
the heavy phase. During the injection, the capillary was rotated
at the speed of 1000–2000 rpm. The diameter of the droplet was
measured at high rotational velocity of 6000–8000 rpm after the
equilibrium was reached. The system reaches the equilibrium when
the diameter of the droplet did not change with time (Drelich et al.,
2002). Since in all of the IFT measurements the system reached
equilibrium after a very short time of about 10 s, the depletion of
co-surfactant into the n-octane phase was considered negligible.
Measurements were carried out in triplicate. The IFT was estimated
using Vonnegut’s equation, which relates IFT to the droplet radius,
rotational velocity, and the densities of the two phases (Vonnegut,
1942).
2.4. Sand pack design and microemulsion flooding
Sand pack flooding tests were conducted to investigate the performance of all the formulated microemulsions in oil recovery. The
sand used in these experiments was composed of SiO2 and CaO
with particle size of 100 mesh or 0.150 mm. The sand was packed
vertically in a glass sand pack holder 45 cm in length and 5 cm in
diameter. Both sides were equipped with stainless steel sieves to
prevent any sand flow. The sieve size was 300 mesh per inch with
sieve opening of 0.053 mm. The sand pack was placed horizontally
and flooded at atmospheric pressure and room temperature. Fig. 1
shows the experimental setup of the flooding system. The measured properties of the sand pack and floodings are listed in Table 2
(sand pack test #1).
First, brine (1 wt% NaCl) was injected for about 3 pore volumes
(PVs), followed by 3 PVs of n-octane to reach the connate water saturation. For the secondary oil recovery, 2 PVs of brine was injected.
Then for the tertiary oil recovery, the sand pack was continuously
flooded with 4 PVs of a prepared triglyceride microemulsion. The
flow rates of the injections were kept constant at 0.83 ml/min, or
about 2 ft/day frontal advance rate in order to mimic real field
injection velocities (Iglauer et al., 2010a,b; Kumar and Mohanty,
2010). The effluents from the sand pack were collected in sample
tubes and the incremental oil recoveries were measured against
time by gas chromatography (GC). The gas chromatograph (Agilent
Technologies, Model 7890A) was equipped with flame ionization
detector (FID) maintained at 300 ◦ C. The column was a DB-1 capillary column (J&W, 40 m × 0.18 mm inner diameter × 0.4 ␮m film
thickness). The column temperature was held at 35 ◦ C for 15 min,
programmed to 70 ◦ C at 1.5 ◦ C/min and then to 130 ◦ C at 30 ◦ C/min
and held at 130 ◦ C for 20 min. The carrier gas was helium at speed of
25 cm/s. The amount of recovered oil was quantitatively expressed
by the term of cumulative tertiary oil recovery, which is the percentage of the volume of produced oil in the tertiary oil recovery
step to the volume of residual oil (remaining oil after secondary oil
recovery step).
The same methodologies of sand pack microemulsion flooding
and IFT measurement were conducted for all microemulsion samples to determine the optimum microemulsion formulation. The
calculated cumulative tertiary oil recovery and IFT were used as
the criteria of selecting the most efficient microemulsion.
2.5. Co-surfactant screening
The aforementioned methodology of triglyceride microemulsion preparation was applied for various types of co-surfactants,
namely IPA, IBA, NBA, TWN20, TWN80, GLY, SM, GM, FA8, FA810,
FA1214, SA, CA, EGEE, and SAP at concentrations of 1, 2, 3 and 4 wt%
of the aqueous phase . The concentration of APG (surfactant) and
NaCl was fixed at 1 and 3 wt% of the aqueous phase. Cumulative
tertiary oil recovery and IFT results were obtained for all of the
Table 2
Summary of the properties of the sand pack floodings for sand pack test #1.
Length
Diameter
Porosity
Permeability
Pore volume (PV)
Connate water saturation
Brine PV (secondary oil recovery)
Residual oil
Flow rate of injections
Microemulsion PV (tertiary oil recovery)
45 cm
5 cm
34%
25 D
299 ml
8%
2
107.83 ml
0.83 ml/min
4
Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
Winsor Type I microemulsion formulations. The co-surfactant of
the microemulsion with the highest tertiary oil recovery and the
lowest IFT is selected as the most effective co-surfactant.
2.6. Optimization of the aqueous phase composition of the
triglyceride microemulsion
2.6.1. Optimization of salinity
Different microemulsion samples were prepared at various
salinities ranging from 0.5 to 12 wt% of the aqueous phase. The concentration of APG (surfactant) and the selected co-surfactant was
fixed at 1 and 2 wt% of the aqueous phase. Cumulative tertiary oil
recovery and IFT results were obtained for all the Winsor Type I
microemulsion formulations. The optimum concentration of NaCl
in the aqueous phase is the salinity at which its microemulsion
yields the highest tertiary oil recovery and the lowest IFT.
2.6.2. Optimization of the co-surfactant concentration
Different microemulsion samples were prepared at various
concentrations of co-surfactant ranging from 0.5 to 4 wt% of the
aqueous phase. The concentration of APG was fixed at 1 wt% of
the aqueous phase. All of the samples were prepared at the determined optimum salinity. Cumulative tertiary oil recovery and IFT
results were obtained for all the Winsor Type I microemulsion formulations. The optimum concentration of the co-surfactant in the
aqueous phase is the concentration at which its microemulsion
yields the highest tertiary oil recovery and the lowest IFT.
2.6.3. Optimization of the surfactant concentration
Different microemulsion samples were prepared at various concentrations of surfactant ranging from 0.25 to 2 wt% of the aqueous
phase. The concentrations of co-surfactant and NaCl in the aqueous phase were fixed at their optimum values. Cumulative tertiary
oil recovery and IFT results were obtained for all the Winsor Type
I microemulsion formulations. The optimum concentration of the
surfactant in the aqueous phase is the concentration at which its
microemulsion yields the highest tertiary oil recovery and the lowest IFT.
2.7. Application of the optimum microemulsion formulation
The same flooding procedure mentioned previously was used
until the sand pack reached the residual oil saturation after secondary oil recovery by water flooding. In the tertiary recovery, 1 PV
of the triglyceride microemulsion with optimized aqueous phase
composition was injected to the sand pack, followed by 1 PV of
polymer solution (1500 ppm xanthan gum in 1 wt% NaCl) to provide mobility control. The viscosity of the polymer solution was
27 cP at 30 ◦ C and measured using a rotational viscometer (Haake
VT550 controlled-rate viscotester, Germany). The viscometer was
equipped with a coaxial cylinder sensor system consisting of a set
of NV cup and stainless steel rotor. Finally 1 PV of brine was injected
into the sand pack as the chasing fluid to push all the injected fluids.
The flow rates of injections were also kept constant at 0.83 ml/min,
or about 2 ft/day frontal advance rate. The produced oil volume
was recorded by GC for both secondary and tertiary oil recovery.
The measured properties of the sand pack and floodings are listed
in Table 3 (sand pack test #2).
In the next step, the efficiency of the formulated microemulsion
with optimized aqueous phase composition and the same polymer solution (1500 ppm xanthan gum in 1 wt% NaCl) in tertiary
oil recovery was determined and compared. The same flooding
procedure was used until the sand pack reached the residual oil
saturation after the secondary oil recovery by water flooding. In
the tertiary recovery, the sand pack was continuously flooded with
4 PVs of optimum triglyceride microemulsion before being flooded
9
Table 3
Summary of the properties of the sand pack floodings for sand pack test #2 and #3.
Length
Diameter
Porosity
Permeability
Pore volume (PV)
Connate water saturation
Brine PV (secondary oil recovery)
Residual oil
Flow rate of injections
Microemulsion PV (tertiary oil recovery)
Polymer PV (tertiary oil recovery)
Viscosity of the polymer solution
Chasing brine PV
Sand pack
test #2
Sand pack
test #3
45 cm
5 cm
34%
25 D
299 ml
8%
2
107.83 ml
0.83 ml/min
1
1
27 cP
1
45 cm
5 cm
34%
25 D
299 ml
8%
2
107.83 ml
0.83 ml/min
0
4
27 cP
0
with 4 PVs of polymer solution (1500 ppm xanthan gum in 1 wt%
NaCl). The produced oil was recorded by GC in tertiary oil recovery.
The measured properties of the sand pack and floodings are listed
in Tables 2 and 3 (sand pack test #1 for microemulsion flooding and
sand pack test #3 for polymer flooding).
3. Results and discussion
3.1. Co-surfactant screening
Some surfactants do not sufficiently reduce interfacial tension
at the oil/water interface to form microemulsions (Myers, 1992).
They may not distribute between the aqueous and oil phase properly (Alany et al., 2000). To overcome this, co-surfactant molecules
are introduced to sufficiently lower the oil/water interfacial tension, fluidize the rigid hydrocarbon region of the interfacial film,
and induce ideal curvature of the interfacial film (Alany et al., 2000).
Co-surfactants are molecules with weak surface-active properties
that are combined with the surfactants to enhance their ability
to reduce the interfacial tension and promote the formation of a
microemulsion (Schick, 1987).
For a co-surfactant-free triglyceride microemulsion sample,
which contains only 1 wt% of APG as surfactant and 3 wt% NaCl in
the aqueous phase, its IFT against n-octane was measured to be
5.3658 mN/m. This value is low but not ultra-low. Thus to reduce
the IFT to ultra-low values, it is essential to select an appropriate
co-surfactant. Selecting an effective co-surfactant could be the first
and the most critical step in synthesizing a triglyceride microemulsion for tertiary oil recovery because the type of co-surfactant might
considerably influence the IFT reduction and consequently the tertiary oil recovery efficiency.
Fig. 2. The IFT of microemulsion samples containing the three lower alkanols against
n-octane.
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Fig. 3. The IFT of microemulsion samples containing the Tweens against n-octane.
Fig. 4. The IFT of microemulsion samples containing the two monooleates against
n-octane.
Fig. 5. The IFT of microemulsion samples containing the five fatty alcohols against
n-octane.
Fig. 6. The IFT of microemulsion samples containing other types of co-surfactants
against n-octane.
Fig. 7. The cumulative tertiary oil recovery of microemulsion samples containing
the three lower alkanols against n-octane.
Fig. 8. The cumulative tertiary oil recovery of microemulsion samples containing
the Tweens against n-octane.
Figs. 2–6 show the IFT variation of the microemulsion samples
with various co-surfactants against n-octane with an increase in
the concentration of co-surfactants. Figs. 7–11 show the cumulative
tertiary oil recovery of the microemulsion samples with an increase
in the concentration of co-surfactants. The whole set of these figures is an indicator of the performance of the co-surfactants used.
In general, the observed reduction in IFT with an increase in the
volume of the co-surfactants shows good performance of the cosurfactant in reducing the IFT.
Increasing the amount of co-surfactant decreases the
hydrophilic–lipophilic balance (HLB) number. The HLB value
is an indication of the oil or water solubility of the microemulsion
(Griffin, 1949). The HLB value characterizes the relative oil and
water solubility of surfactants. Lower HLB number indicates the
Fig. 9. The cumulative tertiary oil recovery of microemulsion samples containing
the two monooleates against n-octane.
Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
11
Fig. 10. The cumulative tertiary oil recovery of microemulsion samples containing
the five fatty alcohols against n-octane.
microemulsion is more oil soluble and vice versa. It is evident that
decreasing the HLB number of a nonionic mixture leads to a change
in the microstructure of the microemulsion from Winsor Type I
to Winsor Type III, and subsequently to Winsor Type II (Wu et al.,
2001). While the microstructure is changing, the IFT decreases to
a minimum before it starts to increase (Wu et al., 2001). The IFT
reaches a minimum in the phase inversion temperature (PIT) point,
which is fairly in the middle of Winsor Type III region (Wu et al.,
2001). It was observed that for all the co-surfactants except GM,
the IFT decreases with the amount of co-surfactant (or decreasing
the HLB number). This trend indicates that the microstructure
of the microemulsions can be Winsor Type I or Winsor Type
III before the PIT at the studied range of co-surfactant. The IFT
variation shows a minimum only for GM in co-surfactant range
of 1–4 wt% of the aqueous phase (Fig. 4). The minimum IFT value
indicates the appearance of Winsor Type III microemulsion. In
other words, the microstructure of the triglyceride microemulsion
with co-surfactant of GM is changed from Winsor Type I to Winsor
Type III microemulsion in the presence of n-octane.
Furthermore, the efficiency of the co-surfactant can also be
estimated from the values of either IFT or the tertiary oil recovery. TWN80, which yields the highest IFT (Fig. 3) and the lowest
tertiary oil recovery (Fig. 8) is considered as the worst choice of
co-surfactant among the co-surfactants studied. In contrast, GM
which yields ultra-low IFT against n-octane (Fig. 4) and the highest tertiary oil recovery (Fig. 9) is considered as the most efficient
co-surfactant among co-surfactants studied. Therefore, GM is the
desired co-surfactant for a triglyceride microemulsion formulation
and it is selected to be one of the components of the triglyceride
microemulsion.
Fig. 11. The cumulative tertiary oil recovery of microemulsion samples containing
other types of co-surfactants against n-octane.
Fig. 12. IFT of microemulsion samples against n-octane for the samples at various
salinities (on left-side y-axis); the cumulative tertiary oil recovery of microemulsion
samples at various salinities (on right-side y-axis). In all the samples, the concentration of APG and GM was maintained at 1 and 2 wt%, respectively.
An appropriate surfactant blend for formulation of a microemulsion can be selected if the HLB of the candidate surfactant blend
(surfactant and co-surfactant) approaches the required HLB of the
oily component for a particular system (Schick, 1987). In addition, in the selection of surfactant blend it is more favorable if the
lipophilic part of the used surfactant matches the oily component
(Prince, 1977). This may be the reason that GM seems to be an
effective co-surfactant for a triglyceride microemulsion.
3.2. Optimization of the aqueous phase composition of the
triglyceride microemulsion
3.2.1. Optimization of salinity
Six microemulsion samples were prepared at salinities of 0.5,
1, 3, 6, 9, and 12 wt% of the aqueous phase. In all the samples,
the concentration of APG and GM was maintained at 1 and 2 wt%,
respectively. Fig. 12 shows both the variation of IFT and cumulative
tertiary oil recovery with salinity. The IFT values on left-side y-axis
of Fig. 12 demonstrate that the IFT of the microemulsion samples
against n-octane is fairly constant at various NaCl concentrations.
The IFT was observed to be quasi-independent of salinity because
the nature of the microemulsion samples is intrinsically nonionic
(Kahlweit et al., 1995a; Balzer and Lüders, 2000; Iglauer et al., 2009).
The mean of the IFT values was found to be 0.0037 ± 0.00005 mN/m,
which is in the ultra-low region (<0.01 mN/m).
In order to investigate the impact of salinity on the performance
of microemulsion flooding in tertiary oil recovery, the sand pack
was flushed with all the six microemulsion samples at various salinities individually. The cumulative tertiary oil recovery results on
the right-side y-axis of Fig. 12 show no variation with NaCl concentration. In other words, the same amount of oil can be attained
using microemulsion samples with different salinities. Therefore,
the salinity of the microemulsion formulation can be adjusted at
any value within the studied range. Thus in this study the salinity
of 3 wt% NaCl was selected and taken as the optimum salinity of the
microemulsion.
3.2.2. Optimization of co-surfactant concentration
The concentration of GM, the co-surfactant, was also optimized by IFT measurements and microemulsion flooding using 8
microemulsion samples at GM concentrations of 0.5, 1, 1.5, 2, 2.5,
3, 3.5, and 4 wt% of the aqueous phase. In all of the samples, the
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Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
Fig. 15. Cumulative total oil recovery in secondary (water flooding) and tertiary
(microemulsion, polymer, and water flooding) recoveries.
Fig. 13. IFT of microemulsion samples against n-octane for the samples at various
concentrations of GM (on left-side y-axis); the cumulative tertiary oil recovery of
microemulsion samples at various concentrations of GM (on right-side y-axis). In all
the samples, the concentration of APG and NaCl was kept at 1 and 3 wt%, respectively.
concentration of APG and NaCl was kept constant at 1 and 3 wt%
(optimum salinity), respectively. Fig. 13 shows both the variation
of IFT and cumulative tertiary oil recovery with the microemulsion
samples at various GM concentrations. The IFT values on left-side yaxis of Fig. 13 decreased to a minimum before it started to increase.
In contrast, the cumulative tertiary oil recovery increased to a maximum before it reduced. It is apparent that the point at which the
IFT is at its minimum value and tertiary oil recovery efficiency is at
its maximum value represents the optimum concentration of GM.
Therefore, based on the experimental data obtained, 3 wt% GM is
selected as the optimum concentration of the co-surfactant in the
aqueous phase of the microemulsion.
3.2.3. Optimization of the concentration of surfactant
Eight microemulsion samples were prepared at APG concentrations of 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, and 2 wt% of the aqueous
phase. In all of the samples, the concentration of GM and NaCl was
kept constant at 3 (optimum concentration of co-surfactant) and
3 wt% (optimum salinity), respectively. Both the variation of IFT and
cumulative tertiary oil recovery with the microemulsion samples
at various APG concentrations are shown in Fig. 14. It was observed
Fig. 14. IFT of microemulsion samples against n-octane for the samples at various
concentrations of APG (on left-side y-axis); the cumulative tertiary oil recovery of
microemulsion samples at various concentrations of APG (on right-side y-axis). In all
the samples, the concentration of GM and NaCl was kept at 3 and 3 wt%, respectively.
that by increasing the APG concentration from 0.25 to 1 wt%, the IFT
between the microemulsion and n-octane yields to the minimum
value of 0.0002 mN/m, while the cumulative tertiary oil recovery
reached to the maximum value of 71.8%. When the concentration
of APG in the aqueous phase of the microemulsion exceeds 1 wt%,
the IFT starts to increase and the cumulative tertiary oil recovery
starts to decrease continuously. It is obvious that the point at which
the IFT and cumulative tertiary oil recovery yield their minimum
and maximum values respectively indicates the optimum concentration of APG. Therefore, based on the collected experimental data,
1 wt% is selected as the optimum concentration of the surfactant in
the aqueous phase of the microemulsion.
3.3. Microemulsion flooding with the optimum microemulsion
formulation
The optimum aqueous phase composition of the triglyceride
microemulsion is 3 wt% NaCl, 3 wt% GM, 1 wt% APG, and 93 wt%
de-ionized water. Fig. 15 shows the total cumulative oil recovery
in secondary and tertiary recoveries for the triglyceride microemulsion with optimum aqueous phase formulation. The cumulative
total oil recovery is the ratio of the produced oil to the initial oil
in place (IOIP) expressed as a percentage. The secondary recovery
includes water flooding (2 PVs), and the tertiary recovery includes
microemulsion (1 PV), polymer (1 PV), and water flooding (1 PV).
Experimental results show that 60.8% of the IOIP was recovered
after the secondary recovery with water flooding. About 39.2% of
the oil still remained in the sand pack after the initial water flooding. To recover the remaining oil, tertiary recovery was carried out.
After the injection of 1 PV of microemulsion flooding with optimum
aqueous phase formulation and viscosity of 3.3 cP, about 46.4% of
the remaining trapped oil after the water flooding was recovered.
As a result the total cumulative oil recovery increased to about 78%
of the IOIP. Then 1 PV polymer solution was injected into the sand
pack and the total cumulative oil recovery increases to about 84%
of the IOIP (59.2% of the trapped oil remaining after water flooding was recovered). Finally, after the injection of 1 PV of water,
the total cumulative oil recovery reached 87% of the IOIP (66.8% of
the trapped oil). The relatively high oil recovery suggests the effectiveness of the optimum triglyceride microemulsion formulation
in enhancing oil recovery.
In one of the recent studies on microemulsion formulation
(Iglauer et al., 2010b), a microemulsion was prepared from APG,
Span20, and n-octane as its surfactant, co-surfactant, and the oil
phase, respectively. Injection of the microemulsion into a sand
pack resulted in the recovery of 94% of the IOIP (Iglauer et al.,
2010b). Although the amount of oil recovery for the triglyceride
microemulsion formulation in this work is a bit less than other
Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
13
composition and n-octane is 0.0002 mN/m. This value is considered
ultra-low. The cumulative tertiary oil recovery reached to a maximum value of 71.8% by the continuous injection of the triglyceride
microemulsion at the optimum aqueous phase composition.
Furthermore, the total oil recovery of 87% after the secondary
and tertiary oil recovery suggests the feasibility in the application
of the optimum triglyceride microemulsion formulation. The oil
recovery efficiency for the formulated microemulsion is considered comparable. Finally, based on the sand pack flooding tests
conducted in this study, the formulated triglyceride microemulsion is able to recover 4.3% additional oil than a typical polymer in
tertiary oil recovery.
Fig. 16. Cumulative tertiary oil recovery in continuous microemulsion and polymer
floodings.
formulations in the literature, this work is considered crucial as
it opens new application of triglyceride microemulsion in tertiary
enhanced oil recovery. The new triglyceride microemulsion formulation is also less toxic and more environmentally friendly than
other microemulsions with a hydrocarbon or a petroleum fraction
as the oil phase (Kahlweit et al., 1995b; Do et al., 2009).
The efficiencies of the formulated triglyceride microemulsion
with optimized aqueous phase composition and the polymer solution in tertiary oil recovery were investigated by continuous
injection (4 PVs) of the chemical. Fig. 16 shows the recovery results.
The cumulative tertiary oil recovery is the ratio of the produced
oil to the trapped oil after water flooding (secondary oil recovery)
expressed as a percentage. As can be seen in Fig. 16, injection of
polymer solution results in higher oil production during the first 1.5
PVs than the injection of the microemulsion. This is due to the viscosity difference of the injected microemulsion and polymer. The
viscosities of the injected microemulsion and the polymer solution
are 3.3 cP and 27 cP, respectively.
Both viscosities are sufficient to sweep oil (with viscosity of
0.55 cP) and brine (with viscosity of 1 cP). However, because of
the higher mobility ratio of polymer compared to microemulsion,
higher oil recoveries were observed in the first 1.5 PVs of chemical injection. Since the viscosity of polymer solution is higher than
microemulsion, it seems the polymer slug moved within the sand
pack like a plug flow. The amount of produced oil was less in polymer flooding than microemulsion flooding during further injection
of the chemical slug from 1.5 PVs up to 4 PVs. Unlike polymer, the
flow of the microemulsion inside the sand pack does not follow plug
flow. However, because the triglyceride microemulsion is capable
of solubilizing the remaining oil besides sweeping it, the final tertiary oil recovery for microemulsion flooding (71.8% of the trapped
oil after water flooding) was found to be higher than that of polymer
flooding (67.5% of the trapped oil after water flooding). Therefore,
microemulsion flooding tends to recover an additional 4.3% of the
trapped oil compared to a polymer flooding.
4. Conclusion
The results of this study showed that palm oil could be used
as an oil phase in the formulation of a pre-prepared triglyceride
microemulsion for enhanced oil recovery. This is true when the
aqueous phase contains APG as its surfactant and GM as its cosurfactant. A triglyceride microemulsion could be obtained by
equal mixing of the oil and aqueous phase, shaking, and standing for 1 week. The aqueous phase composition of the triglyceride
microemulsion was optimized to achieve the lowest interfacial
tension and highest tertiary oil recovery. Optimum composition
of the aqueous phase was found to be 1 wt% APG, 3 wt% NaCl,
3 wt% GM, and 93 wt% de-ionized water. The measured IFT between
the triglyceride microemulsion at the optimum aqueous phase
Acknowledgments
The authors would like to acknowledge the financial support
of the Bright Sparks Program at University of Malaya. They also
would like to acknowledge the support of University of Malaya IPPP
grant, project number: PV021/2011B. Appreciation also goes to BCI
Chemical Corporation Sdn. Bhd. for providing the flooding set-up.
References
Alany, R.G., Rades, T., Agatonovic-Kustrin, S., Davies, N.M., Tucker, I.G., 2000. Effects
of alcohols and diols on the phase behaviour of quaternary systems. Int. J. Pharm.
196, 141–145.
Austad, T., Milter, J., 2000. Surfactant flooding in enhanced oil recovery. In: Surfactants: Fundamentals and Applications in the Petroleum Industry. Cambridge
University Press, UK, pp. 203–250.
Balzer, D., Lüders, H., 2000. Nonionic Surfactants: Alkyl Polyglycosides. Surfactant
Science Series 91, Marcel Dekker, Inc., New York.
Bouabboune, M., Hammouch, N., Benhadid, S., 2006. Comparison between
microemulsion and surfactant solution flooding efficiency for enhanced oil
recovery in TinFouyé oil field. In: The Petroleum Society’s 7th Canadian International Petroleum Conference and 57th Annual Technical Meeting, Calgary,
Alberta, Canada, pp. 1–8, PAPER 2006-058.
Do, L.D., Withayyapayanon, A., Harwell, J.H., Sabatini, D.A., 2009. Environmentally
friendly vegetable oil microemulsions using extended surfactants and linkers. J.
Surfact. Deterg. 12, 91–99.
Drelich, J., Fang, Ch., White, C.L., 2002. Measurement of interfacial tension in
fluid–fluid systems. In: Encyclopedia of Surface and Colloid Science. Marcel
Dekker, Inc., New York, p. 3162.
Engelskirchen, S., Elsner, N., Sottmann, T., Strey, R., 2007. Triacylglycerol microemulsions stabilized by alkyl ethoxylate surfactants – a basic study. Phase behavior,
interfacial tension and microstructure. J. Colloid Interface Sci. 312, 114–121.
Fanun, M., 2010. Formulation and characterization of microemulsions based on
mixed nonionic surfactants and peppermint oil. J. Colloid Interface Sci. 343,
496–503.
Green, D.W., Willhite, G.P., 1998. Enhanced Oil Recovery. Society of Petroleum Engineers Inc., Texas, USA.
Griffin, W.C., 1949. Classification of surface-active agents by “HLB”. J. Soc. Cosmet.
Chem. 1, 311–326.
Hecke, E.V., Catté, M., Poprawski, J., Aubry, J.M., Salager, J.L., 2003. A novel criterion
for studying the phase equilibria of non-ionic surfactant–triglyceride oil–water
systems. Polym. Int. 52, 559–562.
Iglauer, S., Wu, Y., Shuler, P., Tang, Y., Goddard III, W.A., 2009. Alkyl polyglycoside
surfactant-alcohol cosolvent formulations for improved oil recovery. Colloids
Surf., A Physicochem. Eng. Asp. 339, 48–59.
Iglauer, S., Wu, Y., Shuler, P., Tang, Y., Goddard, W., 2010a. Alkyl polyglycoside/1naphthol formulations with ultra-low interfacial tensions against n-octane for
enhanced oil recovery. In: The SPE EUROPEC/EAGE Annual Conference and Exhibition, Barcelona, Spain, pp. 1–11, SPE 130404.
Iglauer, S., Wu, Y., Shuler, P., Tang, Y., Goddard III, W.A., 2010b. New surfactant classes
for enhanced oil recovery and their tertiary oil recovery potential. J. Pet. Sci. Eng.
71, 23–29.
Joubran, R.F., Cornell, D.G., Parris, N., 1993. Microemulsions of triglyceride and nonionic surfactant – effect of temperature and aqueous phase composition. Colloids
Surf. A: Physicochem. Eng. Aspects 80, 153–160.
Jurado, E., Bravo, V., Luzón, G., Fernández-Serrano, M., García-Román, M.,
Altmajer-Vaz, D., Vicaria, J.M., 2007. Hard-surface cleaning using lipases:
enzyme–surfactant interactions and washing tests. J. Surfact. Deterg. 10, 61–70.
Kahlweit, M., Busse, G., Faulhaber, B., 1995a. Preparing microemulsions with alkyl
monoglycosides and the role of n-alkanols. Langmuir 11, 3382–3387.
Kahlweit, M., Busse, G., Faulhaber, B., Eibl, H., 1995b. Preparing nontoxic microemulsions. Langmuir 11, 4185–4187.
Komesvarakul, N., Sanders, M.D., Szekeres, E., Acosta, E.J., Faller, J.F., Mentlik, T.,
Fisher, L.B., Nicoll, G., Sabatini, D.A., Scamehorn, J.F., 2006. Microemulsions of
triglyceride-based oils: the effect of co-oil and salinity on phase diagrams. J.
Cosmet. Sci. 55, 309–325.
14
Z. Jeirani et al. / Industrial Crops and Products 43 (2013) 6–14
Kumar, R., Mohanty, K.K., 2010. ASP flooding of viscous oils. In: The SPE Annual
Technical Conference and Exhibition, Florence, Italy, pp. 1–11, SPE 135265.
Kunieda, H., Asaoka, H., Shinoda, K., 1988. Two types of surfactant phases and
four coexisting liquid phases in a water/nonionic surfactant/triglyceride/
hydrocarbon system. J. Phys. Chem. 92, 185–189.
Myers, D., 1992. Surfactant Science and Technology. VCH Publishers, New York, p.
152.
Paul, B.K., Moulik, S.P., 2001. Uses and applications of microemulsions. Curr. Sci. 80,
990–1001.
Phan, T.T., Attaphong, C., Sabatini, D.A., 2011. Effect of extended surfactant structure
on interfacial tension and microemulsion formation with triglycerides. J. Am.
Oil Chem. Soc. 88, 1223–1228.
Prince, L.M., 1977. Formulation. In: Prince, L.M. (Ed.), Microemulsions: Theory and
Practice. Academic Press, New York, pp. 33–49.
Purwono, S., Murachman, B., 2001. Development of non petroleum base chemicals
for improving oil recovery in Indonesia. In: The SPE Asia Pacific Oil and Gas
Conference and Exhibition, Jakarta, Indonesia, pp. 1–10, SPE 68768.
Putz, A., Chevalier, J.P., Stock, G., Philippot, J., 1981. A field test of microemulsion
flooding, Chateaurenard field, France. J. Pet. Technol. 33, 710–718.
Santanna, V.C., Curbelo, F.D.S., Castro Dantas, T.N., Dantas Neto, A.A., Albuquerque,
H.S., Garnica, A.I.C., 2009. Microemulsion flooding for enhanced oil recovery. J.
Pet. Sci. Eng. 66, 117–120.
Schick, M.J., 1987. Nonionic Surfactants Physical Chemistry. Marcel Dekker, Inc., New
York, p. 447.
Sottmann, T., Strey, R., 1997. Ultralow interfacial tensions in water–nalkane–surfactant systems. J. Chem. Phys. 106, 8606–8615.
Sottmann, T., Stubenrauch, C., 2009. Phase behaviour, interfacial tension and
microstructure of microemulsions. In: Stubenrauch, C. (Ed.), Microemulsions:
Background, New Concepts, Applications, Perspectives. John Wiley & Sons, Ltd.,
Chichester, UK.
Vonnegut, B., 1942. Rotating bubble method for the determination of surface and
interfacial tensions. Rev. Sci. Instrum. 13, 6–9.
Wang, D., Liu, C., Wu, W., Wang, G., 2010. Novel surfactants that attain ultra-low
interfacial tension between oil and high salinity formation water without adding
alkali, salts, co-surfactants, alcohol and solvents. In: The SPE EOR Conference at
Oil & Gas West Asia, Muscat, Oman, pp. 1–11, SPE 127452.
Wu, B., Cheng, H., Childs, J.D., Sabatini, D.A., 2001. Surfactant-enhanced removal
of hydrophobic oils from source zones. In: Smith, J.A., Burns, S.E. (Eds.),
Physicochemical Groundwater Remediation. Plenum Publishers, New York,
p. 246.
Wu, Y., Iglauer, S., Shuler, P., Tang, Y., Goddard, W.A., 2010. Branched alkyl alcohol propoxylated sulfate surfactants for improved oil recovery. Tenside Surfact.
Deterg. 47, 152–161.
Zhao, P., Jackson, A.C., Britton, C., Kim, D.H., Britton, L.N., Levitt, D.B., Pope,
G.A., 2008. Development of high-performance surfactants for difficult oils.
In: The SPE Improved Oil Recovery Symposium, Tulsa, OK, USA, pp. 1–11,
SPE 113432.