Author's Accepted Manuscript

An experimental study on using a nanosurfactant in an EOR process of heavy oil in a

Fractured micromodel
Mahdi Mohajeri, Mahmoud Hemmati

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DOI:
Reference:

S0920-4105(14)00372-6
http://dx.doi.org/10.1016/j.petrol.2014.11.012
PETROL2852

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Journal of Petroleum Science and Engineering

Received date: 1 July 2014

Accepted date: 12 November 2014
Cite this article as: Mahdi Mohajeri, Mahmoud Hemmati, An experimental
study on using a nanosurfactant in an EOR process of heavy oil in a Fractured
micromodel, Journal of Petroleum Science and Engineering, http://dx.doi.org/10.1016/
j.petrol.2014.11.012
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An Experimental Study on Using a Nanosurfactant in an EOR Process of Heavy Oil in a

Fractured Micromodel
1- Mahdi Mohajeri *
Department of Petroleum Engineering, Islamic Azad University, Science and Research Branch, Tehran,
Iran.
2- Mahmoud Hemmati
Research Institute of Petroleum Industry (RIPI), Tehran, Iran.

* E-mail: mohajeri.m90@gmail.com

Abstract
Surfactant flooding is known as a common chemical method for enhancing oil recovery.
Recently, the simultaneous application of nanoparticles and chemical substance has been
considered for improving the efficiency of EOR processes. Nanoparticles along with surfactants,
due to decreasing interfacial tension (IFT) between oil and water, the spontaneous formation of
emulsion, the alteration of porous media wettability, and the modification of flow characters,
lead to improving oil recovery and releasing residual oils remained inside pores. In the present
study, the microscopic and macroscopic efficiency of heavy oil recovery in a fractured 5-spot
model in three cases of injecting, two types of surfactants (SDS as an anionic surfactant) and
(C12TAB as a cationic surfactant), injecting ZrO2 nanoparticles, and simultaneously injecting
the nanoparticles and the surfactants was investigated. Adding the nanoparticles along with SDS
(2000 ppm) decreased IFT by 81%, while the figure for C12TAB was about 70%. Obviously,
SDS surfactant showed better performance than C12TAB in terms of reducing IFT. This means
SDS has a greater impact on decreasing IFT than C12TAB when used either alone or with
nanoparticles. Moreover, the results of sessile drop experiments and wettability measurements

showed that coating with heavy oil, could make an oil-wet surface. While coating with either the
surfactants or the nanoparticles could partially alter the wettability of surface to water-wet,
coating with the surfactants along with the nanoparticles could make a strongly water-wet
surface. Seemingly, during the flooding tests, the distribution of Surfactants containing
nanoparticles in pores and throats showed a strong water-wet condition in microscopic pictures.
In this regard, C12TAB showed better performance in terms of altering wettability than SDS.
This means C12TAB has a greater impact on altering wettability than SDS when used either
alone or with nanoparticles. However, the results of flooding tests showed that adding
nanoparticles to surfactants solutions significantly increased oil recovery. In general, the cationic
surfactant (C12TAB) solution containing nanoparticles enhanced ultimate oil recovery further
than the anionic surfactant (SDS) solution containing nanoparticles. However, the experimental
results showed that the minimum IFT was achieved using SDS either with or without
nanoparticles, while C12TAB/nanoparticles mostly altered the wettability toward a water-wet
condition. In addition, adding the nanoparticles to the surfactant solution lead to the modification
of the flow character from Newtonian to non-Newtonian (pseudoplastic) and a consequent
viscosity increase by 2 times. This can be assumed a great achievement as a nanosurfactant
solution, in addition to its own duty, can be used to control mobility ratio in EOR processes.
Obviously, an appropriate mobility ratio greatly affects the macroscopic oil recovery efficiency.

Keywords: ZrO2 Nanoparticles, Surfactant, Fractured 5-Spot Model, EOR, Wettability

Alteration, IFT Reduction, Rheology Modification

1. Introduction
Nowadays, due to the limitation of light oil reservoirs around the world, enhanced oil recovery
from heavy oil reservoirs has significantly been taken into account. During primary recovery,
due to the high viscosity of oil, just a little amount about 5% can be recovered. Moreover, in
secondary recovery processes like water flooding, because of the undesirable mobility ratio
between oil and water, oil cannot be recovered more than 10%. One of the effective methods,
which is suitable for this kind of reservoirs, is the usage of chemical materials.
Chemical EOR processes encompass a variety of mechanisms, including a reduction in the oilwater interfacial tension [13], surface wettability alteration [48] the use of high viscosity
agents for mobility control [912], the application of thermal methods whereby the viscosity of
oil is decreased by increasing the temperature inside the reservoir [13]. EOR processes can
include one or more of these mechanisms, and to be successful the approach must be
economical, scalable, and reliable. Hence, surfactant flooding as a common chemical method in
order to reduce IFT and capillary forces is significantly used [14-15].
In addition, nanoparticles have been explored for use in a remarkable range of applications [16].
They can be considerably active and used to modify surface properties. According to the
statistics, nanoparticles are significantly used in oil industry. Hence, in some studies have been
reported the applications of nanoparticles in oil industry and classified based on priority.
Researchers have concluded that nanotechnology has the greatest usage in chemical EOR
methods [17]. Therefore, in some studies, the role of nanoparticles in EOR operations has been
reported [18-20]. Hence, researchers have claimed that new type of fluids usually called smart
fluids have become more accessible for the oil and gas industry [21]. The nanofluids are created

by the addition of nanoparticles to fluids for intensification and improvement of some properties
at low volume concentration of the dispersing medium. Then, the main feature of nanofluids is
that their properties greatly depend on the dimensions of nanoparticles added to them [21].
Suspensions of nanodimensional particles have the following advantages: an increase in
sedimentation stability because surface forces easily counterbalance the force of gravity, thermal,
optical, stress-strain, electrical, rheological and magnetic properties that strongly depend on size
and shape of the nanoparticles. It is for this reason that nanofluid properties often exceed the
properties of conventional fluids [22-23]. Furthermore, nanoparticles have been shown to
stabilize foams and emulsions, to change the wettability of rock, and to reduce the IFT of fluid
system [19,20,23,24].
Recently, usage of nanoparticles in chemical injections for improving efficiency has been
significantly investigated. For instance, a study about using an anionic surfactant with the
addition of non-ferrous metal nanoparticles has been performed [23].Hence, the results revealed
that the usage of nanofluid permitted a 70-79% reduction of surface tension. In addition, it was
claimed that in the presence of nanoparticles the adsorption process is more stable. Moreover, in
another research, has been shown that usage of Al2O3 nanoparticles with an anionic surfactant
could alter wettability of system from oil-wet to water-wet and also make an effect on increasing
ultimate oil recovery [24].
In addition, some researchers investigated about results of presence of nanoparticles on changes
rheological and interfacial properties and increase effect of surfactant solution on oil recovery
processes [25-26]. The results of these experimental works showed how dispersed nanoparticles
in an aqueous phase can modify the interfacial properties of the liquid/liquid systems if their
surface is modified by the presence of surfactant.

Seemingly, among the many features that affect the fluid distribution and oil recovery in porous
media, wettability is proven to be a crucial factor [27-28]. Some researches about effects of
nanoparticles on wettability alteration and ultimate oil recovery have been performed. The
results revealed that usage of nanoparticles can change rock wettability and its subsequent effect
on oil recovery. Additionally, some researchers presented extensive literature reviews on the
effect of wettability on microscopic displacement of fluid flow on pore scale [29-35].
However, no studies have been carried out to investigate the effect of nanoparticles along with
surfactants on the pore-scale visualization of the role of ZrO2 nanoparticles on wettability
alteration and IFT reduction during nanosurfactant flooding. Moreover, investigations on the
effects of nanoparticles/aqueous surfactants solutions on different aspects of improving EOR
efficiency have not significantly been conducted yet. Furthermore, the mechanism of aqueous
surfactants containing nanoparticles in improving macroscopic and microscopic efficiency of
heavy oil recovery particularly in a fractured 5-spot model has been less investigated [36-37].
In addition, as it is well known that, in EOR processes, mobility ratio is the mobility of the
injected displacing fluid to that of the oil being displaced. Good mobility control is obtained
when the viscosity of the injected fluid is higher than the viscosity of the oil in the reservoir and
can lead to a piston-like displacement of the oil from the injection well to the production well.
However, poor mobility control due to a lower viscosity of the injected fluid can result in low
recoveries due to viscous fingering [11,38]. Achieving good mobility control in combination
with other mechanisms including low interfacial tension or wettability alteration is therefore
essential for successful chemical EOR. The high viscosity of the injected phase can lead to
improved mobility control [39-40]. A method for achieving high viscosities of the injected
phases and good mobility control is through generation of foams and emulsions, which can form

in the presence of surfactants or nanoparticles. Foams and emulsions are dispersions of one fluid
in a second immiscible fluid, and they typically exhibit high viscosities and shear-thinning
rheological behaviors [41-42]. Nonetheless, investigations about effects of nanoparticles with
aqueous surfactants solutions on rheological properties such as viscosity have not been
significantly studied yet.

It is obvious that, oil recovery efficiency can be determined by using relative permeability test
results; however, due to difficult and costly tests for the whole reservoir, a limited number of
these results are available. Hence, experimental studies at a lower cost and high reproducibility
are done which can be a great advantage.In this respect, micromodels are produced with the
objective of directly observing fluid flow through porous media. Micromodels contain an etched
flow pattern that can be viewed with a microscope. Numerous studies have been performed using
micromodels [43-47].
The transparent materials like glass have been used to construct micromodels and to study
various aspects of micro-displacement. By using micromodels, the motion of the fluids can be
observed and investigated in terms of micro geometry and physical characteristics of the
presented liquids, gases, and solids [44]. The results and findings from micromodel studies can
be used to improve our understanding about microscopic and macroscopic behaviors of
displacement processes, and perhaps the modeling of the flow mechanism. Observation in 5-spot
micromodel can better simulate the behavior in porous media; thus we herein used these types of
micromodels [48-49].

In this study, the microscopic and macroscopic efficiency displacement of heavy oil recovery in
a fractured 5-spot model was studied. Two types of surfactants, namely cationic (C12TAB) and
anionic (SDS) alone, a surfactant solution containing zirconium oxide nanoparticles, and
nanoparticle solutions (ZRSL) were used in the injection process. In addition, the rheological
properties of the nanosuspension were determined using a rotational viscometer at a temperature
of 25 C, and the possibility of the usage of nanosurfactants to control mobility in injections
processes was investigated. Moreover, IFT and wettability measurements for two types of
surfactants alone, surfactant solutions containing nanoparticles, and ZRSL solutions were
conducted.
2. Materials and Methods
Materials that were used for tests are given as follows:
2. 1 Materials
2. 1. 1 Nanoparticle Synthesis
ZrO2 nanoparticles were prepared using the sol-gel method [50]. Zirconium oxychloride
(ZrOCL2. 8H2O) was used as a source of Zr. The starting solution was prepared by mixing 3.2 gr
of Zirconium oxychloride with 2.1 gr of citric acid, 1.2 gr succinic acid, 0.5 gr of CTAB as
surfactant, and 10 ml of ethoxylatednonylphenol, 20 mol EO. The solution was then kept in 80
C for about 4 hrs. The solid product was washed and filtered with ethanol and distilled water.
The sample was then dried in an oven at 110 C for 4 hrs, and finally, it was dehumidified at 800
C for 8 hrs. The produced nanoparticles are seen in Figure 1.

2. 1. 1. 1 Characterization Tests
SEM (Philips XL-30W model) and XRD (3003 PTS Seifert with Cu K radiation, =1.54 oA)
devices were used to investigate the morphology and mineralogy of zirconium oxide. The
properties of synthesized zirconium oxide nanoparticles are given in Table 1.

Table1. Properties of Zirconium Oxide nanoparticles

Particle

Average size(nm)

Specific surface(m2/g)

Bulk density(kg/m3)

ZrO2

14

190

46

Fig1. Synthesized ZrO2 Nanoparticles

2. 1. 2 Surfactant
Surfactants or surface active agents are chemicals substances that are adsorbed on interface
between two fluids [39]. The surface properties are changed with reduction in interfacial tension
(IFT) by surfactants. In this study, two type of surfactants were used, C12TAB as cationic
surfactant and SDS as anionic surfactant. Surfactant properties are given in Table2.

Table2. Surfactant properties

Surfactant

CMC(ppm)[51]

Molecular Weight(g/mol)

CTAB

3100

364.4

SDS

2420

288.38

2. 1. 3 Crude Oil
A heavy crude oil from one of Iranian oilfield was used; its properties are shown in Table 3.
Asphaltine contents are also shown in Table 4.

Table 3. Heavy crude oil properties

API

Density(g/cc)

Viscosity(cp)

Asphaltene(wt%)

Acid

Base

Number(mg Number(mg

21.2

0.91

130.4

KOH/g oil)

KOH/g oil)

2.02

1.79

6.5

Table4. Asphaltine Contents of used crude oil

Asphaltine C

Ash

8.0

1.0

8.4

1.5

1.2

Content
Wt (%)

81.1

2. 2 Experimental Setup
In this work, a fractured 5-spot glass micromodel was constructed and used in the experiments.
The 2D micromodels were fabricated based on a new method using laser technology. Procedural
details of micromodel construction can be found elsewhere [52]. A Schematic of the micromodel
pattern and a close-up view of scanning electron microscop image are shown in Figure 2 and
Figure 3. This pattern was prepared by thin section of carbonate rock from one of Iranian oil
reservoir. Physical and hydraulic properties of the constructed micromodel are shown in Table 5.

Fig 2.A Schematic of Fractured pattern

Fig 3. Close-up of scanning electron microscope image

Table 5. Physical and hydraulic properties of the constructed micromodel

Length (mm)

60

Width (mm)

60

Etched thickness (m)

65

Absolute permeability (md)

250

Porosity (fraction)

52.2

Number of Fracture

Length of Fracture (cm)

Width of fracture (mm)

700

Angle of fracture ()

90

An experimental setup has been designed to perform visualization during experiments including
a camera with a video recording system, a precise pressure transducer and a high precise low rate
Quizix pump which control precisely the flow rate of fluids through micromodel. A schematic of
experimental setup is shown in Figure 4. Cleaning is accomplished by flushing solvent through
the micromodel using Eldex pump. The washing pump included three containers for holding the
cleaning fluids (i.e. distilled water, methylene chloride or acetone and toluene). Fluid saturations
were monitored by taking high quality pictures which can be then analyzed by using image
processing software.
To measure contact angles in different conditions of wettability, the sessile drop method was
used. Measuring contact angle of a surface is one of the methods to evaluate wettability of a
surface. To examine the effect of ZrO2 on contact angle of the glass surface, some experiments
were designed. Nine glass plates with flat surface (12 cm 5 cm 5 mm) were used to measure
contact angles. Before measurements, the surface of them was cleaned by ethanol and then was
dried in an oven for 2 hr set to a temperature of 100 C. To get the reliable results from contact
angle measurements, five points were selected on the surface of the glass. Measurements were
performed for each five points and the average values were calculated.
In addition, rheological properties of the nanosurfactant were determined on rotational
viscosimeter PVS at a temperature of 25 C. Moreover, in IFT measurements, all reported
interfacial tension values have been measured by a drop shape tensiometer DSA30 of Kruss

company. Pendant drop method which is based on Laplace equation and describes relationship
between the difference in pressure and interfacial tension was selected for our purpose.

Fig4. A schematic of experimental setup

2. 3 Experimental Procedure
Before starting the experiments, the micromodel was cleaned with toluene, ethanol and then deionized water. Next, the model was initially saturated with oil (lack of the presence of initial
water) and then solutions were injected with a fixed rate of 0. 0008 (cc/min). Micromodel was
completely horizontal. During injection processes, fluid saturations were monitored by taking
high quality pictures. Amount of oil recovery by examining pictures and diagrams could be
determined. In addition, by investigating microscopic pictures taken during flooding tests,
changes in pore dimensions were investigated.

2. 4 Fluid Injection Scenarios

The first displacement test was surfactant flooding into micromodel. Aqueous surfactants
solutions were prepared at three concentrations ranging from 1000 ppm to 3000 ppm for SDS
and four concentrations ranging from 1000 ppm to 4000 ppm for C12TAB. Using image
analysis, recovery efficiency was measured in terms of pore volume injected fluids. During the
flooding test, high resolution microscopic pictures were continuously taken from the micromodel
to visualize fluid distribution in pores and throats. At the end of the first flooding test, the
micromodel was cleaned by toluene and ethanol, and then dried in an oven set at the temperature
of 150 C for 3 hr. Before performing second test, the micromodel was saturated again with
heavy oil as explained above. Then the test was conducted with nanosurfactants. Nanosurfactants
were prepared by dispersing zirconium oxide nanoparticles in the surfactants at concentration of
100 ppm of nanoparticles in two different concentrations of surfactants, 2000 ppm for SDS and
3000 ppm for C12TAB. All steps in the first test were repeated and then oil recovery was
measured. The flooding test with ZrO2 (100) SDS (2000) was repeated for ZrO2 (100) C12TAB
(3000). All experiments were carried out at fixed injection rate of 0. 0008 cc/min. This flow rate
reasonably simulates fluid flow velocity in the underground oil reservoirs. It should be
mentioned that the distilled water flooding as reference test was conducted. Before performing
third test, the micromodel was saturated again with heavy oil as explained before. Then the test
was run with ZRSL solutions. To prepare the ZRSL, different quantities of ZrO2 nanoparticles
were dispersed in distilled water by means of ultrasonic probe (400 W and 0.5 Hz) for 1 hrs. Six
concentrations of nanoparticles in aqueous solutions were used. After preparation of the samples,
for assurance of the homogeneity and stability of prepared solutions, the solutions were placed

for 3 weeks in a closed transparent bottle. Following this, the ZRSL solutions were re-examined
and no precipitation and agglomerations were detected.

3. Results and discussions

3. 1 Aqueous surfactant flooding
Surfactants by reducing IFT between fluids can improve oil recovery [14-15]. In addition,
surfactants by reducing IFT lead to forming a stable, suspended emulsion. Sometimes,
surfactants depending on the properties of the porous media and substances with which they are
in contact can influence and change the wettability system [53-55]. However, the wettability
system was not altered strongly in this work and just the thickness of the oil layer attached to
pores and throats (further explained in microscopic investigation) was reduced.
In this study, SDS as an anionic surfactant and C12TAB as a cationic surfactant were used. In
this section, the impact of different surfactants at different concentrations was investigated. First,
oil recovery by water flooding as reference test was conducted. Considering Figure 5, oil
recovery by pure water flooding was 20%. Next, surfactant flooding at different concentrations
was conducted. According to the diagrams obtained, the injection of SDS at a concentration of
1000 ppm showed an increase of about 9% compared to the first test (water flooding). Then,
increasing the concentration of SDS to 2000 and 3000 ppm, due to more reduction of IFT, leads
to higher oil recovery. However, as can be seen, there is no significant difference between the
curves of 2000 and 3000 ppm. This is due to the CMC number of SDS which is 2420 ppm and it
means that higher concentrations of CMC have a slight effect (or even sometimes a negative
effect) on enhancing oil recovery.

A similar trend was seen for C12TAB (Figure 6). Therefore, the oil recovery by the injection of
C12TAB showed an increase compared to pure water and an increase in the concentration of
surfactant led to higher oil recovery. Obviously, as can be seen in Figures 5 and 6, the recoveries
of SDS and C12TAB flooding 25% and 36% respectively are higher than pure water, which
shows that the fingering phenomenon (reaching at the end point) in surfactant injection occurred
later compared to water injection. Unlike water, this can be due to the preferable penetration of
surfactants into the matrixes of rock as a result of reducing IFT and significantly increasing
capillary number.
As can be inferred from the comparison between Figure 5 and Figure 6, C12TAB shows better
performance than SDS in terms of ultimate oil recovery. But, to make this comparison more
clearly, oil recovery diagram is plotted in terms of both surfactant concentrations (Figure 7).
Obviously, C12TAB has a greater impact on the ultimate oil recovery than SDS. In fact,
C12TAB results in more interactions between matrix and fracture and, as a consequence of

Oil Recovery(%)

greater penetration into matrix, leads to improved oil recovery.

45
40
35
30
25
20
15
10
5
0

Water
SDS 1000
SDS 2000
SDS 3000
0

0.5

1.5

2.5

Pore Volume Injected(PVI)

Fig5. Oil recovery for different concentrations of SDS

Oil Recovery(%)

50
45
40
35
30
25
20
15
10
5
0

Water
CTAB1000
CTAB2000
CTAB3000
CTAB4000
0

0.5

1.5

2.5

Pore Volume Injected(PVI)

Oil Recovery(%)

Fig6. Oil recovery for different concentrations of CTAB

50
45
40
35
30
25
20
15
10
5
0

SDS
CTAB

1000

2000

3000

4000

Surfactant Concentration(ppm)

Fig7. Oil recovery in terms of concentration of surfactant

3. 2 Aqueous surfactant solutions containing ZrO2 Nanoparticles Flooding

Nanoparticles along with surfactants cause releasing trapped oil in pores and throats. This
happens by many factors such as reducing IFT between oil and water, spontaneous emulsion
formation, the wettability alteration of porous media, the modification of flow character, which
ultimately increase oil recovery significantly.
As can be seen in Figures 8 and 9, oil recovery increases for surfactant solutions containing
nanoparticles. Hence the recovery of ZrO2 (100)/SDS (2000), namely 8%, and ZrO2
(100)/C12TAB (3000), i.e. 14%, are higher than SDS and C12TAB alone. Moreover, the amount
of recovery for ZrO2 (100)/C12TAB (3000) was greater than ZrO2 (100)/SDS (2000). This is due
to the higher activity of C12TAB as a cationic surfactant compared to SDS as an anionic
surfactant. Higher oil recovery can be obtained due to decreasing IFT and altering wettability in
the presence of nanoparticles.
In fact, nanoparticles form a mixed layer with surfactants at the interface between the injected
fluid and oil. This results in increasing the interface and consequently makes a considerable
contribution to reducing IFT. This means that capillary forces considerably decrease and
capillary number will strongly be increased [3]. Furthermore, the results show that the presence
of nanoparticles changes rheological properties and increases the effect of surfactant solution on
oil recovery processes. The observed reduction in interfacial tension and wettability are the result
of nanoparticle presence at the interfacial layers. As a result, using nanoparticles show a 19%
increase in oil recovery when compared to surfactants used alone.

Oil Recovery(%)

50
45
40
35
30
25
20
15
10
5
0

Water
SDS2000
ZrO2 100 SDS
2000
0

0.5

1.5

2.5

Pore Volume Injected(PVI)

Fig8. Effects of SDS containing ZrO2 nanoparticles on oil recovery

60

Oil Recovery(%)

50
40

Water

30
CTAB3000

20
10

ZrO2 100 CTAB

3000

0
0

0.5

1.5

2.5

Pore Volume Injected(PVI)

Fig9. Effects of CTAB containing ZrO2 nanoparticles on oil recovery

In fact, both nanoparticles and surfactants help each other to remain stable and to contribute to
keeping the formed emulsions stable. The presence of suspended nanoparticles in the solution

increases sedimentation stability, because surface forces easily counterbalance the force of
gravity. In addition, it is obvoius that surfactants contribute to the stability of nanoparticles and
emulsions in order to decrease IFT [23,37].

3. 3 Aqueous ZRSL solutions Flooding

The results of oil recovery during ZRSL flooding tests are shown in Figure 10 and Table 6. For
instance, with PVI of 0.5, the ultimate oil recovery by the injection of 100 ppm ZRSL solution is
equal to the ultimate oil recovery by water flooding. This figure gradually grows to 2%
enhancement when 3000 ppm ZRSL is used. This is the optimal concentration of nanoparticles
for the maximum recovery at which the adsorption sites on the pore wall are saturated with ZrO2
nanoparticles. The enhancement of oil displacement efficiency by increasing nanoparticle
concentration can be occurred because of the increase in viscosity and spreading of nanofluids on
the surface [22]. However, beyond a specific limit of nanoparticle concentration, around 3000
ppm, the ultimate oil recovery decreases due to the blockage of pores and throats by the
dispersed nanoparticles. The reduction of ultimate oil recovery at nanoparticle concentration of
4000 ppm can be seen. In general, this trend was seen for different PVI values and consequently
can be concluded that there is a slight enhancement of oil recovery at the optimum concentration
of nanoparticle solutions compared to water flooding, while this growth is less than both
nanosurfactant solutions.

Table6. Effects of ZRSL solutions on oil recovery

PVI

Water
0
19
19
20
20
20. 7

0
0. 5
1
1. 5
2
2. 5

ZRSL10
0
0
19
19. 1
19. 7
20
20. 1

ZRSL50 ZRSL100
0
0
0
0
19. 2
19. 6
19. 4
19. 9
20
20. 5
20. 3
20. 9
20. 5
21. 1

ZRSL200 ZRSL300
0
0
0
0
20
21
20. 3
22. 9
20. 7
27. 4
21
28. 1
21. 9
29. 4

ZRSL400
0
0
17
17
17. 6
18
18. 5

35
30
Oil Recovery(%)

Water
25

ZRSL100

20

ZRSL500

15

ZRSL1000
ZRSL2000

10

ZRSL3000

ZRSL4000

0
0

0.5

1
1.5
Pore Volume Injected(PVI)

2.5

Fig10. Effects of ZRSL solutions on oil recovery

In addition, the whole flooding process is plotted in Figure 11. Although the different floodings
demonstrate an almost similar value up to a PVI of 0.5, they show completely different values
afterward. At a a PVI of 2.5, water flooding experienced the lowest recovery of 19%, while
ZrO2CTAB3000 showed the highest recovery of about 57%. Moreover, ZRSL solutions and both
surfactants used alone showed better performance than water flooding. It should be mentioned
that surfactants used alone showed better performance than nanoparticles alone; the recovery

valuses were 38, 44, and 30 respectively for SDS2000, CTAB3000, and ZRSL3000. However,
the combination of nanoparticles and surfactants indicates the best performance in terms of oil
recovery. In fact, it seems that there is a synergy between nanoparticles and surfactants, which
helps them to stay stable and to contribute to reducing IFT, thereby leading to higher oil
recovery.

60

Oil Recovery(%)

50
40

Water
ZRSL3000

30

CTAB3000
20

ZrO2 100 CTAB 3000

SDS2000

10

ZrO2 100 SDS 2000

0
0

0.5

1.5

2.5

Pore Volume Injected(PVI)

Fig11. Effects of different floodings on oil recovery

3. 2. 1 Effect of Nanoparticles on rheological properties

In the terminology of fluid flow in porous media, mobility of a fluid is defined as the ratio of
relative permeability of the corresponding fluid to its viscosity. In EOR, mobility ratio is the
mobility of the injected displacing fluid to that of the oil being displaced. Good mobility control
is obtained when the viscosity of the injected fluid is higher than the viscosity of the oil in the

reservoir and can lead to a piston-like displacement of the oil from the injection well to the
production well. However, poor mobility control due to a lower viscosity of the injected fluid
can result in low recoveries due to viscous fingering [11,38]. Achieving good mobility control in
combination with other mechanisms including low interfacial tension or wettability alteration is
therefore essential for successful chemical EOR. The high viscosity of the injected phase can
lead to improved mobility control [39-40]. A method for achieving high viscosities of the
injected phases and good mobility control is through generation of foams and emulsions, which
can form in the presence of surfactants or nanoparticles. Foams and emulsions are dispersions of
one fluid in a second immiscible fluid, and they typically exhibit high viscosities and shearthinning rheological behaviors [41-42]. In addition, the shear-thinning behavior of the injected
emulsion is advantageous for achieving high injection rates into the reservoir.
Accordingly, some researchers investigated about the rheology of emulsions formed by
surfactant and nanoparticles and consequently claimed that the rheology is influenced by the
surfactant to nanoparticle concentration ratio [56]. Viscoelastic behavior of the bulk is observed
only over a range of concentration ratios. For instance, in a study of silica nanoparticles with a
cationic surfactant (cetyl trimethylammonium bromide), has been reported that if the molar
concentration of CTAB to silica nanoparticles was about 0.03, a viscoelastic behavior is
observed [56].

Hence, at this study, rheological properties of the surfactant solutions with and without
nanoparticles were determined on rotational viscosimeter PVS at a temperature of 25 C. The
PVS is a dynamic coaxial cylinder, controlled shear rate rheometer. The outer cylinder (sample
cup) is driven by a stepper motor at speeds from 0. 05 rpm to 1000 rpm. The inner cylinder (bob)
contains an RTD probe on the surface to provide temperature measurement where the shear

stress is being measured. Several cup and bob designs with different geometries are available to
suit various applications. We used TA5B5 rotor-bob combination which gave us a possibility to
take measurement in a range from 0.5 to 1 million cP(mPas). All the measurements controlled
and provided under the special software.
As may be seen in Table 7, the dependence of shear stress on shear rate for aqueous solutions of
anionic surfactants either with and without addition of nanoparticles were measured. The results
revealed that adding nanoparticles to surfactants lead to modification of the flow character from
Newtonian to non-Newtonian (Pseudoplastic). The minimal Newtonian viscosity of the
surfactant aqueous solution was 0.96 mPA.s . However, with adding nanoparticles became about
2 times higher and was equal to 1.99 mPA.s.
Modification of the flow character can be assumed a great achievement as a nanosurfactant
solution, in addition to its own duty, can be used to control mobility ratio in EOR processes.
Obviously, an appropriate mobility ratio greatly affects the macroscopic oil recovery efficiency.

Table7. Measured shear stresses and shear rates

Shear Stress (,Pa)

Surfactant

Solution

without nano particles

Shear Rate (, s-1)

Viscosity (mPa.s.)

0.112

100

1.12

0.218

200

1.09

0.428

400

1.07

0.606

600

1.01

0.80

800

1.00

0.99

1000

0.99

Surfactant

Solution

with Nano Particles

1.172

1200

0.97

1.248

1300

0.96

1.1

100

11

1.5

200

7.51

1.9

400

4.70

2.23

600

3.71

2.45

800

3.06

2.55

1000

2.55

2.6

1200

2.16

2.59

1300

1.99

3. 2. 2 Effects of Nanoparticles on IFT Reduction

Another role of the surfactant is to lower the interfacial tension and form an initial dispersion of
air/water or oil/water in case of foam or emulsion, respectively. Once this dispersion is formed
due to shear and a decreased amount of interfacial tension, the stability of foam/emulsion is
augmented by adsorption of nanoparticles at the interface [57]. For example, has been reported
that the usage of silica nanoparticles coated with a polyelectrolyte to stabilize oil-in-water
emulsions [58]. More recently, Saigal et al. reported stable oil-in-water emulsions using silica
nanoparticles coated with a pH responsive polymer, and they found that the most stable
emulsions were formed at lower polymer chain grafting densities [59].

In addition, some researchers investigated about the effects of nanoparticles on IFT reduction on
surfactant solutions [23,32]. They Claimed the Presence of nanoparticles changes rheological
properties and increase effect of surfactant solution on oil recovery processes. First of all, it
changes interfacial tension value of surfactant/oil interface more effectively [25]. Observed
reduction of interfacial tension is the result of nanoparticles presence at the interfacial layers. In
low concentrations of nanoparticles, they are attached to the liquid surface and due to absorption
process decrease surface tension. However, in high concentrations, the nanoparticles nearly
completely remove the surfactant from the bulk aqueous phase and there is no free surfactant
available in the bulk. Thus, for nanoparticles in low concentrations the interfacial tension of the
dispersion is determined by a mixed layer composed by attached nanoparticles and surfactant
adsorbed at the liquid interface [23,26].

Accordingly, the interfacial tensions values were determined in different states. All reported
interfacial tension values were measured by a drop shape tensiometer DSA30 of Kruss company.
Pendant Drop-method based on Laplace equation which describes relationship between the
difference in pressure and interfacial tension was selected for our purpose. The results are shown
in Table 8.
As can be seen, nanoparticles decreased surface tension by 70% when used with a SDS
concentration of 2000 ppm, while the figure for C12TAB was about 81%. In addition,
ZRSL3000 solution, which was chosen before as an optimum concentration, showed an IFT
value of 17.1 (10-3 N/m). Seemingly, although this amount almost showed a same amount
compared to both surfactants alone, it is by far more than nanoparticles/surfactant value. This
means that nanoparticles along with surfactants can strongly decrease the interfacial tension of

oil and water, which can lead to more stable emulsions and justify the enhancement of oil
recovery. In this regard, SDS showed better performance than C12TAB when used either alone
or with nanoparticles.

Table 8. Nanoparticles effect on IFT reduction

IFT(10-3

Concentration(ppm
)

Concentration(ppm)

IFT(10-3 N/m)

N/m)

Concentartion

IFT(10-

of

ZRSL

N/m)

solution(ppm)

SDS

Nanoparti

C12TAB

cles

Nanoparticl
es

2000

16

3000

18.4

2000

100

3.1

3000

100

5.4

3000

3. 2.3 Effects of Nanoparticles on Wettability of System

Measuring contact angle of a surface is one of the methods to evaluate wettability of a surface.
To examine the effect of ZrO2 nanoparticles on contact angle of the glass surface, some
experiments were designed. Nine glass plates with flat surface (12 cm 5 cm 5 mm) were used to
measure contact angles. Before measurements, the surface of them was cleaned by ethanol and
then was dried in an oven for 2 hrs set to a temperature of 100 C. To get the reliable results from
contact angle measurements, five points were selected on the surface of the glass. Measurements
were performed for each five points and the average values were calculated. The first

17.1

measurement was made succeeding coating of the plate with heavy oil for 20 days to provide the
oil-wetting condition. To evaluate the effect of ZrO2 nanoparticles on contact angle and also
surfactant alone of the glass surface, second measurements were performed. To observe the
effect of ZrO2 nanoparticles on wettability, contact angles were measured for two concentrations
of nano solutions, one concentration of two types of surfactants alone and finally for an optimum
concentration of ZRSL solutions. The results are shown in Table 10.
The results of sessile drop experiments and wettability measurements showed that coating with
heavy oil, could make an oil-wet surface. While, coating with both surfactants alone and also
ZRSL solution could partially alter the wettability of surface to water-wet, also coating with
surfactant along with nanoparticles could make a strongly water-wet surface. Furthermore, with
adding ZrO2 nanoparticles to surfactant solutions, the value of contact angles decreased to
approximately 80% and 85% for SDS and C12TAB respectively. As a result, it can be justified
and confirmed the recovery enhancement in flooding tests and fluids distribution in pores and
throats. In fact, these results offer us using the ZrO2 nanoparticles as an additive to aqueous
surfactant solutions for improvement of oil recovery instead/before implementation of other
EOR methods.

In general, considering to experimental results of wettability and IFT measurements, it is seen

that the minimum IFT is achieved by using SDS either with or without nanoparticles, while
C12TAB/nanoparticles mostly alter the wettability toward water-wet condition.

Table9. Contact angle values for different states of coating

Point No.
1
2
3
4
Crude Oil ()
SDS(2000) ()

100
70

102
68

101
71

98
69

5
100
70

C12TAB (3000) ()

63

61

62

63

64

ZrO2 (100)
SDS(2000) ()
ZrO2(100)
CTAB12(3000) ()

30

29

30

31

30

15

14

16

15

14

65

63

64

64

65

ZRSL3000 ()

3. 2. 2 Microscopic and Macroscopic investigation

Using a powerful microscope, which had the ability to enlarge images up to 500 times, highresolution images of residual oil in the dimensions of pores and fluid distribution at porous
media were taken after flooding tests. The constructed micromodel was initially oil-wet. As it is
indicated in Figure 12, which was taken after water flooding, the walls are covered by a layer of
oil. In this image, the brown and white colors indicate oil and injection fluid respectively.
As Figure 13 and Figure 14 show, after aqueous surfactant solution flooding, the wettability of
porous media partially changes to water-wet. Indeed, it can be said that the surfactant solution
could not strongly alter wettability. With a closer investigation of this image, it can be found
that, due to using surfactants, the thickness of the oil layer attached to walls has been decreased
and thus the residual oil saturation is lower than the previous state. In addition, these images
show that C12TAB has a greater impact on wettability than SDS; C12TAB also shows a greater
reduction in the thickness of the oil layer attached to walls, which can be the reason for the
higher oil recovery of C12TAB.

Fig12. Water flooding

Fig13. SDS Flooding

Fig14. CTAB Flooding

Finally, the ability of zirconium oxide nanoparticles to alter the wettability of pore surfaces is
shown in Figures 15 and 16. The flow of nanosurfactant in the medium could release oil from the
walls of pores and throats, and therefore an increase in oil recovery was observed. A reason for
fluid flow behavior during nanosurfactant flooding is the adsorption of ZrO2 nanoparticles onto
medium surface and their ability to change the surface wettability from oil-wet to water-wet. It is
obvious that, among the many features affecting the fluid distribution and oil recovery in porous
media, wettability is proven to be a crucial factor [27-28].

Fig15. SDS containing nanoparticles flooding

Fig16. CTAB containing nanoparticles flooding

Moreover, several images were taken in the macroscopic investigations of oil displacement
during adding surfactants alone and nanosurfactant flooding processes. As indicated in Figures
17 and 18, the presence of nanoparticles leads to better mobility ratio between oil and injection
fluid, which consequently increases oil recovery. This can be because of the increased viscosity
of nanosurfactant solution, which results in a better mobility ratio and less viscosity difference
between oil and injection fluid. Moreover, when compared to using surfactant alone, oil
displacement efficiency increases in nanosurfactant flooding, which is ascribed to higher
reduction of IFT and the strong alteration of wettability from oil-wet to water-wet. As a result, it
can be concluded that the hydrophilic nature of the synthesized ZrO2 nanoparticles cause a
wettability alteration of the micromodel from oil-wet to water-wet.

Fig17. Surfactant Flooding

Fig18. Nanosurfactant Flooding

4. Conclusions

The presence of nanoparticles in surfactant increase significantly oil recovery. This

enhancement generally for C12TAB/ZrO2 is greater than SDS/ZrO2 in terms of oil recovery.
This is due to the higher activity of C12TAB as a cationic surfactant than SDS as an anionic
surfactant.

Investigations on microscopic images show that after nano surfactant flooding, wettability of
pore media alter from oil wet to water-wet. Hydrophilic nature of synthesized ZrO2
nanoparticles causes a wettability alteration of the micromodel from oil-wet to water-wet.

Therefore, in addition to mentioned mechanisms, the alteration of wettability in the presence

of ZrO2 nanoparticles increases significantly oil recovery.

Nanoparticles attached to the liquid interface, due to absorption process reduce interfacial
tension and increase the effect of surfactants on reducing IFT. Nanoparticles reduce surface
tension 81% using SDS of 2000 ppm concentration, while the figure for C12TAB is about
70%.

Adding nanoparticles to the surfactant solution lead to flow character modification from
Newtonian to non-Newtonian. The minimal Newtonian viscosity of nano surfactant is 2
times higher than surfactant alone.

Increasing viscosity by adding nanoparticles can be assumed a great scientific achievement in

which a nanosurfactant solution, in addition to its own duty, can be used as an agent to
control mobility ratio in EOR processes.

In general, the experimental results show that the minimum IFT is achieved by using SDS
either with or without nanoparticles, while C12TAB/nanoparticles mostly alter the
wettability toward a water-wet condition.

Results of this work suggest that zirconium oxide nanoparticles can be used as an additive to
surfactants for the improvement of oil recovery.

Acknowledgment
The authors would like to acknowledge the petroleum laboratory of Islamic Azad University for
providing technical facilities.

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Highligths

Presence

of

ZrO2

nanoparticle

in

surfactant

solution

lead

to

viscosity

enhancement

Presence

of

ZrO2

nanoparticle

in

surfactant

lead

to

improve

considerably

oil recovery

Nanosurfactant

(Surfactant/ZrO2)

has

great

impact

on

wettability

alteration

Nanosurfactant

modify

the

flow

character

from

Newtonian

to

non-

Newtonian

Presence of ZrO2 in interfacial layers lead to a significant reduction of IFT

Values