Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

ISSN: 1556-7036 (Print) 1556-7230 (Online) Journal homepage: http://www.tandfonline.com/loi/ueso20

Application of SiO2 and TiO2 nano particles to

enhance the efficiency of polymer-surfactant
floods
M. H. Sedaghat, H. Mohammadi & R. Razmi
To cite this article: M. H. Sedaghat, H. Mohammadi & R. Razmi (2016) Application of
SiO2 and TiO2 nano particles to enhance the efficiency of polymer-surfactant floods,
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 38:1, 22-28, DOI:
10.1080/15567036.2012.740552
To link to this article: http://dx.doi.org/10.1080/15567036.2012.740552

Published online: 29 Dec 2015.

Submit your article to this journal

Article views: 20

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ueso20
Download by: [University of California, San Diego]

Date: 15 January 2016, At: 13:36

ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS

2016, VOL. 38, NO. 1, 2228
http://dx.doi.org/10.1080/15567036.2012.740552

Application of SiO2 and TiO2 nano particles to enhance the

efficiency of polymer-surfactant floods
M. H. Sedaghata, H. Mohammadib and R. Razmia
Faculty of Chemical Engineering, Islamic Azad University, Dashtestan Branch, Dashtestan, Iran; bFaculty of Chemical
Engineering, Islamic Azad University, Bushehr Branch, Bushehr, Iran

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

ABSTRACT

KEYWORDS

Polymer-surfactant flooding is one of the most novel chemical enhanced oil

recovery methods. Application of Nano particles in enhanced oil recovery
has attracted much interest as well. This work concerns the application of
Nano particles to increase the efficiency of polymer-surfactant flooding in
heavy oil five-spot systems. In this investigation, micromodel setup was
used to monitor the role of Nano particles on wettability alteration during
polymer-surfactant floods. Two common Nano particles, SiO2 and TiO2 as
well as HPAM and SDS as commercial chemicals in enhanced oil recovery,
were used to create five solutions containing Nano particles at different
levels of concentration. Then, contact angle tests and flooding tests were
performed by taking microscopic/macroscopic pictures. According to the
results, since SiO2 Nano particle decrease the contact angle more severely, it
results in a higher oil recovery. Although this decrease is more when SiO2 is
dispersed in water, due to its better absorption on a surface, the wettability
alteration is more obvious during polymer-surfactant flooding because of
the presence of a thinner oily film that intensifies mass transformation from
fluid to the surface. In addition, an increase in the concentration of Nano
particles leads to an increase in the efficiency of oil recovery and wettability
alteration. Furthermore, according to the microscopic pictures, pulling and
emulsification mechanisms are more effective than the wettability alteration mechanism.

Displacement mechanisms;
experimental; Nano
particles; polymer-surfactant
floods; wettability alteration

1. Introduction
Waterflooding is one of the most common conventional methods to increase oil production;
however, most residual oil is difficult to get displaced during this process. Chemical enhanced oil
recovery (EOR) methods are the most novel procedures to increase oil recovery by adding chemicals
to improve the properties of water as the displacing phase.
The main concept of polymer flooding is affecting the sweep efficiency. Sweep efficiency is
defined as the ratio of oil volume contacted by displacing agent to initial volume of oil in place.
Sweep efficiency is influenced by mobility ratio, pore structure, reservoir rock wettability, reservoir
heterogeneity, and properties of fractures (Craig, 1971). Argabright et al. (1982) showed that
hydrolyzed solution of polyacrylamide enhances oil recovery by controlling the water mobility and
increasing the sweep efficiency because of an increase in water viscosity and reduction in its relative
permeability.
One of the most simple and inexpensive EOR methods is dilute surfactant flooding. Surfactants
are absorbed on the interface of liquids and decrease the interfacial tension. Akstinat (1981) surveyed
different surfactants that were used in EOR. He did his experiment in high salinity conditions.
CONTACT Mohammad Sedaghat
m.sedaghat66@gmail.com
Dashtestan Branch, Dashtestan, 7561654657 Iran.
2016 Taylor & Francis

Faculty of Chemical Engineering, Islamic Azad University,

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS

23

Barakat et al. (1983) investigated the role of surfactants chemical structure on determination of
interfacial tension (IFT). Imbibition capillary rate of surfactants and polymer were compared by
Babadagli (2001). He found that adding surfactants increases the ultimate oil recovery.
Polymer and surfactant flooding are two important and high efficiency chemical flooding
processes. However, it seems that a combination of these two processes can have synergistic effects
and so efficiency of both processes can be increased with their combination (Maldal et al., 1998).
Many surfactant-polymer flooding works were performed in the 1970s (Salager et al., 1979; Bennet
et al., 1981). Application of simultaneous polymer and surfactant flooding can improve microscopic
and macroscopic sweep efficiency (Sedaghat et al., 2011).
The tendency of a surface to contact with a fluid is called wettability. This concept is assessed by
measuring the contact angle between a fluid droplet and the surface. If the contact angle is lower
than 60, the fluid makes the surface wet, and if the angle is greater than 90, the fluid does not make
the surface wet. Wettability is affected by: (1) surface adsorption and desorption, (2) rock mineralogy, and (3) the film deposition and spreading capability of the oleic phase (Maghzi et al., 2011).
Usually, the presence of a large polar compound, such as asphaltenes, in the oil phase enables the
adsorption onto the solid surface leaving an oil film, which may alter the rock surface wettability
(Dandekar et al., 2008).
Among the many parameters that influence the fluid flow and oil recovery in porous media,
wettability of the medium is too important (Agbalaka et al., 2008). Some work has been reported in
the literature about the role of wettability on fluid flow in porous media and pore scale microscopic
mechanisms (Sander Suicmez et al., 2008; Jamaloei and Kharrat 2010; Dehghan et al., 2010; Blunt,
2001). In oil-wet rocks, due to the tendency of oil that sticks to the pores walls and traps in dead
ends, the efficiency of waterflooding is lower. Comprehensive investigations have been done on the
wettability effect on fluid flow and displacement mechanisms in porous media (Maghzi et al., 2011);
however, limited surveys have been done on the mechanisms of wettability alteration. Here, Nano
silica, SiO2, with TiO2 during polymer-surfactant flooding has been compared.
In this study, a two-dimensional five-spot glassy micromodel was used to investigate the role of
Nano particles on wettability alteration. Two Nano particles were used to survey this effect on
polymer-surfactant flooding. Since HPAM 3330 and SDS are the most common commercial
materials in this process, they are used as, respectively, polymer and surfactant that constitute the
solutions.

2. Experimental setup
The experimental equipment and micromodel preparation process is the same as that done by
Dehghan et al. (2010). The micromodel is a porous medium with the porosity, permeability, and
coordinate number of 52.48, 1600 mD, and 4, respectively. Its width and length are both 60 mm and
the pores are cubic.
2.1. Test fluids
TiO2 and SiO2 were used as Nano particles in the aqueous displacing phase. The properties of these
materials are shown in Table 1. Also, HPAM 3330 at the concentration of 1200 ppm and SDS at the
concentration of 2000 ppm were used as polymer and surfactant, respectively, to create the polymersurfactant solution with/without Nano particles.
Table 1. Nano Particle Physical Properties.
Particle
SiO2
TiO2

Average Size, nm
14
14

Specific Surface, m2/g

200
110

Bulk Density, kg/m3

48
4,230

24

M. H. SEDAGHAT ET AL.

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

In order to prepare the polymer-surfactant solution, a pre-determined amount of surfactant was

added to a known amount of water to produce a solution with a specific weight fraction. The
powders/crystals are solved in water by stirring. After gaining a homogenous solution, a specific
amount of polymer powder is added to a specific amount of water in order to produce a solution
with a specific weight fraction. Then, this solution is kept at 58C for 12 h. In order to prepare Nano
fluids with specific weight fractions, a pre-determined amount of Nano particles were added to a
known amount of water/polymer-surfactant. It is necessary to stir the solution by ultrasonic
apparatus at 400 W and 0.5 Hz for 1 h.
An Iranian heavy oil sample, with the viscosity and API of 68 cp and 19.4, respectively, at 22C
was used to saturate the model. The viscosity of the polymer-surfactant solution at this experimental
range of shear rate is 2230 cp. The IFT of the solutions with the oil affected by SDS was calculated
at 0.059 dyne/cm.
2.2. Experimental procedure
2.2.1. Contact angle measurements
Assessing the angle between water droplets and the surface is representative of measurement of
wettability of the surface with respect to the water. To investigate the Nano particle effects on
wettability alteration, first, five glassy surfaces are washed by toluene and then dried. The first glass is
submerged by the polymer-surfactant solution; the second one is submerged by SiO2 Nano fluid; the
third one is submerged by TiO2 Nano fluid, the fourth is submerged by the polymer-surfactant
solution containing SiO2 Nano particle, and the fifth is submerged by the polymer-surfactant
solution containing TiO2 Nano particle, like a film of submerging fluid, all for 30 days. For each
case, three droplets of water are dropped on different parts of the glass and the contact angle is
measured. The measurements are done by microscopic pictures taken from the droplets. The
pictures are opened in the software that has a ruler tab to measure contact angles. Also, the contact
angle is measured in the condition that no contact has occurred.
2.2.2. Floods
Each fluid is injected through the model that has not been in contact with any liquid. The pictures
are analyzed to detect recovery versus pore-volume.

3. Results and discussions

3.1. Contact angle results
Table 2 shows the average contact angle of water droplets with the surfaces in contact with aqueous
fluids of SiO2 Nano fluid, TiO2 Nano fluid, polymer-surfactant solution without Nano particles,
polymer-surfactant solution with Sio2 Nano particle, and polymer-surfactant solution with Tio2
Nano particle. As is obvious, comparing all cases with the polymer-surfactant solution without Nano
particle as the reference case, contact of SiO2 Nano fluid with the surface and consequently its
absorption on the surface of the glass leads to the lowest contact angle that shows a serious
Table 2. Contact Angles.
Fluid in Contact
Polymer-surfactant
SiO2
TiO2
Polymer-Surfactant-SiO2
Polymer-Surfactant-TiO2
No contact

Point One,
62
10
14
25
30
135

Point Two,
61
8
16
21
31
135

Point Three,
60
11
14
23
30
137

ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS

25

intensified water-wet condition. Then, it is TiO2 Nano fluid that results in wettability alteration to
water-wet. Polymeric solutions are ranked below the Nano fluids. It seems that absorption of
polymer interrupts the absorption of Nano particles and decreases their efficiency. This lower
absorption is because of the presence of polymer and surfactant molecules. Similarly, the polymeric
solution, which contains SiO2 Nano particle, has resulted in a lower contact angle in comparison
with another Nano-polymeric solution.

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

3.2. The role of concentration of nano particles

Figure 1 shows the oil recovery versus injected pore volume of SiO2 Nano fluid with concentrations
of 0, 500, and 1000 ppm. As apparent, the presence of Nano particles in water results in an increase
in oil recovery, although this increase is not too significant especially in the first pore volumes. Also,
it is obvious that injected fluid with the concentration of 1000 ppm results in a higher oil recovery in
comparison with injected fluid with a concentration of 500 ppm. Thus, an increase in concentration
of Nano particle leads to an increase in adsorption of particles on the surface because of the severe
concentration gradient. Thus, the wettability alteration gets intensified and recovery efficiency is
improved. This effect is more obvious in later pore volumes when the oily films are thinner and the
time has been passed. Time, thickness of the stuck oily film, and concentration are the three key
parameters that control the efficiency of Nano fluid flooding.

3.3. The role of nano particle type

Two different Nano particles were used in the experiments. Figure 1 also shows the oil recovery
versus injected pore volume of SiO2 and TiO2 Nano fluids both at the concentrations of 1000 ppm.
As it is apparent, SiO2 Nano fluid leads to a higher oil recovery in comparison with TiO2 Nano fluid.
It is due to the higher capability of SiO2 to decrease the contact angle, as shown in Table 2. It is also
noticed that Nano fluids do not alter the breakthrough time. But, the comparison shows that in
Nano fluid flooding, after the breakthrough in the later pore volumes, there is a slope in the recovery
line; however, this line in water flooding is approximately horizontal. It is due to an increase in the
contact time of Nano particles with the surface. Thus, Nano fluid flooding efficiency increases with
an increase in flooding time.

Figure 1. Recovery vs. injected pore volume of two Nano particles at different concentartions dispersed in water.

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

26

M. H. SEDAGHAT ET AL.

Figure 2. Recovery vs. injected pore volume of two Nano particles dispersed in polymer-surfactant solution.

3.4. Nano-polymer-surfactant flooding

Figure 2 shows the oil recovery versus injected pore volume for two solutions constituted from
HPAM at a concentration of 1200 ppm and SDS at a concentration of 2000 ppm; one contains SiO2,
however, the other contains TiO2 both with the concentrations of 1000 ppm. As it is obvious, the
Nano-polymer-surfactant solution that contains SiO2 results in a somehow higher ultimate oil
recovery in comparison with that containing TiO2. This is due to the higher capability of SiO2
Nano particle to change the wettability from oil-wet to water-wet. This wettability alteration during
Nano-polymer-surfactant flooding is more significant than one in Nano fluid flooding. This is
because of the effective sweep efficiency of polymer-surfactant solution. Since this solution contains
polymer, it increases the viscosity, which results in a better sweep efficiency. When sweep efficiency
increases, the oily film that has stuck to the walls gets thinner. This thinning causes the Nano
particles to be absorbed easier. The more Nano particle transportation, the more effective the
wettability alteration. On the other hand, during Nano fluid flooding, since the viscosity of water
is not too high, the attached oily layer is thicker and mass transfer is not too effective due to a lower
concentration gradient.
3.5. Displacement mechanisms
Figures 3a, 3b, 3c, and 3d illustrate the residual oil, respectively, during water, SiO2 Nano fluid,
polymer-surfactant, and Nano-polymer-surfactant floods. According to Figures 3a and 3b, the stuck
oily layer is somehow thick; however, this layer is significantly thinner in Figure 3d because of the
presence of polymer. Although SiO2 Nano fluid has changed the contact angles, the role of fluid
viscosity is more identified. The pulling and emulsification mechanisms are more effective than the
wettability alteration mechanism. According to Figure 3d, the injected solution is in contact with the
pores wall in some parts, which means that the wettability has been reversed. It is also apparent in
Figure 3b. The Nano particles can pass the film, reach to the surface, and change the wettability.
Comparison of Figures 3b and 3d gives the conclusion that the wettability alteration is much more
severe when the polymer-surfactant exists. Although emulsification is apparent during polymersurfactant flooding in Figure 3c, no wettability alteration is detected. It is just in Figure 3d that all
pulling, emulsification, and wettability alteration are detected during Nano-polymer-surfactant
flooding. Also, gray parts inside the aqueous phase in Figures 3c and 3d are representative of oil
wad transportation mechanism. Residual oil is transported like suspended wads inside the emulsified
droplets during polymer-surfactant flooding regardless of presence/absence of Nano particles.

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS

27

Figure 3. The micromodel after (a) waterflooding, (b) SiO2 Nano fluid flooding, (c) polymer surfactant flooding, and (d) SiO2polymer surfactant flooding.

4. Conclusions
Based on the obtained results the following conclusions can be drawn:
(1) SiO2 and TiO2 Nano fluids cause a change in the wettability of the system to water-wet and
increase in oil production. SiO2 Nano fluid has a more significant effect on the decrease in
contact angle. Also, adding SiO2 and TiO2 Nano particles to polymer-surfactant solution
leads to an increase in oil production.
(2) SiO2 Nano fluid leads to a higher oil recovery in comparison with TiO2 Nano fluid.
(3) Although the fluid that contains water with dissolved Nano particles results in a lower
contact angle in comparison with the polymer-surfactant solution with dissolved Nano
particles, flooding the polymer-surfactant solution with dissolved Nano particles leads to a
higher oil recovery due to its higher viscosity that leads to thinner films.
(4) Time, thickness of the stuck oily film, and concentration are three main key parameters that
control the efficiency of Nano fluid flooding.
(5) The pulling and emulsification mechanisms are more effective than wettability alteration
mechanism. Thus, focusing on polymer and surfactant properties may be seriously
recommended.
(6) Regardless of presence/absence of Nano particles, oil wad transportation mechanism is an
obvious process during polymer-surfactant flooding.

28

M. H. SEDAGHAT ET AL.

Downloaded by [University of California, San Diego] at 13:36 15 January 2016

References
Agbalaka, C., Dandekar, A. Y., Patil, S. L., Khataniar, S., and Hemsath, J. R. 2008. The effect of wettability on oil
recovery: A review. SPE Paper 114496. SPE Asia Pacific Oil and Gas Conference, Perth, Australia, October 2022.
Akstinat, M. 1981. Surfactants for enhanced oil recovery processes in high salinity systemsProduct selection and
evaluation. In: Fayers, F. J. (Ed.). Enhanced Oil Recovery. New York: Elsevier, pp. 4380.
Argabright, P., Rhudy, J., and Phillips, B. 1982. Partially hydrolyzed polyacrylamides with superior flooding and
injection properties. SPE Annual Technical Conference and Exhibition, New Orleans, Louisiana, September 2629.
Babadagli, T. 2001. Scaling of concurrent and countercurrent capillary imbibition for surfactant and polymer injection
in naturally fractured reservoirs. SPE J. 6:465478.
Barakat, Y., Fortney, L. N., Schechter, R. S., Wade, W. H., Yiv, S. H., and Graciaa, A. 1983. Criteria for structuring
surfactants to maximize solubilization of oil and water: Alkyl benzene sodium sulfonates. J. Colloid Interface Sci.
92:561574.
Bennett, K., Phelps, C., Davis, H., and Scriven, L. 1981. Microemulsion phase behavior observations, thermodynamic
essentials, mathematical simulation. SPE J. 21:747762.
Blunt, M. J. 2001. Flow in porous media, pore-network models and multiphase flow. J. Colloid Interface Sci. 6:197207.
Craig, F. F. 1971. The Reservoir Engineering Aspects of Waterflooding. Monograph Vol. 3, SPE of AIME. New York:
AIME.
Dandekar, A. Y., Patil, S. L., and Khataniar, S. 2008. The effect of wettability on oil recovery: A review. SPE Asia Pacific
Oil and Gas Conference, Perth, Australia, October 2022.
Dehghan, A. A., Farzaneh, S. A., Kharrat, R., Ghazanfari, M. H., and Rashtchian, D. 2010. Pore-level investigation of
heavy oil recovery during water alternating solvent injection process. Transport Porous Med. 83:653666.
Jamaloei, B. Y., and Kharrat, R. 2010. Analysis of microscopic displacement mechanisms of dilute surfactant flooding
in oil-wet and water-wet porous media. Transport Porous Med 81: 119.
Maghzi, A., Mohebbi, A., Kharrat, R., and Ghazanfari, M. H. 2011. Pore-scale monitoring of wettability alteration by
silica nanoparticles during polymer flooding to heavy oil in a five-spot glass micromodel. Transport Porous Media
87:653664.
Maldal, T., Gilje, E., Kristensen, R., Karstad, T., Nordbotten, A., Schilling, B. E. R., and Vikane, O. 1998. Evaluation
and economical feasibility of polymer-assisted surfactant flooding for the Gullfaks Field. SPE Reserv. Eval. Eng.
1:161168.
Salager, J., Morgan, J., Schechter, R., Wade, W., and Vasquez, E. 1979. Optimum formulation of surfactant/water/oil
systems for minimum interfacial tension or phase behavior. SPE J. 19:107115.
Sander Suicmez, V., Piri, M., and Blunt, M. J. 2008. Effects of wettability and pore-level displacement on hydrocarbon
trapping. J. Adv. Water Resour. 31:503512.
Sedaghat, M. H., Ghazanfari, M. H., Masihi, M., and Rashtchian, D. 2011. Experimental investigation of polymer
flooding in fractured heavy oil reservoirs using micromodel systems. 7th International Chemical Engineering
Congress & Exhibition, Kish Island, Iran, November 2124.