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Wettability Alteration in Carbonate

Reservoirs Using Nanofluids
a a b
R. Abhishek , G. Suresh Kumar & R. K. Sapru
a
Petroleum Engineering Programme, Department of Ocean
Engineering, Indian Institute of Technology Madras, Chennai, India
b
Institute of Reservoir Studies, ONGC, Chandkheda Ahmedababad,
India
Published online: 18 May 2015.

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To cite this article: R. Abhishek, G. Suresh Kumar & R. K. Sapru (2015) Wettability Alteration in
Carbonate Reservoirs Using Nanofluids, Petroleum Science and Technology, 33:7, 794-801, DOI:
10.1080/10916466.2015.1014967

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 Petroleum Science and Technology, 33:794801, 2015
Copyright 
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ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2015.1014967

Wettability Alteration in Carbonate Reservoirs

Using Nanofluids

R. Abhishek,1 G. Suresh Kumar,1 and R. K. Sapru2

1
Petroleum Engineering Programme, Department of Ocean Engineering, Indian Institute of
Technology Madras, Chennai, India
2
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Institute of Reservoir Studies, ONGC, Chandkheda Ahmedababad, India

Carbonate reservoirs pose unique challenges to the petroleum industry. Research during the last decade
has shown the potential for application of principles of nanoscience and technology toward solving a
variety of problems faced by the petroleum industry today. The authors investigated the effectiveness of
nanofluids of silane coated silica nanoparticles as in situ reservoir agents. Effects of salinity of dispersing
medium and concentration of nanoparticles on particle size and surface zeta potential were studied to
characterize the stability of nanofluids. Carbonate core samples were taken from an Indian carbonate
reservoir and their wettability was restored. Contact angle measurements were made before and after the
application of nanofluid to investigate the alteration in wettability. Particle size measurements showed
agglomeration of nanoparticles. It was found that the extent of agglomeration was affected by salinity of
the dispersing medium and concentration of nanoparticles. Wettability studies indicated that nanofluids
of silane coated silica can affect wettability change toward a more water wet state. Around 2 g/L was
found to be the optimal concentration for affecting wettability change.
Keywords: nanotechnology, particles size, zeta potential, wettability, EOR, silica

1. INTRODUCTION

Many oil producing regions of the world have reached the stage where the total rate of produc-
tion is in the decline phase (Hite et al., 2004). The older and larger oil fields face abandonment
with more than 50% of the original oil in place (OOIP) unrecovered as the residual oil is outside
the reach of conventional oil production techniques. The major challenge facing the petroleum
industry today is to come up with novel techniques to delay abandonment and increase recov-
eries. Over 60% of the worlds oil and 40% of the worlds natural gas reserves are held in car-
bonate reservoirs. Exploitation of carbonate reservoirs poses unique challenges for the upstream
petroleum industry. Fractured carbonate reservoirs consist of high permeability fractures enveloped
in a low permeability rock matrix. Production through water injection relies on the ability of
the injected fluid to displace the oil through the rock matrix and expel it into the fracture net-
work. The fracture networks are in turn responsible for transporting the oil to the production
well.
Most carbonate reservoirs have complex pore structures and tend to be mixed wet to oil wet
systems (Chilingar and Yen, 1983). When an oil wet system is put on water injection, water tends

Address correspondence to G. Suresh Kumar, Department of Ocean Engineering, Indian Institute of Technology Madras,
Chennai 600036 India. E-mail: gskumar@iitm.ac.in

794
 WETTABILITY ALTERATION IN CARBONATE RESERVOIRS 795

to form continuous finger like channels connecting the larger pores. These channels form a water
front, which in turn displaces the oil in front of it; however the oil in small crevices and pores
is left behind. Over time, water forms unrestricted paths through the rock matrix thereby missing
majority of the residual oil (Anderson, 1987). Thus conventional waterflooding of a fractured car-
bonate reservoir leads to low recoveries typically in the range of 1020% of OOIP. Conversely,
water wet systems, are characterized by spontaneous water imbibition, wherein oil present in
smaller pores is displaced into the center of larger pores so that energy of the system is low-
ered (Anderson, 1987). During water injection, water tends to move as a fairly uniform front
through the rock matrix. The water front gets imbibed into small and medium sized pores dis-
placing the oil into larger pores. The oil moves ahead of the water front. As this front progresses,
each fluid passes through its own pore network. This process is much more effective at expelling
oil into the fracture network. Thus the effectiveness of the water injection process in a fractured
carbonate reservoir can be increased by affecting wettability alteration toward a more water wet
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state.
Application of nanotechnology is relatively new in the petroleum industry (Suliemanov et al.,
2011; Ayatollahi and Zerafat, 2012). Nanofluids which are dispersions of nanoparticles in a dis-
persing medium are employed during corefloods to study their effect on the recovery process.
Nanofluids have low volume concentrations of nanoparticles and tend to have better sedimentation
stability because the surface forces easily counterbalance the force of gravity. Many compounds
such as silicon dioxide (SiO2 ), silane treated silicon dioxide, aluminum oxide (Al2 O3 ), magnesium
oxide (MgO), and zinc oxide (ZnO) have been investigated by researchers (Haroun et al., 2012;
Ogolo et al., 2012; Shahrabadi et al., 2012; Joonakia and Ghanaatiana, 2014) to prove their ef-
fectiveness as in situ reservoir agents that can increase recovery. Despite earlier works in which
silica nanoparticles have been shown to increase recovery during core flood experiments (Haroun
et al., 2012; Ogolo et al., 2012), wettability alteration using nanofluids needs to be explored in
detail because it is the underlying cause of the increase in oil recovery, especially for carbonate
reservoirs. Additionally, the behavior of nanoparticles in the dispersing medium needs to be stud-
ied by characterizing the particles size and zeta potential displayed by the nanoparticles in the
nanofluid.
In this study we aimed to investigate the wettability alteration in carbonate reservoirs using
nanofluids of silane coated silica nanoparticles. We also investigated the effect of different dispersing
mediums and concentration of nanoparticles on particle size and surface zeta potential to remark on
the stability of the nanoparticles in the nanofluids. Contact angle measurements are used to determine
the wettability of the core sample before and after the application of nanofluid. These measurements
are used to determine the optimal concentration of silane coated silica nanofluid to affect wettability
change for carbonate core samples. Core samples for the study were taken from an Indian carbonate
reservoir currently under production by water injection.

2. EXPERIMENTAL

2.1 Materials

Silicon dioxide nanopowder (SiO2 , 95.9+%, 2030 nm, coated with KH570, specific surface area:
110120 m2/g) was obtained from Intelligent Materials Pvt. Ltd. (Nanoshel India). Formation water
(36031.69 ppm salinity) was provided by Institute of Reservoir Studies (IRS), Ahmadabad, Oil and
Natural Gas Corporation Ltd. (ONGC). 3% KCl brine (30000 ppm salinity) was made in distilled
water. The core plugs were taken parallel to the bedding plane from an Indian carbonate reservoir
currently under water injection. The cores were cleaned in a soxylation apparatus with methanol
 796 R. ABHISHEK ET AL.

TABLE 1
Particle Size and Surface Zeta Potential Characterization of Nanofluids

Particle size (nm) values in different Surface zeta potential (mV) values in
dispersing mediums different dispersing mediums
Concentration of Distilled Formation 3% KCl Distilled Formation 3% KCl
nanoparticles (g/l) water water brine water water brine

1 1566.2 3619 5238.6 9.352 5.08 6.782

2 1414.6 1490 3437.6 14.76 34.5 17.636
3 2161.8 611.25 1530.6 27.72 36.4 8.928
4 3740.6 915 3663 32.8 39.6 5.368
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and toluene for 72 h. Thereafter the cores were baked in an oven at 50 C for 24 h. Crude oil (API
gravity 36 ) was used.

2.2 Preparation and Characterization of Nanofluids of Silane Coated Silica

Nanofluids of silane coated silica nanoparticles were prepared at four different concentrations: 1,
2, 3, and 4 g/L. Three sets of nanofluids were prepared in different dispersing mediums: distilled
water, formation water and 3% KCl brine. Each dispersion was stirred on a magnetic stirrer at room
temperature for 5 h. Zetasizer Nano by Malvern Instruments was used to measure the particle size
and surface zeta potential of the silica in the nanofluid. Five measurements were made and a final
averaged value was calculated.

2.3 Contact Angle Measurements

The cleaned carbonate core plug was cut into four smaller cylinders with smooth faces and they
were numbered 1, 2, 3, and 4. A beaker was filled with formation water and its level was marked.
The core pieces were then placed in the beaker standing on their cylindrical surfaces to prevent
deposition of salts on the faces. The core pieces were then aged for a period of four weeks at a
temperature of 60 C. To compensate for evaporation, the level of formation water in the beaker was
periodically checked and makeup distilled water was added to maintain the right concentration of
ions. Thereafter, the core pieces were taken out of the formation water and aged in crude oil for
two days at 60 C in a covered beaker. This was done to restore the wettability at the faces of the
core pieces. Contact angle measurements were made on faces of each core piece to establish their
baseline wettability using Attention Theta apparatus for distilled water, formation water and 3% KCl
brine. Each reading was taken twice and averaged. Thereafter, the four core pieces were placed in
four separate beakers (resting on their cylindrical sides) filled with nanofluids (dispersions of silane
coated silica in 3% KCl brine) of different concentrations (1, 2, 3, and 4 g/L). Core pieces are aged
at ambient conditions (25 C) for 24 h. Thereafter the cores are taken out of the nanofluid and the
contact angle measurements were repeated. Comparison was made between the old values and new
values to determine the reduction in contact angle. Thus the optimal concentration of nanofluid to
affect wettability change was determined. This methodology has been modified from Shahrabadi
et al. (2012).
 WETTABILITY ALTERATION IN CARBONATE RESERVOIRS 797
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FIGURE 1 Particle Size (A) and surface zeta potential (B) characterization of nanofluids.

3. RESULTS AND DISCUSSIONS

3.1 Characterization of Nanofluids

Table 1 contains averaged particle size and surface zeta potential values for silane coated silica
nanoparticles dispersed in different mediums at different concentrations of nanoparticles. The origi-
nal particle size of the nanoparticles was in the range of 2030 nm. Agglomeration of nanoparticles
can be clearly observed in Table 1 as the particle sizes measured in dispersion are in the range of
611.255238.6 nm. Particle size values are plotted against concentration in Figure 1A. Two distinct
trends can be observed in Figure 1A for saline and nonsaline dispersing mediums. For both the
 798 R. ABHISHEK ET AL.

TABLE 2
Contact Angle Values at Restored Wettability and After the Application of Nanofluids

Contact angle values in degrees ( ) with drops of different composition

Wettability post application
Original wettability of nanofluid
Core piece Formation 3% KCl Concentration of Distilled Formation 3% KCl
no. Distilled water water brine nanoparticles (g/l) water water brine

1 110.0575 107.3575 114.68 1 93.8575 78.7375 82.4

2 113.1275 104.99 107.38 2 76.2825 71.165 76.0525
3 107.655 103.8725 108.25 3 73.95 88.3325 82.7825
4 111.6475 109.125 104.925 4 75.36 70.05 77.00375
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saline dispersing mediums: formation water and 3% KCl brine, the particle size falls almost linearly
with increasing concentration from 1 to 3 g/L. Concentration of 3 g/L is the point of inflection,
as beyond this concentration, the particle size increases. However for distilled water (nonsaline)
as the dispersing medium, the particle size almost remains constant with a slight decrease as the
concentration increases from 1 to 2 g/L after which the particles size increases. The lowest parti-
cle size of 611.25 nm corresponds to 3 g/L concentration with formation water as the dispersing
medium. It can be concluded from Figure 1A that agglomeration of nanoparticles occurs and the
degree of agglomeration is clearly affected by the concentration of nanoparticles and the salinity
of the medium. Table 1 also contains averaged surface zeta potential values for silane coated silica
nanoparticles dispersed in different mediums at different concentrations of nanoparticles. The zeta
potential values for different concentrations of silane coated silica nanoparticles in different medi-
ums are plotted in Figure 1B, which is divided into zones of varying degrees of stability depending
upon the range of zeta potential (Kirby, 2010). However the stability of the nanoparticles in the
dispersion is affected by many more factors such as particles size and chemistry of the dispersing
medium, and hence the stability bands in Figure 1B only indicates whether the zeta potential of the
nanoparticles is conducive to stability or not. It is observed from Figure 1B that for 1 g/L concen-
tration, all the nanofluids fall in the unstable zone. Also, the magnitude of zeta potential and hence
the stability of the dispersion increases with increase in concentration of nanoparticles when either
formation water or distilled water is used as the dispersing medium. Dispersions made in distilled
water with concentrations greater than or equal to 2 g/L are found to be most stable as they all fall
in the moderately stable zone. Dispersions in 3% KCl brine show completely different behavior.
The magnitude of zeta potential falls into incipiently stable zone at concentration of 2 g/L. After
this as the concentration increases, the magnitude of zeta potential falls and then goes back into the
unstable zone. It can be concluded from Figure 1B that from point of view of zeta potential, 2 g/L
concentration shows most stability when 3% KCl brine is used as the medium. Also using formation
water as the dispersing medium leads to most stable dispersions.

3.2 Contact Angle Measurements

Table 2 contains averaged contact angle values at restored wettability state and after the application.
Figure 2A shows the schematic diagram of the apparatus for measuring contact angle. The camera
in the apparatus was programmed to capture 100 still images at an interval of 16 msec followed by
50 still images at an interval of 1 sec for each reading. The measurements are made on all the core
pieces to establish their baseline wettability state. It can be observed from Table 2 that the contact
 WETTABILITY ALTERATION IN CARBONATE RESERVOIRS 799
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FIGURE 2 Schematic for contact angle measurement (A) and reduction in contact angle post application of silane
coated silica nanofluid in 3% KCl brine (B).

angles measured are in the range of 103.8725114.68 , thus it can be concluded that the core pieces
are oil wet. Table 2 also contains the values of the contact angle after the application of nanofluid. It
can be observed from Table 2 that the contact angles measured are in the range of 70.0593.8575 .
Comparison of the two set of results from Table 2 shows the range of contact angle values have
come down from 103.8725114.68 to 70.0593.8575 . Thus it can be concluded that the core
pieces have undergone a change in wettability toward a more water-based state. The reduction in
contact angles is calculated. The reduction in contact angle is stated in Table 3 and plotted against
concentration in Figure 2B. The plot can be divided into two parts at the concentration of 2 g/L as
shown in Figure 2B. In the left part of the Figure 2B, the reduction in contact angle and thus the
wettability change toward a more water wet state increases for both formation water and distilled
water. A much sharper increase is observed in the case of distilled water. For 3% KCl brine however,
 800 R. ABHISHEK ET AL.

TABLE 3
Reduction in Contact Angle Due to Application of Nanofluids of Varying Concentrations of Nanoparticles

Contact angle reduction in degrees ( ) with drops of different composition

Concentration of nanoparticles (g/l) Distilled water Formation water 3% KCl brine

1 16.2 28.62 32.28

2 36.845 33.825 31.3275
3 33.705 15.54 25.4675
4 36.2875 39.075 27.8875

the contact angle reduction remains almost unchanged in the left part. In the right part of the figure,
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all the plots follow a similar trend showing a decrease in contact angle reduction as the concentration
increases to 3 g/L followed by an increase at 4 g/L. Thus, it can be concluded from Figure 2B that
the concentration of around 2 g/L is the optimal concentration of nanofluid of silane coated silica
nanoparticles in 3% KCl brine for affecting wettability change as this concentration accounts for a
significant reduction in contact angle.

4. CONCLUSIONS

Based on the inferences made from the experimental results, the following conclusions are drawn:
1. Agglomeration of particles occurs when silane coated silica nanoparticles are dispersed in
water based dispersing mediums.
2. Salinity of the dispersing medium and concentration of nanoparticles has an effect on the
degree of agglomeration of nanoparticles.
3. Silane coated silica nanoparticles can be used in carbonate reservoirs to affect wettability
change toward a more water wet state.
4. We found 2 g/L to be the optimal concentration of silane coated silica nanoparticles in water
based dispersing mediums that significantly alters wettability.
5. Change in wettability toward a more water wet state suggests that silane coated silica
nanoparticles have the potential to be used for enhanced oil recovery applications in carbonate
reservoirs.

ACKNOWLEDGMENTS

The authors would like to acknowledge the Institute of Reservoir Studies, ONGC, Ahmadabad for
providing access to their Petrophysical Laboratory. They would also like to thank Dr. Atindra Shukla
and Dr. Bhavesh Bharatiya at Center for Surface Science and Nanotechnology, Nadaid, Gujarat; and
Mr. A. K. Gupta and Dr. V. K. Mishra at Petrophysical Lab, IRS, ONGC Ahmadabad for their
assistance with the experimental work.

REFERENCES

Anderson, W. G. (1987). Wettability literature survey, part 6: The effects of wettability on waterflooding. J. Pet. Technol.
39:16051622.
Ayatollahi, S., and Zerafat, M. M. (2012). Nanotechnology-assisted EOR techniques: New solutions to old challenges. SPE
157094, SPE International Oilfield Nanotechnology Conference, Noordwijk, the Netherlands, June 1214.
 WETTABILITY ALTERATION IN CARBONATE RESERVOIRS 801

Chilingar, G. V., and Yen, T. F. (1983). Some notes on wettability and relative permeabilities of carbonate reservoir rocks, II.
Energy Sources 7:6775.
Haroun, M., Ansari, A., Kindy, N., Sayed, N., Ali, B., and Sharma, H. (2012). Smart nano-EOR process for Abu Dhabi
carbonate reservoirs. SPE 162386, Abu Dhabi International Petroleum Exhibition & Conference, Abu Dhabi, UAE,
November 1114.
Hite, J. R., Avasthi, S. M., and Bondor, P. L. (2004). Planning EOR projects. SPE 92006, SPE International Petroleum
Conference, Puebla, Mexico, November 79.
Joonakia, E., and Ghanaatiana, S. (2014). The application of nanofluids for enhanced oil recovery: Effects on interfacial
tension and coreflooding process. Pet. Sci. Technol. 32:25992607.
Kirby, B. J. (2010). Micro and nanoscale fluid mechanics: Transport in microfluidic devices. New York: Cambridge University
Press.
Ogolo, N. A., Olafuyi, O. A., and Onyekonwu, M. O. (2012). Enhanced oil recovery using nanoparticles. SPE 160847, SPE
Saudi Arabia Section Technical Symposium and Exhibition, Al-Khobar, Saudi Arabia, April 811.
Shahrabadi, A., Bagherzadeh, H., Roustaei, A., and Golghanddashti, H. (2012). Experimental investigation of HLP nanofluid
Downloaded by [New York University] at 07:50 22 May 2015

potential to enhance oil recovery: A mechanistic approach. SPE 156642, SPE International Oilfield Nanotechnology
Conference, Noordwijk, The Netherlands, June 1214.
Suliemanov, B. A., Ismailov, F. S., and Veliyev, E. F. (2011). Nano fluid for enhanched oil recovery. J. Pet. Sci. Eng.
78:431437.