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Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel
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Carbonate and sandstone reservoirs wettability improvement without

using surfactants for Chemical Enhanced Oil Recovery (C-EOR)

Mahshid Ershadi a, Mahshad Alaei b,, Alimorad Rashidi b, Ali Ramazani a, Sara Khosravani a

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a
b

Department of Chemistry, University of Zanjan, P.O. Box 45195-313, Zanjan, Iran

Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-137, Tehran, Iran

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h i g h l i g h t s

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 Preparation of SilicaMWCNT

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 Preparation of nanouid with the as-

nanohybrid with different methods.

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prepared SilicaMWCNT nanohybrid.

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 Preparation of nanouid with neither

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g r a p h i c a l a b s t r a c t

any surfactant nor any other

ingredients.
 Increasing the water wettability of
carbonate and sandstone reservoirs
by this nanouid.
 Chemical enhanced oil recovery can
be done with this nanouid.

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a r t i c l e
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i n f o

Article history:
Received 30 March 2013
Received in revised form 20 December 2014
Accepted 17 February 2015
Available online xxxx
Keywords:
Silica nanostructures
MWCNTSilica nanohybrids
Surfactants
Wettability alteration
Chemical Enhanced Oil Recovery (C-EOR)
Contact angle
Interfacial tension

a b s t r a c t
In this paper, we have been proposed the preparation of SilicaMWCNT nanohybrid that can increase the
water wettability of carbonate and sandstone reservoirs. Chemical agents such as surfactants have been
used as wettability modiers to increase oil recovery from oil wet carbonate and sandstone reservoirs.
Addition of chemical compounds such as polymers, ionic materials and nanoparticles can improve the
effectiveness of the mentioned chemical agents.
The effectiveness of nanohybrids without using surfactants has not been reported yet and it is still in its
infancy. In this work, the effect of MWCNTSiO2 nanohybrid-based nanouids on the wettability
alteration of a carbonate and a sandstone reservoir rocks was experimentally studied. Therefore,
MWCNTSilica nanohybrid has been prepared by adding the suitable amount of MWCNT in situ of silica
nanostructure preparation. In this research, MWCNTSilica nanohybrid was prepared with ultrasound
assisted solgel method and characterized with X-ray diffraction (XRD), Field Emission Scanning
Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM). The effect of the related
nanouid on the wettability of carbonate and sandstone rocks was investigated by measuring contact
angle and interfacial tension. Results show that the nanouid could signicantly change the water wettability of the mentioned rocks from oil wet to water wet condition without using surfactant.
2015 Published by Elsevier Ltd.

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Corresponding author.
E-mail address: alaiem@ripi.ir (M. Alaei).

1. Introduction

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Nanotechnology opens several opportunities on applications in

the Oil & Gas industry.

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http://dx.doi.org/10.1016/j.fuel.2015.02.060
0016-2361/ 2015 Published by Elsevier Ltd.

Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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Particularly, subsurface applications of nanotechnology seem to

be promising in modifying and monitoring reservoir properties,
such as wettability and interfacial tension between rock and uids.
The capability of SiO2 nanoparticles to alter the wettability of reservoir rock and reduce the interfacial tension (IFT) between crude oil
and brine phases has recently been actively investigated to nd
implementation in enhanced oil recovery (EOR) [1]. The potential
for using nanostructures in enhanced oil recovery have demonstrated that nanostructures can be propagated through a porous media
because of the feasibility of using a stable aqueous dispersion of
nanoparticles to deliver the particles to the O/W interface in a porous media. Carbon nanotubes fused to oxide nanoparticles are able
to stabilize emulsions [2]. Oxide nanoparticles, such as SiO2, have
been found to be effective in stabilizing Pickering emulsions. Since
oxide particles are inherently hydrophilic, the interfacial contact
angle bends the interface concave toward the oil, producing emulsions [37]. Depending on whether the particles are more hydrophilic or more hydrophobic, they tend to stabilize oil-in-water or
water-in-oil emulsions, respectively [5,810]. Particle size [11],
particle concentration [12], oil/water ratio [7,13], pH [14], salt
concentration [15] and solvent type [16] all have been found to be
crucial in determining the resulting emulsion properties.
Enhanced oil recovery is always an important direction for the
oil and gas industry worldwide, especially now when fossil energy
resources have become much more expensive for production and
discovery [1].
Multi walled carbon nanotube (MWCNT)-Silica nanohybrid
structures are very suitable material for enhanced oil recovery in
order to their excellent interfacial activity. In the O/W interface,
they could change the oil properties to mobilize the oil in the reservoir. In the rst glance, it may seem that the use of MWCNT is not
economical. However, the importance of enhanced oil recovery
(EOR) methods becomes sensible by taking into account the fact
that two- third of oil in the reservoirs are extracted through these
methods. Only 1% enhanced oil recovery, produces over 200 billion
dollars in revenue. Therefore, research and analysis on EOR methods can be useful. The use of nanohybrid in EOR is a priority in
research and it is being supported by Department of Energy
(DOE) and Dr. Daniel E. Resasco (University of Oklahoma) [17].
Multi-walled carbon nanotubes have been used in this research
because they are cheaper than single-walled ones. In order to
decrease the cost of raw material, Research Institute of
Petroleum Industry (RIPI) has been constructed the MWCNT
production Demo plant with high production capacity. Therefore,
the price of the MWCNT will be low. On the other hand, for the
preparation of nanouid, only 0.2 wt% nanohybrid is necessary that
is very low dosage. Therefore, the use of MWCNT in the structure of
the desired nanohybrid, will not cause economically problems.
In this work, the effect of MWCNTSiO2 nanohybrid based
nanouids on the wettability alteration of carbonate and sandstone reservoir rocks was experimentally studied.

Generally, the multi-walled carbon nanotube (MWCNT)-silica

nanohybrid can be synthesized through the following two methods: the implementation of silica structures in MWCNT formation
reaction and incorporating MWCNT in the formation reaction of
silica nanostructure. In this research, we have been used the
second method. The most important parameters that affect the
synthesis of nanohybrid through inclusion of MWCNT into silica
structure formation reactions are as follows: nanosilica synthesis
method, type of silica structure that is formed in the nanohybrid
production process and the ratio of silica to MWCNT [18].
Therefore, MWCNTSilica nanohybrid has been prepared by adding
the suitable amount of MWCNT in situ of silica nanostructures
preparation. In this research, MWCNTSilica nanohybrid was
prepared with ultrasound assisted solgel method. The effect of
nanouid on the wettability of carbonate and sandstone rocks
was investigated by measuring contact angle and interfacial tension. Results were shown that the nanouid can signicantly
change the wettability of the rock from oil-wet to water-wet
condition.

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2. Experimental section

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2.1. Materials and characterization

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Tetraethylorthosilicate (TEOS) 99%, absolute ethanol (EtOH)

99.5%, ammonia solution 25% were used as received from Merck
Company. MWCNT was received from Research Institute of
Petroleum Industry (RIPI) that was prepared by chemical vapor
deposition (CVD) method. Kerosene of Tehran Oil Renery was
used as oil-model.
The nanohybrid sample was characterized by Field Emission
Scanning Electron Microscope (FE-SEM) by using a Holland
Phillips XL30 microscope. XRD patterns of the samples were
recorded in ambient air using a Holland Philips X-ray powder
diffraction (Cu Ka, k = 1.5406 ), at scanning speed of 2/min from
20 to 80. Transmission Electron Microscopy (TEM) was performed with a Philips EM 208 FEG instrument operating at 90 kV.

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2.2. Procedures

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2.2.1. Synthesis of MWCNTSilica nanohybrid with solgel method

under ultrasound irradiation
A quantity of 5 ml TEOS was rst dissolved in 30 ml of absolute
ethanol at room temperature for 10 min in ultrasonic bath at different frequencies (30, 40 and 50 kHz). Then 1 ml of distilled water
was dropped into the reaction medium with a feed rate of
0.2 ml min1 to facilitate hydrolysis of TEOS in ultrasonic radiation
[1]. After 1.5 h, appropriate amount of MWCNT was added to the
mixture. Then 2 ml ammonia was fed into the reaction mixture
at a feed rate of 0. 2 ml min1. Sonication was continued for 3 h
and gelation was allowed for 1 h. The gel was centrifuged

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Fig. 1. (a) SEM image and (b) TEM image of MWCNT that was received from Research Institute of Petroleum Industry (RIPI).

Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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(3500 rpm) and washed with ethanol and distilled water. Drying
was carried out using either a conventional oven at 100 C for
24 h or under reduced pressure at 70 C for 24 h.
2.2.2. Preparation of open cap MWCNT
MWCNT that was received from Research Institute of Petroleum
Industry (RIPI) was prepared with chemical vapor deposition (CVD)
method and after thermal treatment for removing the amorphous
carbon, have been acid treated with HCl and HNO3 for removing of
metal oxides that have been used as catalyst. For the preparation
of MWCNTSiO2 nanohybrid, it is necessary to opening the cap of
MWCNT. Therefore, 2 g of MWCNT is added to a mixture of
160 ml distilled water and 140 ml nitric acid and let it was reuxed
for 18 h. After ltration and neutralization with distilled water,
sample was kept in oven to dry.
2.2.3. Nanouid preparation
For the preparation of nanouid with the as-prepared MWCNT
SiO2 nanohybrid in order to the evaluation of contact angle and
interfacial tension properties, 0.2 g of the sample was dispersed
in water ultrasonically.

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3. Results and discussions

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3.1. Modication of MWCNT

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Depending on the hydrophilicity, the nanouid can form O/W or

W/O emulsion in reservoir condition. Therefore, MWCNT was

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modied with nitric acid to enhance its hydrophilicity for producing O/W emulsion.
The SEM and TEM image of MWCNT that was received from
Research Institute of Petroleum Industry (RIPI) demonstrates in
Fig. 1. Obviously the nanotube structure can be seen from SEM
and TEM images (Fig. 1a and b respectively). The TEM image represents that the MWCNT diameter is about 5 nm.
Oxidation of MWCNTs: The generation of oxygenated groups on
a nanotube surface is directly related to the time of treatment with
HNO3. Presumably, these groups reside at the tube ends and also
on the sidewalls, bonded to sp3-like carbons in regions of
increased curvature on the graphitic sheet (e.g., alcohols) or to broken sheet sites with partial loss of conjugation (e.g., ketones, carboxylic acids). Consequently, acid treatment strongly modies
the MWCNT surface by breaking the graphitic sheets and also by
cutting (etching) the tubes.
Therefore, this step must be controlled in order to produce
water-soluble MWCNT without destroying their morphological
characteristics [19]. Fig. 2 shows a schematic of the reaction
mechanism. For Proving the COOH group formation on the
MWCNT, FTIR spectra and TEM image can be used (Fig. 3).
Fourier-transform infrared (FTIR) studies have been performed in
the range 4004000/cm1 for identication of the functional
groups attached on the surface of the MWCNT. The FTIR spectra
of oxidized MWCNT shows four major peaks, located at 3428,
1699 and 1572 cm1 (Fig. 3a). The peak at 3428 cm1 can be
assigned to the OAH stretch from carboxyl groups (O@CAOH and
CAOH). The peak at 1699 cm1 is attributed to the C@O stretching
mode of carboxylic acids. The peak at 1572 cm1 refers to the C@C

Fig. 2. Chemical modication of carbon nanotube (MWCNT) through thermal oxidation.

Fig. 3. (a) FTIR spectra of MWCNTs and (b) TEM image of Opened cap MWCNT.

Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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stretching mode which originates from the backbone of MWCNT.

In addition, the peak at 1044 cm1 is assigned to the CAO stretching vibration. TEM image shows Opened capped MWCNT that was
formed by reuxing with nitric acid (Fig. 3b).
3.2. Synthesis of MWCNTSilica nanohybrid with solgel method
under ultrasound irradiation
Fig. 4a and b show the XRD pattern and FE-SEM image of SiO2
nanoparticles respectively that were prepared with ultrasound

assisted solgel method and Fig. 4c and d show the XRD pattern
and SEM image of MWCNTSiO2 nanohybrid respectively.
X-ray diffraction can be used to study the crystalline structure
of the desired material. XRD patterns of SiO2 nanoparticles,
MWCNTSiO2 nanohybrid and MWCNT were presented in Fig. 4a,
c and f respectively. As can be seen, SiO2 nanoparticles have amorphous structure and the main peaks of MWCNT were appears in
41 and 26. With attention to the XRD pattern of MWCNTSiO2
nanohybrid, SiO2 nanoparticles (with amorphous structure) and
the mentioned main peaks of MWCNT can be seen simultaneously.

Fig. 4. (a and c) XRD patterns of SiO2 nanoparticles and MWCNTSiO2 nanohybrid respectively (b and d) FE-SEM images of SiO2 nanoparticles and MWCNTSiO2 nanohybrid
respectively (e) XRD pattern of MWCNT.

Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
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Fig. 5. Schematic illustration of solgel mechanism.

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The sol gel mechanism demonstrates in Fig. 5. In this step, two

main types of reactions are involved: silanol groups are formed
by hydrolysis (1) and siloxane bridges are formed by a condensation polymerization reaction (2).

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Hydrolysis : SiOC2 H5 4 H2 O ! Si  OH4 4C2 H5 OH

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Condensation : 2Si  OH4 ! 2Si  O  Si 4H2 O

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The condensation rate depends on reaction conditions which

might result in the formation either of a three dimensional
network or in formation of single mono disperse particles
[20,21]. Following the hydrolysis reaction, the condensation
reaction occurs immediately.
Moreover, ammonia works as a basic catalyst to this reaction;
the hydrolysis reaction is probably initiated by the attacks of
hydroxyl anions on TEOS molecules [22].
This suggests that the assemblies of silica nanoparticles on
MWCNT have good stability apparently attributed to the unique
structure. Two kinds of binding forces may be existed between
the silica and MWCNT. Due to the porous nature of MWCNT, silica
precursors would be adsorbed onto the walls of MWCNT during
the solgel process and eventually the silica nanoparticles would
physically anchor onto the MWCNT. On the other hand, as there
are defects existing on the walls of MWCNT (e.g., hydroxyl group
existing on the defects), some silica precursors would covalently

bond to MWCNT [23]. The OH groups act as the centers of molecular adsorption during their specic interaction with adsorbents
capable of forming a hydrogen bonding with the OH groups or
undergoing donoracceptor interaction. On the SiO2 surface, there
also exist surface siloxane groups or ASiAOASiA bridges with
oxygen atoms on the surface [24].
TEM image of nanohybrid shows how silica nanoparticles are
placed inside (Fig. 6a) and coated on the surface of MWCNT
(Fig. 6b).
Nanohybrids actually act as surfactants in oil recovery processes, and they can reduce the interfacial tension (IFT) between oil
and water. In this paper, the nanohybrid acts as surfactant because
of having hydrophilic (MWCNT) and hydrophobic (Silica) ends [25]
and it reduced the IFT between water and kerosene by almost half
of the reference sample. This paper does not study the different
surfactants of oil and kerosene because no type of surfactant or
co-surfactant including alcohols, polymers, or polysaccharide have
been used in the tests. Therefore, the effect of surfactants has not
been taken into consideration, and solely the effect of the nanohybrid has been reported. Resasco et al. [26] showed that in case
nanoparticles and anionic surfactants are used at the same time,
IFT reduction is 70% more than when the surfactant is used alone.
Obviously, IFT becomes ultra low or reaches almost zero by using
nanohybrid and surfactant at the same time. In this paper, since
oil-model is far from ideal conditions and it has low purity, kerosene of Tehran Oil Renery was used as oil model to determine
the performance of nanohybrid. Kerosene is a cut from crude oil
and it is heavier than other hydrocarbons such as n-decane that
used in the previous research paper [27]. Kerosene was also used
to record images with higher resolution for more accurate assessment of IFT and contact angle test. Taking into account the presented reasons, this article does not study the differences between
surfactants in crude oil and in kerosene.

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3.3. Determination of interfacial tension

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For the experiments related to the core oil, oil rock should be
saturated with model oil (kerosene) and nanoparticles. The asprepared hybrid (0.2 wt.%) was dispersed in water without surfactant for the evaluation of nanouid surface tension. This nanouid
has well stability in 70 C (reservoir condition). Mixture of water
and kerosene was prepared as reference sample. As can be seen
in Fig. 7, the necessary information that was taken from the related
photo together the density of the uid were processed with special
soft ware. The surface tension between water and kerosene

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Fig. 6. TEM images of nanohybrid structure (a) silica nanoparticles inside the MWCNT and (b) silica nanoparticles have been coated the MWCNT.

Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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Fig. 7. (a) Water drop in kerosene, (b) nanouid drop in kerosene and (c) surface tension equipment.

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(reference sample) was 53.9 mN/m. Fig. 7a and b shows the water
and nanouid droplet photos in kerosene respectively. The surface
tension between nanouid and kerosene was 27.5 mN/m.
Therefore, the as-prepared MWCNTSiO2 nanohybrid that was prepared with ultrasound solgel method can decrease the reference
sample surface tension in half amount without any surfactant
and stabilizer.

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3.4. Determination of contact angle

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Two types of rocks (Carbonate and sand stone) were selected for
Contact angle tests. For measuring contact angle, the rocks should
be saturated in kerosene (oil model). Two cut pieces of rock (carbonate or sandstone) are placed in kerosene containers separately.
The containers are closed and put in oven at 40 C for 3 days. Then
the rocks are washed with water and put in oven for drying. One of
the dried rocks is placed in the as-prepared nanouid container.
The container is closed and put in oven at 70 C for 3 days. Then
the rock is washed with water and put in oven for drying. After
this, a thin layer of nanohybrid can be seen on the surface of the
rock (Fig. 8a). Thus, one of the rocks is saturated only in kerosene
and the other is saturated rst in kerosene and second in nanouid.
For measuring contact angle, the saturated rock is put in the xed

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Fig. 8. (a) Reservoir rocks in nanouid after 3 days with a layer of nanohybrid. (b)
Schematic of the contact angle measurement in oil media.

Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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Fig. 9. Measurement of contact angle (a) between kerosene drop and sand stone, (b) between kerosene drop and carbonate rock, (c) between kerosene drop and sand stone
rock with a layer of nanouid, (d) between kerosene drop and carbonate rock with a layer of nanouid and (e) contact angle equipment.

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water chamber in contact with kerosene droplet that is injected by

a syringe. The image of the droplet is recorded with a camera. The
related data that obtained from the image were analyzed with a
soft ware. Therefore, the contact angle is measured carefully. In
this condition, contact angle over and below 90 C, represents the
more hydrophilic and the more hydrophobic samples respectively
(Fig. 8b).
As can be seen in Fig. 9a, the contact angle between kerosene
droplet and sandstone rock (that was saturated only in kerosene)
in the water media was 115. Also in Fig. 9b, it is clear that the contact angle between kerosene droplet and carbonate rock in the
water media was 82. The contact angle between kerosene droplet
and sandstone rock (that was saturated in nanouid) in the water
media was 128 (Fig. 9c) and the contact angle between kerosene
droplet and carbonate rock (that was saturated in nanouid) in
the water media was 140 (Fig. 9d). Contact angle equipment
photo was represented in Fig. 9e.
Results show that the nanohybrid causes the addition of contact
angle amount that means the rock wettability altering from oil-wet
to water-wet. By altering the wettability to preferentially

water-wet conditions and reducing the IFT to low values, the forces
that retain oil can be overcome. If wettability is altered to preferentially water-wet conditions and/or capillarity is diminished
through ultralow IFTs buoyancy will still tend to force oil to ow
upward and out of the matrix into the fracture system. The injected
uid in the fractures will replace the displaced oil in the matrix,
and therefore the invasion of the injected uid into the matrix will
continue as long as oil ows out of the matrix. The primary driving
force for spontaneous imbibition in strongly water-wet conditions
is usually the capillary pressure. Reduction of IFT reduces the contribution of capillary imbibition. Buoyancy, as measured by the
product of density difference and the acceleration of gravity, then
becomes the dominant parameter governing the displacement,
even if oil is the wetting phase [28].

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4. Conclusion

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In this research, MWCNTSilica nanohybrid was prepared with

ultrasound assisted sol gel method. The nanouid that was prepared with the as-prepared MWCNTSilica nanohybrid without

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Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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using any surfactant and stabilizer, can be used in chemical

enhanced oil recovery.
The effect of nanouid on the wettability of carbonate and
sandstone samples was investigated by measuring contact angle
and interfacial tension. Results show that the nanouid could
signicantly decrease the interfacial tension and change the wettability of the rock from oil-wet to water-wet condition.

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Acknowledgment

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This work was supported by Research Institute of Petroleum

Industry (RIPI). The authors would like to express their thanks to
the RIPI, Tehran, Iran for their nancial support of this project.

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References

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Please cite this article in press as: Ershadi M et al. Carbonate and sandstone reservoirs wettability improvement without using surfactants for Chemical
Enhanced Oil Recovery (C-EOR). Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.02.060

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