Journal of Molecular Liquids 271 (2018) 795–806

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

A novel nanofluid based on sulfonated graphene for enhanced

oil recovery
Hamideh Radnia a, Alimorad Rashidi b,⁎, Ali Reza Solaimany Nazar c,⁎,
Mohammad Mehdi Eskandari d, Milad Jalilian e
a
Chemical Engineering Department, University of Isfahan, Isfahan, Iran
b
Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran, Iran
c
Chemical Engineering Department, University of Isfahan, Isfahan, Iran
d
Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran, Iran
e
Department of Petroleum Engineering, Ahvaz Faculty of Petroleum Engineering, Petroleum University of Technology, Ahwaz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this study a novel nanofluid based on the sulfonated graphene (G-DS-Su) for enhanced oil recovery is devel-
Received 22 June 2018 oped. Nano porous graphene (NPG) synthesized by chemical vapor deposition method is sulfonated by a new
Received in revised form 1 August 2018 route using 4-sulfobenzenediazonium salt and then chlorosulfonic acid. Presence of\\SO3H group in G-DS-Su
Accepted 12 September 2018
structure is confirmed by the Fourier transform infrared spectroscopy (FTIR) result. This stable functionalized
Available online 13 September 2018
graphene dispersion is applied in core flood experiments. Using G-DS-Su at concentrations of 0.5 and 2 mg/mL
Keywords:
results in 16 and 19% increase in the oil recovery. Prior experiments show that G-DS-Su tends to migrate to the
Displacement mechanism oil/water interface and form emulsions. Moreover, the IFT decreases about 11% in presence of G-DS-Su but an ul-
Enhance oil recovery tralow IFT is not achieved. The contact angle measurements show that the wettability of sandstone surface is al-
Pickering emulsions tered from the oil-wet to the intermediate condition in presence of G-DS-Su. The wettability alteration may be
Sulfonated graphene due to both forming a wedge film in the oil/nanofluid/solid three-phase contact region and the adsorption of
Wettability alteration G-DS-Su onto the sandstone due to the π-π and n-π interactions between the functional groups of sand and G-
DS-Su. Hence, the wettability alteration plays a dominant role in the oil displacement mechanism.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
About two-thirds of the oil in place in many of the world's oil reser-
voirs cannot be recovered by primary and secondary oil recovery
methods [1]. The use of chemical enhanced oil recovery (EOR) methods
is a potential tool to recover oil from hard-to-produce reservoirs. In
chemical EOR, a fluid is usually used for displacing the trapped oil via al-
tering the properties of reservoir fluid and rock such as interfacial ten-
sion, wettability of sand and mobility ratio [2]. A new view of oil
displacement from a solid substrate using nanoparticle dispersions is
proposed by Wasan and Nikolov [3–5]. According to their findings,
nanoparticles can assemble themselves and form a wedge film when
they are in contact with the three-phase contact region of oil droplet,
nanofluid and rock pore surface. This cause a force to be exerted
pointing to vertex of the wedge film which is called the structural
disjoining pressure. The nanoparticles at the vertex are continuously
being driven forward. Ultimately, the oil droplet is detached from the
⁎ Corresponding authors.
E-mail addresses: h.radnia@eng.ui.ac.ir (H. Radnia), rashidiam@ripi.ir (A. Rashidi),
asolaimany@eng.ui.ac.ir (A.R. Solaimany Nazar), eskandarimm@ripi.ir (M.M. Eskandari).
surface of rock pore and is expelled by capillary force. The potentials
of using nanoparticles in enhanced oil recovery are reviewed in litera-
tures [6–8].
Preparation of soluble or dispersible graphene sheets are of crucial
importance for their applications. As well, the agglomeration of
graphene sheets can be prevented by proper covalent functionalization.
The functional groups can be placed at the end of the sheets and/or on
the surface [9]. Pristine graphene can be functionalized by organic func-
tionalities such as free radicals and dienophiles. For example, heating of
a diazonium salt results in a highly reactive free radical which attacks
the sp2 carbon atoms of graphene and forms a covalent bond [10].
This reaction has been used in some researches to decorate graphene
with sulfonic (\\SO3H) groups [11–13].
Recently, application of amphiphilic carbon based materials in
chemical enhance oil recovery has attracted many attentions. Luo
et al. [14] designed and produced a nanofluid of graphene-based amphi-
philic nanosheets that is very effective for flooding experiments. These
solid particles spontaneously approached the oil–water interface and
reduced the interfacial tension, regardless of its surface wettability.
They reported that the appearance of climbing films and the generation
of elastic interfacial films between oil and water interface may be

https://doi.org/10.1016/j.molliq.2018.09.070
0167-7322/© 2018 Elsevier B.V. All rights reserved.
796 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806

Fig. 1. Synthesis of 4-sulfobenzenediazonium salt.

responsible for the high oil recovery efficiency. In another study, the au-
thors used this nanofluid at secondary oil recovery stage which can
eliminate the tertiary stage and save huge amounts of water resource
[15]. They reported increased in oil recovery efficiency by up to 7.5%.
Li et al. [16] introduced a novel nanofluid based on fluorescent carbon
nanoparticles for enhanced oil recovery. The nanofluid showed excel-
lent anti-temperature, anti-salinity, oil displacement and wettability al-
teration properties. Villamizar et al. [17] reported that single-walled
carbon nanotube-silica nanohybrid particles are a very promising mate-
rial that could be used for enhanced oil recovery because of their
interfacial activity. The sand pack studies showed that about half of
the injected particles will go the oil/water interface when the porous
medium contains a residual saturation of hydrocarbon.
In this study, the direct sulfonation of graphene sheets is carried out
to provide a chemical agent for enhance oil recovery. In previous stud-
ies, commonly, reduced graphene oxide (rGO) is used as the initial ma-
terial for sulfonation process [11,18–20]. It is expected that introducing
hydrophilic functional groups to graphene makes it as an amphiphilic
material with hydrophobic basal plane and hydrophilic edges. Several
possible measurements, i.e. contact angle and IFT is conducted to

Fig. 2. Illustration for the preparation of functionalized NPG.

 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806
Fig. 3. (a) EDS analysis and (b) XRD pattern of sandstone sample.
evaluate the behavior of this material at oil, water and sand interface.
These findings help to have a better insight about the oil displacement
mechanism from porous media during core flood experiments.
2. Materials
2.1. Chemicals
Ethanol (C2H6O), methanol (CH3OH), thionyl chloride (SOCl2),
diethylenetriamine (C4H13N3), dichloromethane (CH2Cl2), sodium
dodecylbenzenesulfonates (C18H29NaO3S), chlorosulfonic acid
(ClSO3H), 4-aminobenzenesulfonic acid (C6H7NO3S), sodium nitrite
(NaNO2), hydrochloric acid (HCl), sodium chloride (NaCl) and toluene
(C7H8) are all purchased from Merck (Germany). All reagents are ana-
lytical grade and used without further purification.
2.2. Nano porous graphene (NPG)
NPG is supplied by nanotechnology research center of Research In-
stitute of Petroleum Industry (RIPI). NPG is prepared by special chemical
vapor deposition (CVD) method in a metal oxide nanocatalytic basis.
Briefly, the CVD process is carried out in an electrical furnace with
quartz reactor at 900–1100 °C for 5–30 min using methane as the car-
bon source and hydrogen as the carrier gas at a ratio of 4:1 and total
flow rate of 1000 L/min [21]. The crystal structure of the synthesized
NPG is characterized by X-ray diffraction (XRD) technique (Bruker D8
Advance). The morphology and structure of NPG are considered by
transmission electron microscopy (TEM) technique (JEOL 1200EXII).
Fig. 4. (a) Schematic of the IFT measurement set up, (b) diameters of the pendant drop.
797
2.3. Functionalization of graphene
The 4-sulfobenzenediazonium salt is synthesized following a stan-
dard procedure as shown in Fig. 1. In brief, 5.2 g of 4-aminobenzene sul-
fonic acid is dissolved in 300 mL of water. 28 mL of HCl (20%) is added to
the solution. 2.4 g of sodium nitrite is dissolved in 10 mL of water and
added in drop-wise to the solution while the temperature is maintained
within 0–5 °C. A clear solution is obtained after all the sodium nitrite is
added. After stirring for another 1 h at same temperature, the white pre-
cipitate of 4-sulfobenzenediazonium salt is formed.
The sulfonated graphene is prepared using 4-
sulfobenzenediazonium salt based on the similar procedure reported
by Peng et al. [22]. This functionalized graphene is named as G-DS in
which G stands for graphene, D stands for diazonium and S pointes to
sulfonic groups. In order to prepare G-DS, 2 g of NPG is dispersed in
200 mL water. In a set of experiments 1 g sodium
dodecylbenzensulfonate (SDBS) is added to the graphene dispersion
to perform surfactant wrapped graphene. This dispersion is sonicated
for 5 min.
The graphene dispersion is poured in a 500 mL cylindrical double
walled glass container with water jacket type of construction. The con-
tainer is connected to a circulator (Julabo- F12) for cooling the water
jacket within 0–5 °C. The 4-sulfobenzenediazonium salt solution is
added slowly to the graphene dispersion under mild stirring. The resul-
tant solution is maintained within 0–5 °C for 2 days, and subsequently
allowed to react at room temperature for 2 days. Then the solution tem-
perature is raised to 70 °C for 2 days. The functionalized graphene is sep-
arated though filtration using a Whatman filter paper of grade 42 and
washed with water for several times. The product is also washed with
798 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806
Fig. 5. UV–Vis spectra of G-DS-Su dispersion at different concentrations. The inset shows
the calibration curve for determining G-DS-Su concentration at λmax = 265 nm.
ethanol using Soxhlet extractor. The synthesized G-DS is dried in oven at
60 °C. The synthesis and structure of functionalized graphene are shown
in Fig. 2.
In this study a new route is used to add more solfonate groups to G-
DS and prepare a new functionalized graphene named as G-DS-Su. This
route is shown in Fig. 2. First the OH groups is replaced with Cl using thi-
onyl chloride (SOCl2). For this purpose, 1 g of G-DS is mixed with 40 mL
of SOCl2. The reaction mixture is then continually stirred under
refluxing condition for 72 h. The excess SOCl2 is separated from the
solid product with distillation method. This material (G-DS-Cl) is very
sensitive against moisture. In the next step, the black solid G-DS-Cl is
mixed with 10 mL of diethylenetriamine and 40 mL of dichloromethane
within 0–5 °C. The mixture is kept at ambient temperature for 24 h
under stirring to allow complete reaction. The resulting black suspen-
sion is centrifuged, washed with water and ethanol. The solid product
is dried in oven at 60 °C to obtain the material named as G-DS-DETA.
In the last step, 0.5 g of G-DS-DETA is dispersed in 40 mL of dichloro-
methane. Then 5 mL of chlorosulfonic acid is gradually added to this
mixture under stirring while the temperature of the mixture is kept
within 0–5 °C. Then the temperature is raised and kept at ambient
Fig. 6. Schematic of the core flood set up.
temperature for 24 h under stirring to complete the reaction. The homo-
geneous suspension of functionalized graphene is subsequently centri-
fuged, washed with water and ethanol for several times to purify the
solid product, and then dried in oven at 60 °C. The final product is
named as G-DS-Su.
The functional groups of G-DS, G-DS-DETA and G-DS-Su materials are
characterized using Fourier transform infrared (FTIR) spectra. The FTIR
spectra are collected using these materials diluted in KBr matrix in the
form of pellets applying a JASCO- 6300 spectrometer.
2.4. Fluids
A degassed crude oil from a field in southwest of Iran is used. The
density and viscosity of the crude oil are 0.833 g/L and 35 cp, respec-
tively. Synthetic brine is made with sodium chloride (NaCl) with con-
centration of 100,000 ppm as a base fluid solution for measuring the
porosity of cores. The density of the brine is 1.05 g/L. The functionalized
graphene such as G-DS and G-DS-Su, are easily dispersed in deionized
water to prepare the nanofluids. The nanofluids with various concentra-
tions between 0 and 2 mg/mL are prepared applying a bath sonicator
(Elmasonic-P 120H) at the frequency of 40 kHz and the power of 150
watt for 5 min. The stability of nanofluid is monitored visually during
24 h. The zeta potentials of nanofluid are measured applying a
Malvern-Zetasizer Nano S at 25 °C to have an insight about the stability
of nanofluid at different pH values.
2.5. Sandstone samples
The sandstone cores are obtained from one of the Iranian southwest
oil fields. All core plugs are cleaned by toluene and methanol in a
Soxhlet extractor. Two cores are used in a coreflood process and one is
cut in the form of thin slices for the contact angle experiments. As
well, a portion of the core was crushed for characterization and the ad-
sorption experiments.
A field-emission scanning electron microscopy (FE-SEM) (TESCAN,
MIRA3) equipped with energy dispersive X-ray spectroscopy (EDS)
analysis is applied to identify the sandstone minerals. As expected, the
sandstone mainly contains silicone and oxygen; other elements includ-
ing iron, titanium, potassium, carbon, and aluminum are also found
(Fig. 3(a)). The clay mineralogy of the sandstones is identified and
quantified by XRD pattern (Bruker, D8 ADVANCE). Based on the XRD
 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806 799

Table 1
Dimensions and properties of the core plugs.

Core no. D (cm) L (cm) mdry (g) P·V (cm3) Porosity (%) Permeability (mDarcy) OIP (mL) Soi % Swi %

1 3.697 5.348 131.30 12.05 20.99 142.50 8.4 69.70 30.30

2 3.699 5.607 128.51 10.91 18.11 106.18 7.4 67.82 32.18

results, the sandstone is composed of quartz mineral as major compo- diameter ds at the distance de from the top of the drop. The IFT is then
nent. It also contains potassium feldspar to a lesser extent (Fig. 3(b)). calculated from the following equation.

3. Methods
3.1. Emulsion preparation
The amphiphilic nature of the functionalized graphene (named as G-
DS-Su) is examined by preparing oil in water emulsions. For this pur-
pose, 5 mL of toluene is added to 5 mL of the nanofluid dispersion
with a specific concentration (0–2 mg/L). The vials containing organic
and aqueous phases are placed in an ice-bath for 10 min. Then the mix-
ture is sonicated for 30 s applying a probe sonicator (Misonix-S400)
with auto tuning power in the pulse mode. The vials are also kept in
the ice bath during sonication to prevent temperature increase during
ultrasonic process. The optical micrograph of the prepared emulsions
on the glass slides are taken applying a BM2000 microscope (ECLIPSE
LV100POL, Nikon, Japan) after 24 h of the sample preparation. The aver-
age sizes of the emulsion droplets are determined based on these im-
ages using Digimizer software (version 4.3.5).
3.2. Interfacial tension measurement
The equilibrium interfacial tension (IFT) measurements between the
crude oil and the nanofluids are conducted by the pendant drop method
at ambient condition. The schematic of the IFT measurement setup is
shown in Fig. 4(a). For the IFT measurements, a syringe is fitted with a
U-shape needle with a specified diameter and loaded with the crude
oil. An optically clear vessel is filled with the nanofluid. The concentra-
tions of the nanofluids is varied between 0 and 0.5 mg/mL. The tip of
the U-shaped needle is positioned in the vessel. The crude oil droplet
is positioned at the tip of the needle and then, the image of the drop is
recorded applying a CCD camera equipped with a macro-lens. Finally,
the image of the equilibrium pendant drop is analyzed by the image an-
alyzing software and the IFT is determined.
As Fig. 4(b) shows, two parameters of the pendant drop that are de-
termined experimentally are the equatorial diameter, de, and the
2
Δρgde
IFT ¼ ð1Þ
H
where, g and Δρ are acceleration of gravity and the difference between
the crude oil drop and the aqueous solution densities, respectively. The
shape parameter (H) depends on the value of shape factor (S = ds/de).
3.3. Batch adsorption experiments
The adsorption of G-DS-Su onto the sandstone is investigated by a
batch technique. The adsorption experiments are conducted using the
same procedure described in our previous work [23]. The residual con-
centration of G-DS-Su in the solution is determined by applying a cali-
bration curve obtained through the UV–Vis spectroscopy
measurements (Varian- Cary 50). The optical property of the G-DS-Su
aqueous solution measured by the UV–Vis spectra shows an absorption
peak at 265 nm (Fig. 5).
The inset figure in Fig. 5 shows the UV–Vis absorbance of the G-DS-
Su aqueous solutions at different concentrations at λ = 265 nm. Know-
ing the equilibrium concentration (Ce (mg/mL)) and initial concentra-
tion (C0 (mg/mL)) of G-DS-Su, the amount of G-DS-Su adsorption (%)
is calculated by the following equation.
ðC 0 −C e Þ
Adsorptionð%Þ ¼ ð2Þ
C0
3.4. Contact angle measurement
The contact angle measurements are used to assess the order of wet-
tability alteration of the sandstone slices after aging in nanofluids. Aging
procedure of sandstone slices and contact angle measurements are con-
ducted through the same method described in our previous work [23]. It
should be noted that the wettability of the surface is defined according

Fig. 7. (a) XRD spectra and (b) TEM image of NPG.

800 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806

to the contact angle in three phase system (water, oil and rock surface),
i.e. water wet for the contact angle in the range 0°–75°, intermediate for
the contact angle in the range 75°–115° and oil wet for the contact angle
in the range 115°–180° [24].

3.5. Core flood experiments

3.5.1. Coreflood set up

The schematic of coreflood setup is shown in Fig. 6. The core flooding
apparatus consists of three different stainless steel vessels. The vessels
are filled up each with brine or DI water, the nanofluid and crude oil.
The free floating piston separates the pump fluid from the injected
fluid inside the vessels. The pump injects water as a pump fluid from
bottle through pipes to push the piston plate located inside the cylin-
ders. The oil vessel's outlet line is separated from the other vessel's out-
let to avoid early mixing of the fluids. Valves are installed at inlet and
outlet of the vessels to regulate fluid flow. A bypass flow line is located
to clean the line before injecting another fluid. The influent flow lines
from the vessels are connected to a Hassler type stainless steel core
holder designed for consolidated core plugs. The sandstone cores are
placed inside a robber sleeved core holder, subjected to an external con-
fining pressure. A hand pump is used to fill the annulus between the
robber sleeve and the core holder with water up to the desired pressure
(here almost nearly 1000 psi) in order to prevent the fluid leakage from
the space between the core and the robber sleeve. The differential pres-
sure between two sides of the core holder is recorded by a precision
pressure gauge. The effluent from core is measured using an
accumulator.

3.5.2. Core porosity and permeability measurements

The core plugs dimensions and their dry weights are measured. The
Fig. 8. FTIR spectra of NPG before and after functionalization. core plugs are fully saturated with brine using a vacuum container. The
pore volume and porosity of the cores are calculated using the weight of

Fig. 9. (a) Images of the G-DS and G-DS-Su dispersion and (b) zeta potential of the G-DS-Su dispersion at different pH values.
 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806 801

Fig. 10. Optical micrographs of Pickering emulsions stabilized by G-DS-Su at different concentrations: (a) 0.2, (b) 0.5, (c) 1 and (d) 2 mg/mL. Organic phase: toluene, Oil/water ratio: 1:1.
The average droplet size is presented in each figure.

Fig. 11. Photographs of crude oil drops against nanofluids at different concentrations of G-DS-Su: (a) 0, (b) 0.2 and (c) 0.5 mg/mL. The IFT value is presented in each figure.

brine remained in the cores. The core plugs are flooded by brine at three
different flow rates (0.2, 0.6, 0.8 mL/min) in order to measure the abso-
lute water permeability using Darcy low. Then crude oil is injected into
the core plugs at the rate of 0.1 mL/min until surely no more brine is
produced. The oil in place (OIP) volume is equal to the produced
brine. The oil saturation (Soi) and water saturation (Swi) percent are
also calculated. Then the core plugs are aged in a cell containing crude
oil for 8 weeks to restore the reservoir equilibrium condition. The di-
mensions and mentioned properties of the core plugs are reported in
Table 1.
3.5.3. Coreflooding procedure
The coreflood experiments aim to reveal the nanofluids application
possibility for the enhanced oil recovery in sandstone reservoir rock.

Fig. 12. Schematic of amphiphilic nature of G-DS-Su at the oil/water interface.

802 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806
Fig. 13. The oil droplet on the sandstone surface after aging in (a) crude oil and then the G-DS-Su nanofluid at concentrations of (b) 0, (c) 0.5 and (d) 2 mg/mL.
The flooding experiments are conducted at room temperature. The
water was injected at constant rate of 0.2 mL/min approximately 2 PV.
The volume of effluents (oil and water) was recorded every 5 min.
The water flooding (secondary recovery) was continued until surely
no more oil is produced. Then the injection is continued at constant
rate 0.2 mL/min for approximately 3–4 PV of G-DS-Su as tertiary recov-
ery mode. The G-DS-Su flooding is conducted at two different concen-
trations of 0.5 and 2 mg/mL until no more oil is produced. The
cumulative oil recovery is calculated by Eq. (3).
Produced Oil ðmLÞ
Cumulative Oil Recovery ð%Þ ¼  100
OIP ðmLÞ
It seems that it is not reasonable to compare the cumulative oil re-
covery obtained after G-DS-Su flooding in two cores, because the cores
have different properties such as permeability or porosity which can af-
fect the amount of the recovered oil. In this way, the ratio of oil recovery
after the G-DS-Su flooding (with different concentrations) to the overall
oil recovery is calculated to have a better insight about the effect of G-
DS-Su concentration on the oil recovery.
4. Result and discussion
4.1. NPG characterization
Fig. 7(a) shows the XRD pattern of NPG The characteristic peak of
graphene for (001) plane appears at 2θ = 29.08°, which indicates that
the NPG has few layers of graphene with an interlayer distance of
about 0.31 nm based on Bragg's law (nλ = 2d sinθ) and the number
Fig. 14. The sandstone wettability alteration due to: (a) and (b) structural disjoining pressure mechanism and (c) adsorption of G-DS-Su onto the sandstone.
of graphene layers is about 3. Besides, according to the TEM images
(Fig. 7(b)), the graphene sheets with a porous structure are exfoliated.
4.2. Functionalized graphene characterization
The FTIR spectra of pristine and functionalized graphenes are shown
in Fig. 8. The signal at 1534 cm−1 shows the sp2 character of NPG [25].
The absorption peaks around 1106 cm−1 and 3417 cm−1 may be attrib-
uted to the C\\O and O\\H stretching vibrations, respectively.
The peaks at 1119, 1045 and 1009 cm−1 confirm the presence of sul-
fonic acid group in G-DS which is synthesized in the presence of SDBS
ð3Þ [18]. These peaks are also observed in the spectrum of G-DS prepared
without SDBS. It is concluded that the sulfonated graphene (G-DS) can
be synthesized without using SDBS. Therefore the prepared G-DS with-
out SDBS is used as the initial material for preparing G-DS-DETA. In the
case of G-DS-DETA, the characteristic band at 1513 cm−1 corresponds
to the N\\H bending. The appearance of a relatively broadened band
in 1513 cm−1 indicates the C\\N bond stretching. The two peaks at
3000 to 3400 cm−1 represents the N\\H stretching for amine modified
graphene [25]. The FTIR analysis clearly suggests the presence of\\NH2
groups in G-DS-DETA. The peaks of stretching N\\H are omitted after
sulfonation of G-DS-DETA. The peaks at 1162 and 1034 cm−1 confirm
the presence of a sulfonic acid groups in the G-DS-Su surface.
4.3. Nanofluid stability
The nanofluids of G-DS and G-DS-Su with concentration of 1 mg/L
are used to investigate the dispersion stability using visual observations.
For this purpose, the nanofluids are transferred to transparent vessels
after preparation and monitored for the changes of the dispersion
 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806
Fig. 15. Adsorption of G-DS-Su onto the sandstone.
stability with time. Both of the nanofluids are black in the appearance.
Fig. 9(a) shows the images taken just after preparation and also after
24 h. The settlement of G-DS nanoparticles gradually starts after 4 h.
The variation in dispersion stability of the G-DS nanofluids is mainly
due to the sedimentation process with time. The G-DS nanofluid is intro-
duced as water soluble graphene by Si and Samulski [11], but they did
not investigate the stability of this material with time. However, our ob-
servations show that the G-DS-Su nanofluid is almost stable for 24 h.
This may be due to the presence of more functional groups on its
structure.
The zeta potential variations of G-DS-Su dispersion at different pH
values are shown in Fig. 9(b). The zeta potential (Z. P) of nanofluids at
all pH values are at vicinity of −30 mV indicating stable colloidal sus-
pensions [26]. The negative charge of G-DS-Su surface pertains to the
ionization of the \\SO3H functional groups. The negative sites derived
from the sulfonic groups are enhanced as the pH increases and the sur-
face charge of G-DS-Su becomes more negative at basic pH values which
results in a decrease in the zeta potential values. This suggests that the
stability of G-DS-Su dispersions is due to the electrostatic repulsion,
rather than just its hydrophilicity [23]. The results indicated that the ob-
tained G-DS-Su is well dispersed in water.
Fig. 16. Oil recovery for water flooding and nanofluid flooding for (a) core no. 1 (concentration of G-DS-Su: 0.5 mg/mL) and (b) core no. 2 (concentration of G-DS-Su: 2 mg/mL).
803
4.4. Amphiphilic nature of S-DS-Su
The ability of G-DS-Su for preparing oil in water emulsions at differ-
ent concentrations is investigated. The microscopic images and the av-
erage droplet diameter of the emulsions are presented in Fig. 10. The
emulsion type is determined using the dilution method [27]. Our obser-
vations show that a drop of emulsion disperses in pure water, while, it
remains as a drop in pure oil (here toluene). Therefore, in this case the
emulsion type is inferred to be an oil/water emulsion. Moreover, it is ob-
served that the small amount of G-DS-Su (0.2 mg/mL) can form emul-
sions with an average droplet size of 3.55 μm.
The average droplet size decreases from 3.55 to 1.20 μm as the G-DS-
Su concentration increases from 0.2 to 2 mg/mL. The emulsion droplet
size is a function of the IFT value. The IFT between oil and different
nanofluids are tested to investigate the impact of G-DS-Su on the inter-
facial property of oil and water. The photographs of crude oil drops in DI
water and G-DS-Su dispersion bulk at various concentrations are pre-
sented in Fig. 11. The calculated IFT value is also presented below the
photographs. The IFT of DI water against crude oil is 14.49 mN/m and
is considered as a reference value. The G-DS-Su particle has the ability
to decrease the IFT at the oil–water interface and 12% decreasing of
the reference value at a concentration of 0.5 mg/mL is observed. The
IFT value is sensitive to the nanofluid concentration, and the IFT de-
creases as the nanofluid concentration increases. It is impossible to mea-
sure the IFT value at the nanofluid concentrations higher than
0.5 mg/mL because both the aqueous and organic phases were dark
and the shape of oil drop cannot be analyzed to obtain the IFT value.
As mentioned, the value of IFT for aqueous phase with G-DS-Su is
lower than the IFT value of DI water according to Fig. 11, and it can be
concluded that the aqueous phase contains surface-active agents,
which can act like a surfactant in the interface of crude oil and water.
In detail, the simultaneous presence of the carbon basal plane (hydro-
phobic) and the \\SO3H functional groups (hydrophilic) on a single
molecule makes the G-DS-Su sheets similar to the surface-active agents.
Therefore, thermodynamic stability (i.e., a minimum in free energy or
maximum in entropy of the system) will be achieved when they are ac-
cumulated at the oil/water interface, due to their affinity for both the or-
ganic and aqueous phases [28]. Therefore, with the hydrophilic group
aligned in the aqueous phase and the hydrophobic group in the organic
phase, the G-DS-Su sheets are willingly adsorbed at the water/oil inter-
face, leading to more IFT reduction as solid particle surfactants and
forming a Pickering emulsion. The amphiphilic nature of G-DS-Su sheets
at the oil/water interface is schematically shown in Fig. 12.
804 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806
Table 2
Oil recovery factor of nanofluid flooding at different concentrations.
Core no Nanofluid concentration (mg/mL) Oil recovery percent after
Water flooding
1 0.5 41
2 2 59
4.5. Wettability alteration of sandstone
The contact angle of oil-brine on the surface of sandstone is mea-
sured to assess the wettability alteration of the sandstone slices treated
at different concentrations of G-DS-Su. As Fig. 13(a) shows, the oil-brine
contact angle of the oil treated rock slices are about 165° representing a
strongly oil-wet condition. Treating the rock in DI water changes the
contact angle to 145°. The contact angle of oil on the surface of sand-
stone slides treated in the G-DS-Su dispersion with concentration of
0.5 mg/mL are about 148° which indicates the wettability of the sand-
stone slices changes from strongly the oil-wet to the oil-wet condition.
The contact angle changes to 107° at the G-DS-Su concentration of
2 mg/mL indicating that the wettability of hydrophobic surface is al-
tered from the oil-wet to the intermediate condition.
As mentioned before the nanoparticles (here G-DS-Su) tends to form
a wedge film in the three-phase contact region of the oil droplet,
nanofluid and rock pore surface. As a result, the structural disjoining
pressure is formed pointing to vertex of the wedge film (Fig. 14
(a) and (b)). While the structural disjoining pressure is stronger than
the adsorption force between oil droplet and rock pore surface, the ver-
tex of wedge film keeps moving forward which results in the detach-
ment of the oil droplet from the surface of rock pore [29].
As well, the G-DS-Su particles may be adsorbed on the rock surface
and changes the wettability of the sandstone surface. The adsorption ex-
periments confirm this claim. As Fig. 15 shows, a significant amount of
G-DS-Su is adsorbed onto the sandstone. The adsorption percent in-
creases with an increase in the initial concentration of G-DS-Su and de-
creases with an increase in the pH value.
Fig. 17. The schematic of displacement mechanism of G-DS-Su.
Overall oil recovery Oil recovery to overall oil recovery ratio
after
G-DS-Su flooding Water flooding G-DS-Su flooding
8 49 84 16
14 73 81 19
The used sandstone is mainly composed of quartz mineral as a major
component according to the XRD results. When quartz mineral is im-
mersed in water, the water molecules dissociate onto the silica surface
and the silanol groups (\\SiOH) are formed. The silanol groups are fur-
ther dissociated to\\SiO−. The formation of\\SiO– sites provides neg-
ative charges on the surface of quartz. The surface of G-DS-Su sheets
shows the π-electron-rich regions due to the presence of delocalization
of π electrons in its structure. Besides, there are the \\OH functional
groups on its structure. The adsorption mechanism of G-DS-Su onto
the sandstone may be the same as the mechanism proposed for the ad-
sorption of graphene oxide (GO) onto the sandstone in our previous
work [23]. In brief, the adsorption process may be attributed to the
hydrogen-bonding interaction between the oxygen-containing groups
on the G-DS-Su sheets and the silanol groups of sandstone. Moreover,
n-π interaction between the \\O− groups of sandstone and the π-
electrons of G-DS-Su may also play a role in the adsorption of G-DS-Su
onto the sandstone (Fig. 14(c)). When the surface of the sand is covered
by these hydrophilic groups, a water film is formed and detaches the oil
droplet from the sand surface [7].
4.6. Coreflood experiments
As it is shown in Fig. 16(a) and (b), the oil recovery at the break-
through was 41% and 59% for water flooding in the cores 1 and 2, re-
spectively. The total recovery after injection of about five pore
volumes of the G-DS-Su dispersions was 49 and 73%. Additional oil re-
covery that was observed from the injection of G-DS-Su at concentra-
tions of 0.5 and 2 mg/mL were 8 and 14%, respectively. It indicates the
 H. Radnia et al. / Journal of Molecular Liquids 271 (2018) 795–806
efficiency of the G-DS-Su in enhanced oil recovery. According to the re-
sults, G-DS-Su exhibited an excellent capability that made oil molecules
displace from an oil-wet surface.
The calculated values of oil recovery ratio after water and G-DS-Su
flooding to overall oil recovery are presented in Table 2. It can be ob-
served that 16 and 19% of the recovered oil in the core 1 and 2 is due
to using G-DS-Su at concentrations of 0.5 and 2 mg/mL, respectively.
Luo et al. [14] have designed and produced a nanofluid of graphene-
based amphiphilic nanosheets for using in core flooding experiments.
The result of the core flooding measurement in a core with porosity of
25.8% and permeability of 132 mD showed that the oil enhancement ef-
ficiency of 69.6% after brine flooding and 15.2% by the nanofluid
flooding; which means the ratio of oil recovery after nanofluid flooding
to overall oil recovery is 17.9% which is close to the results obtained in
our study.
4.7. Displacement mechanism
The flow of G-DS-Su dispersion in the core, during coreflood process,
is shown schematically in Fig. 17. When G-DS-Su introduced to the po-
rous media, some of them may adsorb on the sandstone surface and
alter the wettability of the rock and the others may adsorb at the oil/
water interface and decrease the IFT value.
The IFT results showed that adding G-DS-Su decreases the interfacial
tension, but an ultralow IFT was not achieved; in other words, the de-
gree of IFT reduction is not a main parameter in the oil displacement.
Hence, the wettability alteration plays a dominant role in the oil dis-
placement mechanism. The G-DS-Su in the oil/nanofluid/solid three-
phase contact region tends to form a wedge film according to the
model suggested by Wasan et al. [3–5] The interface of oil−water is
moved by the pressure gradient due to this self-arrangement of G-DS-
Su on the solid surface, and the nanofluid spreads beneath the oil
drop. The nanofluid layer appears between the oil and the rock surface
and the G-DS-Su molecules adsorbed onto the rock surface due to the
π-π and n-π interactions. The presence of the hydrophilic functional
groups (\\SO3H) in its structure led to change the rock surface to the
partially water-wet condition. In this stage, a water film is formed
onto the rock surface and the oil droplet is detached easily. This dis-
placement mechanism is also reported by the other researchers using
nanoparticles such as iron oxide (Fe2O3), aluminum oxide (Al2O3), and
silicon oxide treated by silane (SiO2) [1], titanium oxide (TiO2) [30],
SiO2 [31] and fluorescent carbon nanoparticles [16].
5. Conclusion
In this work, the nano porous graphene synthesized by the chemical
vapor deposition method is sulfonated using 4-sulfobenzenediazonium
salt. Then more sulfonated groups are introduced to the functionalized
graphene using chlorosulfonic acid. The final product is named as G-
DS-Su. The FTIR spectra confirm presence of the \\SO3H group in the
G-DS-Su structure. The zeta potential of G-DS-Su dispersions at all pH
values are at vicinity of −30 mV indicating stable colloidal suspensions.
This amphiphilic solid material is applied as a stabilizer to form Picker-
ing emulsions. The average droplet size of emulsions decreases from
3.55 to 1.2 μm with an increase in the G-DS-Su concentrations from
0.2 to 2 mg/mL. The interfacial tension between oil droplet and aqueous
phase decreases about 12% in the presence of 0.5 mg/mL of the G-DS-Su
in aqueous phase. The adsorption results show that the G-DS-Su is
adsorbed onto the sandstone surface. This may be due to the π-π and
n-π interactions between the functional groups and the basal plane of
G-DS-Su sheets with the \\OH groups of quartz mineral of the sand-
stone. The adsorption of G-DS-Su onto the sandstone along with forming
a wedge region at the interface of oil/water/sand is responsible for the
wettability alteration of the sandstone from strongly the oil wet to the
intermediate condition. The core flood experiments show that using
G-DS-Su at concentration of 0.5 and 2 mg/mL enhances the oil recovery
805
about 16 and 19%, respectively in comparison with water flooding. The
dominant oil recovery mechanism is the wettability alteration. Thus, the
direct sulfonation of graphene sheets provide a promising and efficient
chemical agent for the enhance oil recovery.
Acknowledgment
The authors gratefully acknowledge financial support from the Re-
search Institute of Petroleum Industry (RIPI).
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