Petroleum Research 7 (2022) 77e90

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Petroleum Research
journal homepage: http://www.keaipublishing.com/en/journals/
petroleum-research/

Applications of nanoparticles in enhanced oil recovery

Anirbid Sircar*, Kamakshi Rayavarapu, Namrata Bist, Kriti Yadav, Surbhi Singh
Centre of Excellence for Geothermal Energy, Gandhinagar, Raisan, 382007, Gujarat, India

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

Article history: Nanoparticles serve various purposes in the hydrocarbon industry which are utilized to improve the volume of
Received 5 July 2021 oil and gas production. Nanomaterials are used in petroleum applications as nanoparticles, nanosensors,
Received in revised form nanocomposites, coated nanoparticles, nanofluids etc. Thus, the application of nanotechnology in the
20 August 2021
enhanced oil recovery (EOR) method helps to extract the trapped oil present beneath the surface. Some nano
Accepted 22 August 2021
ultra-fine particles are cost-effective and eco-friendly. The injected fluid interacts with the rock/oil system to
Available online 24 August 2021
create a favourable environment for oil recovery. This study focuses on a review of the different types of
nanoparticles and nanomaterials used in petroleum applications. This paper aims to study the classification
Keywords:
Nano technology
and characterization of nanoparticles. This also includes the physiochemical and mechanical properties of
Nanofluids nanomaterials. The study discusses the applications of nanoparticles in chemical, miscible, thermal and mi-
Enhanced oil recovery crobial floodings. It mainly focuses on various mechanisms involved by adding nanoparticles such as
Interfacial tension wettability alteration, IFT reduction, rheology improvement, mobility control etc. This research also addresses
Green nanomaterials new green nanomaterials and nanocomposites, which includes injecting specialized green chemicals (sur-
factants, alcohols, and polymers) that successfully displace oil. The IFT between the displacing fluid and the oil
is reduced due to phase-behaviour properties.
© 2022 The Authors. Publishing services provided by Elsevier B.V. on behalf of KeAi Communication Co.
Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/
by-nc-nd/4.0/).

1. Introduction In the contemporary world, a global economic issue is a

Nanotechnology is the study of controlling matter on a nuclear,
atomic and super molecular nanoscale, which is about 1e100 nm.
Nanoscale has unique optical, magnetic, electrical, and, chemical
properties (Hamad et al., 2020). Nanomaterials have a larger surface
area as compared to large-scale materials with the same mass. They
have high volume concentrations. As material's surface area per mass
increases, a large amount of material can come into contact with an
external environment, which impacts reactivity. Quantum effect, a
larger surface area, and self-assembly are some of the unique prop-
erties of nanomaterials. Novel applications using nanomaterials are
emerging in different sciences such as chemistry, biology, physics,
materials science, and engineering. These are widely used in areas
such as information technology, transportation, medicine, food safety,
energy, and environmental science etc (Kazemzadeh et al., 2019).
During the current global health threat by the novel coronavirus
disease, 2019 (COVID -19) nanotechnology played an important role
in developing vaccines and therapeutic drugs based on nanomedicine
(Yang, 2021).
* Corresponding author.
E-mail address: Anirbid.sircar@spt.pdpu.ac.in (A. Sircar).
decrease in the supply of oil and an increase in the oil price
(Sundaraja et al., 2020). This oil crisis can be reduced by using
advanced technologies and innovative solutions using cost-
effective methods. Advanced technologies include the internet of
things, big data analytics, artificial intelligence, drones. (Sundaraja
et al., 2020; Boul and Ajayan, 2020).
The primary oil recovery methods can extract only 18e20% of
the original oil in place (OOIP). The Enhanced oil recovery method
(EOR) is the process of extracting additional crude oil from oil
reservoirs with a recovery factor of about 30e60% (Torsæter et al.,
2021). In the EOR process, the residual oil is recovered by using
chemical, thermal, miscible and polymer flooding. Although EOR is
an alternative method to recover additional oil there are some
drawbacks which include the degradation of chemicals (polymers
and surfactants) under reservoir conditions, large volume of
chemicals and high cost. Thus, Nanotechnology is profoundly
attractive but challenging in the petroleum industry to enhance oil
recovery due to its unique properties such as wettability alteration,
improvement in the mobility of trapped oil, enhancing the
consolidation of sands and reduction of interfacial tension(IFT)
(Udoh et al.,2021; Rezvani et al., 2020). Nanoparticles are classi-
fied according to their size, morphology, physical, chemical and
mechanical properties (Ealia et al., 2017; khan et al., 2019). Thus

https://doi.org/10.1016/j.ptlrs.2021.08.004
2096-2495/© 2022 The Authors. Publishing services provided by Elsevier B.V. on behalf of KeAi Communication Co. Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
A. Sircar, K. Rayavarapu, N. Bist et al.
the physico-chemical and mechanical properties of each nano-
particle are unique (khan et al., 2019; Li et al., 2021). Depending on
attractive and repulsive forces they can remain free or bound
together. Nanoparticles have a larger surface-area-to-volume ratio
and high chemical reactivity (Berube et al., 2011; Cheraghian
et al., 2020). Similarly, nanoparticles are resistant to degradation
in oil and gas reservoirs with high salinity and temperature
(Cheraghian et al., 2020). These characteristics make them suitable
for various EOR methods.
EOR methods such as chemical, thermal, miscible flooding and
microbial flooding involve different nanofluids (Sun et al., 2017;
Panchal et al., 2021a,b). Nanofluids are synthesized by adding
nanoparticles to fluids. This method intensifies and improves fluid
properties at low volume concentrations of the dispersion medium
(Cheraghian and Hendraningrat, 2016; Druetta and Picchioni,
2019). The most extensively studied nanoparticles are silica nano-
particles, which have shown promising EOR results (Negi et al.,
2021; Nasr et al., 2021a,b). Recent research has looked into the
possibilities of Al2O3, MgO, and Fe2O3 in EOR applications in addi-
tion to SiO2 nanoparticles (Cheraghian and Hendraningrat, 2016;
Pe
rez-Gramatges et al., 2021). Disjoining pressure, injection fluid
viscosity increase, asphaltene precipitation and prevention, inter-
facial tension, wettability alterations are some of the major EOR
mechanisms of nanoparticles (Zaid et al., 2014). They are utilized as
nanofluids, nanoemulsions, nanocatalysts and nanocomposites
(Haruna et al., 2021; Alnarabiji and Husein, 2020).
The objective of this paper is to look into the role of nano-
particles classification and its characterization. The impact of
nanoparticles on various EOR methods and their mechanisms such
as interfacial tension, wettability and rheology is highlighted in this
paper. This paper also discusses the novel green nanomaterials/
nanocomposites which involve injecting specialized green chem-
icals (surfactants/alcohols/polymers) that successfully displace oil.
This is due to phase-behaviour properties to reduce the IFT be-
tween the displacing fluid and the oil.
2. Classification of nanomaterials
Nanomaterials are structural components with a size smaller
than 1 mm with an external dimension in the nanoscale (Mageswari
et al., 2016). Nanomaterials exist in spherical, tubular, and irregular
shapes and can be found in a single, fused, aggregated, or agglom-
erated form. Based on their shape and structure nanomaterials are
classified into three categories such as nanoparticles, nanoclays, and
nanoemulsions are shown in Fig. 1. A nanoparticle is also known as
an ultrafine particle, with a dimension of 1e100 nm (nm) (Patel
et al., 2018). Nanoparticles are classified as organic and inorganic
nanoparticles. Inorganic nanoparticles include metal, ceramic
nanoparticles. Organic nanoparticles are carbon-based nano-
particles, lipid and polymeric nanoparticles. Nanoparticles are clas-
sified further as nanocrystals, nanoclusters, nanotubes, super
molecules etc. Nanoclays are nanoparticles made up of mineral sil-
icate layers with 1 nm thick and 70e150 nm wide (Patel et al., 2018).
Montmorillonite (MMT), kaolinite, and saponite are some examples
of nanoclays. Nanoemulsions are colloidal systems in which the
submicron size varies from 10 to 1,000 nm (Mageswari et al., 2016).
Nanoemulsions are classified as oil in water nanoemulsions, water in
oil nanoemulsions and bicontinuous nanoemulsions.
2.1. Nanoparticles
A nanoparticle size ranges between 1 and 100 nm (Mageswari
et al., 2016). Nanoparticles are found in the form of nanocomposites
or structures. All nanostructures are mainly composed of elementary
units with a low dimension (blocks). They may be zero dimension, one
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Petroleum Research 7 (2022) 77e90
dimension, two dimensions, and three dimensions in which the effect
of size on the resultant characteristic is visible also known as quantum
dots. As depicted in Table 1 nanomaterials are divided into Zero
dimensional (quantum dots), one dimensional (quantum wires), two
dimensional (thin films) and three-dimensional nanoparticles as
building blocks to build nanostructured materials (Strambeanu et al.,
2015). In zero-dimensional nanomaterials, electron movement is
different in all three directions. Electrons can only move in the X-di-
rection in one dimension; in two dimensions, they can only move on
the XeY plane; and in three dimensions, they can move in the X, Y, and
Z directions (Siegel, 1993).
Depending on their material type, nanoparticles are classified as
organic or inorganic. The inorganic salts precipitation, which is
bound to molecules by metallic and covalent interactions produce
inorganic nanoparticles (Sun et al., 2017). The organic nano-
particles are self-assembled into a three-dimensional structure. For
the preparation of organic nanoparticles synthetic and natural
organic compounds such as milk emulsion, protein aggregates,
lipid bodies and other complex structures are used to make organic
nanoparticles (Viruses, etc.) (Mohanraj and Chen, 2006).
2.2. Nanoclays
Nanoclays are nanoparticles made up of mineral silicate layers.
Nanoclays are classified into various classes based on their chemical
composition and nanoparticle morphology. Commonly found
nanoclays are montmorillonite, bentonite, kaolinite, hectorite, and
halloysite. For example, montmorillonite is made up of numerous
overlapping layers of crystal particles with a diameter of
100e200 nm and an average thickness of 0.96 nm (Nezhad and
Cheraghian, 2016). The chemical composition of nanoclays can
be easily determined using inductively coupled plasma; Fourier
transforms infrared spectroscopy, X-ray diffraction and gravimetric
analysis.
Depending on the surface layered charge and the types of
interlayer ions there are two forms of nanoclays such as cationic
and anionic. Preparation of nanoclays and organoclays in aqueous
or solid form employs charged (hydrophilic) molecules such as
phosphonium or imidazolium, alkyl or aryl ammonium. The ion
exchange reaction involves two effects: it increases the distance
between single sheets, allowing organic cation chains to move
between them and it alters each sheet's surface qualities from hy-
drophilic to hydrophobic or organophilic (Uddin, 2008;
Cheraghian, 2017).
2.3. Nanoemulsions
Nanoemulsions are colloidal systems in which the submicron size
varies from 10 to 1,000 nm (Agista et al., 2018). Polymers, droplets,
and solid material are dispersed in a viscous liquid, resulting in an
absorbing soft substance (Agista et al., 2018). The internal phase also
termed as discontinuous phase, is the dispersed phase, while the
dispersion medium is the external phase. Intermediate or interphase
is also known as an emulsifying agent. High energy emulsification
(high-pressure homogenization, Ultrasonication, microfluidizer) and
low energy emulsification (phase inversion temperature, phase
inversion composition and solvent displacement) are two ways for
making nanoemulsions (Kale and Deore, 2017).
3. Characterization of nanoparticles
The characterization or measurement of physical and chemical
properties of nanoparticles is a branch of nanometrology (Shukla
et al., 2018). Thus, identifying suitable characterization methodol-
ogies helps in researching nanoparticle properties (Mughal et al.,
A. Sircar, K. Rayavarapu, N. Bist et al.
Fig. 1. Nanomaterials classification: Nanoparticles, nanoclay, nanoemulsions (modified after Mageswari et al. (2016)).
Table 1
Examples of different nanomaterials dimensions (Mageswari et al., 2016).
Elementary units
Units of 0D (In the monometric range, there are 3 dimensions)
Units of 1D (In the monometric range, there are 2 dimensions)
Units of 2D (In the monometric range, there are 1 dimension)
2021). Characterization of nanoparticles and nanomaterials can be
done by using a variety of techniques such as atomic force micro-
scopy, dynamic light scattering, electron microscopy, FTIR spec-
troscopy, UVevisible spectroscopy, X-ray diffraction, and X-ray
photoelectron spectroscopy (Kumar and Dixit, 2017).
Nanoparticles properties are large surface area, active surfaces,
and unique optical and chemical responses. Nanoparticle-
containing materials have enormous surface areas, which in-
creases rapidly with decreasing in diameter of particle (Shukla
et al., 2018). The surface energy increases as the proportion of
particles on the material's surface increases with the material's area
as shown in Fig. 2. Furthermore, at high temperatures and pres-
sures, this enormous surface to volume ratio acts as a driving force
for diffusion (Abdelrahman and Adel, 2013).
4. Enhanced oil recovery
After primary and secondary oil recovery, more than 50% of the
in-place oil is still trapped in the reservoir (Aljabri et al., 2021). As a
result, tertiary recovery or enhanced oil recovery (EOR) is a process,
which includes chemical flooding, thermal flooding, miscible
flooding etc. for increasing oil production as shown in Fig. 3.
The upstream oil and gas industry might benefit greatly from
advancements in the nanotechnology field based on techniques
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Petroleum Research 7 (2022) 77e90
Examples
Fullerenes, Clusters, powders, molecules, rings, grains, metal carbides
Nanotubes, filaments, fibres, whiskers, belts, spirals, columns, springs,
Layers
that subject equipment materials to difficult operating conditions
(Boul, and Ajayan, 2020). One of the most important sectors of
application for nanoparticles is EOR, which produces higher
amounts of oil during extraction and thus ensures a faster return on
investment (Nourafkan et al., 2018). Several nanoparticles of
various sizes and concentrations have been utilized in a variety of
investigations. The processes at the nanoscale that are connected to
the EOR include wettability, coalescence, transient phenomena and
mass transfer effects (Nworu and Wilberforce Oti 2019; Yu et al.,
2010). Thus, understanding oil phase dispersion, oil drop mobi-
lisation, and oil bank formation are essential at this scale to use the
phenomenon of nanoparticles usage in the EOR process (Panchal
et al., 2021a,b). A wide variety of nanoparticles, such as magne-
sium oxide, aluminium oxide, zinc oxide, zirconium oxide, tin ox-
ide, iron oxide, nickel oxide, hydrophobic silicon oxide, and silicon
oxide treated with silane have found improved recovery and hy-
drocarbon production in several experimental studies conducted
on EOR process (Ogolo et al., 2012).
5. Mechanisms in chemical enhanced oil recovery methods
5.1. Degradation and precipitation
The reduction in physical properties of polymers is due to its
A. Sircar, K. Rayavarapu, N. Bist et al. Petroleum Research 7 (2022) 77e90

Fig. 2. Nanoparticles with a large surface area to volume ratio (modified after Abdelrahman and Adel (2013)).

Fig. 3. Flowsheet of enhanced oil recovery methods, challenges and mechanisms (modified after Cheraghian et al. (2020)).

changes in strength and chemical composition known as degra-
dation. Precipitation is a technique to isolate and purify polymers.
An oil reservoir has certain salinity, temperature and pH. At high
temperatures, high salinity and low pH, some injected compounds
deteriorate and thus become unstable (Mandal, 2015). The vis-
cosity of polymer solution is significantly influenced by polymer
degradation (Rueda et al., 2020). Under saline conditions, the
polymer molecules are screened by cations in the reservoir brine.
Thus at saline conditions it causes macromolecule contraction by
reducing the polymer chain entanglement and hydrodynamic
radius (Saha et al., 2021). Hence, the viscosity of the polymer so-
lution is reduced. Meanwhile, high temperatures induce the poly-
mer to hydrolyze and cause precipitation at divalent ions
80
(Gbadamosi et al., 2018). The acidification of injected chemicals
could be caused by low pH reservoir conditions (Agi et al., 2018).
5.2. Adsorption and retention
Adsorption and retention of chemicals occur during flow
through porous media. These factors depend on the type of
chemicals injected into the reservoir. Chemicals interact with the
reservoir rock in a variety of ways such as electrostatic attraction,
van der Waal forces, steric interaction, lowering the concentration
of chemical solutions injected etc (Jung et al., 2013). Polymer
adsorption is due to the adhesion of polymer molecules onto the
rock surface. Adsorption at the solid-liquid interface occurs due to
A. Sircar, K. Rayavarapu, N. Bist et al. Petroleum Research 7 (2022) 77e90

the transfer of a chemical molecule from the bulk solution phase to

the solid-liquid interface (Scott et al., 2020). Adsorbents include
surfactants and alkali compounds.
Polymer retention is one of the indispensable factors to govern
the propagation of the polymer through porous media (Sorbie,
2013; Gbadamosi et al., 2019a). Mechanical entrapment and
polymer macromolecules' size is the primary reason for the poly-
mer's retention (Kamal et al., 2015; Nourafkan et al., 2021).
Meanwhile, the propagation of polymer flow in the reservoir is
governed by polymer retention and impermeable pore volume
(Behera, and Sangwai, 2020).
Fig. 4 depicts the dynamics of polymer retention in reservoir
rock. Overall, the EOR process' effectiveness and economic viability
are determined by chemical adsorption or retention in porous
media (ShamsiJazeyi et al., 2014). The EOR adsorption or retention
is governed by electrolyte concentration (salinity), reservoir fluid
composition, temperature, pH and the presence of clay mineral
content (Emeka et al., 2020a,b; Mohammadi et al., 2020).

6. Applications of nanoparticles in EOR

Nanotechnology is used in a range of methods in the oil and gas

industry as depicted in Fig. 5 including drilling operations, flow
assurance, cementing, hydraulic fracturing and EOR. Engineered
nanoparticles are combined with fluids injected into the reservoir
to improve the production of oil in the EOR process (Foroozesh and Fig. 5. Application of nanotechnology in EOR (modified after Ali et al. (2020a)).
Kumar 2020). So applications of nanoparticles in different EOR
methods have many challenges for different mechanisms. Nano-
particles are highly attractive due to their characteristics and for EOR applications due to their intriguing properties and innova-
transport behaviour which shows great interest in EOR (Sandeep tive materials generated from the integration of polymers and
et al., 2020). As a result, nanotechnology is the probable solution nanoparticles (Daneshmand et al., 2021; Al-Anssari et al., 2021).
to the majority of issues involved in the oil and gas industry.

6.1. Nanoparticles in chemical flooding 6.1.1. Polymeric nanofluids

Chemical flooding is an oil recovery technique performed by
adding various chemicals to the injected water. Chemical EOR
methods are polymer, alkaline, surfactant, foam and combination
flooding (Alkaline/Surfactant/Polymer). Chemical EOR is a promising
method due to its increased efficiency, technology, economic
viability, and low capital cost (Kazemzadeh et al., 2019). Nano-
particles have recently shown great interest and are being proposed
Polymer-based nanofluids are fluids in which polymer nano-
particles are made by dispersing nanoparticles in polymer solutions
(Ali et al., 2018). Polymer-based nanofluids are divided into two
types based on their preparation methods. They are polymer-
coated nanoparticles and polymer nanoparticles. To overcome the
issues of nanoparticle aggregation and agglomeration in the oil
reservoir environment, polymer-coated nanoparticles are efficient
(Hu et al., 2021). Meanwhile, these polymer nanoparticles were

Fig. 4. Adsorption of polymers in porous media (modified after Sorbie (2013) and Gbadamosi et al. (2019b)), conventional EOR (left), nanofluid EOR (right).

81
A. Sircar, K. Rayavarapu, N. Bist et al.
developed to prevent polymer breakdown under typical reservoir
conditions (Davarpanah, 2020). Thus, nanofluids formed in EOR
due to polymers are efficient in enhancing rheology and mobility
control stability, reducing polymer adsorption, and altering
wettability (Taborda et al., 2021).
6.1.1.1. Enhancing rheology and mobility control stability. The flow
behaviour and deformation characteristics of fluids help to analyze
the viscoelastic properties of a polymer. To prevent viscous
fingering and to maintain a suitable mobility ratio in the reservoir,
rheological behaviour needs to be enhanced. So an injectant is
required for EOR applications. Polymers and nanoparticles deteri-
orate in the environment of reservoir brine (Chaturvedi et al.,
2021). Viscosity loss occurs when the cations present in the
brines contact the amide and carboxylate group molecules of a
polymer (AlamiNia and Khalilinezhad, 2017). The polymer's
interaction with nanoparticles has a synergic effect. It improves
both the polymer's rheology and nanoparticles' stability. The elec-
trostatic attraction of nanoparticles increases in the presence of
brine, causing agglomeration and aggregation and indicating a lack
of surface functionality which is crucial for the EOR process.
6.1.1.2. Adsorption inhibition. The interaction of the polymer with
nanoparticles behaves synergistically. Polymeric nanofluids have less
adsorption on porous media compared to polymer nanoparticles
containing nanoclay. The polymer nanoparticles which are contain-
ing SiO2 nanoparticles showed less adsorption onto sandstone rock
surfaces (Cheraghian et al., 2014; Almahfood et al., 2021).
6.1.1.3. Wettability alteration. Wettability alteration is essential for
improving microscopic displacement efficiency. At the interface of
the nanoparticles in polymer-based nanofluids, an interaction of
repulsive electrostatic forces occurs (Keykhosravi et al., 2021).
Brownian motion causes a two-dimensional layered structure in
nanoparticles. They produce a wedge coating when they come into
contact with an oil-saturated solid surface. Thus the resultant
wedge film is due to nanoparticle arranging at the solideoil-water a
three-phase interface zone (Kumar et al., 2020). This generates a
rise in disjoining pressure, causing the nanofluid phase to spread at
the vertex's wedge and changing the surface's wettability (Jiang
et al., 2017). The mechanisms involved in chemical oil recovery
are wettability alteration, IFT reduction and improved viscosity of
injectant as shown in Fig. 6.
6.1.2. Surfactant nanofluids
Surfactant nanofluid, which combines nanoparticles and sur-
factants, improves microscopic displacement efficiency by reducing
IFT and altering wettability (Almubarak et al., 2020).In the reser-
voir, this nanofluid might be used to create stable foams and
emulsions (Massarweh andAbushaikha 2020). Emulsions ensure
injectant conformance efficiency, while stable foams allow fluid to
be diverted throughout the reservoir from thief zones to reduced
permeability zones (Kesarwani et al., 2021; Mashat et al., 2018).
The IFT and wettability of fluids in a reservoir are key criteria to
consider when evaluating their distribution and flow (Dordzie
et al., 2021). Following secondary oil recovery, some of the oil be-
comes trapped due to capillary forces in the reservoir. A capillary
number is a dimensionless number that represents the capillary
force is seen in equation (1) (Hu et al., 2021).
Nc ¼ m*v=s* cos q (1)
where Nc is capillary number, m is the displacing fluid viscosity
(Pascal-second), v is the displacing Darcy velocity (metre/second), q
is the contact angle, and s is the IFT between the displacing fluid
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Petroleum Research 7 (2022) 77e90
and the displaced fluid (water and oil).
Oil recovery and residual oil saturation are related to Nc. NC rises
as residual oil saturation falls. As a result, a larger Nc results in a
higher oil recovery rate.
6.1.2.1. IFT reduction. Using a spinning drop tensiometer, Liu et al.
(2017) examined the effect of anionic surfactant and silica (SiO2)
nanoparticles for IFT reduction at the oil-water interface to mea-
sure the performance of surfactant nanofluid. The nanosurfactant
produced a four-fold IFT reduction at an overall concentration of
1000 ppm and 8:2 surfactants to SiO2 ratio. At high temperature
and high salinity (HTHS) conditions, nanofluid surfactants for EOR
methods are recommended (Asl et al., 2020; Machale et al., 2020).
Fig. 7 depicts the mechanisms of surfactant and nanoparticle
interaction in porous media. Nanoparticles are very effective and
boost the performance of surfactants by strengthening the governing
mechanism. Moreover, flooding research also suggests that adding
nanoparticles to the surfactant solution boosts oil recovery (Rezaei
et al., 2021). Nanosurfactant mechanisms for lowering IFT at the o/
w interface have been investigated. The investigation shows that the
mix causes the surfactant to adsorb on the nanoparticle surface,
resulting in a hydrophobic nanoparticle surface (Ivanova et al., 2020).
The molecules of surfactants molecules are transported from the
fluid's bulk to the interface by the nanoparticles' Brownian motion
(He et al., 2021). The nano surfactant reduces IFT by minimising
interfacial energy at the interface (Qian et al., 2020a,b). Conventional
surfactants use to desorb from the interface after some time. Nano-
particles prevent surfactant molecules from desorbing from the
interface, resulting in improved IFT reduction (He et al., 2021).
6.1.2.2. Wettability alteration. Nanosurfactant reduces interfacial
tension at the rock/oil/brine contact, resulting in increased wetta-
bility change (Yuan et al., 2021). When oil and water interact with
the surfactant nanofluid, their relative permeability curves alter.
Furthermore, the application of nano surfactants as wettability
alteration modifiers has been shown to increase the amount of oil
recovered from carbonate reservoirs, which are characterized by
low recovery of oil due to intrinsic natural fissures and hydropho-
bicity (Maurya and Mandal 2018). As a result, it indicates that the
water imbibition into the rock matrix is challenging due to the
effects of capillary pressure. Nwidee et al. (2017) investigated a
nanosurfactant concentration on oil-wet limestone at a tempera-
ture range of 0e70  C. The nanoparticles used were ZrO2 and nickel
oxide (NiO), with triton X-100 and CTAB as surfactants in the
formulation. ZrO2/CTAB and NiO/CTAB have a stronger affinity to-
wards the surface of the rock due to their strong electrostatic
contact and have shown improved efficiency of changes in wetta-
bility at all temperature conditions.
6.1.2.3. Adsorption reduction. The loss of surfactant molecules is
due to adsorption onto the subsurface formation rock during the
flooding phase. This is one of the key difficulties with the surfactant
enhanced oil recovery method (Bagrezaie and Pourafshary, 2015;
Qian et al., 2020a,b). Due to surfactant adsorption, the chemical
EOR process may become commercially unviable. As a result,
lowering surfactant adsorption improves oil recovery (Franco
et al., 2020). Yekeen et al. (2017), reported that adding nano-
particles such as SiO2 and Al2O3 prevents kaolinite's surfactant
adsorption. With Al2O3 nanoparticles, the adsorption of SDS on
kaolinite decreases by 38%. With SiO2 nanoparticles, SDS adsorp-
tion reduces by 75% (Wu et al., 2017).
6.1.2.4. Foam and emulsion stability. Foams for the recovery of oil
are formed by gas injection such as nitrogen, air or carbon dioxide
with a foaming agent. The foaming agent contains liquid and the
A. Sircar, K. Rayavarapu, N. Bist et al. Petroleum Research 7 (2022) 77e90

Fig. 6. Mechanisms of nanoparticles in chemical enhanced oil recovery (modified after El Shafey (2017)).

Fig. 7. Surfactants and nanoparticles in porous media (modified after Ali et al. (2018) and Eltoum et al. (2021)).

injected solution is injected into the reservoir. Foams comprise gas foams have two unique functions: (1) mobility control and (2) fluid
dispersion in liquid separated by a porous media lamella, with a gas diversion (Zhu et al., 2021). These techniques help foams to over-
phase on top and the bulk liquid at the bottom. In the reservoir, come problems associated with gas EOR, including gravity override

83
A. Sircar, K. Rayavarapu, N. Bist et al. Petroleum Research 7 (2022) 77e90

and viscous fingering (Sun et al., 2021). Surfactants, polymers, and (APG) which will help recover residual oil from rock pores. Based on
proteins are liquids that act as foaming agents (Wang et al., 2018). interfacial tension measurements, two formulations of DLCP, CNT, and
Foams are combined with polymers to seal high permeability sec- green surfactant mixtures were chosen for core-flood tests to inves-
tions and the polymer is redirected to reduce permeability areas, tigate their potential for EOR. The results yielded 45 percent tertiary
boosting the reservoir's volumetric sweep efficiency (Zhang et al., oil and 89 percent initial oil (OIIP) in one experiment. After water
2021; Wu et al., 2018). Foams that have been stabilized with sur- flooding, this composition produced a substantial amount of addi-
factants are stable (Ibrahim and Nasr-El-Din, 2020). This is tional oil. In another attempt, 27% tertiary oil and 77 percent OIIP was
because the amount of energy required is reduced and thus the yielded (Haq et al., 2020). The other research interest focused on
foam becomes more stable (Liu et al., 2020a). determining the potential of cellulose nanocrystals (CNC) through a
high-temperature core flood experiment. CNC acts as a green EOR
6.1.3. Green nanomaterials and nanocomposites agent for the tertiary recovery process. This study proves that there is
The concept of green nanomaterials and nanocomposites in the a substantial increase in viscosity after 24hrs of heating at 120  C as a
field of EOR for wettability change and reduction of interfacial tension function of higher particle Concentration. Thus CNC possesses great
between oil and water is a proven method by many researchers. In one potential in EOR as an additive if tested under different conditions
study, a polymer-coated ZnO/SiO2 green nanocomposite has been (Aadland et al., 2019).
produced from the pomegranate seed extract. This nanofluid enabled
19.28% higher oil recovery due to a significant reduction in interfacial
tension, higher viscosity, better emulsion stability, and wettability
6.2. Nanoparticles in thermal flooding
alteration towards a stronger water-wet system (Ali et al., 2019). A
recent study synthesized a novel nanocomposite consisting of copper
Heavier organic compounds, such as resins and asphaltenes, are
(II) and titanium oxide nanoparticles and polyacrylamide polymer for
known to be abundant in heavy oil (Shah, 2009). In addition to het-
use as a hybrid agent besides other chemical factors in enhanced oil
erocyclic derivatives, they have a higher concentration of molecules
recovery (EOR) processes. Reduction in water-oil interfacial tension by
with at least 60 carbon atoms. These mixes had high Physio-chemical
about 46% and 90% wettability alteration was observed by using this
properties such as high viscosity, boiling point, and molecular weight
mixture (Bahraminejad et al., 2019). Another study has worked on
(Sharma et al., 2021). This poses immense recovery challenges.
the synthesis of novel nanocomposites made from SiO2@Montmor-
Because oil's mobility is severely limited, and therefore displacement
ilant@Xanthan. Optimization of the concentration of the material
by simple fluids such as water or gas has become ineffective. As a
results in a reduction in interfacial tension, reversal of wettability and
result, recovery factors become limited. Nanomaterials are most
an 11.72% increase in tertiary oil recovery (Nazarahari et al., 2021).
commonly used as nanocatalysts in thermal EOR (Medina et al.,
The usage of extract from pomegranate seeds in the preparation of
2019). Nanocatalysts based on nickel, iron, and cobalt are employed
TiO2/SiO2/poly (acrylamide) as green and economic nanocomposites
in nanoassisted thermal EOR to reduce the viscosity of heavy oil (Luo,
has shown impressive results. The study has shown a reduction in 65%
and Ren, 2021). They can also be utilized in an in situ upgrading
of interfacial tension, alteration of wettability up to 32% and an in-
process known as aqua-thermolysis (Jadhav and Sangawai, 2020).
crease in oil recovery up to 10.5%. The original oil in place has shown
Nanocatalysts have a high surface-to-volume ratio, allowing more oil
an increase in recovery to 46.53% from 36.0% (Ali et al., 2021b).
to be exposed to the catalysts and thus a longer reaction time is
Another research on green nanomaterials has shown utilization of
required to reduce the oil's density/viscosity, as seen in Fig. 8.
extract from commersoniabartramia plant for synthesis of green
Furthermore, with appropriate thermal treatment, the nanoparticles
nanomaterials consisting of composition Fe3O4/eggshell nano-
may be easily separated. Hydrogenation, hydrodesulfurization,
composite. This nanocomposite helped in elevation of the perfor-
hydrodenitrogenation, and hydrocracking are the primary reactions
mance of surfactant and resulted in an increase in the original oil in
that occur during aquathermolysis (Fehr et al., 2020). Bond cleavage
place to 55.15% from 47% (Omidi et al., 2020). Another study tried to
of N, S, and O-containing molecules in the petroleum fraction is also a
develop a novel nanocomposite by CeO2/nanoclay nanocomposite.
prominent cause of this process. At temperatures ranging from 200  C
The Zeta potential peak of a mixture of surfactant and nanocomposite
to 400  C, aquathermolysis causes heavy oil viscosity to be irreversibly
is observed at 500 ppm concentration. The mixture also gives an
reduced (Zhao et al., 2021). According to Vesper bond theory (VBT),
improvement in wettability alteration of 38% in carbonate and 27% in
among C-O, C-S, and C-N chemical bonds, the C-S bond energy is the
sandstone rocks (Javad Nazarahari et al., 2020a, b). A study investi-
least one. Because of this, the C-S bond will break in the process of
gated where green nanocomposite was synthesized from an extract of
aquathermolysis and results in a low amount of sulphur and heavy
Artocarpusaltilis and prepared a mixture of CuO@Fe3O4@xanthan
components such as resin and asphaltenes. The essential component
nanocomposite. The method also resulted in a significant reduction of
of these reactions is the hydrolysis of aliphatic sulphur bonds. The
interfacial tension and the same was observed in the form of contact
reactions as seen in equations (2) and (3) (Romanov, 2011)
angle rise from 28 to 58 in carbonate rock (Manshadet al., 2020). In
another study conducted on the synthesis of titanium oxide nano-
R  S  R þ H2 O/CO þ H2 S
particles from the euphoria condylocarpa extract, where the nano-
particle was grafted on the surface of quartz to develop a green þ Organic molecules that are lighter (2)
nanocomposite. The application of this nanofluid enabled a 21%
Hydrolysis occurs when hydrogen is transferred from water to
increment in OOIP and a significant reduction in interfacial tension
oil via the water gas shift reactions (WGSR)
(Zargar et al., 2020). Another significant study was conducted where
a green nanocomposite was synthesized by using extract of Alocasia
CO þ H2 O / CO2 þ H2 (3)
macrorrhiza plant and preparing a nanofluid with the help of
Fe3O4@SiO2@xanthan nanocomposite. This study reported signifi- Clark et al. (1983) found that utilising aqueous metal salts
cant interfacial tension reduction and change in wettability (Ali et al., instead of water in steam stimulation enhances the asphaltene
2020a). Another research interest on carbon nanoparticles applica- content and viscosity of the recovered oil. The metals' catalytic
tion in EOR has shown great interest (Haq et al., 2020). This study influence on aquathermolysis processes, which has the potential to
aimed to see the effective date Leaf Carbon Particles (DLCP) and Car- improve steam stimulation on heavy oil, is responsible for the
bon Nanotubes (CNT) with the green surfactant alkyl polyglucoside observed benefits (Ahmadlouydarab et al., 2021).
84
A. Sircar, K. Rayavarapu, N. Bist et al. Petroleum Research 7 (2022) 77e90

Fig. 8. Effect of catalyst size on the performance of aquathermolysis in the treatment of oil (modified after Rezk and Allam (2019)).

6.3. Nanoparticles in miscible flooding wettability alteration by nanoparticles are two mechanisms that
can solve the problems of the WAG method. Also, the performance
Natural oil reservoirs have a low recovery factor. The miscible of WAG injection is improved. These reservoirs are good candidates
CO2 displacement mechanism is one of the EOR methods that have for carbon geo-sequestration (CGS) projects (Alansaari and Husein,
the potential to increase oil recovery (Bhatti et al., 2019). So due to 2020).
the difficulties and constraints of water and gas injection, such as
an unfavourable mobility ratio, gravity override and underride, and
6.4. Nanoparticles in microbial flooding
early fingering of injected fluid, water alternating gas (WAG) in-
jection has been used instead of water flooding (Moradi et al.,
Microbial enhanced oil recovery (MEOR) is a promising alter-
2015). Nanotechnology can be used to improve the performance
native oil recovery method that may be capable of recovering up to
of the WAG process by altering the microscopic and macroscopic
50% of residual oil. Biosurfactants, commonly referred to as microbe
sweep efficiencies of the process (Moradi et al., 2015). Injection of
surfactants, are used in this process. Surface tension, emulsification
nanoparticles into subsurface formations as liquid nanodispersions
index, and oil displacement are some of the key screening pro-
has been proposed as a smart alternative to traditional methods in
cedures used to evaluate biosurfactant production (Nehal and
tertiary oil recovery processes from mature oil reservoirs. As
Singh, 2021). The research study combined biosurfactants and
reservoir pressure decreases, the production rate of oil reservoirs
nanoparticles to improve oil recovery (Jacob et al., 2021). Bio-
gradually decreases. Precipitation and deposition of asphaltene are
surfactants are surface-active chemicals that lower interfacial ten-
the reason for this problem (Hassanpour et al., 2018). In the pro-
sion (IFT) between fluid components and improve oil
cess of injecting CO2 into synthetic oils, retardation of precipitation
pseudosolubilization in water by forming smaller oil droplets
of asphaltene was examined (Hassanpour et al., 2018). This
(Khire 2010). The nature of the carbon supply, nitrogen source,
research study shows the impacts of two nanoparticles such as ti-
temperature, aeration, and pH are factors that influence bio-
tanium oxide and iron oxide at various concentrations In terms of
surfactant formation. For biosurfactant production, ammonium
adsorption capacity and affinity, nanoparticle adsorption of
salts and urea are preferable nitrogen sources. Samples have
asphaltene and interaction with precipitated asphaltenes at the
exhibited the highest oil recovery indicating that the Serratia pre-
interface between the two fluids were critical in this process. When
sent in it was very active. Biosurfactants have recently been
these two nanoparticles were compared, Fe3O4 nanoparticles were
developed for the synthesis of nanoparticles of various metals and
found to be more effective than TiO2 at reducing asphaltene pre-
metal oxides, with unique properties such as reducing surface ac-
cipitation at the CO2-water interface. Zhang et al (2018) focussed
tivity at various interfaces, emulsifying properties, and the ability to
on mineral oil-water fluid miscibility with and without the addition
act as a capping, reducing, and stabilising agent, making them a
of surfactant decorated nanoparticles. By using a spinning drop
promising choice in green nanoparticles synthesis (Rane et al.,
tensiometer (SDT), IFT tests were conducted by adding hex-
2021). Another research fabricated the biosurfactant-mediated
adecyltrimethylammonium bromide (CTAB) surfactant-decorated
silver nanocrystals and their applications in enhanced oil recov-
SiO2 nanoparticles at different concentrations. Several character-
ery. As compared to chemically manufactured silver nanoparticles,
ization studies, including interfacial tension (IFT) and contact angle
biosurfactant-based silver nanoparticles are non-toxic and have
measurements, were carried out to investigate the experimental
better stability. Chemical-based Ag nanoparticles have a 14.94
data, which revealed that the Nano-WAG process improved the
percent oil recovery rate, while biosurfactant-based Ag NPs have a
recovery factor by more than 20% when compared to the WAG
14.28 percent oil recovery rate (Elakkiya et al., 2020). The other
method (Zhang et al., 2018). The results show that there is
research study shows a great interest to improve thermal efficiency
adsorption of SiO2 nanoparticles on the rock surface, wettability
through the utilization of porous media by gyrotactic microbe
change from oil-wet to strongly water-wet which affects the re-
dissemination. The gyrotactic microorganisms also improve the
covery, reduction of IFT. Another study proves IFT reduction and
stability of nanofluids (Ahmad et al., 2020). Thus the utilization of
85
A. Sircar, K. Rayavarapu, N. Bist et al.
Table 2
Classification and types of nanoparticles used in EOR Process.
Classification of Importance
nanoparticles
Carbon-based 1. Two main materials such as Carbon
nanoparticles Nanotubes (CNT) a tube that is made of
graphene sheets and fullerenes.
2. CNT’S are 100 times stronger than steel
3. CNTs are thermally and electrically
conductive along the length and non-
conductive across the tube
4. CNT’S had a structure and has a strong
electron affinity.
Metal nanoparticles 1. Metal nanoparticles can be synthesized in a
variety of ways such as chemical,
electrochemical or photochemical methods
2. Metal nanoparticles have high surface
energy and can adsorb tiny molecules.
Lipid-Based 1. Lipid nanoparticles are spherical in shape
nanoparticles and range in diameter from 10 to 100 nm.
2. It is made up of solid lipid and a matrix of
soluble lipophilic molecules.
3. The outer core of these nanoparticles is
stabilized by surfactants and emulsifiers.
Polymeric 1. Organic nanoparticles are polymeric
nanoparticles nanoparticles.
2. These have nanocapsule or nanosphere
features
3. The structure of a nanosphere is like a matrix
whereas the structure of a nanocapsule is
core-shell.
Ceramic nanoparticles 1. Ceramic nanoparticles are prepared by using
oxides, carbides, carbonates, phosphates and
are inorganic solids.
2. Ceramic nanoparticles are chemically inert
and have a high thermal resistance.
Semiconductor 1. Semiconductor nanoparticles belongs to the
nanoparticles groups of II-VI, III-V, or IV-VI from the peri-
odic table.
2. Semiconductor nanoparticles have been
used in photocatalysis, electronics, photo-
optics, and water splitting.
Petroleum Research 7 (2022) 77e90
Type of nanoparticles Highlights
used in EOR
Carbon-based 1. The research study proves that nanoparticles can form
nanoparticles adsorption layers on surfaces of sandstone and significantly
change wettability and IFT.
2. Brine/oil, carbon nanofluid/oil, and graphene nanofluid/oil
show IFT values of 39e40 mN/m, 41e44 mN/m, and 9.8
e11.4 mN/m, respectively.
3. According to spectroscopic investigations graphene has a
stronger contact i.e. higher adsorption on sandstone than
regular carbon nanoparticles
(Yahya et al., 2020)
Silica nanoparticles 1. This research has formulated, characterized, and evaluated
the modified and unmodified silica nanofluids (SNFs) for
EOR.
2. At low concentrations, silica nanofluids (SNFs) changed the
wettability of sandstone core from oil-wet at a contact
angle of 134.7 to water-wet at 54.3 (modified SNF) and
54.5 (unmodified SNF). As compared to unmodified SNF's
the modified SNF's IFT was low.
3. When modified and unmodified SNFs were applied, the oil
recovery of water floods improved to 62.9 percent, 75
percent respectively
(Ngouangna et al., 2020).
Lipid nanostructures as 1. This study evaluates the potential of lipid nanostructures as
surfactant carriers surfactant nanocarriers for the EOR process.
2.In this innovative concept, nanocarriers made up of
hydrophobic nanoparticles (NPs) can store and transport
surfactant molecules through reservoir porous media,
3. This releases the surfactant at the water-oil interface that has
been activated by the nanocarriers' solubilization.
4. Thus there is a possibility of an increase in oil recovery
(Rosestolato et al., 2019) >
Polymer-coated silica 1.Due to increased features such as solubility, stability, emulsion
nanoparticles stabilization, and minimum particle retention on the rock
surface, polymer-coated nanoparticles have been recently pro-
posed for enhanced oil recovery(EOR) in this study
2. Oil recovery properties of nanoparticles were investigated in
this study including interfacial tension (IFT) reduction,
wettability change, and log-jamming effect.
3. The incremental oil recovery in tertiary recovery mode
ranged from 2.6 percent to 5.2 percent OOIP.
4.In the presence of PSiNPs, the IFT between oil and water was
reduced from 10.6 to 2.5e6.8 mN/m, which had a minor effect
on EOR
(Bila et al., 2019
Metal oxide/SiO2 1. In this study, wettability, interfacial tension (IFT), injected
nanocomposites fluid viscosities, nanoparticles retention in porous media
were studied.
2. Carbonate sand pack floodings were used to synthesize and
test Fe3O4/SiO2 and TiO2/SiO2 nanocomposites for EOR
applications.
3. A tertiary SiO2 nanofluid injection at 1500 psi resulted in
incremental Nanoparticle oil recovery, by 14 percent. At
pressures of about 3500 and 1500 psi, Fe3O4/SiO2 and TiO2/
SiO2 nanofluids boosted oil recovery by 24 and 23 percent,
respectively.
(Kazemzadeh et al., 2018)
ZnO nanoparticles 1. The applications of metal-oxide nanoparticles (NPs) to boost
oil recovery (EOR) was found efficient in current research.
2. An electromagnetic (EM) field can also polarize these
nanoparticles, resulting in EM-assisted Nano-EOR, a novel
Nano-EOR technique.
3. The wettability, mobility ratio and interfacial tension (IFT)
were the factors in this mechanism.
4. 0.1 wt percent EM-assisted nanofluid flooding was used for
this research.
5. ZnO produces a maximum oil recovery of 10.39 percent and
13.08 percent of OOIP at electro-magnetic frequencies of
18.8 and 167 MHz, respectively.
(Adil et al., 2020)
86
A. Sircar, K. Rayavarapu, N. Bist et al.
nanoparticles, nanofluids, and nanotechnology is a new advance-
ment in the Energy Industry if implemented in the sector; they will
significantly enhance oil recovery rates.
6.5. Recovery mechanisms of nanoparticles and their applications
in EOR
Nanoparticles are classified according to their size, morphology,
physical and chemical properties. Some of them are carbon-based
nanoparticles, metal, lipid-based, ceramic, polymeric and semi-
conductor nanoparticles. Table 2 depicts the classification of
nanoparticles and their associated properties. It also shows the
types of nanoparticles used in the EOR process which are reported
in various literature reviews and their results are highlighted. A
recovery mechanism of different nanoparticles plays an indis-
pensable tool in increasing oil production in the EOR process (Liu
et al., 2020b). The research study shows that using different
types of nanoparticles improves the recovery of oil. Carbon-based
nanoparticles and lipid-based nanoparticles such as Carbon
Nanotubes (CNT), graphene and nanostructured lipid carriers help
to reduce the IFT and improve oil recovery. Research studies on
metal nanoparticles such as Sio2, Tio2 etc. are promising in EOR
applications (Santamaria et al., 2021; Nasr et al., 2021a,b). These
nanoparticles reduce IFT and oil viscosity, alters wettability, acts as
an oil-water emulsion stabilizer, and produces high recovery fac-
tors. Ceramic nanoparticles are metal oxide nanoparticles such as
aluminium oxide (Al2O3), magnesium oxide (MgO) and Copper
oxide (CuO) etc. helps to reduce oil viscosity and Interfacial tension.
Polymer-based nanoparticles help in reducing IFT, altering wetta-
bility and controlling mobility ratio. A semiconductor nanoparticle
helps to reduce IFT and alters wettability. Thus, each nanoparticle
plays an important role in increasing oil production. But, according
to the study, Sio2 and Tio2 are the most effective and widely used
nanoparticles in the oil and gas industry (Olayiwola and Dejam,
2020). Recovery of oil reached the maximum in Sio2 and Tio2
nanoparticles (Emeka et al., 2020a,b).
7. Conclusions
The present study tries to conduct a systematic assessment of
the applications of nanotechnology to several aspects of the pe-
troleum and natural gas sector. The synthesis and applicability of
smart nanomaterials in hydrocarbon recovery have progressed
rapidly in this field. Several nanoparticles of various sizes and
concentrations are used in the different EOR methods. However,
there are still some issues with implementing this technique into
practice. One of the issues is hunt for a more cost-effective and
reasonable synthetic method. The majority of current synthetic
approaches are reliant on inefficient technology and materials that
are harmful to the environment. A low-cost technique for nano-
material fabrication and delivery is of research interest. Another
challenging aspect is to disperse nanoparticles into reservoirs. An
effective and transportation method is required. Chemical nano-
particles such as Sio2 and Tio2 have shown great potential in
recovery.
Study on green nanomaterials that utilize plant extracts to
prepare nanoparticles also shows great avenues. Green nano-
composites from pomegranate extract, xanthum, egg shell, date
leaf, euphoria condylocarpa etc. are regularly being experimented
by researchers. Positive impacts such as wettability alteration, IFT
reduction and high OOIP have been achieved by this method.
The oil and gas sector will benefit greatly from the stimulation of
ideas and breakthroughs in the field of nanotechnology by sub-
jecting equipment materials to extended working conditions.
Furthermore, the advent of nanotechnology, which is linked to
87
Petroleum Research 7 (2022) 77e90
excellent modelling tools, allows for the characterization of a fluid-
mineral interfacial process that possess flow control and wetta-
bility, providing a thorough understanding of the mechanisms
relating to increased heavy oil recovery.
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